XANES study of elemental mercury oxidation over RuO 2/TiO 2 and selective catalytic reduction catalysts for mercury emissions control

DOE PAGES

Liu, Zhouyang; Li, Can; Sriram, Vishnu; ...

2016-07-25

Linear combination fitting of the X-ray Absorption Near Edge Spectroscopy (XANES) was used to quantify oxidized mercury species over RuO 2/TiO 2 and Selective Catalytic Reduction (SCR) catalysts under different simulated flue gas conditions. Halogen gases play a major role in mercury oxidation. In the absence of halogen gas, elemental mercury can react with sulfur that is contained in both the RuO2/TiO2 and SCR catalysts to form HgS and HgSO 4. In the presence of HCl or HBr gas, HgCl 2 or HgBr 2 is the main oxidized mercury species. When both HCl and HBr gases are present, HgBr2 ismore » the preferred oxidation product and no HgCl 2 can be found. The formation of HgO and HgS cannot be neglected with or without halogen gas. Other simulated flue gas components such as NO, NH 3, SO 2 and CO 2 do not have significant effect on oxidized mercury speciation when halogen gas is present.« less

Geochemistry of minor elements in the Monterey Formation, California; seawater chemistry of deposition

USGS Publications Warehouse

Piper, D.Z.; Isaacs, C.M.

1995-01-01

Approximately 24 samples of the Monterey Formation, Southern California, have been analyzed for their major-element oxide and minor-element content. These analyses allow identification of a detrital fraction, composed of terrigenous quartz, clay minerals, and other Al silicate minerals, and a marine fraction, composed of biogenic silica, calcite, dolomite, organic matter, apatite, and minor amounts of pyrite. The minor-element contents in the marine fraction alone are interpreted to have required, at the time of deposition, a high level of primary productivity in the photic zone and denitrifying bacterial respiration in the bottom water.

Minor Elements in Nakhlite Pyroxenes: Does Cr Record Changes in REDOX Conditions during Crystallization?

NASA Technical Reports Server (NTRS)

McKay, G.; Schwandt, C.; Le, L.; Mikouchi, T.

2007-01-01

Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998

The NO/ONOO-Cycle as the Central Cause of Heart Failure

PubMed Central

Pall, Martin L.

2013-01-01

The NO/ONOO-cycle is a primarily local, biochemical vicious cycle mechanism, centered on elevated peroxynitrite and oxidative stress, but also involving 10 additional elements: NF-κB, inflammatory cytokines, iNOS, nitric oxide (NO), superoxide, mitochondrial dysfunction (lowered energy charge, ATP), NMDA activity, intracellular Ca2+, TRP receptors and tetrahydrobiopterin depletion. All 12 of these elements have causal roles in heart failure (HF) and each is linked through a total of 87 studies to specific correlates of HF. Two apparent causal factors of HF, RhoA and endothelin-1, each act as tissue-limited cycle elements. Nineteen stressors that initiate cases of HF, each act to raise multiple cycle elements, potentially initiating the cycle in this way. Different types of HF, left vs. right ventricular HF, with or without arrhythmia, etc., may differ from one another in the regions of the myocardium most impacted by the cycle. None of the elements of the cycle or the mechanisms linking them are original, but they collectively produce the robust nature of the NO/ONOO-cycle which creates a major challenge for treatment of HF or other proposed NO/ONOO-cycle diseases. Elevated peroxynitrite/NO ratio and consequent oxidative stress are essential to both HF and the NO/ONOO-cycle. PMID:24232452

The Phosphoria Formation at the Hot Springs Mine in Southeast Idaho; a source of selenium and other trace elements to surface water, ground water, vegetation, and biota

USGS Publications Warehouse

Piper, David Z.; Skorupa, J.P.; Presser, T.S.; Hardy, M.A.; Hamilton, S.J.; Huebner, M.; Gulbrandsen, R.A.

2000-01-01

Major-element oxides and trace elements in the Phosphoria Formation at the Hot Springs Mine, Idaho were determined by a series of techniques. In this report, we examine the distribution of trace elements between the different solid components aluminosilicates, apatite, organic matter, opal, calcite, and dolomite that largely make up the rocks. High concentrations of several trace elements throughout the deposit, for example, As, Cd, Se, Tl, and U, at this and previously examined sites have raised concern about their introduction into the environment via weathering and the degree to which mining and the disposal of mined waste rock from this deposit might be accelerating that process. The question addressed here is how might the partitioning of trace elements between these solid host components influence the introduction of trace elements into ground water, surface water, and eventually biota, via weathering? In the case of Se, it is partitioned into components that are quite labile under the oxidizing conditions of subaerial weathering. As a result, it is widely distributed throughout the environment. Its concentration exceeds the level of concern for protection of wildlife at virtually every trophic level.

The aluminosilicate fraction of North Pacific manganese nodules

USGS Publications Warehouse

Bischoff, J.L.; Piper, D.Z.; Leong, K.

1981-01-01

Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (> 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition. ?? 1981.

A highly oxidized atmosphere-ocean system and oceanic molybdenum drawdown during the Paleoproterozoic

NASA Astrophysics Data System (ADS)

Goto, K. T.; Ito, T.; Suzuki, K.; Anbar, A. D.; Gordon, G. W.; Kashiwabara, T.; Takaya, Y.; Shimoda, G.; Nozaki, T.; Kiyokawa, S.; Tetteh, G. M.; Nyame, F. K.

2014-12-01

Multiple lines of evidence suggest that the first major oxidation of the atmosphere-ocean system occurred during the Paleoproterozoic. However, the course of this redox transition remains elusive. A number of large Mn deposits are distributed in Paleoproterozoic sedimentary successions. As Mn is a redox-sensitive element characterized by high redox potential, knowledge of the Mn cycle in Paleoproterozoic seawater may provide insight into redox evolution during this period. Here, we investigate the Mn cycle in Paleoproterozoic seawater based on the Re-Os and Mo isotope compositions, and the abundance of major and trace elements, in Mn-rich sedimentary rocks from the Nsuta deposit of the Birimian Supergroup, Ghana. The Mn ore is composed mainly of rhodochrosite and is distributed at the boundaries between sedimentary rocks and tholeiitic volcanic rocks. The Re-Os isochron age (2217 ± 100 Ma) we obtained was consistent with U-Pb zircon ages of the volcanic rocks. The manganophile elements, except for Mo, show no enrichment, which is similar to modern hydrothermal Mn oxides. The PAAS-normalized REE compositions show positive Ce anomaly, indicative of Ce enrichment due to the oxidation of Ce(III) by Mn(IV). These findings suggest that Mn ore formed from primary precipitation of Mn oxides from hydrothermal fluids as they were mixed with bottom seawater at ~2.2 Ga. Thus, the bottom seawater would have been sufficiently oxygenated for the precipitation of Mn oxides at ~2.2 Ga. The Nsuta ore samples exhibit slight Mo enrichment, but Mo/Mn ratios are orders of magnitude lower than those in modern hydrothermal Mn oxides. We also found that the Mo isotopes in the Nsuta ore are ~0.7‰ heavier than those in modern hydrothermal and hydrogenous Mn oxides. As Mo in hydrothermal Mn oxides is sourced primarily from seawater (Goto et al., in prep), these results may reflect smaller oceanic Mo inventory and heavier seawater Mo isotope composition at 2.2 Ga than those of present-day. Our calculation using a simple mass balance model suggests that substantial removal of light Mo by Mn oxides may have caused such oceanic conditions. Our findings are consistent with the recently proposed 'oxygen overshoot' model (Bekker and Holland, 2012) and low Mo contents in ~2.2-Ga black shales and sedimentary pyrites (e.g., Scott et al., 2008).

OXIDATIVE STRESS AND LIPID MEDIATORS INDUCED IN ALVEOLAR MACHROPHAGES BY ULTRAFINE PARTICLES

EPA Science Inventory

In ambient aerosols, ultrafine particles (UFP) and their agglomerates are considered to be major factors contributing to adverse health effects. Reactivity of agglomerated UFP of elemental carbon (EC), Printex 90, Printex G, and diesel exhaust particles (DEP) was evaluated by the...

Geochemical Fractionations and Mobility of Arsenic, Lead and Cadmium in Sediments of the Kanto Plain, Japan.

NASA Astrophysics Data System (ADS)

Hossain, Sushmita; Oguchi, Chiaki T.; Hachinohe, Shoichi; Ishiyama, Takashi; Hamamoto, Hideki

2014-05-01

Lowland alluvial and floodplain sediment play a major role in transferring heavy metals and other elements to groundwater through sediment water interaction in changing environmental conditions. However identification of geochemical forms of toxic elements such as arsenic (As), lead (Pb) and cadmium (Cd) requires risk assessment of sediment and subsequent groundwater pollution. A four steps sequential extraction procedure was applied to characterize the geochemical fractionations of As, Pb and Cd for 44 sediment samples including one peat sample from middle basin area of the Nakagawa river in the central Kanto plain. The studied sediment profile extended from the bottom of the river to 44 m depth; sediment samples were collected at 1m intervals from a bored core. The existing sedimentary facies in vertical profile are continental, transitional and marine. There are two aquifers in vertical profile; the upper aquifer (15-20m) contains fine to medium sand whereas medium to coarse sand and gravelly sand contain in lower aquifer (37-44m). The total As and Pb contents were measured by the X-Ray Fluorescence analysis which ranged from 4 to 23 mg/kg of As and 10 to 27 mg/kg of Pb in sediment profile. The three trace elements and major heavy metals were determined by ICP/MS and ICP/AES, and major ions were measured by an ion chromatograph. The marine sediment is mainly Ca-SO4 type. The Geochemical analysis showed the order of mobility trends to be As > Pb > Cd for all the steps. The geochemical fractionations order was determined to be Fe-Mn oxide bound > carbonate bound > ion exchangeable > water soluble for As and Pb whereas the order for Cd is carbonate bound > Fe-Mn oxide bound > ion exchangeable > water soluble. The mobility tendency of Pb and Cd showed high in fine silty sediment of marine environment than for those from continental and transitional environments. In the case of As, the potential mobility is very high (>60%) in the riverbed sediments and clayey silt sediment at 13m depth which is just above the upper aquifer. This potential mobility may pose a threat to upper aquifer and riverbed aquatic system. The overall geochemical analysis revealed that the dissolution of Fe-Mn oxide is the most effective mechanism for As, Pb in groundwater however the mobility of Cd is mainly carbonate bound. In the present study, the pollution level is much below from leaching environmental standards (0.01 mg/L) for all three elements and the total content is within the natural abundance of As, Pb and Cd in sediment. The potential mobility of these elements in oxidized fine silty sediment and the possible further effect to the aquifer suggest that shallow groundwater abstraction should be restricted to protect seasonal groundwater fluctuation. Moreover marine sediment containing high total toxic element contents and mobility tendency at changing oxidation and reduction environments requires proper management when sediments are excavated for construction purpose.

Application of major and trace elements as well as boron isotopes for tracing hydrochemical processes: the case of Trifilia coastal karst aquifer, Greece

NASA Astrophysics Data System (ADS)

Panagopoulos, G.

2009-09-01

The Trifilia karst aquifer presents a complex hydrochemical character due to the intricate geochemical processes that take place in the area. Their discernment was achieved by using the chemical analyses of major, trace elements and boron isotopes. Major ion composition indicates mixing between seawater and freshwater is occurring. Five hydrochemical zones corresponding to five respective groundwater types were distinguished, in which the chemical composition of groundwater is influenced mainly due to the different salinization grade of the aquifer. The relatively increased temperature of the aquifer indicates the presence of hydrothermal waters. Boron isotopes and trace elements indicate that the intruding seawater has been hydrothermally altered, as it is shown by the δ11B depleted signature and the increased concentrations of Li and Sr. Trace elements analyses showed that the groundwater is enriched in various metallic elements, which derive from the solid hydrocarbons (bitumens), contained in the carbonate sediments of the Tripolis zone. The concentration of these trace elements depends on the redox environment. Thus, in reductive conditions As, Mn, Co and NH4 concentrations are high, in oxidized conditions the V, Se, Mo, Tl and U concentration increases while Ni is not redox sensitive and present high concentration in both environments.

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.

2009-01-01

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Key Elements of the Chemistry of Cytochrome P-450: The Oxygen Rebound Mechanism.

ERIC Educational Resources Information Center

Groves, John T.

1985-01-01

Discusses the structure and function of the liver protein cytochrome P-450, an important catalyst for a variety of detoxification reactions. Diagnostic substracts for this heme-containing monooxygenase, synthetic modes of the active site, and oxidations with synthetic metalloporphyrins are the major topic areas considered. (JN)

Effects of point defect concentrations of the reactive element oxides on the oxidation kinetics of pure Ni and Ni-Cr alloys

NASA Astrophysics Data System (ADS)

Yan, Ruey-Fong

The addition of some reactive element oxides, e.g. Ysb2Osb3 or ZrOsb2, has significant effects, e.g. improvement in scale adhesion and reduction in oxidation rate, on the oxidation behavior of chromia and alumina scale forming alloys at high temperatures. However, there is little agreement about how a small addition of an oxygen-active element can cause such profound effects. It was the goal of this project to study the growth kinetics of an oxide scale when different reactive-element oxides were added to pure Ni and Ni-Cr alloys and, consequently, to aid in clarifying the mechanism of reactive element effects. The oxidation kinetics were measured using a thermogravimetric analysis (TGA) method and the material characterization of oxide scale was conducted. The relationship between point defect structures and oxidation kinetics was discussed. The results in this research showed that Ysb2Osb3 and ZrOsb2 exhibited the reactive element effects on the oxidation behaviors of Ni and Ni-Cr alloys. In addition, the point defect concentrations of the reactive element oxide, Ysb2Osb3, were changed by doping of different valent oxides. The modification of point defect concentrations of the reactive element oxide dispersed phases did change the oxidation kinetics of the pure Ni and Ni-Cr alloys containing Ysb2Osb3. These results indicate that the transport properties of the reactive element oxide dispersed phases are one of the important factors in determining the growth rate of an oxide scale.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

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

[Molecular mechanisms of ischemic-reperfusion syndrome and its personalized therapy].

PubMed

Grebenchikov, O A; Likhvantsev, V V; Plotnikov, E Iu; Silachev, D N; Pevzner, I B; Zorova, L D; Zorov, D B

2014-01-01

Cardiovascular pathologies are the major causes of morbidity and mortality in the world. Cessation of the blood flow in large vessels, supplying tissues with oxygen and substrates, leads to ischemic conditions accompanied by unwanted shifts of oxidative metabolism and rise of the reactive oxygen species (ROS) generation. Small amounts of ROS are essential elements of the cell metabolism, however pathological elevation of ROS jeopardizes the survival of cells, organs and even organisms. Paradoxically, blood flow restoration during prolonged ischemia leads to oxidative stress that is often fatal for a live system. Oxygen paradox appears to be a limiting factor in clinical practice that intuitively seeks for immediate and complete restoration of a damaged blood flow. Mitochondrion is a major ROS source and a key element of pro-apoptotic signaling, however it is clear, that mitochondria are the main target for anti-ischemic treatment. In the present review we consider two ways of such anti-ischemic strategy, bringing ischemic tolerance to the organ through mitochondrial involvement, such as intrinsic, biological, or artificial, pharmacological adaptive systems (preconditioning). The latter is aimed to simulate elements and high efficiency of intrinsic protective system. The role of antioxidants in anti-ischemic therapy and their effects on preconditioning signaling are discussed in the review.

Synthesis, characterization and application of a nano-manganese-catalyst as an efficient solid catalyst for solvent free selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol

NASA Astrophysics Data System (ADS)

Habibi, Davood; Faraji, Ali Reza

2013-07-01

The object of this study is to synthesize the heterogeneous Mn-nano-catalyst (MNC) which has been covalently anchored on a modified nanoscaleSiO2/Al2O3, and characterized by FT-IR, UV-Vis, CHN elemental analysis, EDS, TEM, and EDX. The method is efficient for the highly selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol without the need to any solvents, using tert-butyl hydroperoxide (TBHP) as an oxidant. Oxidation of ethylbenzene, cyclohexene, and benzylalcohol gave acetophenone, 2-cyclohexene-1-one and benzaldehyde, respectively, as major products. Reaction conditions have been optimized by considering the effect of various factors such as reaction time, amounts of substrates and oxidant, Mn-nano-catalyst and application of various solvents.

Some additional observations on inclusions in the granitic rocks of the Sierra Nevada

USGS Publications Warehouse

Dodge, F.C.W.; Kistler, R.W.

1990-01-01

Microgranular quartz diorite and diorite inclusions are widespread in central Sierra Nevada granitoid rocks and are almost exclusively restricted to hornblende-bearing rocks, most commonly felsic tonalites and mafic granodiorites. The Nd-Sm and Rb-Sr systematics indicate that most inclusions were in isotopic equilibrium with enclosing materials at the time of formation. Silica contents of inclusions and granitoids are contiguous, but inclusions generally contain less than, and granitoids more than, 60% SiO2. Ferric oxide and H2O+ trends relative to SiO2 suggests many inclusions formed as concentrations of hydrous mafic minerals. Variation of other major element oxides and trace elements support this inference. Most inclusions represent fragmented crystal accumulations of early-formed, near-liquidus minerals generated from these previously mixed magmas. -from Authors

Uranium and minor-element partitioning in Fe-Ti oxides and zircon from partially melted granodiorite, Crater Lake, Oregon

USGS Publications Warehouse

Tourrette, T.Z.L.; Burnett, D.S.; Bacon, C.R.

1991-01-01

Crystal-liquid partitioning in Fe-Ti oxides and zircon was studied in partially melted granodiorite blocks ejected during the climactic eruption of Mt. Mazama (Crater Lake), Oregon. The blocks, which contain up to 33% rhyolite glass (75 wt% SiO2), are interpreted to be portions of the magma chamber walls that were torn off during eruption. The glass is clear and well homogenized for all measured elements except Zr. Results for Fe-Ti oxides give DUoxide/liq ??? 0.1. Partitioning of Mg, Mn, Al, Si, V, and Cr in Fe-Ti oxides indicates that grains surrounded by glass are moderately well equilibrated with the melt for many of the minor elements, while those that are inclusions in relict plagioclase are not. Uranium and ytterbium inhomogeneities in zircons indicate that the zircons have only partially equilibrated with the melt and that uranium appears to have been diffusing out of the zircons faster than the zircons were dissolving. Minimum U, Y, and P concentrations in zircons give maximum DUzrc/liq = 13,DYzrc/liq = 23, and DPzrc/liq = 1, but these are considerably lower than reported by other workers for U and Y. Based on our measurements and given their low abundances in most rocks, Fe-Ti oxides probably do not play a major role in U-Th fractionation during partial melting. The partial melts were undersaturated with zircon and apatite, but both phases are present in our samples. This demonstrates an actual case of non-equilibrium source retention of accessory phases, which in general could be an important trace-element fractionation mechanism. Our results do not support the hypothesis that liquid structure is the dominant factor controlling trace-element partitioning in high-silica rhyolites. Rough calculations based on Zr gradients in the glass indicate that the samples could have been partially molten for 800 to 8000 years. ?? 1991.

Chemical weathering indices applied to weathering profiles developed on heterogeneous felsic metamorphic parent rocks

Treesearch

Jason R. Price; Michael A. Velbel

2003-01-01

Chemical weathering indices are commonly used for characterizing weathering profiles by incorporating bulk major element oxide chemistry into a single metric for each sample. Generally, on homogeneous parent rocks, weathering indices change systematically with depth. However, the weathering of heterogeneous metamorphic rocks confounds the relationship between...

Statistical tables and charts showing geochemical variation in the Mesoproterozoic Big Creek, Apple Creek, and Gunsight formations, Lemhi group, Salmon River Mountains and Lemhi Range, central Idaho

USGS Publications Warehouse

Lindsey, David A.; Tysdal, Russell G.; Taggart, Joseph E.

2002-01-01

The principal purpose of this report is to provide a reference archive for results of a statistical analysis of geochemical data for metasedimentary rocks of Mesoproterozoic age of the Salmon River Mountains and Lemhi Range, central Idaho. Descriptions of geochemical data sets, statistical methods, rationale for interpretations, and references to the literature are provided. Three methods of analysis are used: R-mode factor analysis of major oxide and trace element data for identifying petrochemical processes, analysis of variance for effects of rock type and stratigraphic position on chemical composition, and major-oxide ratio plots for comparison with the chemical composition of common clastic sedimentary rocks.

Reduced As Components in Highly Oxidized Environments: Evidence from Full Spectral XANES Imaging using the Maia Massively Parallel Detector

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

Etschmann, B.; Ryan, C; Brugger, J

2010-01-01

Synchrotron X-ray fluorescence (SXRF) and X-ray absorption spectroscopy (XAS) have become standard tools to measure element concentration, distribution at micrometer- to nanometer-scale, and speciation (e.g., nature of host phase; oxidation state) in inhomogeneous geomaterials. The new Maia X-ray detector system provides a quantum leap for the method in terms of data acquisition rate. It is now possible to rapidly collect fully quantitative maps of the distribution of major and trace elements at micrometer spatial resolution over areas as large as 1 x 5 cm{sup 2}. Fast data acquisition rates also open the way to X-ray absorption near-edge structure (XANES) imaging,more » in which spectroscopic information is available at each pixel in the map. These capabilities are critical for studying inhomogeneous Earth materials. Using a 96-element prototype Maia detector, we imaged thin sections of an oxidized pisolitic regolith (2 x 4.5 mm{sup 2} at 2.5 x 2.5 {micro}m{sup 2} pixel size) and a metamorphosed, sedimentary exhalative Mn-Fe ore (3.3 x 4 mm{sup 2} at 1.25 x 5 {micro}m{sup 2}). In both cases, As K-edge XANES imaging reveals localized occurrence of reduced As in parts of these oxidized samples, which would have been difficult to recognize using traditional approaches.« less

Dissolution of Used Nuclear Fuel Using a TBP/N-Paraffin Solvent

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

Rudisill, T. S.; Shehee, T. C.; Jones, D. H.

2017-10-02

The dissolution of unirradiated used nuclear fuel (UNF) pellets pretreated for tritium removal was demonstrated using a tributly phosphate (TBP) solvent. Dissolution of pretreated fuel in TBP could potentially combine dissolution with two cycle of solvent extraction required for separating the actinides and lanthanides from other fission products. Dissolutions were performed using UNF surrogates prepared from both uranyl nitrate and uranium trioxide produced from the pretreatment process by adding selected actinide and stable fission product elements. In laboratory-scale experiments, the U dissolution efficiency ranged from 80-99+% for both the nitrate and oxide surrogate fuels. On average, 80% of the Pumore » and 50% of the Np and Am in the nitrate surrogate dissolved; however, little of the transuranic elements dissolved in the oxide form. The majority of the 3+ lanthanide elements dissolved. Only small amounts of Sr (0-1.6%) and Mo (0.1-1.7%) and essentially no Cs, Ru, Zr, or Pd dissolved.« less

Concretionary manganese-iron oxides in streams and their usefulness as a sample medium for geochemical prospecting

USGS Publications Warehouse

Nowlan, G.A.

1976-01-01

Correlation studies of 400 samples of sieved stream sediments and 325 samples of fluvial, concretionary Mn-Fe oxides from Maine resulted in the separation of elements into the following categories: (1) elements not scavenged by Mn-Fe oxides - B, Cr, K, Mg, Rb, Sc, Ti, V, and Zr; (2) elements probably not scavenged by Mn-Fe oxides - Ag, Be, Ca, Ga, La, Sb, and Y; (3) elements scavenged weakly by Mn-Fe oxides - Cu, Mo, Pb, and Sr; (4) elements scavenged strongly by Mn oxides - Ba, Cd, Co, Ni, Tl, and Zn; and (5) elements scavenged strongly by Fe oxides - As and In. Studies of the scavenged elements showed that the deviation from the mean is characteristically greater in oxide samples as compared to sieved sediments from the same locality. However, a significant increase in contrast between anomalous and background localities, when oxides are the sample medium, more than offsets the disadvantage of data scatter. The use of oxides as a sampling medium clearly and significantly accentuates anomalous localities. In general, non-ratioed data on oxides give very nearly the same results as data consisting of scavenged elements ratioed to Mn and Fe. However, ratioed data expand the geographic area of specific anomalies. Cd and Zn consistently show strong correlations with concretionary Mn-Fe oxides, but their concentrations in the oxides do not generally show as much contrast between anomalous and background localities as do Cu, Mo, and Pb. These latter elements are strongly scavenged where rocks are mineralized. ?? 1976.

Method of making an apparatus for transpiration cooling of substrates such as turbine airfoils

DOEpatents

Alvin, Mary Anne; Anderson, Iver; Heidlof, Andy; White, Emma; McMordie, Bruce

2017-02-28

A method and apparatus for generating transpiration cooling using an oxidized porous HTA layer metallurgically bonded to a substrate having micro-channel architectures. The method and apparatus generates a porous HTA layer by spreading generally spherical HTA powder particles on a substrate, partially sintering under O.sub.2 vacuum until the porous HTA layer exhibits a porosity between 20% and 50% and a neck size ratio between 0.1 and 0.5, followed by a controlled oxidation generating an oxidation layer of alumina, chromia, or silica at a thickness of about 20 to about 500 nm. In particular embodiments, the oxidized porous HTA layer and the substrate comprise Ni as a majority element. In other embodiments, the oxidized porous HTA layer and the substrate further comprise Al, and in additional embodiments, the oxidized porous HTA layer and the substrate comprise .gamma.-Ni+.gamma.'-Ni.sub.3Al.

Study of the Reactive-element Effect in Oxidation of Fe-cr Alloys Using Transverse Section Analytical Electron Microscopy

NASA Technical Reports Server (NTRS)

King, W. E.; Ethridge, E. C.

1985-01-01

The role of trace additions of reactive elements like Y, Ce, Th, or Hf to Cr bearing alloys was studied by applying a new developed technique of transverse section analytical electron microscopy. This reactive-element effect improves the high temperature oxidation resistance of alloys by strongly reducing the high temperature oxidation rate and enhancing the adhesion of the oxide scale, however, the mechanisms for this important effect remain largely unknown. It is indicated that the presence of yttrium affects the oxidation of Fe-Cr-Y alloys in at least two ways. The reactive element alters the growth mechanism of the oxide scale as evidenced by the marked influence of the reactive element on the oxide scale microstructure. The present results also suggest that reactive-element intermetallic compounds, which internally oxidize in the metal during oxidation, act as sinks for excess vacancies thus inhibiting vacancy condensation at the scale-metal interface and possibly enhancing scale adhesion.

Developmental status of thermionic materials.

NASA Technical Reports Server (NTRS)

Yang, L.; Chin, J.

1972-01-01

Description of the reference materials selected for the major components of the unit cell of a thermionic pile element (TFE), the out-of-pile and in-pile test results, and current efforts for improving the life and performance of thermionic fuel elements. The component materials are required to withstand the fuel burnup and fast neutron fluence dictated by the thermionic reactor system. Tungsten was selected as the cladding material because of its compatibility with both the carbide and the oxide fuel materials. Niobium was selected as the collector material because its thermal expansion coefficient matches closely with that of the thin aluminum oxide layer used to electrically insulate the collector from the TFE sheath. An unfueled converter has performed stably over 41,000 hr. Accelerated irradiation tests have attained burnups equivalent to that for 40,000 hr of the thermionic reactor under consideration.

Elemental selenium at nano size possesses lower toxicity without compromising the fundamental effect on selenoenzymes: comparison with selenomethionine in mice.

PubMed

Wang, Huali; Zhang, Jinsong; Yu, Hanqing

2007-05-15

Glutathione peroxidase and thioredoxin reductase are major selenoenzymes through which selenium exerts powerful antioxidant effects. Selenium also elicits pro-oxidant effects at toxic levels. The antioxidant and pro-oxidant effects, or bioavailability and toxicity, of selenium depend on its chemical form. Selenomethionine is considered to be the most appropriate supplemental form due to its excellent bioavailability and lower toxicity compared to various selenium compounds. The present studies reveal that, compared with selenomethionine, elemental selenium at nano size (Nano-Se) possesses equal efficacy in increasing the activities of glutathione peroxidase and thioredoxin reductase but has much lower toxicity as indicated by median lethal dose, acute liver injury, and short-term toxicity. Our results suggest that Nano-Se can serve as an antioxidant with reduced risk of selenium toxicity.

Biogeochemical Cycles of Carbon and Sulfur on Early Earth (and on Mars?)

NASA Technical Reports Server (NTRS)

DesMarais, D. J.

2004-01-01

The physical and chemical interactions between the atmosphere, hydrosphere, geosphere and biosphere can be examined for elements such as carbon (C) and sulfur (S) that have played central roles for both life and the environment. The compounds of C are highly important, not only as organic matter, but also as atmospheric greenhouse gases, pH buffers in seawater, oxidation-reduction buffers virtually everywhere, and key magmatic constituents affecting plutonism and volcanism. S assumes important roles as an oxidation-reduction partner with C and Fe in biological systems, as a key constituent in magmas and volcanic gases, and as a major influence upon pH in certain environments. These multiple roles of C and S interact across a network of elemental reservoirs interconnected by physical, chemical and biological processes. These networks are termed biogeochemical C and S cycles.

Publications - RDF 2016-2 | Alaska Division of Geological & Geophysical

Science.gov Websites

, Major-oxide and trace-element geochemistry of mafic rocks in the Carboniferous Lisburne Group, Ivishak Surveys Skip to content State of Alaska myAlaska My Government Resident Business in Alaska Visiting Alaska State Employees DGGS State of Alaska search Alaska Division of Geological & Geophysical

The effects of trace element content on pyrite oxidation rates

NASA Astrophysics Data System (ADS)

Gregory, D. D.; Lyons, T.; Cliff, J. B.; Perea, D. E.; Johnson, A.; Romaniello, S. J.; Large, R. R.

2017-12-01

Pyrite acts as both an important source and sink for many different metals and metalloids in the environment, including many that are toxic. Oxidation of pyrite can release these elements while at the same time producing significant amounts of sulfuric acid. Such issues are common in the vicinity of abandoned mines and smelters, but, as pyrite is a common accessory mineral in many different lithologies, significant pyrite oxidation can occur whenever pyritic rocks are exposed to oxygenated water or the atmosphere. Accelerated exposure to oxygen can occur during deforestation, fracking for petroleum, and construction projects. Geochemical models for pyrite oxidation can help us develop strategies to mitigate these deleterious effects. An important component of these models is an accurate pyrite oxidation rate; however, current pyrite oxidation rates have been determined using relatively pure pyrite. Natural pyrite is rarely pure and has a wide range of trace element concentrations that may affect the oxidation rate. Furthermore, the position of trace elements within the mineral lattice can also affect the oxidation rate. For example, elements such as Ni and Co, which substitute into the pyrite lattice, are thought to stabilize the lattice and thus prevent pyrite oxidation. Alternatively, trace elements that are held within inclusions of other minerals could form a galvanic cell with the surrounding pyrite, thus enhancing pyrite oxidation rates. In this study, we present preliminary analyses from three different pyrite oxidation experiments each using natural pyrite with different trace element compositions. These results show that the pyrite with the highest trace element concentration has approximately an order of magnitude higher oxidation rate compared to the lowest trace element sample. To further elucidate the mechanisms, we employed microanalytical techniques to investigate how the trace elements are held within the pyrite. LA-ICPMS was used to determine the variability of trace element content from the pyrite samples. These data were then used to select areas of interest for NanoSIMS analyses, which in turn was used to select areas for TEM and APT. These analyses show that the trace element content of pyrite can be highly variable, which may significantly affect the rate of pyrite oxidation.

Top Ten Reasons for DEOX as a Front End to Pyroprocessing

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

B.R. Westphal; K.J. Bateman; S.D. Herrmann

A front end step is being considered to augment chopping during the treatment of spent oxide fuel by pyroprocessing. The front end step, termed DEOX for its emphasis on decladding via oxidation, employs high temperatures to promote the oxidation of UO2 to U3O8 via an oxygen carrier gas. During oxidation, the spent fuel experiences a 30% increase in lattice structure volume resulting in the separation of fuel from cladding with a reduced particle size. A potential added benefit of DEOX is the removal of fission products, either via direct release from the broken fuel structure or via oxidation and volatilizationmore » by the high temperature process. Fuel element chopping is the baseline operation to prepare spent oxide fuel for an electrolytic reduction step. Typical chopping lengths range from 1 to 5 mm for both individual elements and entire assemblies. During electrolytic reduction, uranium oxide is reduced to metallic uranium via a lithium molten salt. An electrorefining step is then performed to separate a majority of the fission products from the recoverable uranium. Although DEOX is based on a low temperature oxidation cycle near 500oC, additional conditions have been tested to distinguish their effects on the process.[1] Both oxygen and air have been utilized during the oxidation portion followed by vacuum conditions to temperatures as high as 1200oC. In addition, the effects of cladding on fission product removal have also been investigated with released fuel to temperatures greater than 500oC.« less

Trace element geochemistry and mineralogy of coal from Samaleswari open cast coal block (S-OCB), Eastern India

NASA Astrophysics Data System (ADS)

Saha, Debasree; Chatterjee, Debashis; Chakravarty, Sanchita; Mazumder, Madhurina

2018-04-01

Coal samples of Samaleswari open cast coal block (S-OCB) are high ash (Aad, mean value 35.43%) and low sulphur content (St, on dry basis, mean value 0.91% < 1%) in quality. The stratigraphic variation of volatile matter and fixed carbon (dry ash-free) reflect a progress of coal metamorphism with depth that accordance to the coal rank variation from lignite to high volatile bituminous in the studied borehole. The younger coal seams have greater detrital minerals (quartz, illite, rutile) influence whereas older coal seams have greater authigenic mineral (kaolinite, dolomite, siderite, apatite) contribution that are possibly due to subsidence and sediment transportation. In S-OCB coal trace elements affinities in-between mineral and organic fraction are identified with statistical hierarchical cluster analysis. The work is further supported by the use of chemical fractionation experiment that reveals the multi mode of occurrence of several environmentally concern and interested trace elements (Sb, As, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, Zn). Among the analysed trace elements Co, Mn and Zn have major silicate association along with significant carbonate/oxide/monosulfide association. Whereas As, Cd, Cu, Pb and Ni have dominant pyritic association with notable silicate and carbonate/oxide/monosulfide association. The rest three elements (Sb, Be, Cr) have principally organic association with minor silicate and carbonate/oxide/monosulfide association. The stratigraphic variation of organo-mineral matrix content and detrital-authigenic mineral ratio are primarily related to coal rank. Geochemical character of coal also reflects a light towards proper utilisation of S-OCB coal from technical and environmental view point.

Oxidation and corrosion resistance of candidate Stirling engine heater-head-tube alloys

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Barrett, C. A.

1984-01-01

Sixteen candidate iron base Stirling engine heater head tube alloys are evaluated in a diesel fuel fired simulator materials test rig to determine their oxidation and corrosion resistance. Sheet specimens are tested at 820 C for 3500 hr in 5 hr heating cycles. Specific weight change data and an attack parameter are used to categorize the alloys into four groups; 10 alloys show excellent for good oxidation and corrosion resistance and six alloys exhibit poor or catastrophic resistance. Metallographic, X-ray, and electron microprobe analyses aid in further characterizing the oxidation and corrosion behavior of the alloys. Alloy compositions, expecially the reactive elements aluminum, titanium, and chromium, play a major role in the excellent oxidation and corrosion behavior of the alloys. The best oxidation resistance is associated with the formation of an iron nickel aluminum outer oxide scale, an intermediate oxide scale rich in chromium and titanium, and an aluminum outer oxide scale adjacent to the metallic substrate, which exhibits a zone of internal oxidation of aluminum and to some extent titanium.

A study on thermal barrier coatings including thermal expansion mismatch and bond coat oxidation

NASA Technical Reports Server (NTRS)

Chang, George C.; Phucharoen, Woraphat; Miller, Robert A.

1986-01-01

The present investigation deals with a plasma-sprayed thermal barrier coating (TBC) intended for high temperature applications to advanced gas turbine blades. Typically, this type of coating system consists of a zirconia-yttria ceramic layer with a nickel-chromium-aluminum bond coat on a superalloy substrate. The problem on hand is a complex one due to the fact that bond coat oxidation and thermal mismatch occur in the TBC. Cracking in the TBC has also been experimentally illustrated. A clearer understanding of the mechanical behavior of the TBC is investigated. The stress states in a model thermal barrier coating as it cools down in air is studied. The powerful finite element method was utilized to model a coating cylindrical specimen. Four successively refined finite element models were developed. Some results obtained using the first two models have been reported previously. The major accomplishment is the successful development of an elastic TBC finite element model known as TBCG with interface geometry between the ceramic layer and the bond coat. An equally important milestone is the near-completion of the new elastic-plastic TBC finite element model called TBCGEP which yielded initial results. Representative results are presented.

Petrography and trace element signatures in silicates and Fe-Ti-oxides from the Lanjiahuoshan deposit, Panzhihua layered intrusion, Southwest China

NASA Astrophysics Data System (ADS)

Gao, Wenyuan; Ciobanu, Cristiana L.; Cook, Nigel J.; Huang, Fei; Meng, Lin; Gao, Shang

2017-12-01

Permian mafic-ultramafic layered intrusions in the central part of the Emeishan Large Igneous Province (ELIP), Southwestern China, host Fe-Ti-V-oxide ores that have features which distinguish them from other large layered intrusion-hosted deposits. The origin of these ores is highly debated. Careful petrographic examination, whole rock analysis, electron probe microanalysis, and measurement and mapping of trace element concentrations by laser ablation inductively coupled plasma mass spectrometry in all major and minor minerals (clinopyroxene, plagioclase, olivine, amphibole, titanomagnetite, ilmenite, pleonaste and pyrrhotite) has been undertaken on samples from the Lanjiahuoshan deposit, representing the Middle, Lower and Marginal Zone of the Panzhihua intrusion. Features are documented that impact on interpretation of intrusion petrology and with implications for genesis of the Fe-Ti-V-oxide ores. Firstly, there is evidence, as symplectites between clinopyroxene and plagioclase, for introduction of complex secondary melts. Secondly, reaction between a late hydrothermal fluid and clinopyroxene is recognized, which has led to formation of hydrated minerals (pargasite, phlogopite), as well as a potassium metasomatic event, postdating intrusion solidification, which led to formation of K-feldspar. Lastly, partitioning of trace elements between titanomagnetite and silicates needs to consider scavenging of metals by ilmenite (Mn, Sc, Zr, Nb, Sn, Hf and Ta) and sulfides, as well as the marked partitioning of Co, Ni, Zn, Ga, As and Sb into spinels exsolved from titanomagnetite. The role of these less abundant phases may have been understated in previous studies, highlighting the importance of petrographic examination of complex silicate-oxide-sulfide assemblages, as well as the need for a holistic approach to trace element analysis, acknowledging all minerals within the assemblage.

The mechanisms of pyrite oxidation and leaching: A fundamental perspective

NASA Astrophysics Data System (ADS)

Chandra, A. P.; Gerson, A. R.

2010-09-01

Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh and reacted pyrite surfaces is needed to identify site specific chemical processes. Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) are two synchrotron based surface spectromicroscopic and microspectroscopic techniques that use XPS- and XANES-imaging to correlate chemistry with topography at a submicron scale. Recent data collected with these two techniques suggests that species are heterogeneously distributed on the surface and oxidation to be highly site specific.

Self-activated ultrahigh chemosensitivity of oxide thin film nanostructures for transparent sensors

PubMed Central

Moon, Hi Gyu; Shim, Young-Soek; Kim, Do Hong; Jeong, Hu Young; Jeong, Myoungho; Jung, Joo Young; Han, Seung Min; Kim, Jong Kyu; Kim, Jin-Sang; Park, Hyung-Ho; Lee, Jong-Heun; Tuller, Harry L.; Yoon, Seok-Jin; Jang, Ho Won

2012-01-01

One of the top design priorities for semiconductor chemical sensors is developing simple, low-cost, sensitive and reliable sensors to be built in handheld devices. However, the need to implement heating elements in sensor devices, and the resulting high power consumption, remains a major obstacle for the realization of miniaturized and integrated chemoresistive thin film sensors based on metal oxides. Here we demonstrate structurally simple but extremely efficient all oxide chemoresistive sensors with ~90% transmittance at visible wavelengths. Highly effective self-activation in anisotropically self-assembled nanocolumnar tungsten oxide thin films on glass substrate with indium-tin oxide electrodes enables ultrahigh response to nitrogen dioxide and volatile organic compounds with detection limits down to parts per trillion levels and power consumption less than 0.2 microwatts. Beyond the sensing performance, high transparency at visible wavelengths creates opportunities for their use in transparent electronic circuitry and optoelectronic devices with avenues for further functional convergence. PMID:22905319

Apollo 15 green glass - Compositional distribution and petrogenesis

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

An investigation of the initiation stage of hot corrosion in Ni-base alloys

NASA Technical Reports Server (NTRS)

Huang, T. T.; Meier, G. H.

1979-01-01

The commercial nickel base alloy, IN-738, and high purity laboratory alloys were prepared to simulate the effects of the major elements in IN-738. Results indicate that the initiation of hot corrosion attack of IN-738 and other similar alloys is the result of local penetration of molten salt through the protective oxide scale.

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

NASA Astrophysics Data System (ADS)

Park, Jung-Woo; Campbell, Ian H.; Ickert, Ryan B.; Allen, Charlotte M.

2013-02-01

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO2 range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7-7.8 ppb Pd, 0.025-0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu-Au deposits.

Chemical composition of HAL, an isotopically-unusual Allende inclusion

NASA Astrophysics Data System (ADS)

Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1982-09-01

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

Chemical composition of HAL, an isotopically-unusual Allende inclusion

NASA Technical Reports Server (NTRS)

Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

1982-01-01

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

A Comparative Analyses of Granulometry, Mineral Composition and Major and Trace Element Concentrations in Soils Commonly Ingested by Humans

PubMed Central

Ngole-Jeme, Veronica M.; Ekosse, Georges-Ivo E.

2015-01-01

This study compared the granulometric properties, mineralogical composition and concentrations of major and trace element oxides of commonly ingested soils (geophagic soil) collected from different countries with a view of understanding how varied they may be in these properties and to understand the possible health implications of ingesting them. Soil samples were collected from three different countries (South Africa, Swaziland and Democratic Republic of Congo (DRC)) and their granulometric properties, concentrations of major and trace element oxides as well as mineralogical composition determined. Differences were observed in the granulometric properties of geophagic soil from the three different countries with most of them having <20% clay content. The soils also showed varied degrees of weathering with values of Chemical Index of Alteration (CIA) and Chemical Index of Weathering (CIW) being between 60% and 99.9% respectively. The mineral assemblages of the soils from South Africa and Swaziland were dominated by the primary minerals quartz and feldspar whereas soils from DRC had more of kaolinite, a secondary mineral than primary minerals. Soils from DRC were associated with silt, clay, Al2O3, and CIA unlike most samples from South Africa which were associated with SiO2, sand, K2O, CaO, and MgO. The soils from Swaziland were closely associated with silt, H2O and Fe2O3(t). These associations reflect the mineralogy of the samples. These soils are not likely to serve as nutrient supplements because of the low concentrations of the nutrient elements contained. The coarse texture of the samples may also result in dental destruction during mastication. Sieving of the soils before ingestion to remove coarse particles is recommended to reduce the potential health threat associated with the ingestion of coarse-textured soils. PMID:26264010

Biogeochemical Cycles of Carbon and Sulfur

NASA Technical Reports Server (NTRS)

DesMarais, David J.; DeVincenzi, D. (Technical Monitor)

2002-01-01

The elements carbon (C) and sulfur (S) interact with each other across a network of elemental reservoirs that are interconnected by an array of physical, chemical and biological processes. These networks are termed the biogeochemical C and S cycles. The compounds of C are highly important, not only as organic matter, but also as atmospheric greenhouse gases, pH buffers in seawater, oxidation-reduction buffers virtually everywhere, and key magmatic constituents affecting plutonism and volcanism. The element S assumes important roles as an oxidation-reduction partner with C and Fe in biological systems, as a key constituent in magmas and volcanic gases, and as a major influence upon pH in certain environments. This presentation describes the modern biogeochemical C and S cycles. Measurements are described whereby stable isotopes can help to infer the nature and quantitative significance of biological and geological processes involved in the C and S cycles. This lecture also summarizes the geological and climatologic aspects of the ancient C and S cycles, as well as the planetary and extraterrestrial processes that influenced their evolution over millions to billions of years.

Dephosphorization of complexly alloyed nickel melts under vacuum induction melting conditions: I. Thermodynamics of dephosphorization

NASA Astrophysics Data System (ADS)

Burtsev, V. T.; Anuchkin, S. N.; Sidorov, V. V.; Rigin, V. E.

2013-01-01

A thermodynamic computer simulation of the oxidation potential of a gas-melt-ceramic (80 wt% MgO, 20 wt % Al2O3) system under vacuum induction furnace conditions is used to find that the major contribution to this potential at temperatures ranging from 1673 to 2273 K is made by a nickel melt with additives of nickel protoxide. This provides the possibility of oxidative dephosphorization of the metallic melt. The computation of the saturated vapor pressure of phosphorus compounds with the IIA group elements shows that the data obtained for magnesium, calcium, and barium metaphosphates and europium orthophosphate at 1873 K indicate the principal possibility of melt dephosphorization by the evaporation of these compounds under oxidative conditions.

The Martian Soil as a Geochemical Sink for Hydrothermally Altered Crustal Rocks and Mobile Elements: Implications of Early MER Results

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Nelson, M. J.; Shearer, C. K.; Draper, D. S.

2005-01-01

Hydrothermal and aqueous alteration can explain some of the exciting results from the MER team s analyses of the martian soil, including the major elements, mobile elements, and the nickel enrichment. Published results from the five lander missions lead to the following conclusions: 1) The soil appears to be globally mixed and basaltic with only small local variations in chemistry. Relative to martian basaltic meteorites and Gusev rocks the soils are depleted in the fluid-mobile element calcium, but only slightly enriched to somewhat depleted in iron oxide. 2) The presence of olivine in the soils based on M ssbauer data argues that the soil is only partly weathered and is more akin to a lunar regolith than a terrestrial soil. 3) The presence of bromine along with sulfur and chlorine in the soils is consistent with addition of a mobile element component to the soil.

Major and minor oxide and trace element determination in silicate rocks by direct current plasma optical emission echelle spectrometry

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

Bankston, D.C.; Humphris, S.E.; Thompson, G.

1979-07-01

A technique for the determination of major concentrations of SiO/sub 2/, Al/sub 2/O/sub 3/, Fe/sub 2/O/sub 3/, MgO, CaO, Na/sub 2/O, and K/sub 2/O, minor levels of TiO/sub 2/, P/sub 2/O/sub 5/, and MnO, and trace concentrations of Ba, Cr, Cu, Ni, Sr, V, and Zn, in semi-microsamples 200 mg) of powdered whole rock, is described. Chemically diverse standard reference rocks are used both for calibration and assessment of accuracy. A lithium metaborate fusion melt of each standard or sample is dissolved in dilute HNO/sub 3/ containing Cs/sup +/ at a level of 0.2% (w/v). The resulting solution is usedmore » to perform all analyses except those for Na/sub 2/O and K/sub 2/O, which are determined in a portion of the original sample solution wherein the Cs/sup +/ concentration has been raised to 0.32% (w/v). Analyses of both portions of each sample solution are performed using an optical emission spectrometer/spectrograph equipped with an echelle monochromator and a dc argon plasma excitation source. Trace element detection limits ranged from 2 ppM for Cu to 15 ppM for Zn. A study of precision based on replicate determinations in three splits of the proposed USGS reference basalt BHVO-1 yielded the following results: (1) For analyses of the major and minor oxide constituents, values of the percent relative standard deviation (RSD) ranged from 1 for CaO, to 21 for P/sub 2/O/sub 5/. 2) For trace element determinations, values of the RSD ranged from 2 for Cu, to 19 for Zn. 2 figures, 11 tables.« less

Effects of Some Light Alloying Elements on the Oxidation Behavior of Fe and Ni-Cr Based Alloys During Air Plasma Spraying

NASA Astrophysics Data System (ADS)

Zeng, Zhensu; Kuroda, Seiji; Kawakita, Jin; Komatsu, Masayuki; Era, Hidenori

2010-01-01

The oxidation behavior of iron binary powders with addition of Si (1, 4 wt.%) and B (1, 3 wt.%) and that of a Ni-Cr based alloy powder with Si (4.3 wt.%), B (3.0 wt.%), and C (0.8 wt.%) additions during atmosphere plasma spray (APS) have been investigated. Analysis of the chemical composition and phases of oxides in the captured in-flight particles and deposited coatings was carried out. The results show that the addition of Si and B to iron effectively reduced the oxygen contents in the coatings, especially during the in-flight period at higher particles temperature. Ni-Cr based alloy powder with Si, B, and C additions reduced the oxidation of the base alloys significantly. Preferential oxidation and subsequent vaporization of Si, B, and C from the surface of the sprayed particles are believed to play a major role in controlling oxidation in the APS process.

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Chemistry of volcanic soils used for agriculture in Brava Island (Cape Verde)

NASA Astrophysics Data System (ADS)

Prudêncio, Maria Isabel; Marques, Rosa; Waerenborgh, João Carlos; José Vieira, Bruno; Dias, Maria Isabel; Rocha, Fernando

2017-04-01

Brava is a small volcanic island located on the south-western part of the Cape Verde archipelago. It is characterized by an irregular plateau between 300 and 976 m above sea level, which is bounded by steep coastal cliffs and cut by fluvial incision in a generally radial drainage pattern. The major volcano-stratigraphic units of the island are: Lower Unit, Middle Unit, Upper Unit, and Sediments. Although Brava is one of the islands with more frequent rainy periods in Cape Verde, the climate is essentially semi-arid, which associated with the rough topography leads to incipient soils. Detailed Fe speciation and chemical composition studies of Cape Verde soils have shown that oxidation is a major weathering mechanism, and high contents of trace elements may occur originated from imbalance of elements in the volcanic parent materials, which can be a threat to the environmental health. The soils mostly used for agriculture in Brava Island are those developed on phonolitic pyroclasts on the plateau and also on sediments. In this work the whole sample (< 2 mm) and the clay-sized fraction (< 2 µm) of these soils were analysed by Mössbauer spectroscopy and neutron activation analysis, aiming to characterize the iron speciation and to determine the concentration and distribution of 30 chemical elements in Brava soils. Mössbauer spectroscopy shows that Fe is more oxidyzed in topsoils developed on sediments (84-87%) than in soils developed on pyroclasts (71-79%). In the clay sized-fraction of all the studied soils only Fe(III) was detected. Iron oxides clearly distinguish the soils derived from the two types of parent materials, hematite being the only Fe oxide present in soils developed on sediments, while maghemite is more abundant in soils developed on pyroclasts. Iron and chromium are depleted in this fine fraction suggesting their occurrence as iron oxides and ferromagnesian minerals present in coarser particles. Among the chemical elements studied, antimony was found to be particularly concentrated in the clay-sized fraction (up to 28 mg/kg) in soils located in the northern part of the island. The existence of significant Sb amounts in the fine particles may contribute to its accumulation in plants both by absorption or by dust deposition onto the plant leaves.

EROD activity, chromosomal damage, and oxidative stress in response to contaminants exposure in tree swallow (Tachycineta bicolor) nestlings from Great Lakes Areas of Concern

USGS Publications Warehouse

Custer, Thomas W.; Custer, Christine M.; Dummer, Paul; Bigorgne, Emilie; Oziolor, Elias; Karouna-Renier, Natalie K.; Schultz, Sandra; Erickson, Richard A.; Aagaard, Kevin; Matson, Cole W.

2017-01-01

Tree swallow, Tachycineta bicolor, nestlings were collected from 60 sites in the Great Lakes, which included multiple sites within 27 Areas of Concern (AOCs) and six sites not listed as AOCs from 2010 to 2014. Nestlings, approximately 12 days-of-age, were evaluated for ethoxyresorufin-O-dealkylase (EROD) activity, chromosomal damage, and six measures of oxidative stress. Data on each of these biomarkers were divided into four equal numbered groups from the highest to lowest values and the groups were compared to contaminant concentrations using multivariate analysis. Contaminant concentrations, from the same nestlings, included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and 17 elements. Alkylated polycyclic aromatic hydrocarbons (aPAHs) and parent PAHs (pPAHs) were measured in pooled nestling dietary samples. Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and pesticides were measured in sibling eggs. Concentrations of aPAHs, pPAHs, chlordane, dieldrin, heptachlor, and PCBs, in that order, were the major contributors to the significant differences between the lowest and highest EROD activities; PFCs, PBDEs, the remaining pesticides, and all elements were of secondary importance. The four categories of chromosomal damage did not separate out well based on the contaminants measured. Concentrations of aPAHs, pPAHs, heptachlor, PCBs, chlordane, and dieldrin were the major contributors to the significant differences between the lowest and highest activities of two oxidative stress measures, total sulfhydryl (TSH) activity and protein bound sulfhydryl (PBSH) activity. The four categories of thiobarbituric acid reacting substances (TBARS), oxidized glutathione (GSSG), reduced glutathione (GSH), and the ratio of GSSG/GSH did not separate well based on the contaminants measured.

EROD activity, chromosomal damage, and oxidative stress in response to contaminants exposure in tree swallow (Tachycineta bicolor) nestlings from Great Lakes Areas of Concern.

PubMed

Custer, Thomas W; Custer, Christine M; Dummer, Paul M; Bigorgne, Emilie; Oziolor, Elias M; Karouna-Renier, Natalie; Schultz, Sandra; Erickson, Richard A; Aagaard, Kevin; Matson, Cole W

2017-12-01

Tree swallow, Tachycineta bicolor, nestlings were collected from 60 sites in the Great Lakes, which included multiple sites within 27 Areas of Concern (AOCs) and six sites not listed as AOCs from 2010 to 2014. Nestlings, approximately 12 days-of-age, were evaluated for ethoxyresorufin-O-dealkylase (EROD) activity, chromosomal damage, and six measures of oxidative stress. Data on each of these biomarkers were divided into four equal numbered groups from the highest to lowest values and the groups were compared to contaminant concentrations using multivariate analysis. Contaminant concentrations, from the same nestlings, included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and 17 elements. Alkylated polycyclic aromatic hydrocarbons (aPAHs) and parent PAHs (pPAHs) were measured in pooled nestling dietary samples. Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and pesticides were measured in sibling eggs. Concentrations of aPAHs, pPAHs, chlordane, dieldrin, heptachlor, and PCBs, in that order, were the major contributors to the significant differences between the lowest and highest EROD activities; PFCs, PBDEs, the remaining pesticides, and all elements were of secondary importance. The four categories of chromosomal damage did not separate out well based on the contaminants measured. Concentrations of aPAHs, pPAHs, heptachlor, PCBs, chlordane, and dieldrin were the major contributors to the significant differences between the lowest and highest activities of two oxidative stress measures, total sulfhydryl (TSH) activity and protein bound sulfhydryl (PBSH) activity. The four categories of thiobarbituric acid reacting substances (TBARS), oxidized glutathione (GSSG), reduced glutathione (GSH), and the ratio of GSSG/GSH did not separate well based on the contaminants measured.

Chemical characterization and oxidative potential of particles emitted from open burning of cereal straws and rice husk under flaming and smoldering conditions

NASA Astrophysics Data System (ADS)

Fushimi, Akihiro; Saitoh, Katsumi; Hayashi, Kentaro; Ono, Keisuke; Fujitani, Yuji; Villalobos, Ana M.; Shelton, Brandon R.; Takami, Akinori; Tanabe, Kiyoshi; Schauer, James J.

2017-08-01

Open burning of crop residue is a major source of atmospheric fine particle emissions. We burned crop residues (rice straws, barley straws, wheat straws, and rice husks produced in Japan) in an outdoor chamber and measured particle mass, composition (elemental carbon: EC, organic carbon: OC, ions, elements, and organic species), and oxidative potential in the exhausts. The fine particulate emission factors from the literature were within the range of our values for rice straws but were 1.4-1.9 and 0.34-0.44 times higher than our measured values for barley straw and wheat straw, respectively. For rice husks and wheat straws, which typically lead to combustion conditions that are relatively mild, the EC content of the particles was less than 5%. Levoglucosan seems more suitable as a biomass burning marker than K+, since levoglucosan/OC ratios were more stable than K+/particulate mass ratios among crop species. Stigmasterol and β-sitosterol could also be used as markers of biomass burning with levoglucosan or instead of levoglucosan. Correlation analysis between chemical composition and combustion condition suggests that hot or flaming combustions enhance EC, K+, Cl- and polycyclic aromatic hydrocarbons emissions, while low-temperature or smoldering combustions enhance levoglucosan and water-soluble organic carbon emissions. Oxidative potential, measured with macrophage-based reactive oxygen species (ROS) assay and dithiothreitol (DTT) assay, of open burning fine particles per particulate mass as well as fine particulate emission factors were the highest for wheat straws and second highest for rice husks and rice straws. Oxidative potential per particulate mass was in the lower range of vehicle exhaust and atmosphere. These results suggest that the contribution of open burning is relatively small to the oxidative potential of atmospheric particles. In addition, oxidative potential (both ROS and DTT activities) correlated well with water-insoluble organic species, suggesting that OC components, especially water-insoluble OC components emitted under non-flaming combustion, have a major impact on oxidative potential.

Direct formation of element chlorides from the corresponding element oxides through microwave-assisted carbohydrochlorination reactions.

PubMed

Nordschild, Simon; Auner, Norbert

2008-01-01

A series of technically and economically important element chlorides-such as SiCl4, BCl3, AlCl3, FeCl2, PCl3 and TiCl4-was synthesized through reactions between hydrogen chloride and the corresponding element oxides in the presence of different carbon sources with microwave assistance. This process route was optimized for demonstration purposes for tetrachlorosilane formation and successfully demonstrates the broad applicability of various silicon oxide-containing minerals and materials for carbohydrochlorination. The chlorination reaction occurs at lower temperatures than with conventional heating in a tubular oven, with substantially shorter reaction times and in better yields: quantitatively in the case of tetrachlorosilane, based on the silicon content of the starting material. The experimental procedure is very simple and provides basic information about the suitability of element compounds, especially element oxides, for carbohydrochlorination. According to the general reaction sequence element oxide-->element-->element chloride used in today's technology, this one-step carbohydrochlorination with hydrogen chloride is considerably more efficient, particularly in terms of energy input and reaction times, avoiding the isolation of the pure elements required for chlorination to give the element chlorides with use of the more corrosive and toxic chlorine gas.

Design and Fabrication of Oxygen/RP-2 Multi-Element Oxidizer-Rich Staged Combustion Thrust Chamber Injectors

NASA Technical Reports Server (NTRS)

Garcia, C. P.; Medina, C. R.; Protz, C. S.; Kenny, R. J.; Kelly, G. W.; Casiano, M. J.; Hulka, J. R.; Richardson, B. R.

2016-01-01

As part of the Combustion Stability Tool Development project funded by the Air Force Space and Missile Systems Center, the NASA Marshall Space Flight Center was contracted to assemble and hot-fire test a multi-element integrated test article demonstrating combustion characteristics of an oxygen/hydrocarbon propellant oxidizer-rich staged-combustion engine thrust chamber. Such a test article simulates flow through the main injectors of oxygen/kerosene oxidizer-rich staged combustion engines such as the Russian RD-180 or NK-33 engines, or future U.S.-built engine systems such as the Aerojet-Rocketdyne AR-1 engine or the Hydrocarbon Boost program demonstration engine. On the current project, several configurations of new main injectors were considered for the thrust chamber assembly of the integrated test article. All the injector elements were of the gas-centered swirl coaxial type, similar to those used on the Russian oxidizer-rich staged-combustion rocket engines. In such elements, oxidizer-rich combustion products from the preburner/turbine exhaust flow through a straight tube, and fuel exiting from the combustion chamber and nozzle regenerative cooling circuits is injected near the exit of the oxidizer tube through tangentially oriented orifices that impart a swirl motion such that the fuel flows along the wall of the oxidizer tube in a thin film. In some elements there is an orifice at the inlet to the oxidizer tube, and in some elements there is a sleeve or "shield" inside the oxidizer tube where the fuel enters. In the current project, several variations of element geometries were created, including element size (i.e., number of elements or pattern density), the distance from the exit of the sleeve to the injector face, the width of the gap between the oxidizer tube inner wall and the outer wall of the sleeve, and excluding the sleeve entirely. This paper discusses the design rationale for each of these element variations, including hydraulic, structural, thermal, combustion performance, and combustion stability considerations. This paper also discusses the fabrication and assembly of the injector components, including the injector body/interpropellant plate, the additive manufactured GRCop-84 faceplate, and the pieces that make up the injector elements including the oxidizer tube, an inlet to the oxidizer tube, and a facenut that includes the fuel tangential inlets and forms the initial recessed volume where oxidizer and fuel first interact. Hot-fire test results of these main injector designs in an integrated test article that includes an oxidizer-rich preburner are described in companion papers at this JANNAF meeting.

Extraterrestrial materials processing and construction. [space industrialization

NASA Technical Reports Server (NTRS)

Criswell, D. R.; Waldron, R. D.; Mckenzie, J. D.

1980-01-01

Three different chemical processing schemes were identified for separating lunar soils into the major oxides and elements. Feedstock production for space industry; an HF acid leach process; electrorefining processes for lunar free metal and metal derived from chemical processing of lunar soils; production and use of silanes and spectrally selective materials; glass, ceramics, and electrochemistry workshops; and an econometric model of bootstrapping space industry are discussed.

Biomedical Implications of Heavy Metals Induced Imbalances in Redox Systems

PubMed Central

Singh, Shweta; Siddiqi, Nikhat J.

2014-01-01

Several workers have extensively worked out the metal induced toxicity and have reported the toxic and carcinogenic effects of metals in human and animals. It is well known that these metals play a crucial role in facilitating normal biological functions of cells as well. One of the major mechanisms associated with heavy metal toxicity has been attributed to generation of reactive oxygen and nitrogen species, which develops imbalance between the prooxidant elements and the antioxidants (reducing elements) in the body. In this process, a shift to the former is termed as oxidative stress. The oxidative stress mediated toxicity of heavy metals involves damage primarily to liver (hepatotoxicity), central nervous system (neurotoxicity), DNA (genotoxicity), and kidney (nephrotoxicity) in animals and humans. Heavy metals are reported to impact signaling cascade and associated factors leading to apoptosis. The present review illustrates an account of the current knowledge about the effects of heavy metals (mainly arsenic, lead, mercury, and cadmium) induced oxidative stress as well as the possible remedies of metal(s) toxicity through natural/synthetic antioxidants, which may render their effects by reducing the concentration of toxic metal(s). This paper primarily concerns the clinicopathological and biomedical implications of heavy metals induced oxidative stress and their toxicity management in mammals. PMID:25184144

Differential Effects of Low-Molecular-Weight Organic Acids on the Mobilization of Soil-Borne Arsenic and Trace Metals.

PubMed

Nworie, Obinna Elijah; Qin, Junhao; Lin, Chuxia

2017-08-21

A batch experiment was conducted to examine the effects of six low-molecular-weight organic acids on the mobilization of arsenic and trace metals from a range of contaminated soils. The results showed that the organic acids behaved differently when reacting with soil-borne As and trace metals. Oxalic acid and acetic acid had the strongest and weakest capacity to mobilize the investigated elements, respectively. The solubilisation of iron oxides by the organic acids appears to play a critical role in mobilizing other trace metals and As. Apart from acidification and complexation, reductive dissolution played a dominant role in the dissolution of iron oxides in the presence of oxalic acid, while acidification tended to be more important for dissolving iron oxides in the presence of other organic acids. The unique capacity of oxalic acid to solubilize iron oxides tended to affect the mobilization of other elements in different ways. For Cu, Mn, and Zn, acidification-driven mobilization was likely to be dominant while complexation might play a major role in Pb mobilization. The formation of soluble Fe and Pb oxalate complexes could effectively prevent arsenate or arsenite from combining with these metals to form solid phases of Fe or Pb arsenate or arsenite.

Risk assessment of trace metals in an extreme environment sediment: shallow, hypersaline, alkaline, and industrial Lake Acıgöl, Denizli, Turkey.

PubMed

Budakoglu, Murat; Karaman, Muhittin; Kumral, Mustafa; Zeytuncu, Bihter; Doner, Zeynep; Yildirim, Demet Kiran; Taşdelen, Suat; Bülbül, Ali; Gumus, Lokman

2018-02-23

The major and trace element component of 48 recent sediment samples in three distinct intervals (0-10, 10-20, and 20-30 cm) from Lake Acıgöl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the < 60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Acıgöl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate.

PubMed

Thorup, Casper; Schramm, Andreas; Findlay, Alyssa J; Finster, Kai W; Schreiber, Lars

2017-07-18

This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. IMPORTANCE Sulfide oxidation and sulfate reduction, the two major branches of the sulfur cycle, are usually ascribed to distinct sets of microbes with distinct diagnostic genes. Here we show a more complex picture, as D. alkaliphilus , with the genomic setup of a sulfate reducer, grows by sulfide oxidation. The high expression of genes typically involved in the sulfate reduction pathway suggests that these genes, including the reductive-type dissimilatory bisulfite reductases, are also involved in as-yet-unresolved sulfide oxidation pathways. Finally, D. alkaliphilus is closely related to cable bacteria, which grow by electrogenic sulfide oxidation. Since there are no pure cultures of cable bacteria, D. alkaliphilus may represent an exciting model organism in which to study the physiology of this process. Copyright © 2017 Thorup et al.

Cyclic Oxidation and Hot Corrosion Behavior of Nickel-Iron-Based Superalloy

NASA Astrophysics Data System (ADS)

Chellaganesh, D.; Adam Khan, M.; Winowlin Jappes, J. T.; Sathiyanarayanan, S.

2018-01-01

The high temperature oxidation and hot corrosion behavior of nickel-iron-based superalloy are studied at 900 ° and 1000 °C. The significant role of alloying elements with respect to the exposed medium is studied in detail. The mass change per unit area was catastrophic for the samples exposed at 1000 °C and gradual increase in mass change was observed at 900 °C for both the environments. The exposed samples were further investigated with SEM, EDS and XRD analysis to study the metallurgical characteristics. The surface morphology has expressed the in situ nature of the alloy and its affinity toward the environment. The EDS and XRD analysis has evidently proved the presence of protective oxides formation on prolonged exposure at elevated temperature. The predominant oxide formed during the exposure at high temperature has a major contribution toward the protection of the samples. The nickel-iron-based superalloy is less prone to oxidation and hot corrosion when compared to the existing alloy in gas turbine engine simulating marine environment.

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

Combined catalysts for the combustion of fuel in gas turbines

DOEpatents

Anoshkina, Elvira V.; Laster, Walter R.

2012-11-13

A catalytic oxidation module for a catalytic combustor of a gas turbine engine is provided. The catalytic oxidation module comprises a plurality of spaced apart catalytic elements for receiving a fuel-air mixture over a surface of the catalytic elements. The plurality of catalytic elements includes at least one primary catalytic element comprising a monometallic catalyst and secondary catalytic elements adjacent the primary catalytic element comprising a multi-component catalyst. Ignition of the monometallic catalyst of the primary catalytic element is effective to rapidly increase a temperature within the catalytic oxidation module to a degree sufficient to ignite the multi-component catalyst.

A Platinum-Enriched gamma+gamma' Two-Phase Bond Coat on Ni-Base Superalloys

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

Zhang, Ying; Pint, Bruce A; Haynes, James A

2005-01-01

Pt-enriched {gamma} + {gamma}{prime} two-phase coating was applied to directionally-solidified Ni-based superalloy Ren{acute e} 142 substrates with three different Hf levels (0.02, 0.76, and 1.37 wt.%). The coating was prepared by electroplating a thin layer of Pt on the superalloy followed by a diffusion treatment. The as-deposited coating exhibited a {gamma} + {gamma}{prime} two-phase microstructure with a major composition of Ni-16Al-18Pt-7Cr-9Co (in at.%) along with some incorporation of refractory elements from the substrates. Cyclic oxidation testing at 1100 C in air indicated improved oxidation resistance of the Ren{acute e} 142 alloys with the Pt-enriched {gamma} + {gamma}{prime} coatings. In addition,more » the oxidation resistance of both uncoated and coated alloys was proportional to the Hf content in the substrate. Compared with the single-phase {beta}-(Ni,Pt)Al coating, slightly higher mass gains and localized spallation were observed on the {gamma} + {gamma}{prime} two-phase coating, which might be due to the segregation of refractory elements and high sulfur levels in these superalloy substrates.« less

Evaluation on chemical stability of lead blast furnace (LBF) and imperial smelting furnace (ISF) slags.

PubMed

Yin, Nang-Htay; Sivry, Yann; Guyot, François; Lens, Piet N L; van Hullebusch, Eric D

2016-09-15

The leaching behavior of Pb and Zn from lead blast furnace (LBF) and imperial smelting furnace (ISF) slags sampled in the North of France was studied as a function of pHs and under two atmospheres (open air and nitrogen). The leaching of major elements from the slags was monitored as a function of pH (4, 5.5, 7, 8.5 and 10) under both atmospheres for different slag-water interaction times (1 day and 9 days). The leaching results were coupled with a geochemical model; Visual MINTEQ version 3.0, and a detailed morphological and mineralogical analysis was performed on the leached slags by scanning and transmission electron microscopy (SEM and TEM). Significant amounts of Ca, Fe and Zn were released under acidic conditions (pH 4) with a decrease towards the neutral to alkaline conditions (pH 7 and 10) for both LBF and ISF slags. On the other hand, Fe leachability was limited at neutral to alkaline pH for both slags. The concentrations of all elements increased gradually after 216 h compared to initial 24 h of leaching period. The presence of oxygen under open-air atmosphere not only enhanced oxidative weathering but also encouraged formation of secondary oxide and carbonate phases. Formation of carbonates and clay minerals was suggested by Visual MINTEQ which was further confirmed by SEM & TEM. The hydration and partial dissolution of hardystonite, as well as the destabilization of amorphous glassy matrix mainly contributed to the release of major elements, whereas the spinel related oxides were resistant against pH changes and atmospheres within the time frame concerned for both LBF and ISF slags. The total amount of Pb leached out at pH 7 under both atmospheres suggested that both LBF and ISF slags are prone to weathering even at neutral environmental conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Vertical distribution of major, minor and trace elements in sediments from mud volcanoes of the Gulf of Cadiz: evidence of Cd, As and Ba fronts in upper layers

NASA Astrophysics Data System (ADS)

Carvalho, Lina; Monteiro, Rui; Figueira, Paula; Mieiro, Cláudia; Almeida, Joana; Pereira, Eduarda; Magalhães, Vítor; Pinheiro, Luís; Vale, Carlos

2018-01-01

Mud volcanoes are feature of the coastal margins where anaerobic oxidation of methane triggers geochemical signals. Elemental composition, percentage of fine particles and loss on ignition were determined in sediment layers of eleven gravity cores retrieved from four mud volcanoes (Sagres, Bonjardim, Soloviev and Porto) and three undefined structures located on the deep Portuguese margin of the Gulf of Cadiz. Calcium was positively correlated to Sr and inversely to Al as well as to most of the trace elements. Vertical profiles of Ba, Cd and As concentrations, and their ratios to Al, in Porto and Soloviev showed pronounced enhancements in the top 50-cm depth. Sub-surface enhancements were less pronounced in other mud volcanoes and were absent in sediments from the structures. These profiles were interpreted as diagenetic enrichments related to the anaerobic oxidation of methane originated from upward methane-rich fluxes. The observed barium fronts were most likely caused by the presence of barite which precipitated at the sulphate-methane transition zone. Cd and As enrichments have probably resulted from successive dissolution/precipitation of sulphides in response to vertical shifts of redox boundaries.

Geochemical and mineralogical interpretation of the Viking inorganic chemical results. [for Martian surface materials

NASA Technical Reports Server (NTRS)

Toulmin, P., III; Rose, H. J., Jr.; Christian, R. P.; Baird, A. K.; Evans, P. H.; Clark, B. C.; Keil, K.; Kelliher, W. C.

1977-01-01

The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

Method for the removal of elemental mercury from a gas stream

DOEpatents

Mendelsohn, Marshall H.; Huang, Hann-Sheng

1999-01-01

A method is provided to remove elemental mercury from a gas stream by reacting the gas stream with an oxidizing solution to convert the elemental mercury to soluble mercury compounds. Other constituents are also oxidized. The gas stream is then passed through a wet scrubber to remove the mercuric compounds and oxidized constituents.

Method for the removal of elemental mercury from a gas stream

DOEpatents

Mendelsohn, M.H.; Huang, H.S.

1999-05-04

A method is provided to remove elemental mercury from a gas stream by reacting the gas stream with an oxidizing solution to convert the elemental mercury to soluble mercury compounds. Other constituents are also oxidized. The gas stream is then passed through a wet scrubber to remove the mercuric compounds and oxidized constituents. 7 figs.

Tracking hydrothermal alteration and mineralization in rock-forming and accessory minerals from the Lyon Mountain Granite and related iron oxide apatite (IOA) ores from the Adirondack Mountains, New York State

NASA Astrophysics Data System (ADS)

Buchanan, A.; Hanchar, J. M.; Steele-MacInnis, M. J.; Crowley, J. L.; Valley, P. M.; Fisher, C. M.; Fedo, C.; Piccoli, P. M.; Fournelle, J.

2012-12-01

The Lyon Mountain granite (LMG) is located in the northeastern Adirondack Mountains in New York State and hosts several low-titanium iron oxide apatite (IOA) ore deposits. The ores are predominately hosted by perthite bearing granite, which has been extensively altered to albite and microcline granite by Na and K metasomatism. This alteration results in several distinct groups of rocks that are dominated by either K or Na addition and a group composed of mixed Na and K addition. The different groups of altered perthite also lie on a trend suggestive of addition of Fe to each, consistent with a secondary mineralization origin. Previous work showed that the host rocks of the IOA ores have zircon with ~1150 Ma cores and 1060-1050 Ma rims and whole grains. This study aims to further constrain the timing of LMG emplacement, subsequent hydrothermal alteration, and Fe mineralization through geochemical analysis of the major, minor, and accessory phases and geochronology of accessory phases. SIMS analyses of zircon from several of the IOA ores reveal at least two periods of growth after LMG magmatism, at 1039 +/- 4.4 Ma and 1016 +/- 7 Ma to 1000 +/- 9 Ma. In situ EMPA and LA-ICPMS trace element analyses of the zircon rims and cores reveal that in two samples the zircon rims are enriched in rare earth elements (REE) compared to their cores, potentially pointing to a hydrothermal origin. Apatite has unusually high REE and Y concentrations (some total REE2O3 > 20 wt. % oxide and up to 8 wt. % oxide Y2O3), as does titanite, which allowed for the in situ analysis of Sm-Nd in apatite and titanite by LA-MC-ICP-MS. Initial Nd isotopic composition of both ore and host rock apatite and host rock titanite are consistent with published Adirondack initial Nd whole rock data, suggesting a local source for REE in these ores. EMPA and LA-ICPMS trace-element analyses of the major rock-forming minerals indicate that the feldspar have undergone Na-metasomatism and are depleted in REEs, perhaps signifying the "local source" and the mechanism of the REE enrichment in the LMG apatite in the IOA ores and host rocks. In contrast, the minor- and trace-element compositions of the other major rock-forming minerals (e.g., clinopyroxene and fayalite) as well as the zircon, and fluorite in the LMG have average igneous granitic trace- and minor-element compositions. To better understand the timing and origin of these post ~1050 Ma events, U-Pb ID-TIMS dating of apatite and titanite, and in situ LA-MC-ICPMS Sm-Nd analysis were done on the ore and host rock samples. Apatite dates range from 1050 to 850 Ma and titanite dates range from ~1015 to 970 Ma. There is significant age variation within samples and within grains. Titanite does not have sufficient spread for accurate Sm-Nd isochron dating and two ore-apatite samples have homogenous initial Nd isotopic and Sm-Nd elemental ratios, precluding calculation of Sm-Nd dates. A third ore sample shows a large spread in Sm-Nd and yields a Sm-Nd isochron date of ~850 Ma, in close agreement with U-Pb apatite dates. The Sm-Nd isochron and U-Pb apatite dates may reflect cooling recorded in these minerals or a younger hydrothermal mineralization event.

Removable preheater elements improve oxide induction furnace

NASA Technical Reports Server (NTRS)

Leipold, M. H.

1964-01-01

Heat and corrosion resistant preheater elements are used in oxide induction furnaces to raise the temperature to the level for conducting electricity. These preheater elements are then removed and the induction coil energized.

Selenate reduction to elemental selenium by anaerobic bacteria in sediments and culture: biogeochemical significance of a novel, sulfate-independent respiration

USGS Publications Warehouse

Oremland, Ronald S.; Hollibaugh, James T.; Maest, Ann S.; Presser, Theresa S.; Miller, Laurence G.; Culbertson, Charles W.

1989-01-01

Interstitial water profiles of SeO42−, SeO32−, SO42−, and Cl− in anoxic sediments indicated removal of the seleno-oxyanions by a near-surface process unrelated to sulfate reduction. In sediment slurry experiments, a complete reductive removal of SeO42− occurred under anaerobic conditions, was more rapid with H2 or acetate, and was inhibited by O2, NO3−, MnO2, or autoclaving but not by SO42− or FeOOH. Oxidation of acetate in sediments could be coupled to selenate but not to molybdate. Reduction of selenate to elemental selenium was determined to be the mechanism for loss from solution. Selenate reduction was inhibited by tungstate and chromate but not by molybdate. A small quantity of the elemental selenium precipitated into sediments from solution could be resolublized by oxidation with either nitrate or FeOOH, but not with MnO2. A bacterium isolated from estuarine sediments demonstrated selenate-dependent growth on acetate, forming elemental selenium and carbon dioxide as respiratory end products. These results indicate that dissimilatory selenate reduction to elemental selenium is the major sink for selenium oxyanions in anoxic sediments. In addition, they suggest application as a treatment process for removing selenium oxyanions from wastewaters and also offer an explanation for the presence of selenite in oxic waters.

Elemental Geochemistry of Samples From Fault Segments of the San Andreas Fault Observatory at Depth (SAFOD) Drill Hole

NASA Astrophysics Data System (ADS)

Tourscher, S. N.; Schleicher, A. M.; van der Pluijm, B. A.; Warr, L. N.

2006-12-01

Elemental geochemistry of mudrock samples from phase 2 drilling of the San Andreas Fault Observatory at Depth (SAFOD) is presented from bore hole depths of 3066 m to 3169 m and from 3292 m to 3368 m, which contain a creeping section and main trace of the fault, respectively. In addition to preparation and analysis of whole rock sample, fault grains with neomineralized, polished surfaces were hand picked from well-washed whole rock samples, minimizing the potential contamination from drilling mud and steel shavings. The separated fractions were washed in deionized water, powdered using a mortar and pestle, and analyzed using an Inductively Coupled Plasma- Optical Emission Spectrometer for major and minor elements. Based on oxide data results, systematic differences in element concentrations are observed between the whole rock and fault rock. Two groupings of data points are distinguishable in the regions containing the main trace of the fault, a shallow part (3292- 3316 m) and a deeper section (3320-3368 m). Applying the isocon method, assuming Zr and Ti to be immobile elements in these samples, indicates a volume loss of more than 30 percent in the shallow part and about 23 percent in the deep part of the main trace. These changes are minimum estimates of fault-related volume loss, because the whole rock from drilling samples contains variable amount of fault rock as well. Minimum estimates for volume loss in the creeping section of the fault are more than 50 percent when using the isocon method, comparing whole rock to plucked fault rock. The majority of the volume loss in the fault rocks is due to the dissolution and loss of silica, potassium, aluminum, sodium and calcium, whereas (based on oxide data) the mineralized surfaces of fractures appear to be enriched in Fe and Mg. The large amount of element mobility within these fault traces suggests extensive circulation of hydrous fluids along fractures that was responsible for progressive dissolution and leaching of the wall rock during faulting.

Oxidation of As(III) to As(V) using ozone microbubbles.

PubMed

Khuntia, Snigdha; Majumder, Subrata Kumar; Ghosh, Pallab

2014-02-01

The use of ozone in the treatment of water and wastewater is rapidly increasing due to its high oxidizing power. Arsenic is one the most toxic elements found in water. As(III) and As(V) are the major sources of arsenic poisoning. It is known that As(V) can be more easily removed from water by adsorptive methods than As(III). In this work, oxidation of more toxic As(III) to less toxic As(V) was studied in a pilot-plant by using ozone microbubbles. The microbubbles were effective in dissolving ozone in water. The oxidation was fast over a wide range of pH (e.g., 4-9). The role of hydroxyl radical in the oxidation of As(III) under acidic conditions was investigated by using 2-propanol as the hydroxyl radical scavenger. Under acidic conditions, the addition of 2-propanol slowed down the oxidation, which proves that hydroxyl radicals were involved in the oxidation process. The effect of carbonate ions on the rate of oxidation was investigated. It was found that the generation of carbonate ion radical from the carbonate ion accelerated the oxidation of As(III). The kinetics of oxidation of As(III) by ozone was studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Materials and methods for the separation of oxygen from air

DOEpatents

MacKay, Richard; Schwartz, Michael; Sammells, Anthony F.

2003-07-15

Metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes having the formula: O.sub.5+z where: x and x' are greater than 0; y and y' are greater than 0; x+x' is equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides, Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof and B" is Co or Mg, with the exception that when B" is Mg, A' and A" are not Mg. The metal oxides are useful for preparation of dense membranes which may be formed from dense thin films of the mixed metal oxide on a porous metal oxide element. The invention also provides methods and catalytic reactors for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula.

The reactive element effect of yttrium and yttrium silicon on high temperature oxidation of NiCrAl coating

NASA Astrophysics Data System (ADS)

Ramandhany, S.; Sugiarti, E.; Desiati, R. D.; Martides, E.; Junianto, E.; Prawara, B.; Sukarto, A.; Tjahjono, A.

2018-03-01

The microstructure formed on the bond coat affects the oxidation resistance, particularly the formation of a protective oxide layer. The adhesion of bond coat and TGO increased significantly by addition of reactive element. In the present work, the effect of yttrium and yttrium silicon as reactive element (RE) on NiCrAl coating was investigated. The NiCrAl (without RE) and NiCrAlX (X:Y or YSi) bond coating were deposited on Hastelloy C-276 substrate by High Velocity Oxygen Fuel (HVOF) method. Isothermal oxidation was carried out at 1000 °C for 100 hours. The results showed that the addition of RE could prevent the breakaway oxidation. Therefore, the coating with reactive element were more protective against high temperature oxidation. Furthermore, the oxidation rate of NiCrAlY coating was lower than NiCrAlYSi coating with the total mass change was ±2.394 mg/cm2 after 100 hours of oxidation. The thickness of oxide scale was approximately 1.18 μm consisting of duplex oxide scale of spinel NiCr2O4 in outer scale and protective α-Al2O3 in inner scale.

Sensitivity of trace element pyritization to pyrite oxidation processes

NASA Astrophysics Data System (ADS)

Moreira, Manuel; Díaz, Rut; Mendoza, Ursula; Capilla, Ramses; Böttcher, Michael; Luiza Albuquerque, Ana; Machado, Wilson

2014-05-01

Total trace elements concentration variability in marine sediments has been widely used as a proxy for redox conditions and marine paleoprodutivity. However, partial extraction procedures reduce influences of detrital sedimentary fractions, and information on trace element geochemical partitioning can contribute to provide comprehensive evidences on elemental sensitivity to particular processes. The potential effect of sedimentary pyrite re-oxidative cycling on the degree of trace metal pyritization (DTMP) has not been previously evaluated. This study investigates this effect in 4 sediment cores from the continental shelf under the influence of a tropical upwelling system (Cabo Frio, Brazil). The relation of DTMP with stable isotope signals (δ34SCRS) of chromium reducible sulfur, which becomes lighter in response to intense pyrite re-oxidative cycling in the study area, suggests high (As, Cd and Mn), low (Cu and Zn) or negligible (Cr and Ni) re-oxidation influences. The oldest, pyrite-richer sediments provide an apparent threshold for intense pyrite re-oxidation, after which most trace elements (As, Cd, Zn and Mn) presented more accentuated pyritization. A middle shelf core presented negative correlations of reactive (HCl-soluble) Mn, Cu and Ni with pyrite iron, suggesting Mn oxide (and associated metals) depletion in reaction with pyrite. Results provided evidences for coupled influences from both aerobic and anaerobic oxidative processes on trace elements incorporation into pyrite. Pyrite δ34S signatures under the oxic bottom water from the study area were similar to those from euxinic sedimentary environments, suggesting that pyrite re-oxidative cycling can affect trace element susceptibility to be incorporated and preserved into pyrite in a wide range of sedimentary conditions. The evaluation of trace elements sensitivity to these processes can contribute to improve the use of multiple DTMP data (e.g., as paleoredox proxies). Considering that S re-oxidative cycling is ubiquitous in many sedimentary conditions, such coupled use of DTMP and δ34SCRS proxies can be possibly applied to a large variety of sedimentary environments.

Sulfur, sulfides, oxides and organic matter aggregated in submarine hydrothermal plumes at 9°50‧N East Pacific Rise

NASA Astrophysics Data System (ADS)

Breier, J. A.; Toner, B. M.; Fakra, S. C.; Marcus, M. A.; White, S. N.; Thurnherr, A. M.; German, C. R.

2012-07-01

Deep-sea hydrothermal plume particles are known to sequester seawater trace elements and influence ocean-scale biogeochemical budgets. The relative importance of biotic versus abiotic oxidation-reduction and other particle-forming reaction, however, and the mechanisms of seawater trace element sequestration remain unknown. Suspended particulate material was collected from a non-buoyant hydrothermal plume by in situ filtration at 9°50‧N East Pacific Rise during a 3-day, 24 sample, time-series. Twenty-three samples were digested for total elemental analysis. One representative sample was selected for particle-by-particle geochemical analyses including elemental composition by X-ray fluorescence, speciation of Fe, S, and C by 1s X-ray absorption near edge structure spectroscopy, and X-ray diffraction. Consistent with past studies, positive linear correlations were observed for P, V, As, and Cr with Fe in the bulk chemistry. Arsenic was associated with both Fe oxyhydroxides and sulfides but not uniformly distributed among either mineral type. Particle aggregation was common. Aggregates were composed of minerals embedded in an organic matrix; the minerals ranged from <20 nm to >10 μm in diameter. The speciation of major mineral forming elements (Fe, Mn, S) was complex. Over 20 different minerals were observed, nine of which were either unpredicted by thermodynamic modeling or had no close match in the thermodynamic database. Sulfur-bearing phases consisted of polysulfides (S6, S8), and metal sulfides (Fe, Cu, Zn, Mn). Four dominant species, Fe oxyhydroxide, Fe monosulfide, pyrrhotite, and pyrite, accounted for >80% of the Fe present. Particulate Mn was prevalent in both oxidized and reduced minerals. The organic matrix was: (1) always associated with minerals, (2) composed of biomolecules, and (3) rich in S. Possible sources of this S-rich organic matter include entrained near vent biomass and in situ production by S-oxidizing microorganisms. These results indicate that particle aggregation with organic material is prevalent in dispersing hydrothermal plume fluxes, as well as in sinking particulate matter at this site. Particle aggregation and organic coatings can influence the reactivity, transport, and residence time of hydrothermal particles in the water column. Thus a biogeochemical approach is critical to understanding the net effect of hydrothermal fluxes on ocean and sedimentary trace element budgets.

Molybdenite Mineral Evolution: A Study Of Trace Elements Through Time

NASA Astrophysics Data System (ADS)

McMillan, M. M.; Downs, R. T.; Stein, H. J.; Zimmerman, A.; Beitscher, B. A.; Sverjensky, D. A.; Papineau, D.; Armstrong, J. T.; Hazen, R. M.

2010-12-01

Mineral evolution explores changes through time in Earth’s near-surface mineralogy, including diversity of species, relative abundances of species, and compositional ranges of major, minor and trace elements. Such studies elucidate the co-evolution of the geosphere and biosphere. Accordingly, we investigated trace and minor elements in molybdenite (MoS2) with known ages from 3 billion years to recent. Molybdenite, the commonest mineral of Mo, may prove to be a useful case study as a consequence of its presence in Earth’s early history, the effects of oxidation on Mo mobility, and the possible role of Mo mineral coevolution with biology via its role in the nitrogen fixation enzyme nitrogenase. We employed ICPMS, SEM and electron microprobe analyses to detect trace and minor elements. We detected significant amounts of Mn and Cu (~100 ppm) and greater amounts of Fe, W, and Re (to ~4000 ppm). Molybdenites commonly contain micro inclusions, resulting in local concentrations in otherwise homogeneous samples. Inhomogeneities in Fe, Zn and Sn concentrations, for example, point to the presence of pyrite, sphalerite and cassiterite inclusions, respectively. Analyses examined as a function of time reveal that samples containing significant concentrations (>200 ppm, compared to average values < 100 ppm) of W and Re formed primarily within the last billion years. These trends may reflect changes in the mobility of W and Re in oxic hydrothermal fluids at shallow crustal conditions following the Great Oxidation Event.

Compositional and mineralogical zoning by inward crystallization of mafic magma: evidence from the Guwoon hornblende gabbro-diorite Complex, Hwacheon, Korea.

NASA Astrophysics Data System (ADS)

Park, Y.-R.; Kim, G.-Y.

2009-04-01

The small body, ca. 1.3 by 1.6km, of a hot-air ballon shape hornblende gabbro - diorite Complex, in Gowoonri, Hwacheon, Korea consists of marginal diorite and central hornblende gabbro. The volumetrically dominant hornblende gabbro in the core of the Complex shows a zoned distribution with three layers distinguished by different dominant mafic mineral phases. From the margin toward the core of the hornblende gabbro body, the domintant mafic minerals change from amphibole phenocryst of nearly rounded shape in cross section with pyroxene pseudomorph through prismatic shape of amphibole to polycrystalline biotite aggregates. Systematic variations in geochemical characteristics among three distinct zones of hornblende gabbro body are also observed. From the outer zone toward the core, major oxides such as MnO, MgO, and CaO show a decreasing tendency, whereas total FeO/(total FeO + MgO) value shows an increasing tendency. Concentrations of trace elements also show systematic variations. Where incompatible elements such as Ba and Th increase, compatible elements like Cr and Sc decrease from the margin toward the core. The zonal distribution divided by change in dominant mafic mineral phase from pyroxene through amphibole to biotite, and systematic compositional changes in both major and trace elements from the outer zone toward the core of the hornblende gabbro body suggest that an inward crystallization mechanism played a major role in the formation of the hornblende gabbro in Guwoonri, Hwacheon, Korea.

Spectral Interferences Manganese (Mn) - Europium (Eu) Lines in X-Ray Fluorescence Spectrometry Spectrum

NASA Astrophysics Data System (ADS)

Tanc, Beril; Kaya, Mustafa; Gumus, Lokman; Kumral, Mustafa

2016-04-01

X-ray fluorescence (XRF) spectrometry is widely used for quantitative and semi quantitative analysis of many major, minor and trace elements in geological samples. Some advantages of the XRF method are; non-destructive sample preparation, applicability for powder, solid, paste and liquid samples and simple spectrum that are independent from chemical state. On the other hand, there are some disadvantages of the XRF methods such as poor sensitivity for low atomic number elements, matrix effect (physical matrix effects, such as fine versus course grain materials, may impact XRF performance) and interference effect (the spectral lines of elements may overlap distorting results for one or more elements). Especially, spectral interferences are very significant factors for accurate results. In this study, semi-quantitative analyzed manganese (II) oxide (MnO, 99.99%) was examined. Samples were pelleted and analyzed with XRF spectrometry (Bruker S8 Tiger). Unexpected peaks were obtained at the side of the major Mn peaks. Although sample does not contain Eu element, in results 0,3% Eu2O3 was observed. These result can occur high concentration of MnO and proximity of Mn and Eu lines. It can be eliminated by using correction equation or Mn concentration can confirm with other methods (such as Atomic absorption spectroscopy). Keywords: Spectral Interferences; Manganese (Mn); Europium (Eu); X-Ray Fluorescence Spectrometry Spectrum.

Iron and sulfur isotope constraints on redox conditions associated with the 3.2 Ga barite deposits of the Mapepe Formation (Barberton Greenstone Belt, South Africa)

NASA Astrophysics Data System (ADS)

Busigny, Vincent; Marin-Carbonne, Johanna; Muller, Elodie; Cartigny, Pierre; Rollion-Bard, Claire; Assayag, Nelly; Philippot, Pascal

2017-08-01

The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dissolved sulfate (SO42-), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by reducing conditions, with low oceanic sulfate concentration (<10 μM) relative to present day levels of 28,000 μM. In order to better assess the redox state of the paleo-atmosphere and -oceans, we examined Fe and S isotope compositions in a sedimentary sequence from the 3.2 Ga-old Mendon and Mapepe formations (Kaapvaal craton, South Africa), recovered from the drill-core BBDP2 of the Barberton Barite Drilling Project. Major elements were also analyzed to constrain the respective imprints of detrital vs metasomatic processes, in particular using Al, Ti and K interrelations. Bulk rock Fe isotope compositions are linked to mineralogy, with δ56Fe values varying between -2.04‰ in Fe sulfide-dominated barite beds, to +2.14‰ in Fe oxide-bearing cherts. δ34S values of sulfides vary between -10.84 and +3.56‰, with Δ33S in a range comprised between -0.35 and +2.55‰, thus supporting an O2-depleted atmosphere (<10-5 PAL). Iron isotope variations together with major element correlations show that, although the sediments experienced a pervasive stage of hydrothermal alteration, the rocks preserved a primary/authigenic signature predating subsequent hydrothermal stage. Highly positive δ56Fe values recorded in primary Fe-oxides from ferruginous cherts support partial Fe oxidation in a reducing oceanic environment (O2 < 10-4 μM), but are incompatible with a model of complete oxidation at the redox boundary of a stratified water column. Iron oxide precipitation under low O2 levels was likely mediated by anoxygenic photosynthesis, and/or abiotic photo-oxidation processes. Our results are consistent with global anoxic conditions in the 3.2 Ga-old sediments, implying that the barite deposits were most likely sourced by atmospheric photolysis of S gases produced by large subaerial volcanic events, and possibly SO42- produced by magmatic SO2 disproportionation in hydrothermal systems.

Re-187 Os-187 Isotopic and Highly Siderophile Element Systematics of Group IVB Irons

NASA Technical Reports Server (NTRS)

Honesto, J.; McDonough, W. F.; Walker, R. J.; McCoy, T. J.; Ash, R. D.

2005-01-01

Study of the magmatic iron meteorite groups permits constraints to be placed on the chemical and isotopic composition of parent bodies, and the timing of, and crystal-liquid fractionation processes involved in the crystallization of asteroidal cores. Here we examine Re-Os isotopic and trace elemental systematics of group IVB irons. Compared to most irons, the irons comprising this group are enriched in some of the most refractory siderophile elements, yet highly-depleted in most volatile siderophile elements. These characteristics have been attributed to processes such as high temperature condensation of precursor materials and oxidation in the parent body. Most recently it has been suggested that both processes may be involved in the chemical complexity of the group. Here, high precision isotopic and highly siderophile element (HSE) concentrations are used to further examine these possible origins, and the crystallization history of the group. In addition, we have begun to assess the possibility of relating certain ungrouped irons with major groups via multi-element, trace element modeling. In a companion abstract, the isotopic and trace element systematics of the ungrouped iron Tishomingo are compared with the IVB irons.

Trace elements distributions at Datoko-Shega artisanal mining site, northern Ghana.

PubMed

Arhin, Emmanuel; Boansi, Apea Ohene; Zango, M S

2016-02-01

Environmental geochemistry classifies elements into essential, non-essential and toxic elements in relationship to human health. To assess the environmental impact of mining at Datoko-Shega area, the distributions and concentrations of trace elements in stream sediments and soil samples were carried out. X-ray fluorescence analytical technique was used to measure the major and trace element concentrations in sediments and modified fire assay absorption spectrometry in soils. The results showed general depletion of major elements except titanium oxide (TiO2) compared to the average crustal concentrations. The retention of TiO2 at the near surface environment probably was due to the intense tropical weathering accompanied by the removal of fine sediments and soil fractions during the harmattan season by the dry north-east trade winds and sheet wash deposits formed after flash floods. The results also showed extreme contamination of selenium (Se), cadmium (Cd) and mercury (Hg), plus strong contaminations of arsenic (As) and chromium (Cr) in addition to moderate contamination of lead (Pb) in the trace element samples relative to crustal averages in the upper continental crust. However Hg, Pb and Cd concentrations tend to be high around the artisanal workings. It was recognised from the analysis of the results that the artisanal mining activity harnessed and introduces some potentially toxic elements such as Hg, Cd and Pb mostly in the artisan mine sites. But the interpretation of the trace element data thus invalidates the elevation of As concentrations to be from the mine operations. It consequently noticed As values in the mine-impacted areas to be similar or sometimes lower than As values in areas outside the mine sites from the stream sediment results.

Single element injector cold flow testing for STME swirl coaxial injector element design

NASA Technical Reports Server (NTRS)

Hulka, J.; Schneider, J. A.

1993-01-01

An oxidizer-swirled coaxial element injector is being investigated for application in the Space Transportation Main Engine (STME). Single element cold flow experiments were conducted to provide characterization of the STME injector element for future analysis, design, and optimization. All tests were conducted to quiescent, ambient backpressure conditions. Spray angle, circumferential spray uniformity, dropsize, and dropsize distribution were measured in water-only and water/nitrogen flows. Rupe mixing efficiency was measured using water/sucrose solution flows with a large grid patternator for simple comparative evaluation of mixing. Factorial designs of experiment were used for statistical evaluation of injector geometrical design features and propellant flow conditions on mixing and atomization. Increasing the free swirl angle of the liquid oxidizer had the greatest influence on increasing the mixing efficiency. The addition of gas assistance had the most significant effect on reducing oxidizer droplet size parameters and increasing droplet size distribution. Increasing the oxidizer injection velocity had the greatest influence for reducing oxidizer droplet size parameters and increasing size distribution for non-gas assisted flows. Single element and multi-element subscale hot fire testing are recommended to verify optimized designs before committing to the STME design.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

PubMed

Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro

2014-03-01

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. Copyright © 2013 Elsevier B.V. All rights reserved.

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen (Inventor)

1999-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a percursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

1999-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate-solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Bonding of sapphire to sapphire by eutectic mixture of aluminum oxide and zirconium oxide

NASA Technical Reports Server (NTRS)

Deluca, J. J. (Inventor)

1975-01-01

Bonding of an element comprising sapphire, ruby or blue sapphire to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide is discussed. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

Structural aspects of denitrifying enzymes.

PubMed

Moura, I; Moura, J J

2001-04-01

The reduction of nitrate to nitrogen gas via nitrite, nitric oxide and nitrous oxide is the metabolic pathway usually known as denitrification, a key step in the nitrogen cycle. As observed for other elemental cycles, a battery of enzymes are utilized, namely the reductases for nitrate, nitrite, nitric oxide and nitrous oxide, as well as multiple electron donors that interact with these enzymes, in order to carry out the stepwise reactions that involve key intermediates. Because of the importance of this pathway (of parallel importance to the nitrogen-fixation pathway), efforts are underway to understand the structures of the participating enzymes and to uncover mechanistic aspects. Three-dimensional structures have been solved for the majority of these enzymes in the past few years, revealing the architecture of the active metal sites as well as global structural aspects, and possible mechanistic aspects. In addition, the recognition of specific electron-transfer partners raises important questions regarding specific electron-transfer pathways, partner recognition and control of metabolism.

Liquid fuel injection elements for rocket engines

NASA Technical Reports Server (NTRS)

Cox, George B., Jr. (Inventor)

1993-01-01

Thrust chambers for liquid propellant rocket engines include three principal components. One of these components is an injector which contains a plurality of injection elements to meter the flow of propellants at a predetermined rate, and fuel to oxidizer mixture ratio, to introduce the mixture into the combustion chamber, and to cause them to be atomized within the combustion chamber so that even combustion takes place. Evolving from these injectors are tube injectors. These tube injectors have injection elements for injecting the oxidizer into the combustion chamber. The oxidizer and fuel must be metered at predetermined rates and mixture ratios in order to mix them within the combustion chamber so that combustion takes place smoothly and completely. Hence tube injectors are subject to improvement. An injection element for a liquid propellant rocket engine of the bipropellant type is provided which includes tangential fuel metering orifices, and a plurality of oxidizer tube injection elements whose injection tubes are also provided with tangential oxidizer entry slots and internal reed valves.

Geochemistry and mineralogy of fly-ash from the Mae Moh lignite deposit, Thailand

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

Hart, B.R.; Powell, M.A.; Fyfe, W.S.

The concentration of 21 elements in fly ash from three boilers (75 MW, 150 MW, and 300 MW) at the EGAT power plant, Mae Moh, Thailand, were determined by INAA. The concentration of 10 major elements was determined by XRF. As, Co, Cr, Ni, Mo, and Sb generally increase in concentration going from bottom ash (BA) through the sequence of electrostatic precipitator ashes (ESPA) and reach maxima of As (352 ppm), Co (45 ppm), Cr (105 ppm), Mo (32 ppm), Ni (106 ppm), and Sb (15 ppm) in the ESPA. Ce, Cs, Fe, Hf, La, Sc, Ta, Tb, and Ybmore » did not exhibit concentration trends or are variable except in the case of one boiler, which showed an increase going from BA to ESPA. Only Br decreased in composition going from BA to ESPA. Rb, Sm, U, and Th showed marked variation in trends. The major elements identified by EDS were Al, Si, S, K, Ca, Fe, and Ba, with minor amounts of Mg, Na, Ti, Mn, and Sr. Al, Si, K, and Ca occur together and are present in most of the fly-ash particles. Ba was found as a major component with Ca, Al, and Si. Fe and Ca are usually associated with sulfur. Some small spheres (< 5 {mu}m) are comprised almost entirely of Fe (probably as oxide). Symplectite textures are noted in high-Fe phases. All elements except Br are significantly enriched in the fly ash relative to the coal, which contains 35% ash. Particle chemistry is consistent with the major mineral phases identified by XRD, which include: quartz, magnetite, mullite, gehlenite, anorthite, hematite, anhydrite, and clinopyroxene.« less

The relationship between CK and CV chondrites

NASA Astrophysics Data System (ADS)

Greenwood, R. C.; Franchi, I. A.; Kearsley, A. T.; Alard, O.

2010-03-01

CK chondrites are highly oxidized meteorites containing abundant magnetite and trace amounts of Fe,Ni metal. Although the group is predominately composed of equilibrated meteorites (types 4-6), in recent years a significant number of new samples have been classified as being either CK3 or CK3-anomalous. These unequilibrated CKs often display a close affinity with members of the CV oxidized subgroup. CKs and CVs (oxidized subgroup) may therefore form a continuum and by implication could be derived from a single common parent body. To investigate the relationship between these two groups a detailed study of the oxygen isotope composition, opaque mineralogy and major and trace element geochemistry of a suite of CV and CK chondrites has been undertaken. The results of oxygen isotope analysis confirm the close affinity between CV and CK chondrites, while excluding the possibility of a linkage between the CO and CK groups. Magnetites in both CV and CK chondrites show significant compositional similarities, but high Ti contents are a diagnostic feature of the latter group. The results of major and trace element analysis demonstrate that both CV and CK chondrites show overlapping variation. Supporting evidence for a single common source for both groups comes from their similar cosmic-ray exposure age distributions. Recent reflectance spectral analysis is consistent with both the CVs and CKs being derived from Eos family asteroids, which are believed to have formed by the catastrophic disruption of a single large asteroid. Thus, a range of evidence appears to be consistent with CV and CK chondrites representing samples from a single thermally stratified parent body. In view of the close similarity between CV and CK chondrites some modification of the present classification scheme may be warranted, possibly involving integration of the two groups. One means of achieving this would be to reassigned CK chondrites to a subgroup of the oxidized CVs. It is recognized that a full evaluation of this proposal may require further study of the still poorly understood CK3 chondrites.

All oxide semiconductor-based bidirectional vertical p-n-p selectors for 3D stackable crossbar-array electronics

PubMed Central

Bae, Yoon Cheol; Lee, Ah Rahm; Baek, Gwang Ho; Chung, Je Bock; Kim, Tae Yoon; Park, Jea Gun; Hong, Jin Pyo

2015-01-01

Three-dimensional (3D) stackable memory devices including nano-scaled crossbar array are central for the realization of high-density non-volatile memory electronics. However, an essential sneak path issue affecting device performance in crossbar array remains a bottleneck and a grand challenge. Therefore, a suitable bidirectional selector as a two-way switch is required to facilitate a major breakthrough in the 3D crossbar array memory devices. Here, we show the excellent selectivity of all oxide p-/n-type semiconductor-based p-n-p open-based bipolar junction transistors as selectors in crossbar memory array. We report that bidirectional nonlinear characteristics of oxide p-n-p junctions can be highly enhanced by manipulating p-/n-type oxide semiconductor characteristics. We also propose an associated Zener tunneling mechanism that explains the unique features of our p-n-p selector. Our experimental findings are further extended to confirm the profound functionality of oxide p-n-p selectors integrated with several bipolar resistive switching memory elements working as storage nodes. PMID:26289565

Parallels between major depressive disorder and Alzheimer's disease: role of oxidative stress and genetic vulnerability.

PubMed

Rodrigues, Roberto; Petersen, Robert B; Perry, George

2014-10-01

The thesis of this review is that oxidative stress is the central factor in major depressive disorder (MDD) and Alzheimer's disease (AD). The major elements involved are inflammatory cytokines, the hypothalamic-pituitary axis, the hypothalamic-pituitary gonadal, and arginine vasopressin systems, which induce glucocorticoid and "oxidopamatergic" cascades when triggered by psychosocial stress, severe life-threatening events, and mental-affective and somatic diseases. In individuals with a genomic vulnerability to depression, these cascades may result in chronic depression-anxiety-stress spectra, resulting in MDD and other known depressive syndromes. In contrast, in subjects with genomic vulnerability to AD, oxidative stress-induced brain damage triggers specific antioxidant defenses, i.e., increased levels of amyloid-β (Aβ) and aggregation of hyper-phosphorylated tau, resulting in paired helical filaments and impaired functions related to the ApoEε4 isoform, leading to complex pathological cascades culminating in AD. Surprisingly, all the AD-associated molecular pathways mentioned in this review have been shown to be similar or analogous to those found in depression, including structural damage, i.e., hippocampal and frontal cortex atrophy. Other interacting molecular signals, i.e., GSK-3β, convergent survival factors (brain-derived neurotrophic factor and heat shock proteins), and transition redox metals are also mentioned to emphasize the vast array of intermediates that could interact via comparable mechanisms in both MDD and AD.

PARALLELS BETWEEN MAJOR DEPRESSIVE DISORDER AND ALZHEIMER’S DISEASE: ROLE OF OXIDATIVE STRESS AND GENETIC VULNERABILITY

PubMed Central

Rodrigues, Roberto; Petersen, Robert B.

2014-01-01

The thesis of this review is that oxidative stress is the central factor in major depressive disorder (MDD) and Alzheimer’s disease (AD). The major elements involved are inflammatory cytokines, the hypothalamic pituitary axis, the hypothalamic pituitary gonadal, and arginine vasopressin systems, which induce glucocorticoid and “oxidopamatergic” cascades when triggered by psychosocial stress, severe life threatening events, and mental-affective and somatic diseases. In individuals with a genomic vulnerability to depression these cascades may result in chronic depression-anxiety-stress spectra, resulting in MDD and other known depressive syndromes. In contrast, in subjects with genomic vulnerability to Alzheimer’s disease, oxidative stress-induced brain damage triggers specific antioxidant defenses, i.e. increased levels of amyloid-β (Aβ) and aggregation of hyper-phosphorylated tau, resulting in paired helical filaments and impaired functions related to the ApoEε4 isoform, leading to complex pathological cascades culminating in AD. Surprisingly, all the AD associated molecular pathways mentioned in this review have been shown to be similar or analogous to those found in depression, including structural damage, i.e. hippocampal and frontal cortex atrophy. Other interacting molecular signals, i.e. GSK-3β, convergent survival factors (brain-derived neurotrophic factor and heat shock proteins), and transition-redox metals are also mentioned to emphasize the vast array of intermediates that could interact via comparable mechanisms in both MDD and AD. PMID:24927694

Investigation of processes controlling summertime gaseous elemental mercury oxidation at midlatitudinal marine, coastal, and inland sites

NASA Astrophysics Data System (ADS)

Ye, Zhuyun; Mao, Huiting; Lin, Che-Jen; Kim, Su Youn

2016-07-01

A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate the oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (AI; marine), Thompson Farm (TF; coastal, rural), and Pack Monadnock (PM; inland, rural, elevated). The chemical mechanism in this box model included the most up-to-date Hg and halogen chemistry. As a result, the box model was able to simulate reasonably the observed diurnal cycles of gaseous oxidized mercury (GOM) and chemical speciation bearing distinct differences between the three sites. In agreement with observations, simulated GOM diurnal cycles at AI and TF showed significant daytime peaks in the afternoon and nighttime minimums compared to flat GOM diurnal cycles at PM. Moreover, significant differences in the magnitude of GOM diurnal amplitude (AI > TF > PM) were captured in modeled results. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80-99 % of total GOM production during daytime. H2O2-initiated GEM oxidation was significant (˜ 33 % of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL) atmosphere, Br and BrO became dominant GEM oxidants, with mixing ratios reaching 0.1 and 1 pptv, respectively, and contributing ˜ 70 % of the total GOM production during midday, while O3 dominated GEM oxidation (50-90 % of GOM production) over the remaining day when Br and BrO mixing ratios were diminished. The majority of HgBr produced from GEM+Br was oxidized by NO2 and HO2 to form brominated GOM species. Relative humidity and products of the CH3O2+BrO reaction possibly significantly affected the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas-particle partitioning could potentially be important in the production of GOM as well as Br and BrO at the marine site.

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

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

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Determination of major elements by wavelength-dispersive X-ray fluorescence spectrometry and trace elements by inductively coupled plasma mass spectrometry in igneous rocks from the same fused sample (110 mg)

NASA Astrophysics Data System (ADS)

Amosova, Alena A.; Panteeva, Svetlana V.; Chubarov, Victor M.; Finkelshtein, Alexandr L.

2016-08-01

The fusion technique is proposed for simultaneous determination of 35 elements from the same sample. Only 110 mg of rock sample was used to obtain fused glasses for quantitative determination of 10 major elements by wavelength dispersive X-ray fluorescence analysis, 16 rare earth elements and some other trace elements by inductively coupled plasma mass spectrometry analysis. Fusion was performed with 1.1 g of lithium metaborate and LiBr solution as the releasing agent in platinum crucible in electric furnace at 1100 °C. The certified reference materials of ultramafic, mafic, intermediate and felsic igneous rocks have been applied to obtain the calibration curves for rock-forming oxides (Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, Fe2O3) and some trace elements (Ba, Sr, Zr) determination by X-ray fluorescence analysis. The repeatability does not exceed the allowable standard deviation for a wide range of concentrations. In the most cases the relative standard deviation was less than 5%. Obtained glasses were utilized for the further determination of rare earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and some other (Ba, Sr, Zr, Rb, Cs, Y, Nb, Hf, Ta, Th and U) trace elements by inductively coupled plasma mass spectrometry analysis with the same certified reference materials employed. The results could mostly be accepted as satisfactory. The proposed procedure essentially reduces the expenses in comparison with separate sample preparation for inductively coupled plasma mass spectrometry and X-ray fluorescence analysis.

Application of Standards-Based Quantitative SEM-EDS Analysis to Oxide Minerals

NASA Astrophysics Data System (ADS)

Mengason, M. J.; Ritchie, N. W.; Newbury, D. E.

2016-12-01

SEM and EPMA analysis are powerful tools for documenting and evaluating the relationships between minerals in thin sections and for determining chemical compositions in-situ. The time and costs associated with determining major, minor, and some trace element concentrations in geologic materials can be reduced due to advances in EDS spectrometer performance and the availability of software tools such as NIST DTSA II to perform multiple linear least squares (MLLS) fitting of energy spectra from standards to the spectra from samples recorded under the same analytical conditions. MLLS fitting is able to overcome spectral peak overlaps among the transition-metal elements that commonly occur in oxide minerals, which had previously been seen as too difficult for EDS analysis, allowing for rapid and accurate determination of concentrations. The quantitative use of EDS is demonstrated in the chemical analysis of magnetite (NMNH 114887) and ilmenite (NMNH 96189) from the Smithsonian Natural History Museum Microbeam Standards Collection. Average concentrations from nine total spots over three grains are given in mass % listed as (recommended; measured concentration ± one standard deviation). Spectra were collected for sixty seconds live time at 15 kV and 10 nA over a 12 micrometer wide scan area. Analysis of magnetite yielded Magnesium (0.03; 0.04 ± 0.01), Aluminum (none given; 0.040 ± 0.006), Titanium (0.10; 0.11 ± 0.02), Vanadium (none given; 0.16 ± 0.01), Chromium (0.17; 0.14 ± 0.02), and Iron (70.71, 71.4 ± 0.2). Analysis of ilmenite yielded Magnesium (0.19; 0.183 ± 0.008), Aluminum (none given; 0.04 ± 0.02), Titanium (27.4, 28.1 ± 0.1), Chromium (none given; 0.04 ± 0.01), Manganese (3.69; 3.73 ± 0.03), Iron (36.18; 35.8 ± 0.1), and Niobium (0.64; 0.68 ± 0.03). The analysis of geologic materials by standards-based quantitative EDS can be further illustrated with chemical analyses of oxides from ocean island basalts representing several locations globally to illustrate the suitability of the method to the goal of evaluating trends in major and minor element concentrations and variability among locations. The shorter collection times of EDS, compared to WDS, allow greater sampling of the populations of oxides present as fine-grained quench products in addition to sampling larger inclusions hosted by silicate minerals.

Scalable and sustainable electrochemical allylic C-H oxidation

NASA Astrophysics Data System (ADS)

Horn, Evan J.; Rosen, Brandon R.; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

2016-05-01

New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”. Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact.

Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

NASA Astrophysics Data System (ADS)

Salavati-Niasari, Masoud; Bazarganipour, Mehdi

2009-06-01

Hydroxyl functionalized copper(II) Schiff-base, N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH) 2-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH) 2-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the "neat" complexes than over the encapsulated complexes.

Transformation of mercury speciation through the SCR system in power plants.

PubMed

Yang, Hong-min; Pan, Wei-ping

2007-01-01

Coal-fired utility boilers are now identified as the largest source of mercury in the United States. There is speculation that the installation of selective catalytic reduction (SCR) system for reduction of NOx can also prompt the oxidation and removal of mercury. In this paper, tests at six full-scale power plants with similar type of the SCR systems are conducted to investigate the effect of the SCR on the transformation of mercury speciation. The results show that the SCR system can achieve more than 70%-80% oxidation of elemental mercury and enhance the mercury removal ability in these units. The oxidation of elemental mercury in the SCR system strongly depends on the coal properties and the operation conditions of the SCR systems. The content of chloride in the coal is the key factor for the oxidization process and the maximum oxidation of elemental mercury is found when chloride content changes from 400 to 600 ppm. The sulfur content is no significant impact on oxidation of elemental mercury.

OXIDATION OF TRANSURANIC ELEMENTS

DOEpatents

Moore, R.L.

1959-02-17

A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

The chemical characteristics of ground water near Fairbanks, Alaska: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1998

USGS Publications Warehouse

Farmer, G. Lang; Goldfarb, Richard J.; Lilly, Michael R.; Bolton, Bob; Meier, Allen L.; Sanzolone, Richard F.

2000-01-01

Major- and trace-element abundances, and Sr and Pb isotopic compositions, of ground waters in and near Fairbanks, Alaska, were determined to characterize their chemical characteristics and to assess the factors controlling variations in dissolved arsenic concentrations. Collected samples show majorelement (Ca>Mg>Na>K) and strontium and lead isotopic compositions characteristic of waters that have interacted with lithologies comprising the Fairbanks Schist. Dissolved arsenic concentrations are not highly correlated with the abundances of other major and trace elements in these waters; however, waters with high arsenic concentrations (5.4 to 450 parts per billion) tend to have relatively high concentrations of antimony (as much as 1.7 ppb). The correlation between arsenic and antimony suggests that both elements were derived from the oxidation of hypogene sulfide minerals (arsenopyrite) that originally formed within the Fairbanks Schist during hydrothermal activity associated with the emplacement of Cretaceous granitic rocks. Variations in measured arsenic concentrations are due, in part, to the variations in the original abundance of upgradient sulfide minerals from a given well or spring. However, speciation studies on the ground water containing the highest concentration of arsenic in this study (450 ppb) demonstrate that the arsenic occurs primarily in its reduced form (As(III)). In agreement with previous studies, we conclude that relatively reducing ground waters have the highest potential for high arsenic concentrations due to greater mobility of As(III) relative to its oxidized counterpart (As(V)). In light of this conclusion, additional studies are being undertaken to determine how seasonal variations in ground-water redox affect arsenic mobility

Synthesis of Ti Oxides at Reducing Conditions: Implications for Beamline Standards and Cosmochemistry

NASA Technical Reports Server (NTRS)

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

2017-01-01

These initial experiments demonstrate the great potential for synthesizing customized compounds for use as standards, or in buffering experiments at reducing conditions. We are also investigating Cr and V oxides, as well as compounds containing these elements such as FeV2O4 and FeCr2O4. Oxygen fugacity exerts a major control on mineral major element chemistry and elemental valence of minerals in any plane-tary compositional system [1]. For Earth, Fe is multivalent ranging from nearly Fe0 at low fO2 in the deep mantle to Fe2+ to Fe3+ at high low fO2. For solar nebular and meteoritic materials fO2 ranges from near IW to 10 log fO2 units below the IW buffer [1]. Phases in CAIs, for example, contain no Fe2+, but may contain Ti4+, Ti3+, or Ti2+, and Cr3+ or Cr2+, and V3+ or V2+ [1,2,3]. De-tailed study of inclusions may reveal important differences in fO2 thus reflecting different environments in the solar nebula [4]. XANES, FEG-SEM, and TEM can reveal such variations in micro and nano samples such as Stardust and cosmic dust particles [5], but successful application to reduced conditions depends upon the availability of well characterized standards. Acquiring appropriate standards for reduced phases that contain Ti3+ or Ti2+, Cr3+ or Cr2+, and V3+ or V2+ can be a challenge. Here we report our preliminary results at synthesizing reduced Ti bearing standards, and focus on the preliminary characterization.

A survey of 16 rare Earth elements in the major foods in China.

PubMed

Jiang, Ding Guo; Yang, Jie; Zhang, Shuo; Yang, Da Jin

2012-06-01

The aim of this survey was to investigate the level of contamination of the most consumed foods in China with 16 rare earth elements (REEs), and to provide the basic data for establishing and revising food safety standards for REEs. Sixteen REEs in foods were measured by inductively coupled plasma-mass spectrometry (ICP-MS) in the labs of the Centers for Disease Control and Prevention of four provinces and two municipalities, during 2009-2010. 1 231 samples were analyzed and 19 121 concentration data of 16 REEs were collected. The REEs levels in the investigated foods varied significantly. The concentrations of cerium (Ce), dysprosium (Dy), yttrium (Y), lanthanum (La), and neodymium (Nd) were relatively high, while the remaining eleven REEs were at low levels. The mean values of total rare earth element oxides (REOs) in cereals, fresh vegetables, fresh aquatic products, fresh meats and eggs varied from 0.052 mg/kg to 0.337 mg/kg. 16 REEs in the major foods were at very low contamination levels in the investigated regions. Copyright © 2012 The Editorial Board of Biomedical and Environmental Sciences. Published by Elsevier B.V. All rights reserved.

NOVEL OXIDANT FOR ELEMENTAL MERCURY CONTROL FROM FLUE GAS

EPA Science Inventory

A novel economical oxidant has been developed for elemental mercury (Hg(0)) removal from coal-fired boilers. The oxidant was rigorously tested in a lab-scale fixed-bed system with the Norit America's FGD activated carbon (DOE's benchmark sorbent) in a typical PRB subbituminous/l...

[Removal Characteristics of Elemental Mercury by Mn-Ce/molecular Sieve].

PubMed

Tan, Zeng-qiang; Niu, Guo-ping; Chen, Xiao-wen; An, Zhen

2015-06-01

The impregnation method was used to support molecular sieve with active manganese and cerium components to obtain a composite molecular sieve catalyst. The mercury removal performance of the catalyst was studied with a bench-scale setup. XPS analysis was used to characterize the sample before and after the modification in order to study the changes in the active components of the catalyst prepared. The results showed that the catalyst carrying manganese and cerium components had higher oxidation ability of elemental mercury in the temperature range of 300 degrees C - 450 degrees C, especially at 450 degrees C, the oxidation efficiency of elemental mercury was kept above 80%. The catalyst had more functional groups that were conducive to the oxidation of elemental mercury, and the mercury removal mainly depended on the chemical adsorption. The SO2 and NO in flue gas could inhibit the oxidation of elemental mercury to certain extent.

Determination of the oxidation states of metals and metalloids: An analytical review

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.

2013-12-01

The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

Use of chemical mechanical polishing in micromachining

DOEpatents

Nasby, Robert D.; Hetherington, Dale L.; Sniegowski, Jeffry J.; McWhorter, Paul J.; Apblett, Christopher A.

1998-01-01

A process for removing topography effects during fabrication of micromachines. A sacrificial oxide layer is deposited over a level containing functional elements with etched valleys between the elements such that the sacrificial layer has sufficient thickness to fill the valleys and extend in thickness upwards to the extent that the lowest point on the upper surface of the oxide layer is at least as high as the top surface of the functional elements in the covered level. The sacrificial oxide layer is then polished down and planarized by chemical-mechanical polishing. Another layer of functional elements is then formed upon this new planarized surface.

Method for combined removal of mercury and nitrogen oxides from off-gas streams

DOEpatents

Mendelsohn, Marshall H [Downers Grove, IL; Livengood, C David [Lockport, IL

2006-10-10

A method for removing elemental Hg and nitric oxide simultaneously from a gas stream is provided whereby the gas stream is reacted with gaseous chlorinated compound to convert the elemental mercury to soluble mercury compounds and the nitric oxide to nitrogen dioxide. The method works to remove either mercury or nitrogen oxide in the absence or presence of each other.

Oxidation of hydrogen halides to elemental halogens

DOEpatents

Rohrmann, Charles A.; Fullam, Harold T.

1985-01-01

A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

Oxidation corrosion resistant superalloys and coatings

NASA Technical Reports Server (NTRS)

Jackson, Melvin R. (Inventor); Rairden, III, John R. (Inventor)

1978-01-01

An article of manufacture having improved high temperature oxidation and corrosion resistance comprising: (a) a superalloy substrate containing a carbide reinforcing phase, and (b) a coating consisting of chromium, aluminum, carbon, at least one element selected from iron, cobalt or nickel, and optionally an element selected from yttrium or the rare earth elements.

Oxidation corrosion resistant superalloys and coatings

NASA Technical Reports Server (NTRS)

Jackson, Melvin R. (Inventor); Rairden, III, John R. (Inventor)

1980-01-01

An article of manufacture having improved high temperature oxidation and corrosion resistance comprising: (a) a superalloy substrate containing a carbide reinforcing phase, and (b) a coating consisting of chromium, aluminum, carbon, at least one element selected from iron, cobalt or nickel, and optionally an element selected from yttrium or the rare earth elements.

New functionalities in abundant element oxides: ubiquitous element strategy

PubMed Central

Hosono, Hideo; Hayashi, Katsuro; Kamiya, Toshio; Atou, Toshiyuki; Susaki, Tomofumi

2011-01-01

While most ceramics are composed of ubiquitous elements (the ten most abundant elements within the Earth's crust), many advanced materials are based on rare elements. A ‘rare-element crisis’ is approaching owing to the imbalance between the limited supply of rare elements and the increasing demand. Therefore, we propose a ‘ubiquitous element strategy’ for materials research, which aims to apply abundant elements in a variety of innovative applications. Creation of innovative oxide materials and devices based on conventional ceramics is one specific challenge. This review describes the concept of ubiquitous element strategy and gives some highlights of our recent research on the synthesis of electronic, thermionic and structural materials using ubiquitous elements. PMID:27877391

Element mobility studies of two drill-cores from the Götemar Granite (Kråkemåla test site), southeast Sweden

USGS Publications Warehouse

Smellie, John A.T.; Stuckless, John S.

1985-01-01

The pervasive alteration and the more recent mobilisation of U are evident to a depth of at least 600 m. The effects are most prevalent along major fracture zones and within the upper 250–300 m of one drill-hole where a high frequency of crush zones has been noted. Higher Fe oxidation ratios, higher Rb contents, lower U contents and correspondingly higher Th/U ratios, all characterise this zone.

The major-element composition of Mercury's surface from MESSENGER X-ray spectrometry.

PubMed

Nittler, Larry R; Starr, Richard D; Weider, Shoshana Z; McCoy, Timothy J; Boynton, William V; Ebel, Denton S; Ernst, Carolyn M; Evans, Larry G; Goldsten, John O; Hamara, David K; Lawrence, David J; McNutt, Ralph L; Schlemm, Charles E; Solomon, Sean C; Sprague, Ann L

2011-09-30

X-ray fluorescence spectra obtained by the MESSENGER spacecraft orbiting Mercury indicate that the planet's surface differs in composition from those of other terrestrial planets. Relatively high Mg/Si and low Al/Si and Ca/Si ratios rule out a lunarlike feldspar-rich crust. The sulfur abundance is at least 10 times higher than that of the silicate portion of Earth or the Moon, and this observation, together with a low surface Fe abundance, supports the view that Mercury formed from highly reduced precursor materials, perhaps akin to enstatite chondrite meteorites or anhydrous cometary dust particles. Low Fe and Ti abundances do not support the proposal that opaque oxides of these elements contribute substantially to Mercury's low and variable surface reflectance.

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

Gschneidner, Jr., Karl A.; Schmidt, Frederick A.

A carbothermic reduction method is provided for reducing a La-, Ce-, MM-, and/or Y-containing oxide in the presence of carbon and a source of a reactant element comprising Si, Ge, Sn, Pb, As, Sb, Bi, and/or P to form an intermediate alloy material including a majority of La, Ce, MM, and/or Y and a minor amount of the reactant element. The intermediate material is useful as a master alloy for in making negative electrode materials for a metal hydride battery, as hydrogen storage alloys, as master alloy additive for addition to a melt of commercial Mg and Al alloys, steels,more » cast irons, and superalloys; or in reducing Sm.sub.2O.sub.3 to Sm metal for use in Sm--Co permanent magnets.« less

Correlation among electronegativity, cation polarizability, optical basicity and single bond strength of simple oxides

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

Dimitrov, Vesselin, E-mail: vesselin@uctm.edu; Komatsu, Takayuki, E-mail: komatsu@mst.nagaokaut.ac.jp

2012-12-15

A suitable relationship between free-cation polarizability and electronegativity of elements in different valence states and with the most common coordination numbers has been searched on the basis of the similarity in physical nature of both quantities. In general, the cation polarizability increases with decreasing element electronegativity. A systematic periodic change in the polarizability against the electronegativity has been observed in the isoelectronic series. It has been found that generally the optical basicity increases and the single bond strength of simple oxides decreases with decreasing the electronegativity. The observed trends have been discussed on the basis of electron donation ability ofmore » the oxide ions and type of chemical bonding in simple oxides. - Graphical abstract: This figure shows the single bond strength of simple oxides as a function of element electronegativity. A remarkable correlation exists between these independently obtained quantities. High values of electronegativity correspond to high values of single bond strength and vice versa. It is obvious that the observed trend in this figure is closely related to the type of chemical bonding in corresponding oxide. Highlights: Black-Right-Pointing-Pointer A suitable relationship between free-cation polarizability and electronegativity of elements was searched. Black-Right-Pointing-Pointer The cation polarizability increases with decreasing element electronegativity. Black-Right-Pointing-Pointer The single bond strength of simple oxides decreases with decreasing the electronegativity. Black-Right-Pointing-Pointer The observed trends were discussed on the basis of type of chemical bonding in simple oxides.« less

Characteristics and environmental aspects of slag: a review

USGS Publications Warehouse

Piatak, Nadine M.; Parsons, Michael B.; Seal, Robert R.

2015-01-01

The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

OH-initiated heterogeneous aging of highly oxidized organic aerosol

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

Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.

2011-12-05

The oxidative evolution (“aging”) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics—1,2,3,4-butanetetracarboxylic acid (C{sub 8}H{sub 10}O{sub 8}), citric acid (C{sub 6}H{sub 8}O{sub 7}), tartaric acid (C{sub 4}H{sub 6}O{sub 6}), and Suwannee River fulvic acid—were oxidized by gas-phase OH in amore » flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.« less

Uptake of elements from seawater by ferromanganese crusts: Solid-phase associations and seawater speciation

USGS Publications Warehouse

Koschinsky, A.; Hein, J.R.

2003-01-01

Marine Fe-Mn oxyhydroxide crusts form by precipitation of dissolved components from seawater. Three hydrogenetic crust samples (one phosphatized) and two hydrothermal Mn-oxide samples were subjected to a sequential-leaching procedure in order to determine the host phases of 40 elements. Those host-phase associations are discussed with respect to element speciation in seawater. The partitioning of elements between the two major phases, Mn oxide and Fe oxyhydroxide, can in a first-order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater, as has been proposed in earlier models. Free and weakly complexed cations, such as alkali and alkaline earth metals, Mn, Co, Ni, Zn, T1(I), and partly Y, are sorbed preferentially on the negatively charged surface of the MnO2 in hydrogenetic crusts. The driving force is a strong coulombic interaction. All neutral or negatively charged chloro (Cd, Hg, T1), carbonate (Cu, Y, Pb, and U), and hydroxide (Be, Sc, Ti, Fe, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, Bi, Th, and T1(III)) complexes and oxyanions (V, Cr, As, Se, Mo, and W) bind to the slightly positively charged surface of the amorphous FeOOH phase. While coulombic interaction can explain the sorption of the negatively charged species, the binding of neutral species is based on specific chemical interaction. Organic complexation of elements in deep-ocean water seems to be at most of minor importance. Surface oxidation can explain some strong metal associations, e.g. of Co and T1 with the MnO2 and Te with the FeOOH. Sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface. Differences in the associations of some metals between the non-phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico-chemical environments of formation and speciations in oxic seawater vs. less-oxic fluids, especially for the redox-sensitive metals such as Mo and V. These environmental-related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth. ?? 2003 Elsevier Science B.V. All rights reserved.

Use of chemical mechanical polishing in micromachining

DOEpatents

Nasby, R.D.; Hetherington, D.L.; Sniegowski, J.J.; McWhorter, P.J.; Apblett, C.A.

1998-09-08

A process for removing topography effects during fabrication of micromachines. A sacrificial oxide layer is deposited over a level containing functional elements with etched valleys between the elements such that the sacrificial layer has sufficient thickness to fill the valleys and extend in thickness upwards to the extent that the lowest point on the upper surface of the oxide layer is at least as high as the top surface of the functional elements in the covered level. The sacrificial oxide layer is then polished down and planarized by chemical-mechanical polishing. Another layer of functional elements is then formed upon this new planarized surface. 4 figs.

Association of Serum Concentration of Different Trace Elements with Biomarkers of Systemic Oxidant Status in Dairy Cattle.

PubMed

Abuelo, Angel; Hernandez, Joaquín; Alves-Nores, Víctor; Benedito, José L; Castillo, Cristina

2016-12-01

There has been some recent criticism about the reliability of the assays commonly used to measure oxidant status in cattle, because some recent publications suggested that the concentration of different trace elements influences the results of these assays. The aim of this study was to test the correlation in 502 bovine serum samples between the concentration of several trace elements (Br, Co, Cr, Cu, Fe, I, Mn, Mo, Ni, Se, Sr, V and Zn) and markers of oxidant status (reactive oxygen species (ROS) and total serum antioxidant capacity (SAC)). The Oxidative Stress index (OSi) was also calculated as ROS/SAC. Some significant correlations were found, although weak (|ρ| < 0.50). Therefore, the relationships observed might be attributed to the different pro- and antioxidant effect of the different elements rather than to the assays detecting these elements instead of the oxidised molecules or total antioxidant potential, respectively. The OSi was poorly correlated (|ρ| ≤ 0.36) with the concentration of the studied trace elements, and therefore, its use is recommended to assess shifts in the systemic redox balance.

Study of groundwater arsenic pollution in Lanyang Plain using multivariate statistical analysis

NASA Astrophysics Data System (ADS)

chan, S.

2013-12-01

The study area, Lanyang Plain in the eastern Taiwan, has highly developed agriculture and aquaculture, which consume over 70% of the water supplies. Groundwater is frequently considered as an alternative water source. However, the serious arsenic pollution of groundwater in Lanyan Plain should be well studied to ensure the safety of groundwater usage. In this study, 39 groundwater samples were collected. The results of hydrochemistry demonstrate two major trends in Piper diagram. The major trend with most of groundwater samples is determined with water type between Ca+Mg-HCO3 and Na+K-HCO3. This can be explained with cation exchange reaction. The minor trend is obviously corresponding to seawater intrusion, which has water type of Na+K-Cl, because the localities of these samples are all in the coastal area. The multivariate statistical analysis on hydrochemical data was conducted for further exploration on the mechanism of arsenic contamination. Two major factors can be extracted with factor analysis. The major factor includes Ca, Mg and Sr while the minor factor includes Na, K and As. This reconfirms that cation exchange reaction mainly control the groundwater hydrochemistry in the study area. It is worth to note that arsenic is positively related to Na and K. The result of cluster analysis shows that groundwater samples with high arsenic concentration can be grouped into that with high Na, K and HCO3. This supports that cation exchange would enhance the release of arsenic and exclude the effect of seawater intrusion. In other words, the water-rock reaction time is key to obtain higher arsenic content. In general, the major source of arsenic in sediments include exchangeable, reducible and oxidizable phases, which are adsorbed ions, Fe-Mn oxides and organic matters/pyrite, respectively. However, the results of factor analysis do not show apparent correlation between arsenic and Fe/Mn. This may exclude Fe-Mn oxides as a major source of arsenic. The other sources will be evaluated by more trace elements, such as rare earth elements.

The elements of life and medicines

PubMed Central

Chellan, Prinessa; Sadler, Peter J

2015-01-01

Which elements are essential for human life? Here we make an element-by-element journey through the periodic table and attempt to assess whether elements are essential or not, and if they are, whether there is a relevant code for them in the human genome. There are many difficulties such as the human biochemistry of several so-called essential elements is not well understood, and it is not clear how we should classify elements that are involved in the destruction of invading microorganisms, or elements which are essential for microorganisms with which we live in symbiosis. In general, genes do not code for the elements themselves, but for specific chemical species, i.e. for the element, its oxidation state, type and number of coordinated ligands, and the coordination geometry. Today, the biological periodic table is in a position somewhat similar to Mendeleev's chemical periodic table of 1869: there are gaps and we need to do more research to fill them. The periodic table also offers potential for novel therapeutic and diagnostic agents, based on not only essential elements, but also non-essential elements, and on radionuclides. Although the potential for inorganic chemistry in medicine was realized more than 2000 years ago, this area of research is still in its infancy. Future advances in the design of inorganic drugs require more knowledge of their mechanism of action, including target sites and metabolism. Temporal speciation of elements in their biological environments at the atomic level is a major challenge, for which new methods are urgently needed. PMID:25666066

The elements of life and medicines.

PubMed

Chellan, Prinessa; Sadler, Peter J

2015-03-13

Which elements are essential for human life? Here we make an element-by-element journey through the periodic table and attempt to assess whether elements are essential or not, and if they are, whether there is a relevant code for them in the human genome. There are many difficulties such as the human biochemistry of several so-called essential elements is not well understood, and it is not clear how we should classify elements that are involved in the destruction of invading microorganisms, or elements which are essential for microorganisms with which we live in symbiosis. In general, genes do not code for the elements themselves, but for specific chemical species, i.e. for the element, its oxidation state, type and number of coordinated ligands, and the coordination geometry. Today, the biological periodic table is in a position somewhat similar to Mendeleev's chemical periodic table of 1869: there are gaps and we need to do more research to fill them. The periodic table also offers potential for novel therapeutic and diagnostic agents, based on not only essential elements, but also non-essential elements, and on radionuclides. Although the potential for inorganic chemistry in medicine was realized more than 2000 years ago, this area of research is still in its infancy. Future advances in the design of inorganic drugs require more knowledge of their mechanism of action, including target sites and metabolism. Temporal speciation of elements in their biological environments at the atomic level is a major challenge, for which new methods are urgently needed.

Trace elements are associated with urinary 8-hydroxy-2'-deoxyguanosine level: a case study of college students in Guangzhou, China.

PubMed

Lu, Shaoyou; Ren, Lu; Fang, Jianzhang; Ji, Jiajia; Liu, Guihua; Zhang, Jianqing; Zhang, Huimin; Luo, Ruorong; Lin, Kai; Fan, Ruifang

2016-05-01

Many trace heavy elements are carcinogenic and increase the incidence of cancer. However, a comprehensive study of the correlation between multiple trace elements and DNA oxidative damage is still lacking. The aim of this study is to investigate the relationships between the body burden of multiple trace elements and DNA oxidative stress in college students in Guangzhou, China. Seventeen trace elements in urine samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG), a biomarker of DNA oxidative stress, was also measured using liquid chromatography tandem mass spectrometer (LC-MS/MS). The concentrations of six essential elements including manganese (Mn), copper (Cu), nickel (Ni), selenium (Se), strontium (Sr), and molybdenum (Mo), and five non-essential elements including arsenic (As), cadmium (Cd), aluminum (Al), stibium (Sb), and thallium (Tl), were found to be significantly correlated with urinary 8-OHdG levels. Moreover, urinary levels of Ni, Se, Mo, As, Sr, and Tl were strongly significantly correlated with 8-OHdG (P < 0.01) concentration. Environmental exposure and dietary intake of these trace elements may play important roles in DNA oxidative damage in the population of Guangzhou, China.

Tissue-Specific Regulation of the Contents and Correlations of Mineral Elements in Hens by Zinc Oxide Nanoparticles.

PubMed

Zhao, Yong; Feng, Yan-Ni; Li, Lan; Zhang, Hong-Fu; Zhang, Yu-Na; Zhang, Peng-Fei; Liu, Xin-Qi; Zhang, Wei-Dong; Huang, Ting-Ting; Zhao, Li; Shen, Wei; Hao, Zhi-Hui

2017-06-01

Due to their small size, zinc oxide (ZnO) nanoparticles (NPs) are readily absorbed and easily cross biological barriers, which make them promising candidates as diet additives. However, some studies have reported that ZnO NPs cause toxicity; therefore, their safety and potency as diet additives for farm animals should be established. This study was the first to fully evaluate the effects of ZnO NPs on the homeostasis of eight elements in seven organs/tissues. The regulation of element homeostasis was found to be organ specific with no influence on oxidation status, anti-oxidation capability, or organ damage. ZnO NPs may specifically regulate the homeostasis of mineral elements and affect the following correlations: (1) between the element content in each organ and the concentration of Zn used in ZnSO 4 or ZnO NP treatments; (2) between ZnO NP and ZnSO 4 treatments for the same element in each organ; and (3) between elements (in each organ in ZnSO 4 or ZnO NP treatments) in layers' organs/tissues. The use of ZnO NPs as diet additives for animals should be implemented cautiously because, among other uncertainties, they may affect mineral element content.

Characterisation of oxidation products of 1,1-dimethylhydrazine by high-resolution orbitrap mass spectrometry.

PubMed

Ul'yanovskii, N V; Kosyakov, D S; Pikovskoi, I I; Khabarov, Yu G

2017-05-01

1,1-Dimethylhydrazine is used as a fuel for carrier rockets in the majority of countries implementing space exploration programs. Being highly reactive, 1,1-dimethylhydrazine easily undergoes oxidative transformation with the formation of a number of toxic, mutagenic, and teratogenic compounds. The use of high-resolution mass spectrometry for the study of the reaction of 1,1-dimethylhydrazine oxidation with hydrogen peroxide in aqueous solution allowed us to find hundreds of nitrogen-containing products of the CHN and CHNO classes, formed via radical processes. The vast majority of the compounds have not been previously considered as possible products of the transformation of rocket fuel. We have shown that the oxidation of 1,1-dimethylhydrazine proceeds in two stages, with the formation of a great number of complex unstable intermediates that contain up to ten nitrogen atoms. These intermediates are subsequently converted into final reaction products with a concomitant decrease in the average molecular weight. The intermediates and final products of the oxidative transformation of 1,1-dimethylhydrazine were characterised on the basis of their elemental composition using van Krevelen diagrams and possible compounds corresponding to the most intense peaks in the mass spectra were proposed. The data obtained are indicative of the presence of the following classes of heterocyclic nitrogen-containing compounds among the oxidation products: imines, piperidines, pyrrolidines, dihydropyrazoles, dihydroimidazoles, triazoles, aminotriazines, and tetrazines. The results obtained open up possibilities for the targeted search and identification of new toxic products of the degradation of rocket fuel and, as a result, a more adequate assessment of the ecological consequences of space-rocket activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interplay of water and reactive elements in oxidation of alumina-forming alloys.

PubMed

Mortazavi, N; Geers, C; Esmaily, M; Babic, V; Sattari, M; Lindgren, K; Malmberg, P; Jönsson, B; Halvarsson, M; Svensson, J E; Panas, I; Johansson, L G

2018-06-11

High-temperature alloys are crucial to many important technologies that underpin our civilization. All these materials rely on forming an external oxide layer (scale) for corrosion protection. Despite decades of research on oxide scale growth, many open questions remain, including the crucial role of the so-called reactive elements and water. Here, we reveal the hitherto unknown interplay between reactive elements and water during alumina scale growth, causing a metastable 'messy' nano-structured alumina layer to form. We propose that reactive-element-decorated, hydroxylated interfaces between alumina nanograins enable water to access an inner cathode in the bottom of the scale, at odds with the established scale growth scenario. As evidence, hydride-nanodomains and reactive element/hydrogen (deuterium) co-variation are observed in the alumina scale. The defect-rich alumina subsequently recrystallizes to form a protective scale. First-principles modelling is also performed to validate the RE effect. Our findings open up promising avenues in oxidation research and suggest ways to improve alloy properties.

Sulfur isotopic evidence for the origin of elemental sulfur in gas hydrate-bearing sediments of the northern South China Sea

NASA Astrophysics Data System (ADS)

Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn

2017-04-01

Elemental sulfur is a common intermediate in the sulfur cycle and contributes significantly to the fractionation of stable sulfur isotopes in different reservoirs in shelfal marine sediments (e.g., Canfield and Thamdrup, 1994). However, no study dedicated to the isotopic composition of elemental sulfur in seep environments has been conducted to the best of our knowledge, thus limiting further insight into the biochemical pathways involving elemental sulfur in such environments. In this study, elemental sulfur and pyrite were extracted from the sediment of a 200-m long gas hydrate-bearing core, which was obtained from the gas hydrate drilling expedition to the northern South China Sea in 2013 (Zhang et al., 2015). The sulfur isotopic composition of elemental sulfur was found to vary from -16 to +23 per mill, and pyrite yielded values ranging from -34 to +18 per mill. Interestingly, elemental sulfur revealed higher 34S contents (up to 30 per mill) than the associated pyrite in most sediment layers. Since elemental sulfur is only produced during oxidative pathways in the sulfur cycle, the studied elemental sulfur apparently represents the oxidation product of hydrogen sulfide by various electron acceptors such as Mn(IV) oxides or Fe(III) oxides (e.g., Thamdrup et al., 1993; Yao and Millero, 1996). Since there is little sulfur isotope fractionation for oxidative processes (Fry et al., 1986), the enrichment of elemental sulfur in 34S points to a pool of hydrogen sulfide depleted in 32S, which is best interpreted to result from sulfate-driven anaerobic oxidation of methane. References: Canfield D.E. and Thamdrup B. (1994) The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur. Science 266, 1973. Fry B., Cox J., Gest H. and Hayer J.M. (1986) Discrimination between 34S and32S during bacterial metabolism of inorganic sulfur compounds. J. Bacteriol. 165, 328-330. Thamdrup B., Finster K., Hansen W. and Bak F. (1993) Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron and manganese. Appl. Env. Microbiol. 59, 101-108. Yao W. and Millero F.J. (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar. Chem. 52, 1-16. Zhang G., Liang J., Lu J.A., Yang S., Zhang M., Holland M., Schultheiss P., Su X., Sha Z., Xu H., Gong Y., Fu S., Wang L. and Kuang Z. (2015) Geological features, controlling factors and potential prospects of the gas hydrate occurrence in the east part of the Pearl River Mouth Basin, South China Sea. Mar. Pet. Geol. 67, 356-367.

Application of Developed APCVD Transparent Conducting Oxides and Undercoat Technologies for Economical OLED Lighting

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

Silverman, Gary S.; Bluhm, Martin; Coffey, James

2011-01-02

Economics is a key factor for application of organic light emitting diodes (OLED) in general lighting relative to OLED flat panel displays that can handle high cost materials such as indium tin oxide (ITO) or Indium zinc oxide (IZO) as the transparent conducting oxide (TCO) on display glass. However, for OLED lighting to penetrate into general illumination, economics and sustainable materials are critical. The issues with ITO have been documented at the DOE SSL R&D and Manufacturing workshops for the last 5 years and the issue is being exaserbated by export controls from China (one of the major sources ofmore » elemental indium). Therefore, ITO is not sustainable because of the fluctuating costs and the United States (US) dependency on other nations such as China. Numerous alternatives to ITO/IZO are being evaluated such as Ag nanoparticles/nanowires, carbon nanotubes, graphene, and other metal oxides. Of these other metal oxides, doped zinc oxide has attracted a lot of attention over the last 10 years. The volume of zinc mined is a factor of 80,000 greater than indium and the US has significant volumes of zinc mined domestically, resulting in the ability for the US to be self-sufficient for this element that can be used in optoelectonic applications. The costs of elemental zinc is over 2 orders of magnitude less than indium, reflecting the relative abundance and availablility of the elements. Arkema Inc. and an international primary glass manufacturing company, which is located in the United States, have developed doped zinc oxide technology for solar control windows. The genesis of this DOE SSL project was to determine if doped zinc oxide technology can be taken from the commodity based window market and translate the technology to OLED lighting. Thus, Arkema Inc. sought out experts, Philips Lighting, Pacific Northwest National Laboratories (PNNL) and National Renewable Research Laboratories (NREL), in OLED devices and brought them into the project. This project had a clear focus on economics and the work plan focused both on doped ZnO process and OLED device structure that would be consistent with the new TCO. The team successfully made 6 inch OLEDs with a serial construction. More process development is required to optimize commercial OLED structures. Feasibility was demonstrated on two different light extraction technologies: 1/4 lambda refractive index matching and high-low-high band pass filter. Process development was also completed on the key precursors for the TCO, which are ready for pilot-plant scale-up. Subsequently, Arkema has developed a cost of ownership model that is consistent with DOE SSL R&D Manufacturing targets as outlined in the DOE SSL R&D Manufacturing 2010 report. The overall outcome of this project was the demonstration that doped zinc oxide can be used for OLED devices without a drop-off in performance while gaining the economic and sustainable benefits of a more readily available TCO. The broad impact of this project, is the facilitation of OLED lighting market penetration into general illumination, resulting in significant energy savings, decreased greenhouse emissions, with no environmental impact issues such as mercury found in Fluorescent technology.« less

Acidithiobacillus caldus Sulfur Oxidation Model Based on Transcriptome Analysis between the Wild Type and Sulfur Oxygenase Reductase Defective Mutant

PubMed Central

Chen, Linxu; Ren, Yilin; Lin, Jianqun; Liu, Xiangmei; Pang, Xin; Lin, Jianqiang

2012-01-01

Background Acidithiobacillus caldus (A. caldus) is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs) for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox) system (omitting SoxCD), non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR). The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system. Results An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor) was created and its growth abilities were measured in media using elemental sulfur (S0) and tetrathionate (K2S4O6) as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR) of the wild type and the Δsor mutant in S0 and K2S4O6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO) and heterodisulfide reductase (HDR), the truncated Sox pathway, and the S4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media. Conclusion An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized. PMID:22984393

The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

NASA Astrophysics Data System (ADS)

Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

2015-12-01

The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0.006). With C/3He ratios an order of magnitude greater than MORB this suggests that the primitive mantle is a more carbonated and oxidized source than the depleted upper mantle.

Encapsulation of high temperature thermoelectric modules

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

Salvador, James R.; Sakamoto, Jeffrey; Park, Youngsam

A method of encapsulating a thermoelectric device and its associated thermoelectric elements in an inert atmosphere and a thermoelectric device fabricated by such method are described. These thermoelectric devices may be intended for use under conditions which would otherwise promote oxidation of the thermoelectric elements. The capsule is formed by securing a suitably-sized thin-walled strip of oxidation-resistant metal to the ceramic substrates which support the thermoelectric elements. The thin-walled metal strip is positioned to enclose the edges of the thermoelectric device and is secured to the substrates using gap-filling materials. The strip, substrates and gap-filling materials cooperatively encapsulate the thermoelectricmore » elements and exclude oxygen and water vapor from atmospheric air so that the elements may be maintained in an inert, non-oxidizing environment.« less

Phase discrimination of uranium oxides using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Campbell, Keri R.; Wozniak, Nicholas R.; Colgan, James P.; Judge, Elizabeth J.; Barefield, James E.; Kilcrease, David P.; Wilkerson, Marianne P.; Czerwinski, Ken R.; Clegg, Samuel M.

2017-08-01

Nuclear forensics goals for characterizing samples of interest include qualitative and quantitative analysis of major and trace elements, isotopic analysis, phase identification, and physical analysis. These samples may include uranium oxides UO2, U3O8, and UO3, which play an important role in the front end of the nuclear fuel cycle, from mining to fuel fabrication. The focus of this study is to compare the ratios of the intensities of uranium and oxygen emission lines which can be used to distinguish between different uranium oxide materials using Laser-Induced Breakdown Spectroscopy (LIBS). Measurements at varying laser powers were made under an argon atmosphere at 585 Torr to ensure the oxygen emission intensity was originating from the sample, and not from the atmosphere. Fifteen uranium emission lines were used to compare experimental results with theoretical calculations in order to determine the plasma conditions. Using a laser energy of 26 mJ, the uranium lines 591.539 and 682.692 nm provide the highest degree of discrimination between the uranium oxides. The study presented here suggests that LIBS is useful for discriminating uranium oxide phases, UO2, U3O8, and UO3.

Impact of oxidation on protein therapeutics: Conformational dynamics of intact and oxidized acid-β-glucocerebrosidase at near-physiological pH

PubMed Central

Bobst, Cedric E; Thomas, John J; Salinas, Paul A; Savickas, Philip; Kaltashov, Igor A

2010-01-01

The solution dynamics of an enzyme acid-β-glucocerebrosidase (GCase) probed at a physiologically relevant (lysosomal) pH by hydrogen/deuterium exchange mass spectrometry (HDX-MS) reveals very uneven distribution of backbone amide protection across the polypeptide chain. Highly mobile segments are observed even within the catalytic cavity alongside highly protective segments, highlighting the importance of the balance between conformational stability and flexibility for enzymatic activity. Forced oxidation of GCase that resulted in a 40–60% reduction in in vitro biological activity affects the stability of some key structural elements within the catalytic site. These changes in dynamics occur on a longer time scale that is irrelevant for catalysis, effectively ruling out loss of structure in the catalytic site as a major factor contributing to the reduction of the catalytic activity. Oxidation also leads to noticeable destabilization of conformation in remote protein segments on a much larger scale, which is likely to increase the aggregation propensity of GCase and affect its bioavailability. Therefore, it appears that oxidation exerts its negative impact on the biological activity of GCase indirectly, primarily through accelerated aggregation and impaired trafficking. PMID:20945356

Nano-thick calcium oxide armed titanium: boosts bone cells against methicillin-resistant Staphylococcus aureus

NASA Astrophysics Data System (ADS)

Cao, Huiliang; Qin, Hui; Zhao, Yaochao; Jin, Guodong; Lu, Tao; Meng, Fanhao; Zhang, Xianlong; Liu, Xuanyong

2016-02-01

Since the use of systemic antibiotics for preventing acute biomaterial-associated infections (BAIs) may build up bacterial resistance and result in huge medical costs and unpredictable mortality, new precaution strategies are required. Here, it demonstrated that titanium armed with a nano-thick calcium oxide layer was effective on averting methicillin-resistant Staphylococcus aureus (MRSA) infections in rabbits. The calcium oxide layer was constructed by, firstly, injecting of metallic calcium into titanium via a plasma immersion ion implantation process, and then transforming the outer most surface into oxide by exposing to the atmosphere. Although the calcium oxide armed titanium had a relative low reduction rate (~74%) in growth of MRSA in vitro, it could markedly promote the osteogenic differentiation of bone marrow stem cells (BMSCs), restore local bone integration against the challenge of MRSA, and decrease the incidence of MRSA infection with a rate of 100% (compared to the titanium control). This study demonstrated for the first time that calcium, as one of the major elements in a human body, could be engineered to avert MRSA infections, which is promising as a safe precaution of disinfection for implantable biomedical devices.

Nano-thick calcium oxide armed titanium: boosts bone cells against methicillin-resistant Staphylococcus aureus

PubMed Central

Cao, Huiliang; Qin, Hui; Zhao, Yaochao; Jin, Guodong; Lu, Tao; Meng, Fanhao; Zhang, Xianlong; Liu, Xuanyong

2016-01-01

Since the use of systemic antibiotics for preventing acute biomaterial-associated infections (BAIs) may build up bacterial resistance and result in huge medical costs and unpredictable mortality, new precaution strategies are required. Here, it demonstrated that titanium armed with a nano-thick calcium oxide layer was effective on averting methicillin-resistant Staphylococcus aureus (MRSA) infections in rabbits. The calcium oxide layer was constructed by, firstly, injecting of metallic calcium into titanium via a plasma immersion ion implantation process, and then transforming the outer most surface into oxide by exposing to the atmosphere. Although the calcium oxide armed titanium had a relative low reduction rate (~74%) in growth of MRSA in vitro, it could markedly promote the osteogenic differentiation of bone marrow stem cells (BMSCs), restore local bone integration against the challenge of MRSA, and decrease the incidence of MRSA infection with a rate of 100% (compared to the titanium control). This study demonstrated for the first time that calcium, as one of the major elements in a human body, could be engineered to avert MRSA infections, which is promising as a safe precaution of disinfection for implantable biomedical devices. PMID:26899567

Nano-thick calcium oxide armed titanium: boosts bone cells against methicillin-resistant Staphylococcus aureus.

PubMed

Cao, Huiliang; Qin, Hui; Zhao, Yaochao; Jin, Guodong; Lu, Tao; Meng, Fanhao; Zhang, Xianlong; Liu, Xuanyong

2016-02-22

Since the use of systemic antibiotics for preventing acute biomaterial-associated infections (BAIs) may build up bacterial resistance and result in huge medical costs and unpredictable mortality, new precaution strategies are required. Here, it demonstrated that titanium armed with a nano-thick calcium oxide layer was effective on averting methicillin-resistant Staphylococcus aureus (MRSA) infections in rabbits. The calcium oxide layer was constructed by, firstly, injecting of metallic calcium into titanium via a plasma immersion ion implantation process, and then transforming the outer most surface into oxide by exposing to the atmosphere. Although the calcium oxide armed titanium had a relative low reduction rate (~74%) in growth of MRSA in vitro, it could markedly promote the osteogenic differentiation of bone marrow stem cells (BMSCs), restore local bone integration against the challenge of MRSA, and decrease the incidence of MRSA infection with a rate of 100% (compared to the titanium control). This study demonstrated for the first time that calcium, as one of the major elements in a human body, could be engineered to avert MRSA infections, which is promising as a safe precaution of disinfection for implantable biomedical devices.

Asphalt pavement aging and temperature dependent properties using functionally graded viscoelastic model

NASA Astrophysics Data System (ADS)

Dave, Eshan V.

Asphalt concrete pavements are inherently graded viscoelastic structures. Oxidative aging of asphalt binder and temperature cycling due to climatic conditions being the major cause of non-homogeneity. Current pavement analysis and simulation procedures dwell on the use of layered approach to account for these non-homogeneities. The conventional finite-element modeling (FEM) technique discretizes the problem domain into smaller elements, each with a unique constitutive property. However the assignment of unique material property description to an element in the FEM approach makes it an unattractive choice for simulation of problems with material non-homogeneities. Specialized elements such as "graded elements" allow for non-homogenous material property definitions within an element. This dissertation describes the development of graded viscoelastic finite element analysis method and its application for analysis of asphalt concrete pavements. Results show that the present research improves efficiency and accuracy of simulations for asphalt pavement systems. Some of the practical implications of this work include the new technique's capability for accurate analysis and design of asphalt pavements and overlay systems and for the determination of pavement performance with varying climatic conditions and amount of in-service age. Other application areas include simulation of functionally graded fiber-reinforced concrete, geotechnical materials, metal and metal composites at high temperatures, polymers, and several other naturally existing and engineered materials.

Oxide-based method of making compound semiconductor films and making related electronic devices

DOEpatents

Kapur, Vijay K.; Basol, Bulent M.; Leidholm, Craig R.; Roe, Robert A.

2000-01-01

A method for forming a compound film includes the steps of preparing a source material, depositing the source material on a base and forming a preparatory film from the source material, heating the preparatory film in a suitable atmosphere to form a precursor film, and providing suitable material to said precursor film to form the compound film. The source material includes oxide-containing particles including Group IB and IIIA elements. The precursor film includes non-oxide Group IB and IIIA elements. The compound film includes a Group IB-IIIA-VIA compound. The oxides may constitute greater than about 95 molar percent of the Group IB elements and greater than about 95 molar percent of the Group IIIA elements in the source material. Similarly, non-oxides may constitute greater than about 95 molar percent of the Group IB elements and greater than about 95 molar percent of the Group IIIA elements in the precursor film. The molar ratio of Group IB to Group IIIA elements in the source material may be greater than about 0.6 and less than about 1.0, or substantially greater that 1.0, in which case this ratio in the compound film may be reduced to greater than about 0.6 and less than about 1.0. The source material may be prepared as an ink from particles in powder form. The oxide-containing particles may include a dopant, as may the compound film. Compound films including a Group IIB-IVA-VA compound may be substituted using appropriate substitutions in the method. The method, also, is applicable to fabrication of solar cells and other electronic devices.

Method for production of magnesium

DOEpatents

Diaz, Alexander F.; Howard, Jack B.; Modestino, Anthony J.; Peters, William A.

1998-01-01

A continuous process for the production of elemental magnesium is described. Magnesium is made from magnesium oxide and a light hydrocarbon gas. In the process, a feed stream of the magnesium oxide and gas is continuously fed into a reaction zone. There the magnesium oxide and gas are reacted at a temperature of about 1400.degree. C. or greater in the reaction zone to provide a continuous product stream of reaction products, which include elemental magnesium. The product stream is continuously quenched after leaving the reaction zone, and the elemental magnesium is separated from other reaction products.

Method for production of magnesium

DOEpatents

Diaz, A.F.; Howard, J.B.; Modestino, A.J.; Peters, W.A.

1998-07-21

A continuous process for the production of elemental magnesium is described. Magnesium is made from magnesium oxide and a light hydrocarbon gas. In the process, a feed stream of the magnesium oxide and gas is continuously fed into a reaction zone. There the magnesium oxide and gas are reacted at a temperature of about 1400 C or greater in the reaction zone to provide a continuous product stream of reaction products, which include elemental magnesium. The product stream is continuously quenched after leaving the reaction zone, and the elemental magnesium is separated from other reaction products. 12 figs.

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Ming, Douglas W.; Gellert, Ralf; Clark, Benton C.; Morris, Richard V.; Yen, Albert S.; Arvidson, Raymond E.; Crumpler, Larry S.; Farrand, William H.; Grant, John A.;

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

NASA Astrophysics Data System (ADS)

Ming, D. W.; Mittlefehldt, D. W.; Gellert, R.; Clark, B. C.; Morris, R. V.; Yen, A. S.; Arvidson, R. E.; Crumpler, L. S.; Farrand, W. H.; Grant, J. A., III; Jolliff, B. L.; Parker, T. J.; Peretyazhko, T.

2014-12-01

Mars Exploration Rover Opportunity is exploring Noachian age rocks of the rim of 22 km diameter Endeavour crater. Overlying the pre-impact lithologies and rim breccias is a thin apron of fine-grained sediments, the Grasberg fm, forming annuli on the lower slopes of rim segments. Hesperian Burns fm sandstones overly the Grasberg fm. Grasberg rocks have major element compositions that are distinct from Burns fm sandstones, especially when comparing interior compositions exposed by the Rock Abrasion Tool. Grasberg rocks are also different from Endeavour rim breccias, but have general compositional similarities to them. Grasberg sediments are plausibly fine-grained materials derived from the impact breccias. Veins of CaSO4 transect Grasberg fm rocks demonstrating post-formation aqueous alteration. Minor/trace elements show variations consistent with mobilization by aqueous fluids. Grasberg fm rocks have low Mn and high Fe/Mn ratios compared to the other lithologies. Manganese likely was mobilized and removed from the Grasberg host rock by redox reactions. We posit that Fe2+ from acidic solutions associated with formation of the Burns sulfate-rich sandstones acted as an electron donor to reduce more oxidized Mn to Mn2+. The Fe contents of Grasberg rocks are slightly higher than in other rocks suggesting precipitation of Fe phases in Grasberg materials. Pancam spectra show that Grasberg rocks have a higher fraction of ferric oxide minerals than other Endeavour rim rocks. Solutions transported Mn2+ into the Endeavour rim materials and oxidized and/or precipitated it in them. Grasberg has higher contents of the mobile elements K, Zn, Cl, and Br compared to the rim materials. Similar enrichments of mobile elements were measured by the Spirit APXS on West Spur and around Home Plate in Gusev crater. Enhancements in these elements are attributed to interactions of hydrothermal acidic fluids with the host rocks. Interactions of fluids with the Grasberg fm postdate the genesis of the Endeavour rim phyllosilicates. The aqueous alteration history of Endeavour rim rocks is complicated by different styles of alteration that have spanned the Noachian and Hesperian. Late stage acidic aqueous alteration of Grasberg fm materials is likely penecontemporaneous with the diagenesis of the sulfate-rich sediments of Meridiani Planum.

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

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

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew

Despite the numerous studies on changes within the reservoir following CO2 injection and the effects of CO2 release into overlying aquifers, little or no literature is available on the effect of CO2 release on rock between the storage reservoirs and subsurface. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in this intermediate zone. After rocks reacted with CO2, liquid analysis showed an increase of major elements (e.g., Ca, and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower concentrations were observed in N2 controls. In experimentsmore » with As/Cd and/or organic spikes, representing potential contaminants in the CO2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less

Electron spectroscopy imaging and surface defect configuration of zinc oxide nanostructures under different annealing ambient

NASA Astrophysics Data System (ADS)

Ann, Ling Chuo; Mahmud, Shahrom; Bakhori, Siti Khadijah Mohd

2013-01-01

In this study, electron spectroscopy imaging was used to visualize the elemental distribution of zinc oxide nanopowder. Surface modification in zinc oxide was done through annealing treatment and type of surface defect was also inferred from the electron spectroscopy imaging investigation. The micrographs revealed the non-stoichiometric distribution of the elements in the unannealed samples. Annealing the samples in nitrogen and oxygen ambient at 700 °C would alter the density of the elements in the samples as a result of removal or absorption of oxygen. The electrical measurement showed that nitrogen annealing treatment improved surface electrical conductivity, whereas oxygen treatment showed an adverse effect. Observed change in the photoluminescence green emission suggested that oxygen vacancies play a significant role as surface defects. Structural investigation carried out through X-ray diffraction revealed the polycrystalline nature of both zinc oxide samples with hexagonal phase whereby annealing process increased the crystallinity of both zinc oxide specimens. Due to the different morphologies of the two types of zinc oxide nanopowders, X-ray diffraction results showed different stress levels in their structures and the annealing treatment give significant effect to the structural stress. Electron spectroscopy imaging was a useful technique to identify the elemental distribution as well as oxygen defect in zinc oxide nanopowder.

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

Geochemistry of the Serifos calc-alkaline granodiorite pluton, Greece: constraining the crust and mantle contributions to I-type granitoids

NASA Astrophysics Data System (ADS)

Stouraiti, C.; Baziotis, I.; Asimow, P. D.; Downes, H.

2017-11-01

The Late Miocene (11.6-9.5 Ma) granitoid intrusion on the island of Serifos (Western Cyclades, Aegean Sea) is composed of syn- to post-tectonic granodiorite with quartz monzodiorite enclaves, cut by dacitic and aplitic dikes. The granitoid, a typical I-type metaluminous calcic amphibole-bearing calc-alkaline pluton, intruded the Cycladic Blueschists during thinning of the Aegean plate. Combining field, textural, geochemical and new Sr-Nd-O isotope data presented in this paper, we postulate that the Serifos intrusion is a single-zoned pluton. The central facies has initial 87Sr/86Sr = 0.70906 to 0.7106, ɛNd(t) = - 5.9 to - 7.5 and δ18Οqtz = + 10 to + 10.6‰, whereas the marginal zone (or border facies) has higher initial 87Sr/86Sr = 0.711 to 0.7112, lower ɛ Nd(t) = - 7.3 to - 8.3, and higher δ18Οqtz = + 10.6 to + 11.9‰. The small range in initial Sr and Nd isotopic values throughout the pluton is paired with a remarkable uniformity in trace element patterns, despite a large range in silica contents (58.8 to 72 wt% SiO2). Assimilation of a crustally derived partial melt into the mafic parental magma would progressively add incompatible trace elements and SiO2 to the evolving mafic starting liquid, but the opposite trend, of trace element depletion during magma evolution, is observed in the Serifos granodiorites. Thermodynamic modeling of whole-rock compositions during simple fractional crystallization (FC) or assimilation-fractional crystallization (AFC) processes of major rock-forming minerals—at a variety of pressure, oxidation state, and water activity conditions—fails to reproduce simultaneously the major element and trace element variations among the Serifos granitoids, implying a critical role for minor phases in controlling trace element fractionation. Both saturation of accessory phases such as allanite and titanite (at SiO2 ≥ 71 wt%)(to satisfy trace element constraints) and assimilation of partial melts from a metasedimentary component (to match isotopic data) must have accompanied fractional crystallization of the major phases.

The Easternmost Southwest Indian Ridge: A Laboratory to Study MORB and Oceanic Gabbro Petrogenesis in a Very Low Melt Supply Context

NASA Astrophysics Data System (ADS)

Paquet, M.; Cannat, M.; Hamelin, C.; Brunelli, D.

2014-12-01

Our study area is located at the ultra-slow Southwest Indian Ridge, east of the Melville Fracture Zone, between 61 and 67°E. The melt distribution in this area is very heterogeneous, with corridors of ultramafic seafloor where plate separation is accommodated by large offset normal faults [Sauter, Cannat et al., 2013]. These ultramafic corridors also expose rare gabbros and basalts. We use the major and trace elements composition of these magmatic rocks to document the petrogenesis of MORB in this exceptionnally low melt supply portion of the MOR system. Basalts from the easternmost SWIR represent a global MORB end-member for major element compositions [Meyzen et al., 2003], with higher Na2O and Al2O3 wt%, and lower CaO and FeO wt% at a given MgO. Within this group, basalts from the ultramafic corridors have particularly high Na2O, low CaO and FeO wt%. Best fitting calculated liquid lines of descent are obtained for crystallization pressures of ~8 kbar. Gabbroic rocks recovered in the ultramafic corridors include gabbros, oxide-gabbros and variably impregnated peridotites. This presentation focuses on these impregnated samples, where cpx have high Mg#, yet are in equilibrium with the nearby basalts in terms of their trace element compositions. Plagioclase An contents vary over a broad range, and there is evidence for opx resorption. These characteristics result from melt-mantle interactions in the axial lithosphere, which may explain several peculiar major element characteristics of the basalts. Similar interactions probably occur beneath ridges at intermediate to slow and ultraslow spreading rates. We propose that they are particularly significant in our study area due to its exceptionnally low integrated melt-rock ratio.

Arsenic Exposure and Toxicology: A Historical Perspective

PubMed Central

Hughes, Michael F.; Beck, Barbara D.; Chen, Yu; Lewis, Ari S.; Thomas, David J.

2011-01-01

The metalloid arsenic is a natural environmental contaminant to which humans are routinely exposed in food, water, air, and soil. Arsenic has a long history of use as a homicidal agent, but in the past 100 years arsenic, has been used as a pesticide, a chemotherapeutic agent and a constituent of consumer products. In some areas of the world, high levels of arsenic are naturally present in drinking water and are a toxicological concern. There are several structural forms and oxidation states of arsenic because it forms alloys with metals and covalent bonds with hydrogen, oxygen, carbon, and other elements. Environmentally relevant forms of arsenic are inorganic and organic existing in the trivalent or pentavalent state. Metabolism of arsenic, catalyzed by arsenic (+3 oxidation state) methyltransferase, is a sequential process of reduction from pentavalency to trivalency followed by oxidative methylation back to pentavalency. Trivalent arsenic is generally more toxicologically potent than pentavalent arsenic. Acute effects of arsenic range from gastrointestinal distress to death. Depending on the dose, chronic arsenic exposure may affect several major organ systems. A major concern of ingested arsenic is cancer, primarily of skin, bladder, and lung. The mode of action of arsenic for its disease endpoints is currently under study. Two key areas are the interaction of trivalent arsenicals with sulfur in proteins and the ability of arsenic to generate oxidative stress. With advances in technology and the recent development of animal models for arsenic carcinogenicity, understanding of the toxicology of arsenic will continue to improve. PMID:21750349

Catalog of Mount St. Helens 2004 - 2005 Tephra Samples with Major- and Trace-Element Geochemistry

USGS Publications Warehouse

Rowe, Michael C.; Thornber, Carl R.; Gooding, Daniel J.; Pallister, John S.

2008-01-01

This open-file report presents a catalog of information about 135 ash samples along with geochemical analyses of bulk ash, glass and individual mineral grains from tephra deposited as a result of volcanic activity at Mount St. Helens, Washington, from October 1, 2004 until August 15, 2005. This data, in conjunction with that in a companion report on 2004?2007 Mount St. Helens dome samples by Thornber and others (2008a) are presented in support of the contents of the U.S. Geological Survey Professional Paper 1750 (Sherrod and others, ed., 2008). Readers are referred to appropriate chapters in USGS Professional Paper 1750 for detailed narratives of eruptive activity during this time period and for interpretations of sample characteristics and geochemical data presented here. All ash samples reported herein are currently archived at the David A. Johnston Cascades Volcano Observatory in Vancouver, Washington. The Mount St. Helens 2004?2005 Tephra Sample Catalogue along with bulk, glass and mineral geochemistry are tabulated in 6 worksheets of the accompanying Microsoft Excel file, of2008-1131.xls. Samples in all tables are organized by collection date. Table 1 is a detailed catalog of sample information for tephra deposited downwind of Mount St. Helens between October 1, 2004 and August 18, 2005. Table 2 provides major- and trace-element analyses of 8 bulk tephra samples collected throughout that interval. Major-element compositions of 82 groundmass glass fragments, 420 feldspar grains, and 213 mafic (clinopyroxene, amphibole, hypersthene, and olivine) mineral grains from 12 ash samples collected between October 1, 2004 and March 8, 2005 are presented in tables 3 through 5. In addition, trace-element abundances of 198 feldspars from 11 ash samples (same samples as major-element analyses) are provided in table 6. Additional mineral and bulk ash analyses from 2004 and 2005 ash samples are published in chapters 30 (oxide thermometry; Pallister and others, 2008), 32 (amphibole major elements; Thornber and others, 2008b) and 37 (210Pb; 210Pb/226Pa; Reagan and others, 2008) of U.S. Geological Survey Professional Paper 1750 (Sherrod and others, 2008). A brief overview of sample collection methods is given below as an aid to deciphering the tephra sample catalog. This is followed by an explanation of the categories of sample information (column headers) in table 1. A summary of the analytical methods used to obtain the geochemical data in this report introduces the presentation of major- and trace-element geochemistry of Mount St. Helens 2004?2005 tephra samples in tables 2?6. Rhyolite glass standard analyses are reported (Appendix 1) to demonstrate the accuracy and precision of similar glass analyses presented herein.

Amorphous semiconducting and conducting transparent metal oxide thin films and production thereof

DOEpatents

Perkins, John; Van Hest, Marinus Franciscus Antonius Maria; Ginley, David; Taylor, Matthew; Neuman, George A.; Luten, Henry A.; Forgette, Jeffrey A.; Anderson, John S.

2010-07-13

Metal oxide thin films and production thereof are disclosed. An exemplary method of producing a metal oxide thin film may comprise introducing at least two metallic elements and oxygen into a process chamber to form a metal oxide. The method may also comprise depositing the metal oxide on a substrate in the process chamber. The method may also comprise simultaneously controlling a ratio of the at least two metallic elements and a stoichiometry of the oxygen during deposition. Exemplary amorphous metal oxide thin films produced according to the methods herein may exhibit highly transparent properties, highly conductive properties, and/or other opto-electronic properties.

Effect of reactive element oxide coating on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; El Messki, S.

2004-05-01

The influence of yttrium oxide coating (processed by the sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373 K. The scale growth kinetics of the uncoated alloy obey a parabolic rate law during the whole oxidation test, whereas the kinetic curves of the Y-coated specimen exhibit an initial transient stage for the first few hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not provide the beneficial effect usually ascribed to reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constant values are strictly identical for both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen comprised, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO 3, Y 3Al 5O 12) located in the outermost part of the layer.

Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

NASA Technical Reports Server (NTRS)

Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

2007-01-01

Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Astrophysics Data System (ADS)

Canfield, Donald E.; Des Marais, David J.

1993-08-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works located in Guerrero Negro, Baja California Sur, Mexico. Included in the budget are measured rates of O 2 production, sulfate reduction, and elemental exchange across the mat/brine interface, day and night, at various temperatures and times of the year. We infer from this data the various sinks for O 2, as well as the sources of carbon for primary production. To summarize, although seasonal variability exists, a major percentage of the O 2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O 2 that diffused into the mat was used to oxidize sulfide, with O 2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O 2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Also, oxygenic photosynthesis was the most important process of carbon fixation, although anoxygenic photosynthesis may have been important at low light levels during some times of the year. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount. These mats are thus closely coupled systems where rapid rates of photosynthesis both require and fuel rapid rates of heterotrophic carbon oxidation.

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.

Contrast in air pollution components between major streets and background locations: Particulate matter mass, black carbon, elemental composition, nitrogen oxide and ultrafine particle number

NASA Astrophysics Data System (ADS)

Boogaard, Hanna; Kos, Gerard P. A.; Weijers, Ernie P.; Janssen, Nicole A. H.; Fischer, Paul H.; van der Zee, Saskia C.; de Hartog, Jeroen J.; Hoek, Gerard

2011-01-01

Policies to reduce outdoor air pollution concentrations are often assessed on the basis of the regulated pollutants. Whether these are the most appropriate components to assess the potential health benefits is questionable, as other health-relevant pollutants may be more strongly related to traffic. The aim of this study is to compare the contrast in concentration between major roads and (sub)urban background for a large range of pollutants and to analyze the magnitude of the measured difference in the street - background for major streets with different street configurations. Measurements of PM 10, PM 2.5, particle number concentrations (PNC), black carbon (BC), elemental composition of PM 10 and PM 2.5 and NO x were conducted simultaneously in eight major streets and nine (sub)urban background locations in the Netherlands. Measurements were done six times for a week during a six month period in 2008. High contrasts between busy streets and background locations in the same city were found for chromium, copper and iron (factor 2-3). These elements were especially present in the coarse fraction of PM. In addition, high contrasts were found for BC and NO x (factor 1.8), typically indicators of direct combustion emissions. The contrast for PNC was similar to BC. NO 2 contrast was lower (factor 1.5). The largest contrast was found for two street canyons and two streets with buildings at one side of the street only. The contrast between busy streets and urban background in NO 2 was less than the contrast found for BC, PNC and elements indicative of non-exhaust emissions, adding evidence that NO 2 is not representing (current) traffic well. The study supports a substantial role for non-exhaust emissions including brake- and tyre wear and road dust in addition to direct combustion emissions. Significant underestimation of disease burden may occur when relying too much on the regulated components.

Geochemical Study on an Abandoned Copper Smelting Plant Using Rare Earth Elements

NASA Astrophysics Data System (ADS)

Sun, S. H.

2017-12-01

The Shuei Nan Dong Copper Smelting Plant smelting is located on the northern coast of New Taipei City, Taiwan. The plant built in 1906 for but has been shut down since 1987. However, the watershed is continuing to discharge acid mine water into the sea; and, the acid mine drainage releases high amounts of sulfate, heavy metals without any treatment. In this study, the water samples were sequentially collected along the main channel and its tributaries in the watershed. The results of hydrochemical analysis show that the untreated inflow water can be characterized with low pH value of <3 and enriched sulfate, copper and arsenic. However, the water is much less contaminated in the upstream area until a major tributary converge. The results of principal component analysis (PCA) demonstrate that the first principal component (PC) can explain >80% of the total variance and almost all chemical components have high loadings in the PC. Therefore, the hydrochemical properties in the watershed are mainly dominated by the mixing process between main channel and the major tributary but the geochemical reactions during flow down the channel is insignificant. Rare earth elements (REE) are an excellent tracer, which can indicate sources of chemical components and geochemical reactions in water. The analysis results demonstrate two distinct REE patterns. The water with low REE can be characterized by prominent Eu positive anomaly and Ce negative anomaly, which may result from the alteration of Na-plagioclase in sandstone and oxidation reaction when contact with air, respectively. On the contrary, the water with high REE shows only minor Ce negative anomaly and insignificant Eu positive anomaly. In addition, there is an enrichment of middle REE in high-REE water, which is quite different with the REE pattern of pyrite. According to the Grawunder's study (2014), it corresponds to the complexation to sulphite during pyrite oxidation. It is worth noting that REE show no considerable fractionation along the channel and confirms the results from PCA. It can be derived that the water may not reached equilibrium condition. A simple aerated retention pool could dramatically reduce the pollutants due to coprecipitation of iron oxide and aluminum oxide.

Biogeochemical Cycling of Fe, S, C, N, and Mo in the 3.2 Ga ocean: Constraints from DXCL-DP Black Shales from Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Naraoka, H.; Ikehara, M.; Ito, T.; Kiyokawa, S.

2014-12-01

Records of geochemical cycling of bio-essential, redox-sensitive elements have keys to decipher mysteries of the co-evolution of Earth and life. To obtain insight into biogeochemical cycling of those elements and early evolution of microbial biosphere from high-quality samples, we drilled through Mesoarchean strata in coastal Pilbara (Dixon Island-Cleaverville Drilling Project, see Yamaguchi et al., 2009; Kiyokawa et al., 2012), and obtained 3.2 Ga old drillcores (CL1, CL2, and DX) of sulfide-rich black shales in the Cleaverville Group, Pilbara Supergroup. We conducted a systematic geochemical study involving sequential extractions of Fe, S, C, and N for phase-dependent contents (e.g., pyrite-Fe, reactive-Fe, highly reactive-Fe, unreactive-Fe, pyrite-S, sulfate-S, organic-S, elemental-S, Corg, Ccarb, Norg, and Nclay) and their stable isotope compositions, micro FT-IR and laser Raman spectroscopy for extracted kerogen, in addition to major and trace (redox-sensitive; e.g., Mo) element analysis, for >100 samples. Here we integrate our recent multidisciplinary investigations into the redox state of ocean and nature of microbial biosphere in the ocean 3.2 Ga ago. All of the obtained data are very difficult to explain only by geochemical processes in strictly anoxic environments, where both atmosphere and oceans were completely anoxic, like an environment before the inferred "Great Oxidation Event" when pO2 was lower than 0.00001 PAL (e.g., Holland, 1994). Our extensive data set consistently suggests that oxygenic photosynthesis, bacterial sulfate reduction, and microbially mediated redox-cycling of nitrogen, possibly involving denitrification and N2-fixation, are very likely to have been operating, and may be used as a strong evidence for at least local and temporal existence of oxidized environment as far back as 3.2 Ga ago. Modern-style biogeochemical cycling of Fe, S, C, N, and Mo has been operating since then. The atmosphere-hydrosphere system 3.2 Ga ago would have been sufficiently oxidized to allow redox-cycling of elements during deposition of the sediments, ~800 Ma earlier than commonly thought. Our suggestions have far-reaching and astrobiological implications for earlier evolution of the surface environment, especially redox state, and marine microbial biosphere.

Fabrication and Testing of a Tubular Thermoelectric Module Based on Oxide Elements

NASA Astrophysics Data System (ADS)

Merkulov, O. V.; Politov, B. V.; Chesnokov, K. Yu.; Markov, A. A.; Leonidov, I. A.; Patrakeev, M. V.

2018-02-01

A thermoelectric module with a tubular design, considered as particularly promising for energy recovery from hot exhaust gases of vehicles was fabricated and successfully tested under laboratory condition. The module included 24 functional oxide elements synthesized by conventional methods. Elements of p-type were made of cobalt-based oxide Ca2.7Bi0.3Co4O9, while n-type elements were produced from manganese-based oxide CaMn0.95Ta0.05O3. The module was assembled using silver paste and clamping mechanisms, with the thermoelectric elements electrically connected in series by metal plates (copper, silver) and placed around the hot tube. The output power of 138 mW was achieved under a temperature gradient of 430°C with a hot side temperature of 514°C. The tested module is characterized by an advantageous manufacturing factor of 0.87 at the contact resistance of 0.44 Ω, but a relatively low output power density per volume and per mass. Possible means by which the module's operational characteristics could be improved are considered.

URANIUM OXIDE-CONTAINING FUEL ELEMENT COMPOSITION AND METHOD OF MAKING SAME

DOEpatents

Handwerk, J.H.; Noland, R.A.; Walker, D.E.

1957-09-10

In the past, bodies formed of a mixture of uranium dioxide and aluminum powder have been used in fuel elements; however, these mixtures were found not to be suitable when exposed to temperatures of about 600 deg C, because at such high temperatures the fuel elements were distorted. If uranosic oxide, U/sub 3/O/sub 8/, is substituted for UO/sub 2/, the mechanical properties are not impaired when these materials are used at about 600 deg C and no distortion takes place. The uranosic oxide and aluminum, both in powder form, are first mixed, and after a homogeneous mixture has been obtained, are shaped into fuel elements by extrusion at elevated temperature. Magnesium powder may be used in place of the aluminum.

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

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

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

1986-10-20

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

Distribution and size fractionation of elemental sulfur in aqueous environments: The Chesapeake Bay and Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Findlay, Alyssa J.; Gartman, Amy; MacDonald, Daniel J.; Hanson, Thomas E.; Shaw, Timothy J.; Luther, George W.

2014-10-01

Elemental sulfur is an important intermediate of sulfide oxidation and may be produced via abiotic and biotic pathways. In this study the concentration and size fractionation of elemental sulfur were measured in two different sulfidic marine environments: the Chesapeake Bay and buoyant hydrothermal vent plumes along the Mid-Atlantic Ridge. Nanoparticulate sulfur (<0.2 μm) was found to comprise up to 90% of the total elemental sulfur in anoxic deep waters of the Chesapeake Bay. These data were compared with previous studies of elemental sulfur, and represent one of the few reports of nanoparticulate elemental sulfur in the environment. Additionally, a strain of phototrophic sulfide oxidizing bacteria isolated from the Chesapeake Bay was shown to produce elemental sulfur as a product of sulfide oxidation. Elemental sulfur concentrations are also presented from buoyant hydrothermal vent plumes located along the Mid-Atlantic Ridge. In the Mid-Atlantic Ridge plume, S0 concentrations up to 33 μM were measured in the first meter of rising plumes at three different vent sites, and nanoparticulate S0 was up to 44% of total elemental sulfur present.

Roles of Cationic and Elemental Calcium in the Electro-Reduction of Solid Metal Oxides in Molten Calcium Chloride

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Jiang, Kai; Ma, Meng; Wang, Dihua; Jin, Xianbo; Chen, George Z.

2007-06-01

Previous work, mainly from this research group, is re-visited on electrochemical reduction of solid metal oxides, in the form of compacted powder, in molten CaCl2, aiming at further understanding of the roles of cationic and elemental calcium. The discussion focuses on six aspects: 1.) debate on two mechanisms proposed in the literature, i. e. electro-metallothermic reduction and electro-reduction (or electro-deoxidation), for the electrolytic removal of oxygen from solid metals or metal oxides in molten CaCl2; 2.) novel metallic cavity working electrodes for electrochemical investigations of compacted metal oxide powders in high temperature molten salts assisted by a quartz sealed Ag/AgCl reference electrode (650 ºC- 950 ºC); 3.) influence of elemental calcium on the background current observed during electrolysis of solid metal oxides in molten CaCl2; 4.) electrochemical insertion/ inclusion of cationic calcium into solid metal oxides; 5.) typical features of cyclic voltammetry and chronoamperometry (potentiostatic electrolysis) of metal oxide powders in molten CaCl2; and 6.) some kinetic considerations on the electrolytic removal of oxygen.

Geochemistry and genesis of the angrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Lindstrom, Marilyn M.

1990-01-01

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

Transition metals in superheat melts

NASA Technical Reports Server (NTRS)

Jakes, Petr; Wolfbauer, Michael-Patrick

1993-01-01

A series of experiments with silicate melts doped with transition element oxides was carried out at atmospheric pressures of inert gas at temperatures exceeding liquidus. As predicted from the shape of fO2 buffer curves in T-fO2 diagrams the reducing conditions for a particular oxide-metal pair can be achieved through the T increase if the released oxygen is continuously removed. Experimental studies suggest that transition metals such as Cr or V behave as siderophile elements at temperatures exceeding liquidus temperatures if the system is not buffered by the presence of other oxide of more siderophile element. For example the presence of FeO prevents the reduction of Cr2O3. The sequence of decreasing siderophility of transition elements at superheat conditions (Mo, Ni, Fe, Cr) matches the decreasing degree of depletion of siderophile elements in mantle rocks as compared to chondrites.

Process for producing metal compounds from graphite oxide

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2000-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Process for Producing Metal Compounds from Graphite Oxide

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2000-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Identification and distribution of sulfate reducing bacteria and sulphur-oxidising bacteria in northern South China Sea

NASA Astrophysics Data System (ADS)

Mao, S.; Zhu, X.; Guan, H.; Wu, D.; Wu, N.

2015-12-01

Fatty acids are one of the major components in modern marine sediments. It is well known that the saturated short-chain FAs were typically to be from vascular plants, algae, bacteria, and other sources, while the saturated long-chain FAs are the major components found in leaf waxes, suberin, and cutin in terrestrial higher plants. So the lipid biomarkers of fatty acids in Site 4B from Shenhu Area, northern South China Sea were investigated in Recent research supported from the 973 Program (2009CB219506), and the resources of branched fatty acids and monounsaturated fatty acids were mainly discussed. The results reveal that i/a15:0, i/a17:0, 16:1ω5, 18:1ω9 and 10me16:0 are derived from sulfate reducing bacteria (SRB), while 16:1ω7t/c and 18:1ω7 are originated from sulphur-oxidising bacteria (SOB). The biomakers of methanotrophs such as 16:1ω6/8 and 18:1ω6/8 were not detected in the sediments which coincide with more positive carbon isotope values of the fatty acids in the sediments. The stable relationship between SRB and SOB below 97cm in the sediments reflects the relative stable oxidative and reductive depositional environment which may be connected with the sulphur cycle in the sediments, that is carried out as sulfate is reduced to sulfide, and then sulfide is oxidized to sulfate and elemental sulfur, at last elemental sulfur is disproportionated to sulfide and sulfate. The frequently changed relationship of SRB and SOB above 97cm in the sediments indicates intensely changing oxidative and reductive sedimental environment, that may related with diapir structure around Site 4B, which also brings about hydrocarbon seepage leading to increasing biomass at 97cm.

METHOD OF PREPARING A FUEL ELEMENT FOR A NUCLEAR REACTOR

DOEpatents

Handwerk, J.H.; BAch, R.A.

1959-08-18

A method is described for preparing a reactor fuel element by forming a mixture of thorium dioxide and an oxide of uranium, the uranium being present. In an oxidation state at least as high as it is in U/sub 3/O/sub 8/, into a desired shape and firing in air at a temperature siifficiently high to reduce the higher uranium oxide to uranium dioxide.

SRF niobium characterization using SIMS and FIB-TEM

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

Stevie, F. A.

2015-12-04

Our understanding of superconducting radio frequency (SRF) accelerator cavities has been improved by elemental analysis at high depth resolution and by high magnification microscopy. This paper summarizes the technique development and the results obtained on poly-crystalline, large grain, and single crystal SRF niobium. Focused ion beam made possible sample preparation using transmission electron microscopy and the images obtained showed a very uniform oxide layer for all samples analyzed. Secondary ion mass spectrometry indicated the presence of a high concentration of hydrogen and the hydrogen content exhibited a relationship with improvement in performance. Depth profiles of carbon, nitrogen, and oxygen didmore » not show major differences with heat treatment. Niobium oxide less than 10 nm thick was shown to be an effective hydrogen barrier. Niobium with titanium contamination showed unexpected performance improvement.« less

Sulfur oxidation to sulfate coupled with electron transfer to electrodes by Desulfuromonas strain TZ1

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

Zhang, T; Bain, TS; Barlett, MA

2014-01-02

Microbial oxidation of elemental sulfur with an electrode serving as the electron acceptor is of interest because this may play an important role in the recovery of electrons from sulfidic wastes and for current production in marine benthic microbial fuel cells. Enrichments initiated with a marine sediment inoculum, with elemental sulfur as the electron donor and a positively poised (+300 mV versus Ag/AgCl) anode as the electron acceptor, yielded an anode biofilm with a diversity of micro-organisms, including Thiobacillus, Sulfurimonas, Pseudomonas, Clostridium and Desulfuromonas species. Further enrichment of the anode biofilm inoculum in medium with elemental sulfur as the electronmore » donor and Fe(III) oxide as the electron acceptor, followed by isolation in solidified sulfur/Fe(III) medium yielded a strain of Desulfuromonas, designated strain TZ1. Strain TZ1 effectively oxidized elemental sulfur to sulfate with an anode serving as the sole electron acceptor, at rates faster than Desulfobulbus propionicus, the only other organism in pure culture previously shown to oxidize S with current production. The abundance of Desulfuromonas species enriched on the anodes of marine benthic fuel cells has previously been interpreted as acetate oxidation driving current production, but the results presented here suggest that sulfur-driven current production is a likely alternative.« less

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

NASA Astrophysics Data System (ADS)

Mercadier, Julien; Cuney, Michel; Cathelineau, Michel; Lacorde, Mathieu

2011-02-01

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation-reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6-1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution-precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400-300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.

In situ X-ray diffraction contribution to the study of reactive element oxide coating effect on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; Perrier, S.; El Messki, S.

2004-11-01

The influence of yttrium oxide coating (processed by sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373K. The scale growth kinetic of the uncoated alloy obeys a parabolic rate law during the whole oxidation test whereas the kinetic curve of the Y-coated specimen exhibits an initial transient stage during the first hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not conduct to the beneficial effect usually ascribed to the reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constants values are strictly identical for the both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen revealed, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO{3}, Y{3}Al{5}O{12}) located in the outermost part of the layer.

Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds.

PubMed

Zhang, Lanjun; Li, Zenghua; Li, Jinhu; Zhou, Yinbo; Yang, Yongliang; Tang, Yibo

2015-12-11

This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30°C to 80°C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80°C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO₂ being released at 130°C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS). The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What's more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal.

Marine chemistry of the permian phosphoria formation and basin, Southeast Idaho

USGS Publications Warehouse

Piper, D.Z.

2001-01-01

Major components in the Meade Peak Member of the Phosphoria Formation are apatite, dolomite, calcite, organic matter, and biogenic silica-a marine fraction; and aluminosilicate quartz debris-a terrigenous fraction. Samples from Enoch Valley, in southeast Idaho, have major element oxide abundances of Al2O3, Fe2O3, K2O, and TiO2 that closely approach the composition of the world shale average. Factor analysis further identifies the partitioning of several trace elements-Ba, Ga, Li, Sc, and Th and, at other sites in southeast Idaho and western Wyoming, B, Co, Cs, Hf, Rb, and Ta-totally into this fraction. Trace elements that fail to show such correlations or factor loadings include Ag, As, Cd, Cr, Cu, Mo, Ni, Se, the rare earth elements (REE), U, V, and Zn. Their terrigenous contribution is determined from minimum values of trace elements versus the terrigenous fraction. These minima too define trace element concentrations in the terrigenous fraction that approximately equal their concentrations in the world shale average. The marine fraction of trace elements represents the difference between the bulk trace element content of a sample and the terrigenous contribution. Of the trace elements enriched above a terrigenous contribution, Ag, Cr, Cu, Mo, and Se show strong loadings on the factor with an organic matter loading and U and the REE on the factor with a strong apatite loading. Cd, Ni, V, and Zn do not show a strong correlation with any of the marine components but are, nonetheless, strongly enriched above a terrigenous contribution. Interelement relationships between the trace elements identify two seawater sources-planktonic debris and basinal bottom water. Relationships between Cd, Cu, Mo, Zn, and possibly Ni and Se suggest a solely biogenic source. Their accumulation rates, and that of PO3-4, further identify the level of primary productivity as having been moderate and the residence time of water in the basin at 4.5 yr. Enrichments of Cr, U, V, and the REE, above both terrigenous and biogenic contributions, define bottom-water redox conditions as having been oxygen depleted, that is, denitrifying but not sulfate reducing.

Superconducting structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2003-04-01

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Superconducting Structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2005-09-13

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Metal Oxides in Surface Sediment Control Nickel Bioavailability to Benthic Macroinvertebrates.

PubMed

Mendonca, Raissa M; Daley, Jennifer M; Hudson, Michelle L; Schlekat, Christian E; Burton, G Allen; Costello, David M

2017-11-21

In aquatic ecosystems, the cycling and toxicity of nickel (Ni) are coupled to other elemental cycles that can limit its bioavailability. Current sediment risk assessment approaches consider acid-volatile sulfide (AVS) as the major binding phase for Ni, but have not yet incorporated ligands that are present in oxic sediments. Our study aimed to assess how metal oxides play a role in Ni bioavailability in surficial sediments exposed to effluent from two mine sites. We coupled spatially explicit sediment geochemistry (i.e., separate oxic and suboxic) to the indigenous macroinvertebrate community structure. Effluent-exposed sites contained high concentrations of sediment Ni and AVS, though roughly 80% less AVS was observed in surface sediments. Iron (Fe) oxide mineral concentrations were elevated in surface sediments and bound a substantial proportion of Ni. Redundancy analysis of the invertebrate community showed surface sediment geochemistry significantly explained shifts in community abundances. Relative abundance of the dominant mayfly (Ephemeridae) was reduced in sites with greater bioavailable Ni, but accounting for Fe oxide-bound Ni greatly decreased variation in effect thresholds between the two mine sites. Our results provide field-based evidence that solid-phase ligands in oxic sediment, most notably Fe oxides, may have a critical role in controlling nickel bioavailability.

Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

DOEpatents

Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

2005-11-08

A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

NEUTRONIC REACTOR FUEL ELEMENT

DOEpatents

Shackleford, M.H.

1958-12-16

A fuel element possessing good stability and heat conducting properties is described. The fuel element comprises an outer tube formed of material selected from the group consisting of stainhess steel, V, Ti. Mo. or Zr, a fuel tube concentrically fitting within the outer tube and containing an oxide of an isotope selected from the group consisting of U/sup 235/, U/sup 233/, and Pu/sup 239/, and a hollow, porous core concentrically fitting within the fuel tube and formed of an oxide of an element selected from the group consisting of Mg, Be, and Zr.

NOVEL OXIDANT FOR ELEMENTAL MERCURY CONTROL FROM FLUE GAS

EPA Science Inventory

The primary objective of this study is to develop and test advanced noncarbonaceous solid sorbent materials suitable for removing the elemental form of mercury from power plant emissions. An efficient and cost-effective novel Hg(0) oxidant was evaluated in a lab-scale fixed-bed ...

Effects of urban air pollutants on elemental accumulation and identification of oxidative stress biomarkers in the transplanted lichen Pseudovernia furfuracea.

PubMed

Oztetik, Elif; Cicek, Arzu

2011-07-01

Determining the origins of heavy metals, their accumulation, and their detoxification mechanisms constitutes a major problem in understanding environmental pollution in urban areas. The objective of this study was to detect the relative air quality in Eskisehir city center (Turkey) through the transplanted epiphytic lichen Pseudovernia furfuracea as a biomonitor of the concentrations of some heavy metals accumulated and to describe their toxic effects on lichen physiology during the study period of one year. The influence of heavy metal accumulations on macroelement levels were also examined. In addition to analysis of B, K, Ca, P, S, Al, Fe, Mg, Mn, Ni, Zn, Pb, and Cu, total soluble proteins and oxidative stress parameters through glutathione (GSH) contents and glutathione S-transferase (GST) activities were also determined. Results indicate that, although the heavy metal concentrations were found to be gradually increased from the unpolluted control zone to the city center, the concentrations of macroelements S and Ca were higher in the polluted area. However, B, K, Mg, and P elements were found to be higher in the unpolluted area than in the polluted zones. It seems that heavy metals induce oxidative stress in lichens; we found enhancement of GSH concentrations and GST activity. Most probably, the expected destruction in this organism was reduced by the intervention of antioxidant capacity. Therefore, this report confirms the fact that the epiphytic lichen P. furfuracea is a good model for biomonitoring atmospheric quality for a long-term transplantation study, and oxidative stress parameters stand out as a tool for an early environment assessment of other physiological parameters. Copyright © 2011 SETAC.

Technological pretreatment of the synchysite non-oxidized ore

NASA Astrophysics Data System (ADS)

Munkhtsetseg, B.; Burmaa, G.

2013-06-01

Mongolia has rich deposits of rare, precious, and poly-metallic ores. Nowadays, it is important to research separation of rare earth elements oxides concentrates from the ores, analyze their unique physical chemical characteristics, and purified it. Our investigation on raw materials focuses on rare earth non-oxidized ores. Main mineral in this rock sample is Synchysite (LnCa(CO3)2F. We did technological and thermal pretreatment: direct sulphurization (H2SO4), sulphurization with subsequent roasting (800°C+H2SO4), sulphurization prior to roasting (H2SO4+650°C). Sulphurization method based on dissolution of rare earth mineral into sulfuric acid (93%) according to the reaction. The amount of rare earth element oxides is almost 10 times greater (29.16%) after direct sulphurization process, almost 8 times greater (21.14%) after sulphurization with subsequent roasting, and almost 20 times greater (44.62%) after sulphurization prior to roasting process. After those technological pretreatment raw material's micro elements Thorium and Uranium contents are reduced as follows: H2SO4>800°C+H2SO4>H2SO4+650°C. These results show that cerium group rare earth elements have very good solubility in water at +2°C temperature and decreasing micro elements content uranium and thorium good pretreatment condition is prior to roasting (H2SO4+650°C) of synchysite non-oxidized ore.

Effects of water vapor on the oxidation behavior of alumina and chromia forming superalloys at temperatures between 700°C and 1000°C

NASA Astrophysics Data System (ADS)

Hance, Kivilcim Onal

Several superalloys and Ni-Cr alloys were tested at temperatures between 700°C and 1000°C in dry air and in air/H2O mixtures, whereby the effects of water vapor on the formation of alumina and chromia scales were investigated. The experimental parameters included temperature of testing, composition of the reactive gases, thermal cycling and the composition of the underlying alloy. Water vapor affected the oxidation characteristics of alumina and chromia in different ways. Selective oxidation of Al was not favored in air/H 2O mixtures and at low reaction temperatures. The alloy composition was critical in developing and maintaining continuous protective scales. For alumina-forming systems, higher Al and Cr contents were found to be beneficial for improved resistance against attack. Significant additions of Hf to the alloys resulted in accelerated internal oxidation at 1000°C. Transient oxidation was more profound in air/H2O mixtures in comparison to dry air. The adherence of scales was adversely affected by water vapor at 1000°C. Water vapor did not affect the selective oxidation of Cr. The major impact of H2O on chromia scales was the accelerated formation of volatile Cr-species which makes the underlying alloy more vulnerable to attack by reactive gases. These reactions were not significant in dry air at 900°C and below. The transient oxidation was not adversely affected by water vapor on Ni-Cr systems. The scale spallation was more profound in dry air. The study showed that the main degradation mechanism for chromia in wet air was the formation of vapor Cr-species. On the contrary, scale spallation was more detrimental in dry air. Additions of Ce improved the adherence of chromia in each environment. Ce furthermore decreased the chromia formation rate in dry air. It was not clear if the element had the same effect in air/H2O. The presence of water vapor affected the morphology of chromia. The thin external TiO2 that developed over chromia on IN 738 reduced the vaporization of chromia. This indicated that the oxidation resistance of chromia formers can be improved by alloying with elements that would diffuse to the oxide/gas interface and develop an external scale.

High quality transparent conducting oxide thin films

DOEpatents

Gessert, Timothy A.; Duenow, Joel N.; Barnes, Teresa; Coutts, Timothy J.

2012-08-28

A transparent conducting oxide (TCO) film comprising: a TCO layer, and dopants selected from the elements consisting of Vanadium, Molybdenum, Tantalum, Niobium, Antimony, Titanium, Zirconium, and Hafnium, wherein the elements are n-type dopants; and wherein the transparent conducting oxide is characterized by an improved electron mobility of about 42 cm.sup.2/V-sec while simultaneously maintaining a high carrier density of .about.4.4e.times.10.sup.20 cm.sup.-3.

On the potential increase of the oxidative stress status in patients with abdominal aortic aneurysm.

PubMed

Pincemail, J; Defraigne, J O; Cheramy-Bien, J P; Dardenne, N; Donneau, A F; Albert, A; Labropoulos, N; Sakalihasan, N

2012-01-01

Abdominal aortic aneurysm (AAA) is a major cause of preventable deaths in older patients. Oxidative stress has been suggested to play a key role in the pathogenesis of AAA. However, only few studies have been conducted to evaluate the blood oxidative stress status of AAA patients. Twenty seven AAA patients (mean age of 70 years) divided into two groups according to AAA size (≤ 50 or > 50 mm) were compared with an age-matched group of 18 healthy subjects. Antioxidants (vitamins C and E, β-carotene, glutathione, thiols, and ubiquinone), trace elements (selenium, copper, zinc, and copper/zinc ratio) and markers of oxidative damage to lipids (lipid peroxides, antibodies against oxidized patients, and isoprostanes) were measured in each subject. The comparison of the three groups by ordinal logistic regression showed a significant decrease of the plasma levels of vitamin C (P = 0.011), α-tocopherol (P = 0.016) but not when corrected for cholesterol values, β-carotene (P = 0.0096), ubiquinone (P = 0.014), zinc (P = 0.0035), and of selenium (P = 0.0038), as AAA size increased. By contrast, specific markers of lipid peroxidation such as the Cu/Zn ratio (P = 0.046) and to a lesser extent isoprostanes (P = 0.052) increased. The present study emphasizes the potential role of the oxidative stress in AAA disease and suggests that an antioxidant therapy could be of interest to delay AAA progression.

Involvement of Superoxide Dismutases in the Response of Escherichia coli to Selenium Oxides

PubMed Central

Bébien, Magali; Lagniel, Gilles; Garin, Jérôme; Touati, Danièle; Verméglio, André; Labarre, Jean

2002-01-01

Selenium can provoke contrasting effects on living organisms. It is an essential trace element, and low concentrations have beneficial effects, such as the reduction of the incidence of cancer. However, higher concentrations of selenium salts can be toxic and mutagenic. The bases for both toxicity and protection are not clearly understood. To provide insights into these mechanisms, we analyzed the proteomic response of Escherichia coli cells to selenate and selenite treatment under aerobic conditions. We identified 23 proteins induced by both oxides and ca. 20 proteins specifically induced by each oxide. A striking result was the selenite induction of 8 enzymes with antioxidant properties, particularly the manganese and iron superoxide dismutases (SodA and SodB). The selenium inductions of sodA and sodB were controlled by the transcriptional regulators SoxRS and Fur, respectively. Strains with decreased superoxide dismutase activities were severely impaired in selenium oxide tolerance. Pretreatment with a sublethal selenite concentration triggered an adaptive response dependent upon SoxRS, conferring increased selenite tolerance. Altogether, our data indicate that superoxide dismutase activity is essential for the cellular defense against selenium salts, suggesting that superoxide production is a major mechanism of selenium toxicity under aerobic conditions. PMID:11872706

Geochemistry of sediments in the Northern and Central Adriatic Sea

NASA Astrophysics Data System (ADS)

De Lazzari, A.; Rampazzo, G.; Pavoni, B.

2004-03-01

Major, minor and trace elements, loss of ignition, specific surface area, quantities of calcite and dolomite, qualitative mineralogical composition, grain-size distribution and organic micropollutants (PAH, PCB, DDT) were determined on surficial marine sediments sampled during the 1990 ASCOP (Adriatic Scientific Cooperative Program) cruise. Mineralogical composition and carbonate content of the samples were found to be comparable with data previously reported in the literature, whereas geochemical composition and distribution of major, minor and trace elements for samples in international waters and in the central basin have never been reported before. The large amount of information contained in the variables of different origin has been processed by means of a comprehensive approach which establishes the relations among the components through the mathematical-statistical calculation of principal components (factors). These account for the major part of data variance loosing only marginal parts of information and are independent from the units of measure. The sample descriptors concerning natural components and contamination load are discussed by means of a statistical model based on an R-mode Factor analysis calculating four significant factors which explain 86.8% of the total variance, and represent important relationships between grain size, mineralogy, geochemistry and organic micropollutants. A description and an interpretation of factor composition is discussed on the basis of pollution inputs, basin geology and hydrodynamics. The areal distribution of the factors showed that it is the fine grain-size fraction, with oxides and hydroxides of colloidal origin, which are the main means of transport and thus the principal link between chemical, physical and granulometric elements in the Adriatic.

The cyclic oxidation resistance at 1200 C of beta-NiAl, FeAl, and CoAl alloys with selected third element additions

NASA Technical Reports Server (NTRS)

Barrett, C. A.; Titran, R. H.

1992-01-01

The intermetallic compounds Beta-NiAl, FeAl, and CoAl were tested in cyclic oxidation with selected third element alloy additions. Tests in static air for 200 1-hr cycles at 1200 C indicated by specific weight change/time data and x-ray diffraction analysis that the 5 at percent alloy additions did not significantly improve the oxidation resistance over the alumina forming baseline alloys without the additions. Many of the alloy additions were actually deleterious. Ta and Nb were the only alloy additions that actually altered the nature of the oxide(s) formed and still maintained the oxidation resistance of the protective alumina scale.

Diversity of Mn oxides produced by Mn(II)-oxidizing fungi

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

Santelli, Cara M.; Webb, Samuel M.; Dohnalkova, Alice

Manganese (Mn) oxides are environmentally abundant, highly reactive mineral phases that mediate the biogeochemical cycling of nutrients, contaminants, carbon, and numerous other elements. Despite the belief that microorganisms (specifically bacteria and fungi) are responsible for the majority of Mn oxide formation in the environment, the impact of microbial species, physiology, and growth stage on Mn oxide formation is largely unresolved. Here, we couple microscopic and spectroscopic techniques to characterize the Mn oxides produced by four different species of Mn(II)-oxidizing Ascomycete fungi (Plectosphaerella cucumerina strain DS2psM2a2, Pyrenochaeta sp. DS3sAY3a, Stagonospora sp. SRC1lsM3a, and Acremonium strictum strain DS1bioAY4a) isolated from acid minemore » drainage treatment systems in central Pennsylvania. The site of Mn oxide formation varies greatly among the fungi, including deposition on hyphal surfaces, at the base of reproductive structures (e.g., fruiting bodies), and on envisaged extracellular polymers adjacent to the cell. The primary product of Mn(II) oxidation for all species growing under the same chemical and physical conditions is a nanoparticulate, poorly-crystalline hexagonal birnessite-like phase resembling synthetic d-MnO2. The phylogeny and growth conditions (planktonic versus surface-attached) of the fungi, however, impact the conversion of the initial phyllomanganate to more ordered phases, such as todorokite (A. strictum strain DS1bioAY4a) and triclinic birnessite (Stagonospora sp. SRC1lsM3a). Our findings reveal that the species of Mn(II)-oxidizing fungi impacts the size, morphology, and structure of Mn biooxides, which will likely translate to large differences in the reactivity of the Mn oxide phases.« less

Establishment of chronic hepatitis C virus infection: Translational evasion of oxidative defence

PubMed Central

Chan, Shiu-Wan

2014-01-01

Hepatitis C virus (HCV) causes a clinically important disease affecting 3% of the world population. HCV is a single-stranded, positive-sense RNA virus belonging to the genus Hepacivirus within the Flaviviridae family. The virus establishes a chronic infection in the face of an active host oxidative defence, thus adaptation to oxidative stress is key to virus survival. Being a small RNA virus with a limited genomic capacity, we speculate that HCV deploys a different strategy to evade host oxidative defence. Instead of counteracting oxidative stress, it utilizes oxidative stress to facilitate its own survival. Translation is the first step in the replication of a plus strand RNA virus so it would make sense if the virus can exploit the host oxidative defence in facilitating this very first step. This is particularly true when HCV utilizes an internal ribosome entry site element in translation, which is distinctive from that of cap-dependent translation of the vast majority of cellular genes, thus allowing selective translation of genes under conditions when global protein synthesis is compromised. Indeed, we were the first to show that HCV translation was stimulated by an important pro-oxidant-hydrogen peroxide in hepatocytes, suggesting that HCV is able to adapt to and utilize the host anti-viral response to facilitate its own translation thus allowing the virus to thrive under oxidative stress condition to establish chronicity. Understanding how HCV translation is regulated under oxidative stress condition will advance our knowledge on how HCV establishes chronicity. As chronicity is the initiator step in disease progression this will eventually lead to a better understanding of pathogenicity, which is particularly relevant to the development of anti-virals and improved treatments of HCV patients using anti-oxidants. PMID:24659872

Out of Balance—Systemic Iron Homeostasis in Iron-Related Disorders

PubMed Central

Steinbicker, Andrea U.; Muckenthaler, Martina U.

2013-01-01

Iron is an essential element in our daily diet. Most iron is required for the de novo synthesis of red blood cells, where it plays a critical role in oxygen binding to hemoglobin. Thus, iron deficiency causes anemia, a major public health burden worldwide. On the other extreme, iron accumulation in critical organs such as liver, heart, and pancreas causes organ dysfunction due to the generation of oxidative stress. Therefore, systemic iron levels must be tightly balanced. Here we focus on the regulatory role of the hepcidin/ferroportin circuitry as the major regulator of systemic iron homeostasis. We discuss how regulatory cues (e.g., iron, inflammation, or hypoxia) affect the hepcidin response and how impairment of the hepcidin/ferroportin regulatory system causes disorders of iron metabolism. PMID:23917168

Element mobilization and immobilization from carbonate rocks between CO2 storage reservoirs and the overlying aquifers during a potential CO2 leakage.

PubMed

Lawter, Amanda R; Qafoku, Nikolla P; Asmussen, R Matthew; Kukkadapu, Ravi K; Qafoku, Odeta; Bacon, Diana H; Brown, Christopher F

2018-04-01

Despite the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in this intermediate zone. After rocks reacted with CO 2 -acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2 -reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2 -laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

DOE PAGES

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew; ...

2018-01-04

In spite of the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in thismore » intermediate zone. Furthermore, after rocks reacted with CO 2-acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less

Nutrient and trace-element enrichment of Coeur d'Alene Lake, Idaho

USGS Publications Warehouse

Woods, P.F.; Beckwith, M.A.

1996-01-01

The limnological characteristics and geochemistry of lakebed sediments in Coeur d'Alene Lake, a 129-square-kilometer, natural lake in northern Idaho, were assessed during 1991-92 because of the possible interaction of nutrient enrichment with the highly enriched trace-element concentrations stored in the lakebed. The lake was classified as oligotrophic during 1991-92 on the basis of annual geometric mean concentrations, in micrograms per liter, of total phosphorus (4.1), total nitrogen (247), and chlorophyll-a (0.54). Despite its oligotrophy, the lake developed a substantial hypolimnetic dissolved-oxygen deficit in both years during the later stage of thermal stratification. The lake's current trophic state of oligotrophic differs from the mesotrophic ranking it received in 1975 during the National Eutrophication Survey. The shift in trophic state was consistent with nutrient-load reductions that have occurred within the lake's 9,690-square-kilometer drainage basin since the early 1970's. Approximately 85 percent of the lakebed's surface area was highly enriched in antimony, arsenic, cadmium, lead, mercury, silver, and zinc. Mean total concentrations, in milligrams per kilogram, for cadmium, lead, and zinc in the enriched lakebed sediments were, respectively, 62, 1,900, and 3,600. In contrast, the concentrations of cadmium, lead, and zinc in unenriched lakebed sediments in the lake's southern end were, respec- tively, 2.8, 24, and 110 milligrams per kilogram. The vast majority of the trace elements in the surficial and subsurface sediments were associated with ferric oxides, not sulfides as previously postulated. Under reducing conditions, such as within as anoxic hypolimnon, the ferric oxide- associated trace elements would be readily soluble and available for release into the overlying water column. (USGS)

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

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

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew

In spite of the numerous studies on changes within the reservoir following CO 2 injection and the effects of CO 2 release into overlying aquifers, little or no literature is available on the effect of CO 2 release on rock between the storage reservoirs and subsurface. This is important, because the interactions that occur in this zone between the CO 2 storage reservoir and the subsurface may have a significant impact on risk analysis for CO 2 storage projects. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in thismore » intermediate zone. Furthermore, after rocks reacted with CO 2-acidified 0.01 M NaCl, liquid analysis showed an increase of major elements (e.g., Ca and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower aqueous concentrations of these elements were observed in N 2 control experiments, likely due to differences in pH between the CO 2 and N 2 experiments. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO 2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO 2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO 2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.« less

Autothermal reforming catalyst having perovskite structure

DOEpatents

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Mobility of major and trace elements in a coupled groundwater-surface water system: Merced River, CA

NASA Astrophysics Data System (ADS)

Wildman, R. A.; Domagalski, J. L.; Hering, J. G.

2004-12-01

Trace element transport in coupled surface water/groundwater systems is controlled not only by advective flow, but also by redox reactions that affect the partitioning of various elements between mobile and immobile phases. These processes have been examined in the context of a field project conducted by the U.S. Geological Survey (USGS) as part of the National Water-Quality Assessment (NAWQA) program. The Merced River flows out of Yosemite National Park and the Sierra Nevada foothills and into California's Central Valley, where it joins the San Joaquin River. Our field site is approximately twenty river kilometers from the confluence with the San Joaquin River. This deep alluvial plain has minimal topography. Agricultural development characterizes the land surrounding this reach of river; consequently, the hydrology is heavily influenced by irrigation. Riverbed groundwater samples were collected from ten wells aligned in two transects across the river located approximately 100 m apart. The wells were sampled from depths of 0.5 m, 1 m, and 3 m below the sediment-water interface. Groundwater flowpath samples were taken from wells positioned on a path perpendicular to the river and located 100 m, 500 m, and 1000 m from the river. The saturated groundwater system exists from 7 to 40 m below the surface and is confined below by a clay layer. Each well location samples from 3-5 depths in this surface aquifer. Samples were collected in December 2003, March-April, June-July, and October 2004. This served to provide an evenly-spaced sampling frequency over the course of a year, and also to allow observation of trends coinciding with the onset of winter, the spring runoff, and early and late summer irrigation. An initial survey of the elements in the riverbed samples was conducted using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS). Elements for further study were selected based on variability in this survey, either with respect to depth or location, as well as to cover a range of expected geochemical behaviors. Further ICP-MS measurements focused on eight elements: strontium, barium, uranium, molybdenum, manganese, iron, phosphorus, and bromine. Bromine is a conservative tracer. Molybdenum, manganese, and iron will precipitate when oxidized, and uranium will precipitate when reduced. Strontium and barium are not redox-active but may be affected by dissolution-precipitation and sorption reactions. Phosphorus is a nutrient that will cycle actively in areas of biological productivity. Generally, these elements appear to behave as expected based on physical waterflow and assumed redox conditions. The two transects of wells across the river bracket a zone of known denitrification, which implies that sediment conditions favor oxidation upriver and reduction downriver. This trend is borne out both by the redox-sensitive elements at each transect, and by the strontium and barium, which bind to precipitated iron and manganese oxides in oxidizing conditions and are released into the dissolved state in reducing conditions. The flowpath samples appear to be enriched in strontium, phosphorus, and bromine when compared to the riverbed samples, and they are depleted in manganese and iron.

Rare Earth and other Chemical Elements Accumulation in Vines of Fogo Island (Cape Verde)

NASA Astrophysics Data System (ADS)

Marques, Rosa; Prudêncio, Maria Isabel; Rocha, Fernando; Dias, Maria Isabel; Franco, Dulce

2017-04-01

The Fogo Island is the fourth bigger island of the Cape Verde (central Atlantic Ocean). This archipelago is located 570 kilometres off the coast of West Africa, and is characterized by a semi-arid climate. The volcanic soils of the caldera of this island, with an active volcanism during historical times, have been used for viticulture. The study of uptake of chemical elements by vines - absorption and translocation to grapes - grown in soils developed on alkaline pyroclasts is the main goal of this work. The concentrations of 27 chemical elements in bark, leafs and grapes of two vines, as well as in the corresponding soils (< 2 mm) were determined by instrumental neutron activation analysis. Irradiations of milled samples and standards were made in the core grid of the Portuguese Research Reactor (CTN/IST, Bobadela). The distribution patterns of the enrichment factors (EF) in the different parts of the plants are similar for the two sampling sites. Significant EF were found for the majority of the chemical elements studied, in the several parts of the plants, particularly in grapes where Cr, As, Sb and U are accumulated (EF > 50). The bioavailable fraction of Cr and As in these soils may be due to the low percentage of iron oxides (particularly in the form of nanoparticles), which play an important role in the retention of these elements. The factors responsible for the phytoavailability of Sb in soils and its uptake by plants it's still poorly known. Although the Sb concentrations in earth's crust are low, higher concentrations of this element in soils may be related with hydrothermal and volcanic processes. Also, the temperature may influence the accumulation of Sb in plants, with an increase of the Sb uptake by plants at higher temperatures, due to an increased desorption rate of Sb from soil particles. Concerning U, its mobility and dispersion in soils is controlled by its oxidation state, its adsorption capacity in clay minerals or iron oxides, and the ability to form more or less soluble complexes. Although U concentrations in these volcanic soils are low, there is a fraction available for absorption and accumulation by grapes. Concerning the rare earth elements (REE), it should be noted that the light REE are not enriched in any part of the vines studied, and only the heavy REE are enriched in grapes (EF = 20-50); this can be explained by the preferential uptake of the heavy REE, after primary minerals breakdown and the formation of more soluble compounds. The significant accumulation of several chemical elements found in grapes of Fogo Island can be mainly explained by a geogenic origin.

Ferulic Acid Orchestrates Anti-Oxidative Properties of Danggui Buxue Tang, an Ancient Herbal Decoction: Elucidation by Chemical Knock-Out Approach

PubMed Central

Gong, Amy G. W.; Huang, Vincent Y.; Wang, Huai Y.; Lin, Huang Q.; Dong, Tina T. X.; Tsim, Karl W. K.

2016-01-01

Ferulic acid, a phenolic acid derived mainly from a Chinese herb Angelica Sinensis Radix (ASR), was reported to reduce the formation of free radicals. Danggui Buxue Tang (DBT), a herbal decoction composing of Astragali Radix (AR) and ASR, has been utilized for more than 800 years in China having known anti-oxidative property. Ferulic acid is a major active ingredient in DBT; however, the role of ferulic acid within the herbal mixture has not been resolved. In order to elucidate the function of ferulic acid within this herbal decoction, a ferulic acid-depleted herbal decoction was created and named as DBTΔfa. The anti-oxidative properties of chemically modified DBT decoction were systemically compared in cultured H9C2 rat cardiomyoblast cell line. The application of DBT and DBTΔfa into the cultures showed functions in (i) decreasing the reactive oxygen species (ROS) formation, detected by laser confocal; (ii) increasing of the activation of Akt; (iii) increasing the transcriptional activity of anti-oxidant response element (ARE); and (iv) increasing the expressions of anti-oxidant enzymes, i.e. NQO1 and GCLM. In all scenario, the aforementioned anti-oxidative properties of DBTΔfa in H9C2 cells were significantly reduced, as compared to authentic DBT. Thus, ferulic acid could be an indispensable chemical in DBT to orchestrate multi-components of DBT as to achieve maximal anti-oxidative functions. PMID:27824860

Ferulic Acid Orchestrates Anti-Oxidative Properties of Danggui Buxue Tang, an Ancient Herbal Decoction: Elucidation by Chemical Knock-Out Approach.

PubMed

Gong, Amy G W; Huang, Vincent Y; Wang, Huai Y; Lin, Huang Q; Dong, Tina T X; Tsim, Karl W K

2016-01-01

Ferulic acid, a phenolic acid derived mainly from a Chinese herb Angelica Sinensis Radix (ASR), was reported to reduce the formation of free radicals. Danggui Buxue Tang (DBT), a herbal decoction composing of Astragali Radix (AR) and ASR, has been utilized for more than 800 years in China having known anti-oxidative property. Ferulic acid is a major active ingredient in DBT; however, the role of ferulic acid within the herbal mixture has not been resolved. In order to elucidate the function of ferulic acid within this herbal decoction, a ferulic acid-depleted herbal decoction was created and named as DBTΔfa. The anti-oxidative properties of chemically modified DBT decoction were systemically compared in cultured H9C2 rat cardiomyoblast cell line. The application of DBT and DBTΔfa into the cultures showed functions in (i) decreasing the reactive oxygen species (ROS) formation, detected by laser confocal; (ii) increasing of the activation of Akt; (iii) increasing the transcriptional activity of anti-oxidant response element (ARE); and (iv) increasing the expressions of anti-oxidant enzymes, i.e. NQO1 and GCLM. In all scenario, the aforementioned anti-oxidative properties of DBTΔfa in H9C2 cells were significantly reduced, as compared to authentic DBT. Thus, ferulic acid could be an indispensable chemical in DBT to orchestrate multi-components of DBT as to achieve maximal anti-oxidative functions.

Scalable and Sustainable Electrochemical Allylic C–H Oxidation

PubMed Central

Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

2016-01-01

New methods and strategies for the direct functionalization of C–H bonds are beginning to reshape the fabric of retrosynthetic analysis, impacting the synthesis of natural products, medicines, and even materials1. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C–H functionalization due to the utility of enones and allylic alcohols as versatile intermediates, along with their prevalence in natural and unnatural materials2. Allylic oxidations have been featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”3. Despite many attempts to improve the efficiency and practicality of this powerful transformation, the vast majority of conditions still employ highly toxic reagents (based around toxic elements such as chromium, selenium, etc.) or expensive catalysts (palladium, rhodium, etc.)2. These requirements are highly problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. As such, this oxidation strategy is rarely embraced for large-scale synthetic applications, limiting the adoption of this important retrosynthetic strategy by industrial scientists. In this manuscript, we describe an electrochemical solution to this problem that exhibits broad substrate scope, operational simplicity, and high chemoselectivity. This method employs inexpensive and readily available materials, representing the first example of a scalable allylic C–H oxidation (demonstrated on 100 grams), finally opening the door for the adoption of this C–H oxidation strategy in large-scale industrial settings without significant environmental impact. PMID:27096371

Calculated power distribution of a thermionic, beryllium oxide reflected, fast-spectrum reactor

NASA Technical Reports Server (NTRS)

Mayo, W.; Lantz, E.

1973-01-01

A procedure is developed and used to calculate the detailed power distribution in the fuel elements next to a beryllium oxide reflector of a fast-spectrum, thermionic reactor. The results of the calculations show that, although the average power density in these outer fuel elements is not far from the core average, the power density at the very edge of the fuel closest to the beryllium oxide is about 1.8 times the core avearge.

PROCESS FOR PRODUCTION OF URANIUM HEXAFLUORIDE

DOEpatents

Fowler, R.D.

1958-11-01

A process is described for the manufacture of uranium bexafluoride which consists in contacting an oxide of uranium simultaneously with elemental carbon and elemental fluorine at an elevated temperature, using a proportion of the carbon to the oxide about 50% in excess of that theoretically required to combine with f the oxygen as C0/.sub 2/. The process has the advantage that the uranium oxide is reduced by tbe carbon aad converted to the hexafluoride in a single operation.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E [Ames, IA; Terpstra, Robert L [Ames, IA

2012-06-12

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E.; Terpstra, Robert L.

2010-04-20

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Influence of Minor Alloying Elements on Selective Oxidation and Reactive Wetting of CMnSi TRIP Steel during Hot Dip Galvanizing

NASA Astrophysics Data System (ADS)

Cho, Lawrence; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

2014-09-01

The influence of the addition of minor alloying elements on the selective oxidation and the reactive wetting of CMnSi transformation-induced plasticity (TRIP) steels was studied by means of galvanizing simulator tests. Five TRIP steels containing small alloying additions of Cr, Ni, Ti, Cu, and Sn were investigated. After intercritical annealing (IA) at 1093 K (820 °C) in a N2 + 5 pct H2 gas atmosphere with a dew point of 213 K (-60 °C), two types of oxides were formed on the strip surface: Mn-rich xMnO·SiO2 ( x > 1.5) and Si-rich xMnO·SiO2 ( x < 0.3) oxides. The addition of the minor alloying elements changed the morphology of the Si-rich oxides from a continuous film to discrete islands and this improved the wettability by molten Zn. The improved wetting effect of the minor alloying elements was attributed to an increased area fraction of the surface where the oxides were thinner, enabling a direct unhindered reaction between Fe and the Al in the liquid Zn and the formation of the inhibition layer during the hot dip galvanizing. The addition of a small amount of Sn is shown to significantly decrease the density of Zn-coating defects on CMnSi TRIP steels.

Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts

NASA Astrophysics Data System (ADS)

Anenburg, Michael; Mavrogenes, John A.

2016-11-01

Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed, nanonuggets cannot be removed by oxidation or dissolution, but only by PGM coarsening. Sulfur-poor PGE ore deposits commonly contain more PGE than permitted by existing estimates of equilibrium solubility in silicate melts. This is commonly explained by initial scavenging of PGE by sulfide liquids followed by S-loss, but evidence for S-loss is not conclusive. We suggest that nanonuggets may be a means to transport PGE from source regions to form ore deposits, followed by direct PGM crystallisation from silicate melt without intermediate concentration by sulfide liquids.

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †

PubMed Central

2018-01-01

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed. PMID:29677107

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †.

PubMed

Afzal, Adeel; Dickert, Franz L

2018-04-20

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed.

Formation of early-middle Miocene red beds in the South China Sea: element geochemistry and mineralogy analysis

NASA Astrophysics Data System (ADS)

Lyu, X.; Liu, Z.

2017-12-01

The formation of oceanic red beds that usually present oxic and oligotrophic conditions with low sedimentation rate has been used to trace depositional paleoenvironment and paleoclimate change. Red beds overlying oceanic basalts were drilled at two adjacent Sites U1433 and U1434 of IODP Expedition 349 in the Southwest Subbasin of the South China Sea. The occurrence of early-middle Miocene red beds may indicate that at that time there was oxic and quiet marine environment in the deep South China Sea. To understand their formation of red-color, local depositional condition, and potential paleoceanographic significance, major elements (XRF), trace and rare earth elements (ICP-MS), Fe chemical speciation (modified sequential iron extraction procedure), and Fe oxic minerals (CBD and DRS) were analyzed. Geochemical and mineralogical data reveal that hematite and goethite are responsible for the reddish color and red beds were deposited under highly oxic, oligotrophic conditions with a little later hydrothermal influence in the South China Sea. Our results indicate that: (1) after treatment using the CBD procedure, the red samples presented a change in color to greenish, showing the iron oxides being responsible for the sediment color; (2) enriched Mn, depleted U, S enrichment factors, and negative Ce anomaly show that the water mass was pre-oxidized before transported to the study location; (3) low primary productivity was inferred from the lower P, Ba enrichment factors in red beds compared to non-red beds; (4) the excess Mo influx at the bottom may come from the later hydrothermal input; (5) the diverse Ca enrichment factors and correlations between Fe and Al suggest different allogenic sources for red beds at our two sites. We conclude that the red beds at Sites U1433 and U1434 despite their diverse sources both developed in externally oxidized water mass and low primary productivity conditions, and partially altered by hydrothermal fluids after their pelagic deposition. In the Miocene, the South China Sea was open to the western Pacific, and our study suggests an oxidized deepwater environment in the Pacific during the Miocene.

Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

NASA Astrophysics Data System (ADS)

Platt, P.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

2014-11-01

Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal-oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations.

New alloys to conserve critical elements. [replacing chromium in steels

NASA Technical Reports Server (NTRS)

Stephens, J. R.

1978-01-01

Previous studies and surveys on availability of domestic reserves have shown that chromium is a most critical element within the U.S. metal industry. More precisely, the bulk of chromium is consumed in the production of stainless steels, specifically Type 304 stainless steel (304SS) which contains 18% Cr. The present paper deals with means of reducing chromium in commercial stainless steels by substituting more abundant or less expensive elements with the intent of maintaining the properties of 304SS. The discussion focuses on some of the oxidation and corrosion properties of new substitute stainless steels with only 12% Cr, which represents a potential saving of 33% of the chromium consumed in the production of 304SS. The alloying elements substituted for Cr in 304SS are selected according to their potential for protective oxide formation during high-temperature oxidation; these are Al, Si, Ti, Y, and misch metal which is 99.7% rare-earth metals containing 50 to 55% cerium. Other alloying elements to impart corrosion resistance are Mn, Mo, and V.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Rieken, Joel

2013-12-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with an introduced reactive species than does the alloying element and wherein one or more atomizing parameters is/are modified to controllably reduce the amount of the reactive species, such as oxygen, introduced into the atomized particles so as to reduce anneal times and improve reaction (conversion) to the desired strengthening dispersoids in the matrix. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies are made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Synthesis and characterisation of PuPO4 - a potential analytical standard for EPMA actinide quantification

NASA Astrophysics Data System (ADS)

Wright, K. E.; Popa, K.; Pöml, P.

2018-01-01

Transmutation nuclear fuels contain weight percentage quantities of actinide elements, including Pu, Am and Np. Because of the complex spectra presented by actinide elements using electron probe microanalysis (EPMA), it is necessary to have relatively pure actinide element standards to facilitate overlap correction and accurate quantitation. Synthesis of actinide oxide standards is complicated by their multiple oxidation states, which can result in inhomogeneous standards or standards that are not stable at atmospheric conditions. Synthesis of PuP4 results in a specimen that exhibits stable oxidation-reduction chemistry and is sufficiently homogenous to serve as an EPMA standard. This approach shows promise as a method for producing viable actinide standards for microanalysis.

BONDING ALUMINUM METALS

DOEpatents

Noland, R.A.; Walker, D.E.

1961-06-13

A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

Leaching mechanisms of constituents from fly ash under the influence of humic acid.

PubMed

Zhao, Shengxin; Chen, Zhonglin; Shen, Jimin; Kang, Jing; Zhang, Jin; Shen, Yanqing

2017-01-05

As a low-cost material for adsorption, FA is one of the most efficient adsorbents of HA. However, the leaching of elements from FA is problematic during utilization in water treatment. In this investigation, the potential leaching behaviors of Calcium, Arsenic, Born, Chromium, and other elements from FA in HA solution were studied via batch test. The data show that HA had an effect on the leaching of each element of FA, depending on the pH, the initial concentration of HA and the addition of calcium oxide (CaO). The Langmuir isotherm could better fit the equilibrium data in different initial concentrations of HA from 10 to 100mg/L. Because of the interaction between HA and the FA leaching elements, multi-layer adsorption occurred when the initial concentration of HA was more than 100mg/L. The pH and free CaO content played major roles in HA adsorption and FA leaching. Using SEM and XRD to characterize the solid of FA being mixed with CaO treated in solution, the results demonstrated that the reaction between FA and CaO could generate crystal minerals, such as portlandite, gismondine, ettringite (AFt) and calcite, which effectively restrained the leaching of elements, reduced secondary pollution. Copyright © 2016 Elsevier B.V. All rights reserved.

Metal-silicate partitioning and the light element in the core (Invited)

NASA Astrophysics Data System (ADS)

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

2009-12-01

Most attempts to constrain the concentrations of “light” elements in the Earth’s core rely either on cosmochemical arguments or on arguments based on the densities and equations of state of Fe-alloys containing the element of concern. Despite its utility, the latter approach yields a wide range of permissible compositions and hence weak constraints. The major problem with the cosmochemical approach is that the abundances in the bulk Earth of all the candidate “light” elements- H, C, O, Si and S are highly uncertain because of their volatile behavior during planetary accretion. In contrast, refractory elements appear to be in approximately CI chondritic relative abundances in the Earth. This leads to the potential for using the partitioning of refractory siderophile elements between the mantle and core to constrain the concentrations of light elements in the core. Recent experimental metal-silicate partitioning data, coupled with mantle abundances of refractory siderophile elements (e.g. Wade and Wood, EPSL v.236, 78—95,2005; Kegler et. al. EPSL v.268, 28-40,2008) have shown that the core segregated from the mantle under high pressure conditions (~40 GPa). If a wide range of elements, from very siderophile, (e.g. Mo) through moderately (Ni, Co, W) to weakly siderophile (V, Cr, Nb, Si) are considered, the Earth also appears to have become more oxidized during accretion. Metal-silicate partitioning of some elements is also sensitive to the light element content of the metal. For example, Nb and W partitioning depend strongly on carbon, Mo on silicon and Cr on sulfur. Given the measured mantle abundances of the refractory elements, these observations enable the Si and C contents of the core to be constrained at ~5% and <2% respectively while partitioning is consistent with a cosmochemically-estimated S content of ~2%.

The Role of Hydrous Slab Melts in the Sulfur Content, Metal Content, and Oxidation State of Primitive Arc Magmas in the Southern Cascades

NASA Astrophysics Data System (ADS)

Muth, M.; Wallace, P. J.; Walowski, K. J.

2017-12-01

Arc magmas have an oxidized signature (higher Fe3+/∑Fe) relative to MORB. This oxidized signature could be developed during crustal differentiation or be derived from slab components such as hydrous melts and ­fluids. Previous work in the Lassen region of the Cascade arc shows evidence for the addition of a hydrous slab component to the mantle wedge beneath the southern Cascades [1]. Here we investigate whether this hydrous slab component is linked to the oxidation state of primitive magmas using the sulfur, metal, and trace element concentrations of olivine-hosted melt inclusions. Melt inclusions were selected from the tephra of three cinder cones in Lassen volcanic field and analyzed for trace elements and metals (Cu, Zn, Sn) using LA-ICPMS and for major elements, S, and Cl using EMPA. Sulfur concentrations in individual melt inclusions range from 900 to 2200 ppm. Cu, Zn, and Sn concentrations in individual melt inclusions range from 17 to 167 ppm, 65 to 127 ppm, and 0.4 to 1.4 ppm, respectively. Average sulfur concentrations are different for each of the three cinder cones, and individual melt inclusion S/Dy values correlate well with Sr/Nd values. This is an indication that, like other volatiles, sulfur is supplied to the mantle wedge by a slab-derived component. To assess whether this sulfur-carrying slab component affects the oxidation state of the mantle wedge during melting, we used estimates of sulfur content at sulfide saturation to place a minimum bound on fO2 values for the primitive magmas at each cinder cone. These values range from QFM to QFM + 1.5. Despite this wide range of fO2 values, the concentrations of Cu and other metals are low relative to values predicted by partial melting of the mantle wedge during relatively oxidized (greater than QFM + 1.3) conditions [2], and do not vary systematically with indicators of slab component addition such as Sr/Nd. This suggests that metals are not derived from the slab component and/or that residual sulfide is present during melting across the wide range of fO2 values. This observation is also consistent with the addition of a sulfur-carrying slab component to the mantle wedge. Future work will compare these observations to direct measurement of Fe3+/∑Fe and S6+/∑S using XANES. [1] Walowski et al. 2016, EPSL. [2] Lee et al. 2012, Science.

Preliminary Results from the Viking X-ray Fluorescence Experiment: The First Sample from Chryse Planitia, Mars.

PubMed

Toulmin, P; Clark, B C; Baird, A K; Keil, K; Rose, H J

1976-10-01

Iron, calcium, aluminum, silicon, and sulfur are major elements in the first surface sample of Mars that has been analyzed by the Viking x-ray fluorescence spectrometer. Titanium is present in minor quantities. This is consistent with the sample being a mixture of fine silicate and oxide mineral grains, with a significant proportion of sulfates, possibly hydrated. Ferric oxide is regarded as the red pigmenting agent on the martian surface, but if it coats silicate grains, the coatings must be very thin (

Preliminary results from the Viking X-ray fluorescence experiment - The first sample from Chryse Planitia, Mars

NASA Technical Reports Server (NTRS)

Toulmin, P., III; Rose, H. J., Jr.; Clark, B. C.; Baird, A. K.; Keil, K.

1976-01-01

Iron, calcium, aluminum, silicon, and sulfur are major elements in the first surface sample of Mars that has been analyzed by the Viking X-ray fluorescence spectrometer. Titanium is present in minor quantities. This is consistent with the sample's being a mixture of fine silicate and oxide mineral grains, with a significant proportion of sulfates, possibly hydrated. Ferric oxide is regarded as the red pigmenting agent on the Martian surface, but if it coats silicate grains, the coatings must be very thin or discontinuous. A high abundance of Fe, relatively low abundances of Al, Rb, Sr, and Zr, and a high Ca/K ratio are distinctive features of the spectra. Preliminary determinations indicate the following abundances (as percentages by weight): Fe, 14 plus or minus 2; Ti, less than 1; S, 2 to 5; the Ca/K ratio by weight is greater than 5.

Preliminary results from the viking x-ray fluorescence experiment: The first sample from chryse planitia, Mars

USGS Publications Warehouse

Toulmin, P.; Clark, B. C.; Baird, A.K.; Keil, Klaus; Rose, H.J.

1976-01-01

Iron, calcium, aluminum, silicon, and sulfur are major elements in the first surface sample of Mars that has been analyzed by the Viking x-ray fluorescence spectrometer. Titanium is present in minor quantities. This is consistent with the sample being a mixture of fine silicate and oxide mineral grains, with a significant proportion of sulfates, possibly hydrated. Ferric oxide is regarded as the red pigmenting agent on the martian surface, but if it coats silicate grains, the coatings must be very thin (??? 2 micrometers) or discontinuous. A high abundance of Fe, relatively low abundances of Al, Rb, Sr, and Zr, and a high Ca/K ratio are distinctive features of the spectra. Preliminary determinations indicate the following abundances (as percentages by weight): Fe, 14 ?? 2; Ti < 1; S, 2 to 5; the Ca/K ratio by weight is greater than 5.

Pyrometallurgical Extraction of Valuable Elements in Ni-Metal Hydride Battery Electrode Materials

NASA Astrophysics Data System (ADS)

Jiang, Yin-ju; Deng, Yong-chun; Bu, Wen-gang

2015-10-01

Gas selective reduction-oxidation (redox) and melting separation were consecutively applied to electrode materials of AB5-type Ni-metal hydride batteries leading to the production of a Ni-Co alloy and slag enriched with rare earth oxides (REO). In the selective redox process, electrode materials were treated with H2/H2O at 1073 K and 1173 K (800 °C and 900 °C). Active elements such as REs, Al, and Mn were oxidized whereas relatively inert elements such as Ni and Co were transformed into their elemental states in the treated materials. SiO2 and Al2O3 powders were added into the treated materials as fluxes which were then melted at 1823 K (1550 °C) to yield a Ni-Co alloy and a REO-SiO2-Al2O3-MnO slag. The high-purity Ni-Co alloy produced can be used as a raw material for AB5-type hydrogen-storage alloy. The REO content in slag was very high, i.e., 48.51 pct, therefore it can be used to recycle rare earth oxides.

Full reactor coolant system chemical decontamination qualification programs

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

Miller, P.E.

1995-03-01

Corrosion and wear products are found throughout the reactor coolant system (RCS), or primary loop, of a PWR power plant. These products circulate with the primary coolant through the reactor where they may become activated. An oxide layer including these activated products forms on the surfaces of the RCS (including the fuel elements). The amount of radioactivity deposited on the different surface varies and depends primarily on the corrosion rate of the materials concerned, the amount of cobalt in the coolant and the chemistry of the coolant. The oxide layer, commonly called crud, on the surfaces of nuclear plant systemsmore » leads to personnel radiation exposure. The level of the radiation fields from the crud increases with time from initial plant startup and typically levels off after 4 to 6 cycles of plant operation. Thereafter, significant personnel radiation exposure may be incurred whenever major maintenance is performed. Personnel exposure is highest during refueling outages when routine maintenance on major plant components, such as steam generators and reactor coolant pumps, is performed. Administrative controls are established at nuclear plants to minimize the exposure incurred by an individual and the plant workers as a whole.« less

Metal oxide nanoparticle-modified graphene oxide for removal of elemental mercury.

PubMed

Liu, Yuxi; Chen, Gang; Tian, Chong; Gupta, Rajender; Wang, Xiaogang; Zeng, Hongbo

2018-06-05

Mercury is an extremely toxic element that is primarily released by anthropogenic activities and natural sources. Controlling Hg emissions, especially from coal combustion flue gas, is of practical importance in protecting the environment and preventing human health risks. In the present work, three metal oxides (MnO 2 , CuO, and ZnO) were loaded on graphene oxide (GO) sorbents (designated as MnO 2 -GO, CuO-GO, and ZnO-GO). All three adsorbents were successfully synthesized and were well characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicated that the metal oxide nanoparticles (NPs) successfully decorated the GO. The elemental Hg adsorption capabilities of the three sorbents were subsequently evaluated using an in-house built setup for cold vapour atomic fluorescence spectrophotometry (CVAFS) with argon as the carrier gas for mercury detection. The testing temperature ranged from 50°C to 200°C at intervals of 50°C. MnO 2 -GO showed an excel lent Hg 0 adsorption capacity via chemisorption from 50 to 150°C and a mercury removal efficiency as high as 85% at 200°C, indicating that the MnO 2 -NP-modified GO is applicable for enhancing gas-phase elemental mercury removal. However, neither CuO-GO nor ZnO-GO performed well. This work provides useful insights into the development of novel sorbent materials for the elemental mercury removal from flue gases.

Framboidal iron oxide: Chondrite-like material from the black mat, Murray Springs, Arizona

NASA Astrophysics Data System (ADS)

Fayek, Mostafa; Anovitz, Lawrence M.; Allard, Lawrence F.; Hull, Sharon

2012-02-01

At the end of the Pleistocene a Younger Dryas "black mat" was deposited on top of the Pleistocene sediments in many parts of North America. A study of the magnetic fraction (~ 10,900 ± 50 B.P.) from the basal section of the black mat at Murray Springs, AZ revealed the presence of amorphous iron oxide framboids in a glassy iron-silica matrix. These framboids are very similar in appearance and chemistry to those reported from several types of carbonaceous chondrites. The glass contains iron, silicon, oxygen, vanadium and minor titanium, while the framboidal particles contain calcium as well. The major element chemistry of both the spherules and the glass matrix are consistent with the chemistry of material associated with meteorite impact sites and meteorites. Electron microscopy confirms that the glassy material is indeed amorphous, and also shows that what appear to be individual oxide particles are amorphous as well. The latter appears consistent with their overall morphology that, while euhedral, typically shows significant fracture. Based on these data, we argue that these particles are the product of a hypervelocity impact.

Low TCR nanocomposite strain gages

NASA Technical Reports Server (NTRS)

Gregory, Otto J. (Inventor); Chen, Ximing (Inventor)

2012-01-01

A high temperature thin film strain gage sensor capable of functioning at temperatures above 1400.degree. C. The sensor contains a substrate, a nanocomposite film comprised of an indium tin oxide alloy, zinc oxide doped with alumina or other oxide semiconductor and a refractory metal selected from the group consisting of Pt, Pd, Rh, Ni, W, Ir, NiCrAlY and NiCoCrAlY deposited onto the substrate to form an active strain element. The strain element being responsive to an applied force.

Element Distribution in the Oxygen-Rich Side-Blow Bath Smelting of a Low-Grade Bismuth-Lead Concentrate

NASA Astrophysics Data System (ADS)

Yang, Tianzu; Xiao, Hui; Chen, Lin; Chen, Wei; Liu, Weifeng; Zhang, Duchao

2018-03-01

Oxygen-rich side-blow bath smelting (OSBS) technology offers an efficient method for processing complex bismuth-lead concentrates; however, the element distributions in the process remain unclear. This work determined the distributions of elements, i.e., bismuth, lead, silver, copper, arsenic and antimony, in an industrial-scale OSBS process. The feed, oxidized slag and final products were collected from the respective sampling points and analyzed. For the oxidative smelting process, 65% of bismuth and 76% of silver in the concentrate report to the metal alloy, whereas less lead reports to the metal ( 31%) than the oxidized slag ( 44%). Approximately 50% of copper enters the matte, while more than 63% of arsenic and antimony report to the slag. For the reductive smelting process, less than 4.5% of bismuth, lead, silver and copper in the oxidized slag enter the reduced slag, indicating high recoveries of these metal values.

Element Distribution in the Oxygen-Rich Side-Blow Bath Smelting of a Low-Grade Bismuth-Lead Concentrate

NASA Astrophysics Data System (ADS)

Yang, Tianzu; Xiao, Hui; Chen, Lin; Chen, Wei; Liu, Weifeng; Zhang, Duchao

2018-06-01

Oxygen-rich side-blow bath smelting (OSBS) technology offers an efficient method for processing complex bismuth-lead concentrates; however, the element distributions in the process remain unclear. This work determined the distributions of elements, i.e., bismuth, lead, silver, copper, arsenic and antimony, in an industrial-scale OSBS process. The feed, oxidized slag and final products were collected from the respective sampling points and analyzed. For the oxidative smelting process, 65% of bismuth and 76% of silver in the concentrate report to the metal alloy, whereas less lead reports to the metal ( 31%) than the oxidized slag ( 44%). Approximately 50% of copper enters the matte, while more than 63% of arsenic and antimony report to the slag. For the reductive smelting process, less than 4.5% of bismuth, lead, silver and copper in the oxidized slag enter the reduced slag, indicating high recoveries of these metal values.

Oxidation and methylation of dissolved elemental mercury by anaerobic bacteria

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

Hu, Haiyan; Lin, Hui; Zheng, Wang

2013-08-04

Methylmercury is a neurotoxin that poses significant health risks to humans. Some anaerobic sulphate- and iron-reducing bacteria can methylate oxidized forms of mercury, generating methylmercury1-4. One strain of sulphate-reducing bacteria (Desulfovibrio desulfuricans ND132) can also methylate elemental mercury5. The prevalence of this trait among different bacterial strains and species remains unclear, however. Here, we compare the ability of two strains of the sulphate-reducing bacterium Desulfovibrio and one strain of the iron-reducing bacterium Geobacter to oxidise and methylate elemental mercury in a series of laboratory incubations. Experiments were carried out under dark, anaerobic conditions, in the presence of environmentally-relevant concentrations ofmore » elemental mercury. We report differences in the ability of these organisms to oxidise and methylate elemental mercury. In line with recent findings5, we show that Desulfovibrio desulfuricans ND132 can both oxidise and methylate elemental mercury. However, the rate of methylation of elemental mercury is only about one third the rate of methylation of oxidized mercury. We also show that Desulfovibrio alaskensis G20 can oxidise, but not methylate, elemental mercury. Geobacter sulfurreducens PCA is able to oxidise and methylate elemental mercury in the presence of cysteine. We suggest that the activity of methylating and non-methylating bacteria may together enhance the formation of methylmercury in anaerobic environments.« less

Surface protection coating material for controlling the decay of major construction stone

NASA Astrophysics Data System (ADS)

Arun, T.; Ray, D. K.; Gupta, V. P.; Panda, S. S.; Sahoo, P. K.; Ghosh, Jaydip; Sengupta, Pranesh; Satyam, P. V.

2017-05-01

Degradation of the building stones are creating instability in the old building and monuments which is to be protected. To investigate the characteristics of such a stones used for the construction in eastern India, we have collected the khondalite stones. The microstructural and elemental composition analysis of the khondalite stones are analyzed by using SEM, EDX and PIXE trace elemental analysis. We have prepared surface protection coating material with graphene oxide and cobalt ferrite as a base material along with other residuals. The prepared coating materials is coated on the galvanized iron substrate for further characterization. The surface morphology characteristics of the coating material is analyzed by SEM and AFM. The corrosion resistance characteristics of the prepared coating material is studied by the electrochemical impedance spectroscopy. The results suggests that the prepared coating material can be used as a surface protection materials to control the self-destruction of khondalite stones.

Electron microprobe mineral analysis guide

NASA Technical Reports Server (NTRS)

Brown, R. W.

1980-01-01

Electron microprobe mineral analysis guide is a compilation of X-ray tables and spectra recorded from various mineral matrices. Spectra were obtained using electron microprobe, equipped with LiF geared, curved crystal X-ray spectrometers, utilizing typical analytical operating conditions: 15 Kv acceleration potential, 0.02 microampere sample current as measured on a clinopyroxene standard (CP19). Tables and spectra are presented for the majority of elements, fluorine through uranium, occurring in mineral samples from lunar, meteoritic and terrestrial sources. Tables for each element contain relevant analytical information, i.e., analyzing crystal, X-ray peak, background and relative intensity information, X-ray interferences and a section containing notes on the measurement. Originally intended to cover silicates and oxide minerals the tables and spectra have been expanded to cover other mineral phases. Electron microprobe mineral analysis guide is intended as a spectral base to which additional spectra can be added as the analyst encounters new mineral matrices.

Geologic Field Notes, Geochemical Analyses, and Field Photographs of Outcrops and Rock Samples from the Big Delta B-1 Quadrangle, East-Central Alaska

USGS Publications Warehouse

Day, Warren C.; O'Neill, J. Michael

2008-01-01

The U.S. Geological Survey, in cooperation with the Alaska Department of Natural Resources Division of Mining, Land, and Water, has released a geologic map of the Big Delta B-1 quadrangle of east-central Alaska (Day and others, 2007). This companion report presents the major element oxide and trace element geochemical analyses, including those for gold, silver, and base metals, for representative rock units and for grab samples from quartz veins and mineralized zones within the quadrangle. Also included are field station locations, field notes, structural data, and field photographs based primarily on observations by W.C. Day with additions by J.M. O'Neill and B.M. Gamble, all of the U.S. Geological Survey. The data are provided in both Microsoft Excel spread sheet format and as a Microsoft Access database.

Anaerobically Grown Escherichia coli Has an Enhanced Mutation Rate and Distinct Mutational Spectra

PubMed Central

Shewaramani, Sonal; Finn, Thomas J.; Kassen, Rees; Rainey, Paul B.

2017-01-01

Oxidative stress is a major cause of mutation but little is known about how growth in the absence of oxygen impacts the rate and spectrum of mutations. We employed long-term mutation accumulation experiments to directly measure the rates and spectra of spontaneous mutation events in Escherichia coli populations propagated under aerobic and anaerobic conditions. To detect mutations, whole genome sequencing was coupled with methods of analysis sufficient to identify a broad range of mutational classes, including structural variants (SVs) generated by movement of repetitive elements. The anaerobically grown populations displayed a mutation rate nearly twice that of the aerobic populations, showed distinct asymmetric mutational strand biases, and greater insertion element activity. Consistent with mutation rate and spectra observations, genes for transposition and recombination repair associated with SVs were up-regulated during anaerobic growth. Together, these results define differences in mutational spectra affecting the evolution of facultative anaerobes. PMID:28103245

Combining CMPO and HEH[EHP] for Separating Trivalent Lanthanides from the Transuranic Elements

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

Braley, Jenifer C.; Lumetta, Gregg J.; Carter, Jennifer C.

2013-09-05

Combining octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) into a single process solvent for separating transuranic elements from liquid high-level waste is explored. The lanthanides and americium can be co-extracted from HNO3 into 0.2 mol/L CMPO + 1.0 mol/L HEH[EHP] in n-dodecane. The extraction is relatively insensitive to the HNO3 concentration within 0.1 to 5 mol/L HNO3. Americium can be selectively stripped from the CMPO/HEH[EHP] solvent into a citrate-buffered N-(2-hydroxyethyl)ethylenediaminetriacetic acid solution . Separation factors >14 can be achieved in the range pH 2.5 to 3.7, and the separation factors are relatively insensitive to pH, a major advantagemore » of this solvent formulation.« less

Compositional variation of glauconites in Upper Cretaceous-Paleogene sedimentary iron-ore deposits in South-eastern Western Siberia

NASA Astrophysics Data System (ADS)

Rudmin, Maxim; Banerjee, Santanu; Mazurov, Aleksey

2017-06-01

Glauconite occurs either as unaltered greenish or as altered brownish variety in Upper Cretaceous-Palaeocene sediments in the southeastern corner of Western Siberia. Studied section within the Bakchar iron-ore deposit includes Ipatovo, Slavgorod, Gan'kino and Lyulinvor formations, which are represented by sandstones, siltstones, claystones and oolitic ironstones of coastal-marine facies. The origin of unaltered glauconite is explained by the ;verdissement theory;. Transgressions during Lower Coniacian, Santonian and Campanian favored the formation of unaltered glauconites in dysoxic to anoxic conditions. Subaerial exposure of glauconite resulted in leaching of potassium, oxidation of iron and formation of iron hydroxides in Upper Coniacian, Maastrichtian and Palaeocene. Glauconite ultimately converts to leptochlorite and hydrogoethite by this alteration. Abundant microscopic gold inclusions, besides sulphides, sulphates, oxides and silicates characterize this glauconite. Mineral inclusions include precious, rare metals and non-ferrous metals. The concentration of gold in glauconite may be as high as 42.9 ppb. Abundant inclusions of various compositions in glauconites indicate enrichment of marine sediments in precious and non-precious metals. While major element composition of glauconites is affected by subaerial exposure, the broadly similar micro-inclusions in both altered and unaltered varieties are possibly related to the comparatively immobile nature of REE and trace elements.

Charge transfer in rectifying oxide heterostructures and oxide access elements in ReRAM

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

Stefanovich, G. B.; Pergament, A. L.; Boriskov, P. P.

2016-05-15

The main aspects of the synthesis and experimental research of oxide diode heterostructures are discussed with respect to their use as selector diodes, i.e., access elements in oxide resistive memory. It is shown that charge transfer in these materials differs significantly from the conduction mechanism in p–n junctions based on conventional semiconductors (Si, Ge, A{sup III}–B{sup V}), and the model should take into account the electronic properties of oxides, primarily the low carrier drift mobility. It is found that an increase in the forward current requires an oxide with a small band gap (<1.3 eV) in the heterostructure composition. Heterostructuresmore » with Zn, In–Zn (IZO), Ti, Ni, and Cu oxides are studied; it is found that the CuO–IZO heterojunction has the highest forward current density (10{sup 4} A/cm{sup 2}).« less

COSIMA-Rosetta calibration for in situ characterization of 67P/Churyumov-Gerasimenko cometary inorganic compounds

NASA Astrophysics Data System (ADS)

Krüger, Harald; Stephan, Thomas; Engrand, Cécile; Briois, Christelle; Siljeström, Sandra; Merouane, Sihane; Baklouti, Donia; Fischer, Henning; Fray, Nicolas; Hornung, Klaus; Lehto, Harry; Orthous-Daunay, Francois-Régis; Rynö, Jouni; Schulz, Rita; Silén, Johan; Thirkell, Laurent; Trieloff, Mario; Hilchenbach, Martin

2015-11-01

COmetary Secondary Ion Mass Analyzer (COSIMA) is a time-of-flight secondary ion mass spectrometry (TOF-SIMS) instrument on board the Rosetta space mission. COSIMA has been designed to measure the composition of cometary dust particles. It has a mass resolution m/Δm of 1400 at mass 100 u, thus enabling the discrimination of inorganic mass peaks from organic ones in the mass spectra. We have evaluated the identification capabilities of the reference model of COSIMA for inorganic compounds using a suite of terrestrial minerals that are relevant for cometary science. Ground calibration demonstrated that the performances of the flight model were similar to that of the reference model. The list of minerals used in this study was chosen based on the mineralogy of meteorites, interplanetary dust particles and Stardust samples. It contains anhydrous and hydrous ferromagnesian silicates, refractory silicates and oxides (present in meteoritic Ca-Al-rich inclusions), carbonates, and Fe-Ni sulfides. From the analyses of these minerals, we have calculated relative sensitivity factors for a suite of major and minor elements in order to provide a basis for element quantification for the possible identification of major mineral classes present in the cometary particles.

Biomarker sensing using nanostructured metal oxide sensors

NASA Astrophysics Data System (ADS)

Kalyanasundaram, Krithika

Resistive Chemical sensors are those gas sensitive materials, typically semiconducting metal oxides, that change their electrical properties in response to a change in the ambient. The key features of a chemosensor are sensitivity, selectivity, response time and sensor stability. The hypothesis of this work is that, since metal oxides are polymorphic compounds, the crystal structure of the specific polymorph determines the relative gas selectivity of the material; also that the morphology of the sensing element determines the gas sensitivity limit. This work focuses on the synthesis of nanostructured metal oxides for chemosensors used in selective 'biomarker' detection. Biomarkers are chemical compounds, products of human metabolism which act as specific disease markers. The biomarkers studied in this work include NO, isoprene, NH3, ethanol and acetone which can all be found in exhaled human breath and which allow the non-invasive detection of a range of diseases. Sensors based on three different metal oxides-MoO3, WO 3, and TiO2 were fabricated using sol-gel, electrospinning and spray pyrolysis techniques and tested both as single elements and in an array configuration (electronic nose). The effects of the processing method used, grain size and shape and crystal phase of the material produced, and temperature effects of postsynthesis processing and sensing have been evaluated. Structural characterization has been carried out using X-Ray Diffraction, Scanning and High Resolution Transmission Electron Microscopy, while spectroscopic measurements using XPS, Raman and In-situ FTIR provide valuable information about the surface-analyte interactions. This work has shown that the use of monoclinic polymorph of WO3 yields a selective response to NO, while the other phase of the same oxide give a non-selective chemical response. The orthorhombic phase of MoO 3 exhibits specificity to NH3. An explanation for the variable sensing properties is given based on the gas interactions with the given polymorph involving adsorption/reaction processes. Another major finding of this work is that there was orders of magnitude increase in gas sensitivity when high aspect ratio nanowires as opposed to nanoparticles of the same diameter were used.

Effects of molybdenum and cadmium on the oxidative damage and kidney apoptosis in Duck.

PubMed

Shi, Lele; Cao, Huabin; Luo, Junrong; Liu, Ping; Wang, Tiancheng; Hu, Guoliang; Zhang, Caiying

2017-11-01

Molybdenum (Mo) is an essential element for human beings and animals; however, high dietary intake of Mo can lead to adverse reactions. Cadmium (Cd) is one of the major transitional metals which has toxic effects in animals. To investigate the co-induced toxic effects of Mo and Cd on oxidative damage and kidney apoptosis in duck, 120 ducks were randomly divided into control group and 5 treatment groups which were treated with a commercial diet containing different dosages of Mo and Cd. Kidney samples were collected on the 60th and 120th days to determine the mRNA expression levels of ceruloplasmin (CP), metallothionein (MT), Bak-1, and Caspase-3 by quantitative RT-PCR. Additionally, we also determined the antioxidant activity indexes and contents of Mo, Cd, copper (Cu), iron (Fe), zinc (Zn), and selenium (Se) in serum. Meanwhile, ultrastructural changes of the kidney were observed. The results showed that glutathione reductase (GR) activity and CP level in serum were decreased in combination groups. In addition, the antioxidant indexes were decreased in co-treated groups compared with single treated groups. The mRNA expression levels of Bak-1 and Caspase-3 increased in co-treated groups. The mRNA expression level of CP in high-dose combination group was downregulated, while the mRNA expression of MT was upregulated except for low-dose Mo group. Additionally, in the later period the content of Cu in serum decreased in joint groups while the contents of Mo and Cd increased. In addition, ultrastructural changes showed mitochondrial crest fracture, swelling, deformed nuclei, and karyopyknosis in co-treated groups. Taken together, it was suggested that dietary Mo and Cd might lead to oxidative stress, kidney apoptosis and disturb homeostasis of trace elements in duck, and it showed a possible synergistic relationship between the two elements. Copyright © 2017 Elsevier Inc. All rights reserved.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

PubMed Central

Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

2017-01-01

Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid production, and mixed valence state sulfur species generated by the oxidation of the two different substrates suggests a metabolic flexibility in response to sulfur substrate availability. Our results demonstrate that microbial processing of mixed-valence-state sulfur species generates a significant sulfur isotope fractionation in acidic environments and oxidation of mixed-valence state sulfur species may produce sulfate with characteristic sulfur and oxygen isotope signatures. Elemental sulfur and tetrathionate are not only intermediate-valence state sulfur compounds that play a central role in sulfur oxidation pathways, but also key factors in shaping these isotope patterns. PMID:28861071

Flow of essential elements in subcellular fractions during oxidative stress.

PubMed

Lago, Larissa; Nunes, Emilene A; Vigato, Aryane A; Souza, Vanessa C O; Barbosa, Fernando; Sato, João R; Batista, Bruno L; Cerchiaro, Giselle

2017-02-01

Essential trace elements are commonly found in altered concentrations in the brains of patients with neurodegenerative diseases. Many studies in trace metal determination and quantification are conducted in tissue, cell culture or whole brain. In the present investigation, we determined by ICP-MS Fe, Cu, Zn, Ca, Se, Co, Cr, Mg, and Mn in organelles (mitochondria, nuclei) and whole motor neuron cell cultured in vitro. We performed experiments using two ways to access oxidative stress: cell treatments with H 2 O 2 or Aβ-42 peptide in its oligomeric form. Both treatments caused accumulation of markers of oxidative stress, such as oxidized proteins and lipids, and alteration in DNA. Regarding trace elements, cells treated with H 2 O 2 showed higher levels of Zn and lower levels of Ca in nuclei when compared to control cells with no oxidative treatments. On the other hand, cells treated with Aβ-42 peptide in its oligomeric form showed higher levels of Mg, Ca, Fe and Zn in nuclei when compared to control cells. These differences showed that metal flux in cell organelles during an intrinsic external oxidative condition (H 2 O 2 treatment) are different from an intrinsic external neurodegenerative treatment.

The role of oxidative damage in poor scalp health: ramifications to causality and associated hair growth.

PubMed

Schwartz, J R; Henry, J P; Kerr, K M; Mizoguchi, H; Li, L

2015-12-01

The oxidative stress element of unhealthy scalp leads to compromised pre-emergent hair formation and poorly formed hair as it grows. Only cosmetic solutions can minimize the impact of unhealthy hair and to achieve healthy looking and feeling hair, the scalp health must be normalized first. The objectives of this research were to both investigate whether oxidative stress was a relevant aetiological element in scalp dandruff and seborrhoeic dermatitis and whether scalp condition affects the quality of hair that grows from it. Further, this research was designed to determine whether an effective anti-dandruff shampoo would repair and protect the scalp and pre-emergent hair from oxidative stress. This study demonstrated that oxidative stress is an aetiological element relevant to the dandruff condition and that a potentiated ZPT shampoo effectively improves scalp condition, including a reduction in oxidative stress. The compromised hair condition associated with dandruff is concomitantly improved when the scalp condition is improved. It appears that there is a direct link between hair quality and scalp health. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Patchy distribution of magma that fed the Bishop Tuff supereruption: Evidence from matrix glass major and trace-element compositions

NASA Astrophysics Data System (ADS)

Gualda, G. A. R.; Ghiorso, M. S.; Hurst, A. A.; Allen, M. C.; Bradshaw, R. W.

2017-12-01

For more than 40 years, the Bishop Tuff has been the archetypical example of a singular, zoned magma body that fed a supereruption. Early-erupted material is pyroxene-free and crystal poor (<20 wt. %), presumably erupted from the upper parts of the magma body; late-erupted material is orthopyroxene and clinopyroxene-bearing, commonly more crystal rich (up to 30 wt. % crystals), and presumably tapped magma from the lower portions of the magma body. Fe-Ti oxide compositions suggest higher crystallization temperatures for late-erupted magmas (as high as 820 °C) than for early-erupted magmas (as low as 700 °C). Pressures and temperatures derived from major element compositions of glass inclusions led Gualda & Ghiorso (2013, CMP) to suggest an alternative model of lateral juxtaposition of two main magma bodies - each one feeding early-erupted and late-erupted units. Chamberlain et al. (2015, JPet) and Evans et al. (2016, AmMin) recently disputed this interpretation. We present a large dataset of matrix glass compositions for 161 pumice clasts that span the stratigraphy of the deposit. We calculate crystallization pressures based on major-element glass compositions using rhyolite-MELTS geobarometry, and crystallization temperatures based on Zr in glass using zircon saturation geothermometry. We apply the same methods to 1538 major-element and 615 trace-element analyses from Chamberlain et al. The results overwhelmingly demonstrate that there is no difference in crystallization temperature or pressure between early and late-erupted magmas. Crystallization pressures and temperatures are unimodal, with modes of 150 MPa and 730 °C (calibration of Watson & Harrison). Our results strongly support lateral juxtaposition of two main magma bodies. Smaller units recognized by Chamberlain et al. crystallized at the same pressures as the main bodies - this suggests the coexistence of larger and smaller magma bodies at the time of the Bishop Tuff supereruption. We compare our findings for the Bishop Tuff with results for very large and supereruptions elsewhere in the world. We argue that supereruptions typically mobilize a complex patchwork of magma bodies that reside within specific levels of the crust. They reveal moments of high-melt productivity in the crust, unlike what we observe in the Earth today.

Sub-Model Partial Least Squares for Improved Accuracy in Quantitative Laser Induced Breakdown Spectroscopy

NASA Astrophysics Data System (ADS)

Anderson, R. B.; Clegg, S. M.; Frydenvang, J.

2015-12-01

One of the primary challenges faced by the ChemCam instrument on the Curiosity Mars rover is developing a regression model that can accurately predict the composition of the wide range of target types encountered (basalts, calcium sulfate, feldspar, oxides, etc.). The original calibration used 69 rock standards to train a partial least squares (PLS) model for each major element. By expanding the suite of calibration samples to >400 targets spanning a wider range of compositions, the accuracy of the model was improved, but some targets with "extreme" compositions (e.g. pure minerals) were still poorly predicted. We have therefore developed a simple method, referred to as "submodel PLS", to improve the performance of PLS across a wide range of target compositions. In addition to generating a "full" (0-100 wt.%) PLS model for the element of interest, we also generate several overlapping submodels (e.g. for SiO2, we generate "low" (0-50 wt.%), "mid" (30-70 wt.%), and "high" (60-100 wt.%) models). The submodels are generally more accurate than the "full" model for samples within their range because they are able to adjust for matrix effects that are specific to that range. To predict the composition of an unknown target, we first predict the composition with the submodels and the "full" model. Then, based on the predicted composition from the "full" model, the appropriate submodel prediction can be used (e.g. if the full model predicts a low composition, use the "low" model result, which is likely to be more accurate). For samples with "full" predictions that occur in a region of overlap between submodels, the submodel predictions are "blended" using a simple linear weighted sum. The submodel PLS method shows improvements in most of the major elements predicted by ChemCam and reduces the occurrence of negative predictions for low wt.% targets. Submodel PLS is currently being used in conjunction with ICA regression for the major element compositions of ChemCam data.

Acid Sulfate Alteration on Mars

NASA Technical Reports Server (NTRS)

Ming, D. W.; Morris, R. V.

2016-01-01

A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Acid sulfate alteration has been identified at all three landing sites visited by NASA rover missions (Spirit, Opportunity, and Curiosity). Spirit landed in Gusev crater in 2004 and discovered Fe-sulfates and materials that have been extensively leached by acid sulfate solutions. Opportunity landing on the plains of Meridiani Planum also in 2004 where the rover encountered large abundances of jarosite and hematite in sedimentary rocks. Curiosity landed in Gale crater in 2012 and has characterized fluvial, deltaic, and lacustrine sediments. Jarosite and hematite were discovered in some of the lacustrine sediments. The high elemental abundance of sulfur in surface materials is obvious evidence that sulfate has played a major role in aqueous processes at all landing sites on Mars. The sulfate-rich outcrop at Meridiani Planum has an SO3 content of up to 25 wt.%. The interiors of rocks and outcrops on the Columbia Hills within Gusev crater have up to 8 wt.% SO3. Soils at both sites generally have between 5 to 14 wt.% SO3, and several soils in Gusev crater contain around 30 wt.% SO3. After normalization of major element compositions to a SO3-free basis, the bulk compositions of these materials are basaltic, with a few exceptions in Gusev crater and in lacustrine mudstones in Gale crater. These observations suggest that materials encountered by the rovers were derived from basaltic precursors by acid sulfate alteration under nearly isochemical conditions (i.e., minimal leaching). There are several cases, however, where acid sulfate alteration minerals (jarosite and hematite) formed in open hydrologic systems, e.g., in Gale crater lacustrine mudstones. Several hypotheses have been suggested for the aqueous formation of sulfate-bearing phases under acidic conditions on the surface of Mars including (1) sulfuric acid weathering of basaltic materials; (2) oxidative weathering of ultramafic igneous rocks containing sulfides; (3) acid fog weathering of basaltic materials, and (4) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity as iron was oxidized on exposure to O2 or photo-oxidized by ultraviolet radiation at the martian surface. Next, we briefly describe evidence for these hypothesis.

Iron-magnesium alloy in the Earth's Core

NASA Astrophysics Data System (ADS)

Dubrovinskaia, N.; Dubrovinsky, L.; Abrikosov, I.

2005-12-01

Composition of the Earth's outer core is a geochemical parameter crucial for understanding the evolution and current dynamics of our planet. Since it was recognized that the liquid metallic outer core is about 10% less dense than pure iron, different elements lighter than iron, including Si, S, O, C, and H, were proposed as major or at least significantly abundant in Earth's core. However, combination of experimental results with theoretical and geochemical considerations shows that it is unlikely that any one of these elements can account for the density deficit on its own. In series of experiments in a multianvil apparatus and in electrically- and laser-heated diamond anvil cells, we demonstrate that high pressure promotes solubility of magnesium in iron and at megabar pressure range more than 10 at% of Mg can dissolve in Fe. At pressures above 95 to 100 GPa, molten iron reacts with periclase MgO forming an iron-magnesium alloy and iron oxide. Our observations suggest that magnesium can be an important light element in Earth's outer core, but it cannot account for the seismologically determined density deficit on its own.

Multiscale model of metal alloy oxidation at grain boundaries

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

Sushko, Maria L.; Alexandrov, Vitali Y.; Schreiber, Daniel K.

2015-06-07

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model at experimentally relevant length scales is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides.more » The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2 - 1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide.« less

Field occurrence and geochemical characteristics of the baryte mineralization in Lessel and Ihugh areas, Lower Benue Trough, Nigeria

NASA Astrophysics Data System (ADS)

Labe, Ngukposu A.; Ogunleye, Paul O.; Ibrahim, Aliyu A.

2018-06-01

The Lessel and Ihugh areas are underlain by Precambrian rocks comprising of banded gneiss, medium-grained muscovite granite, coarse-grained biotite muscovite granite, and Turonian arenaceous Lessel Sandstone in the Lower Benue Trough, southeastern Nigeria. Baryte mineralization occurs at Lessel-Mbagwa, Ihugh and Bunde commonly as vein and cavity type deposits within NE-SW and NW-SE trending fracture zones. Major oxides and trace element analysis of baryte and the host rocks was undertaken using Inductively Coupled Plasma Mass Spectrometry (ICP-MS), in order to establish the geochemical characteristics and to constrain the origin of the baryte mineralization. The data revealed enrichment in Ba and Sr and depletion in SiO2, TiO2, Al2O3, Fe2O3, MgO, CaO, Na2O, K2O, LILEs, HFSEs relative to background values obtained from sandstones and granitic rocks in the area. Baryte mineralization from Lessel-Mbagwa, Bunde and Ihugh is marked by positive Gd (17.1-21.4) and negative Eu (0.02-0.05) anomalies. Negative Ce anomaly (0.06) is evident in barytes from Lessel-Mbagwa and Bunde whereas baryte from Ihugh is characterized by positive Ce anomaly (1.3). The structurally controlled nature of the mineralization, depleted major and trace elements concentration in the barytes in addition to REE anomalies indicate that mixing of a strongly differentiated residual Ba-bearing fluid and sulphur-rich seawater occurred under low temperature and oxidizing-reducing conditions. The tectonic event which occurred during the Santonian to Early Campanian reactivated the NE-SW, NW-SE structural pathways in the basement gneiss and also created similar structures in the Turonian Lessel Sandstone.

Phase transitions in MgSiO3 post-perovskite in super-Earth mantles

NASA Astrophysics Data System (ADS)

Umemoto, Koichiro; Wentzcovitch, Renata M.; Wu, Shunqing; Ji, Min; Wang, Cai-Zhuang; Ho, Kai-Ming

2017-11-01

The highest pressure form of the major Earth-forming mantle silicate is MgSiO3 post-perovskite (PPv). Understanding the fate of PPv at TPa pressures is the first step for understanding the mineralogy of super-Earths-type exoplanets, arguably the most interesting for their similarities with Earth. Modeling their internal structure requires knowledge of stable mineral phases, their properties under compression, and major element abundances. Several studies of PPv under extreme pressures support the notion that a sequence of pressure induced dissociation transitions produce the elementary oxides SiO2 and MgO as the ultimate aggregation form at ∼3 TPa. However, none of these studies have addressed the problem of mantle composition, particularly major element abundances usually expressed in terms of three main variables, the Mg/Si and Fe/Si ratios and the Mg#, as in the Earth. Here we show that the critical compositional parameter, the Mg/Si ratio, whose value in the Earth's mantle is still debated, is a vital ingredient for modeling phase transitions and internal structure of super-Earth mantles. Specifically, we have identified new sequences of phase transformations, including new recombination reactions that depend decisively on this ratio. This is a new level of complexity that has not been previously addressed, but proves essential for modeling the nature and number of internal layers in these rocky mantles.

Selective oxidation of alkanes and/or alkenes to valuable oxygenates

DOEpatents

Lin, Manhua; Pillai, Krishnan S.

2011-02-15

A catalyst, its method of preparation and its use for producing at least one of methacrolein and methacrylic acid, for example, by subjecting isobutane or isobutylene or a mixture thereof to a vapor phase catalytic oxidation in the presence of air or oxygen. In the case where isobutane alone is subjected to a vapor phase catalytic oxidation in the presence of air or oxygen, the product is at least one of isobutylene, methacrolein and methacrylic acid. The catalyst comprises a compound having the formula A.sub.aB.sub.bX.sub.xY.sub.yZ.sub.zO.sub.o wherein A is one or more elements selected from the group of Mo, W and Zr, B is one or more elements selected from the group of Bi, Sb, Se, and Te, X is one or more elements selected from the group of Al, Bi, Ca, Ce, Co, Fe, Ga, Mg, Ni, Nb, Sn, W and Zn, Y is one or more elements selected from the group of Ag, Au, B, Cr, Cs, Cu, K, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Re, Ru, Sn, Te, Ti, V and Zr, and Z is one or more element from the X or Y groups or from the following: As, Ba, Pd, Pt, Sr, or mixtures thereof, and wherein a=1, 0.05

Dispersoid reinforced alloy powder and method of making

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

Anderson, Iver E.; Terpstra, Robert L.

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Dispersoid reinforced alloy powder and method of making

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

Anderson, Iver E.; Terpstra, Robert L.

2017-10-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Publications - RDF 2009-1 v. 1.2 | Alaska Division of Geological &

Science.gov Websites

main content DGGS RDF 2009-1 v. 1.2 Publication Details Title: Geochemical, major-oxide, minor-oxide , M.B., Szumigala, D.J., Andrew, J.E., Newberry, R.J., and Athey, J.E., 2009, Geochemical, major-oxide prospect; Keevy Peak Formation; LEA Creek prospect; Major Oxides; Mississippian; Newman Creek; Newman Creek

The chemistry and mineralogy of haloed burrows in pelagic sediment at DOMES Site A: The equatorial North Pacific

USGS Publications Warehouse

Piper, D.Z.; Rude, P.D.; Monteith, S.

1987-01-01

The chemical and mineralogical composition of burrowed sediment, recovered in 66 box cores at latitude 9??25???N and longitude 151??15???W in the equatorial Pacific, demonstrates the important role of infauna in determining the geochemistry of pelagic sediment. Haloed burrows, approximately 3 cm across, were present in many of the cores. Within early Tertiary sediment that was covered by less than 5 cm of surface Quaternary sediment in several cores, the burrows in cross-section consist of three units: (1) a dark yellowish-brown central zone of Quaternary sediment surrounded, by (2) a pale yellowish-orange zone (the halo) of Tertiary sediment, which is surrounded by (3) a metal-oxide precipitate; the enclosing Tertiary sediment is dusky brown. Several elements - Mn, Ni, Cu, Co, Zn, Sb and Ce - have been leached from the light-colored halo, whereas Cr, Cs, Hf, Rb, Sc, Ta, Th, U, the rare earth elements exclusive of Ce, and the major oxides have not been leached. The metal-oxide zone, 1-5 mm thick, contains as much as 16% MnO2, as the mineral todorokite. The composition of the todorokite, exclusive of the admixed Tertiary sediment, resembles the composition of the metal deficit of the halo and also the composition of surface ferromanganese nodules that have been interpreted as having a predominantly diagenetic origin. Thus bioturbation contributes not only to the redistribution of metals within pelagic sediment, but also to the accretion of ferromanganese nodules on the sea floor. ?? 1987.

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

USGS Publications Warehouse

Bacon, C.R.

1989-01-01

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

Sulfide oxidation under chemolithoautotrophic denitrifying conditions.

PubMed

Cardoso, Ricardo Beristain; Sierra-Alvarez, Reyes; Rowlette, Pieter; Flores, Elias Razo; Gómez, Jorge; Field, Jim A

2006-12-20

Chemolithoautotrophic denitrifying microorganisms oxidize reduced inorganic sulfur compounds coupled to the reduction of nitrate as an electron acceptor. These denitrifiers can be applied to the removal of nitrogen and/or sulfur contamination from wastewater, groundwater, and gaseous streams. This study investigated the physiology and kinetics of chemolithotrophic denitrification by an enrichment culture utilizing hydrogen sulfide, elemental sulfur, or thiosulfate as electron donor. Complete oxidation of sulfide to sulfate was observed when nitrate was supplemented at concentrations equal or exceeding the stoichiometric requirement. In contrast, sulfide was only partially oxidized to elemental sulfur when nitrate concentrations were limiting. Sulfide was found to inhibit chemolithotrophic sulfoxidation, decreasing rates by approximately 21-fold when the sulfide concentration increased from 2.5 to 10.0 mM, respectively. Addition of low levels of acetate (0.5 mM) enhanced denitrification and sulfate formation, suggesting that acetate was utilized as a carbon source by chemolithotrophic denitrifiers. The results of this study indicate the potential of chemolithotrophic denitrification for the removal of hydrogen sulfide. The sulfide/nitrate ratio can be used to control the fate of sulfide oxidation to either elemental sulfur or sulfate. Copyright 2006 Wiley Periodicals, Inc.

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1993-01-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Occurrences, uses, and properties of chromium.

PubMed

Barnhart, J

1997-08-01

Chromium is the 21st most abundant element in the Earth's crust with a mean concentration in United States soils of about 40 mg/kg. Although it exists in several oxidation states, the zero, trivalent, and hexavalent states are the most important in commercial products and the environment. Nearly all naturally occurring chromium is in the trivalent state, usually in combination with iron or other metal oxides. Although only about 15% of the chromium mined is used in the manufacture of chemicals, most applications of chromium utilize the chemistry of chromium. For instance, the "stainless" nature of stainless steel is due to the chemical properties of the chromium oxides which form on the surface of the alloy. Similarly, the protective properties of chrome plating of metals, chromated copper arsenate (CCA) treatment of wood, and chrome tanning of leather are all dependent on chromium chemistry. The key to these uses is that under typical environmental and biological conditions of pH and oxidation-reduction potential, the most stable form of chromium is the trivalent oxide. This form has very low solubility and low reactivity resulting in low mobility in the environment and low toxicity in living organisms. In this paper the chemical properties of chromium are discussed for the major commercial products in the context of the Eh-pH diagram for chromium. Copyright 1997 Academic Press.

Thermal oxidative degradation reactions of perfluoroalkylethers

NASA Technical Reports Server (NTRS)

Paciorek, K. L.; Ito, T. I.; Kratzer, R. H.

1981-01-01

The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

Thermal oxidation of single crystal aluminum antimonide and materials having the same

DOEpatents

Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.

2012-12-25

In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.

Influence of frequency on the structure of zirconium oxide coatings deposited from aqueous electrolytes under microplasma oxidation

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

Gubaidulina, Tatiana A., E-mail: goub2002@mail.ru; Sergeev, Viktor P., E-mail: vserg@mail.tomsknet.ru; Fedorischeva, Marina V., E-mail: fmw@ispms.tsc.ru

2015-10-27

The work describes the microplasma oxidation (MPO) of zirconium surface resulting in the formation of zirconium oxide Zr-Al-Nb-O. We have used novel power supply to deposit oxide ceramic coatings by MPO and studied the effect of current density on the phase structure of oxide ceramic coatings. The size of microcracks in the coatings was determined at different frequencies. We have also used EVO50c scanning election microscope with an attachment for elemental analysis to study the morphology and elemental composition of oxide ceramic coating. In addition, we have established the influence of the frequency on the phase composition of the coating:more » at the frequency of 2500 Hz, the fraction of monoclinic phase was 18%, while the fraction of tetragonal phase amounted to 72%. The oxide ceramic coating produced at 250 Hz contained 38% of monoclinic phase and 62% of tetragonal phase; in addition, it had no buildups and craters.« less

Quantitative Relationships between Photosynthetic, Nitrogen Fixing, and Fermentative H2 Metabolism in a Photosynthetic Microbial Mat

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Albert, Daniel B.; Bebout, Brad M.; Turk, Kendra A.; DesMarais, David J.

2004-01-01

The ultimate potential of any microbial ecosystem to contribute chemically to its environment - and therefore, to impact planetary biogeochemistry or to generate recognizable biosignatures - depends not only on the individual metabolic capabilities of constituent organisms, but also on how those capabilities are expressed through interactions with neighboring organisms. This is particularly important for microbial mats, which compress an extremely broad range of metabolic potential into a small and dynamic system. H2 participates in many of these metabolic processes, including the major elemental cycling processes of photosynthesis, nitrogen fixation, sulfate reduction, and fermentation, and may therefore serve as a mediator of microbial interactions within the mat system. Collectively, the requirements of energy, electron transfer, and biomass element stoichiometry suggest quantitative relationships among the major element cycling processes, as regards H2 metabolism We determined experimentally the major contributions to 32 cycling in hypersaline microbial mats from Baja California, Mexico, and compared them to predicted relationships. Fermentation under dark, anoxic conditions is quantitatively the most important mechanism of H2 production, consistent with expectations for non-heterocystous mats such as those under study. Up to 16% of reducing equivalents fixed by photosynthesis during the day may be released by this mechanism. The direct contribution of nitrogen fixation to H2 production is small in comparison, but this process may indirectly stimulate substantial H2 generation, by requiring higher rates of fermentation. Sulfate reduction, aerobic consumption, diffusive and ebulitive loss, and possibly H2-based photoreduction of CO2 serve as the principal H2 sinks. Collectively, these processes interact to create an orders-of-magnitude daily variation in H2 concentrations and fluxes, and thereby in the oxidation-reduction potential that is imposed on microbial processes occuring within the mat matrix.

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

USGS Publications Warehouse

Hatch, J.R.; Leventhal, M.S.

1997-01-01

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography. The partial oxidation process has likely led to a redistribution of sulfur and sulfide-forming elements into other organic-rich lithologies in the section. The altered/oxidized shales are nongenerative with respect to hydrocarbon generation.

Global perspectives on oxidative weathering of organic carbon in sedimentary rocks

NASA Astrophysics Data System (ADS)

Dellinger, M.; Hilton, R. G.; West, A. J.; Horan, K.; Gaillardet, J.

2016-12-01

Over geological timescales, the oxidation of organic carbon in sedimentary rocks is major source of carbon dioxide (CO2) to the atmosphere. The global magnitude of this flux remains poorly constrained, but it is likely to be between 40-100 x 1012 g C yr-1, similar to the CO2 emissions from volcanism. The rates of CO2 emission ultimately set the rate of silicate weathering by carbonic acid and new organic carbon burial, which act together to stabilise the climate system. To constrain how the geological carbon cycle operates and modifies Earth's climate over millions of years, we must better understand the controls on the oxidation of sedimentary rock-derived organic carbon (`petrogenic' OC, OCpetro). Here we examine new and published constraints on OCpetro oxidation flux, which come from indirect measurements (e.g. trace element proxies such as rhenium) and direct measurements (e.g. CO2 trapping and 14C). Existing datasets track the gaseous and dissolved products of weathering as well as the solid residues over a range of spatial scales, from soil profiles to large river catchments. Although the datasets are still sparse, they indicate that physical denudation plays a major role in setting OCpetro oxidation flux. These measurements are interrogated in the framework of a catchment-scale numerical model of OCpetro oxidation. By harnessing approaches developed to examine and quantify acid-hydrolysis reactions (i.e. silicate mineral weathering by carbonic acid) the model considers realistic geochemical processes and the links between erosion and weathering. Key parameters emerge, such as the `weathering thickness' which describes a depth to which oxidative waters penetrate. The reaction kinetics of OCpetro remain poorly constrained, but nevertheless, the model predicts that the kinetic limitation of OCpetro oxidation is not reached until physical erosion rates exceed 2 mm yr-1, which is much higher than for CO2 consumption by silicate weathering. These findings mirror data on sulphide oxidation, demonstrating that physical erosion can drive an important CO2 release to the atmosphere both from inorganic and organic reduced phases in sedimentary rocks. The degree to which this release is compensated by CO2 drawdown associated with the erosion and transfer of biospheric OC will also be considered.

Chemical and mineralogical evaluation of slag products derived from the pyrolysis/melting treatment of MSW.

PubMed

Saffarzadeh, Amirhomayoun; Shimaoka, Takayuki; Motomura, Yoshinobu; Watanabe, Koichiro

2006-01-01

This paper provides the results of studies on the characteristics of novel material derived from pyrolysis/melting treatment of municipal solid waste in Japan. Slag products from pyrolysis/melting plants were sampled for the purpose of detailed phase analysis and characterization of heavy metal-containing phases using optical microscopy, electron probe microanalysis (EPMA), XRF and XRD. The study revealed that the slag material contains glass (over 95%), oxide and silicate minerals (spinel, melilite, pseudowollastonite), as well as individual metallic inclusions as the major constituents. A distinct chemical diversity was discovered in the interstitial glass in terms of silica content defined as low and high silica glass end members. Elevated concentrations of Zn, Cr, Cu, Pb and Ba were recorded in the bulk composition. Cu, Pb and Ba behave as incompatible elements since they have been markedly characterized as part of polymetallic alloys and insignificantly sulfides in the form of spherical metallic inclusions associated with tracer amounts of other elements such as Sb, Sn, Ni, Zn, Al, P and Si. In contrast, an appreciable amount of Zn is retained by zinc-rich end members of spinel and partially by melilite and silica glass. Chromium exhibits similar behavior, and is considerably held by Cr-rich spinel. The intense incorporation of Zn and Cr into spinel indicates the very effective enrichment of these two elements into phases more environmentally resistant than glass. There was no evidence, however, that Cu and Pb enter into the structure of the crystalline silicates or oxides that may lead to their easier leachability upon exposure to the environment.

Trace elements and oxidative stress levels in the blood of painters in Lagos, Nigeria: occupational survey and health concern.

PubMed

Awodele, Olufunsho; Akinyede, Akin; Babawale, Omotola Opeyemi; Coker, Herbert A Babatunde; Akintonwa, Alade

2013-06-01

Adverse effects attributed to exposure to paints are currently a concern because of the continued widespread use of paint containing trace elements. Thus, occupational survey amongst painters in Lagos and determination of trace elements and oxidative stress parameters were carried out. Descriptive cross-sectional survey was done using a standardized questionnaire to obtain job safety-related information. Forty-eight percent of the painters were aware of hazards associated with painting and 52 % of these workers were aware of the necessary precautionary measures during painting. There were no significant differences (p ≥ 0.05) between the levels of trace elements in the blood of painters and the control subjects. However, there was a significance increase (p ≤ 0.0001) in the level of malondialdehyde and a decrease (p ≤ 0.001) in the levels of reduced glutathione, superoxide dismutase, and catalase of the painters compared to the control. An increase in oxidative stress parameters may not only be due to trace element concentrations, but also the painters' exposure to some petrochemical solvents during mixing of paints.

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

DOE PAGES

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

2017-03-28

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

Positive anomalous concentrations of Pb in some gabbroic rocks of Afikpo basin southeastern Nigeria.

PubMed

Onwualu-John, J N

2016-08-01

Gabbroic rocks have intruded the sedimentary sequence at Ameta in Afikpo basin southeastern Nigeria. Petrographic and geochemical features of the rocks were studied in order to evaluate their genetic and geotectonic history. The petrographic results show that the rocks contain plagioclase, olivine, pyroxene, biotite, iron oxide, and traces of quartz in three samples. Major element characteristics show that the rocks are subalkaline. In addition, the rocks have geochemical characteristics similar to basaltic andesites. The trace elements results show inconsistent concentrations of high field strength elements (Zr, Nb, Th, Ta), moderate enrichment of large-ion lithophile elements (Rb, Sr, Ba) and low concentrations of Ni and Cr. Rare earth element results show that the rocks are characterized by enrichment of light rare earth elements, middle rare earth elements enrichment, and depletion of heavy rare earth elements with slight positive europium anomalies. Zinc concentrations are within the normal range in basaltic rocks. There are extremely high concentrations of Pb in three of the rock samples. The high Pb concentrations in some of these rocks could be as a result of last episodes of magmatic crystallization. The rocks intruded the Asu River Group; organic components in the sedimentary sequence probably contain Pb which has been assimilated into the magma at the evolutionary stage of the magma. Weathering of some rocks that contain galena could lead to an increase in the concentration of lead in the gabbroic rocks, especially when the migration and crystallization of magma take place in an aqueous environment. Nevertheless, high concentration of lead is hazardous to health and environment.

Development of phase analysis methods of impurity elements in alloys based on iron and nickel

NASA Astrophysics Data System (ADS)

Andreeva, N. A.; Anuchkin, S. N.; Volchenkova, V. A.; Kazenas, E. K.; Penkina, T. N.; Fomina, A. A.

2018-04-01

Using the method of AES with ICP, new methods have been developed for quantifying the content of various forms of existence of impurity elements: Al-Al2O3; Zr-ZrO2 in alloys based on iron (Fe-Sn) and nickel (Ni-Sn). Open systems were used to dissolve Al and Zr. To translate difficult-to-open aluminum oxides (corundum) and zirconium oxide (baddeleyite) into the solution, accelerated techniques were developed using the microwave system Mars 5. To confirm the completeness of the dissolution of oxides, a classical scheme of alloy fusion with alkali metal salts was used. Optimal analytical parameters for determining the elements: Al and Zr were chosen. The influence of matrix elements (iron and nickel) and methods of its elimination were studied. This made it possible to determine the elements in a wide concentration range from 1 • 10-3 to n% Al and from 1 • 10-4 to n% Zr without preliminary separation of the matrix with good metrological characteristics. The relative standard deviation (Sr) does not exceed 0,2. The separate determination of the contents of aluminum and aluminium oxide in the model melt of Fe-Sn-Al2O3 and zirconium and zirconium oxide in the Ni-Sn-ZrO2 model melt allowed us to estimate the number of nanoparticles participating in the heterophase interaction with tin and retired to the interface in the form of ensembles and the number of nanoparticles present in the melt and affecting the crystallization process and the structure of the metal.

Efficient growth of HTS films with volatile elements

DOEpatents

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

1998-12-22

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

Atmospheric Oxidation of Squalene: Molecular Study Using COBRA Modeling and High-Resolution Mass Spectrometry

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

Fooshee, David R.; Aiona, Paige K.; Laskin, Alexander

2015-10-22

Squalene is a major component of skin and plant surface lipids, and is known to be present at high concentrations in indoor dust. Its high reactivity toward ozone makes it an important ozone sink and a natural protectant against atmospheric oxidizing agents. While the volatile products of squalene ozonolysis are known, the condensed-phase products have not been characterized. We present an analysis of condensed-phase products resulting from an extensive oxidation of squalene by ozone probed by electrospray ionization (ESI) high-resolution mass spectrometry (HR-MS). A complex distribution of nearly 1,300 peaks assignable to molecular formulas is observed in direct infusion positivemore » ion mode ESI mass spectra. The distribution of peaks in the mass spectra suggests that there are extensive cross-coupling reactions between hydroxy-carbonyl products of squalene ozonolysis. To get additional insights into the mechanism, we apply a Computational Brewing Application (COBRA) to simulate the oxidation of squalene in the presence of ozone, and compare predicted results with those observed by the HR-MS experiments. The system predicts over one billion molecular structures between 0-1450 Da, which correspond to about 27,000 distinct elemental formulas. Over 83% of the squalene oxidation products inferred from the mass spectrometry data are matched by the simulation. Simulation indicates a prevalence of peroxy groups, with hydroxyl and ether groups being the second-most important O-containing functional groups formed during squalene oxidation. These highly oxidized products of squalene ozonolysis may accumulate on indoor dust and surfaces, and contribute to their redox capacity.« less

The chemistry of the superheavy elements. II. The stability of high oxidation states in group 11 elements: Relativistic coupled cluster calculations for the di-, tetra- and hexafluoro metallates of Cu, Ag, Au, and element 111

NASA Astrophysics Data System (ADS)

Seth, Michael; Cooke, Fiona; Schwerdtfeger, Peter; Heully, Jean-Louis; Pelissier, Michel

1998-09-01

The stability of the high oxidation states +3 and +5 in Group 11 fluorides is studied by relativistic Møller-Plesset (MP) and coupled cluster methods. Higher metal oxidation states are stabilized by relativistic effects. As a result, the hexafluoro complex of the Group 11 element with nuclear charge 111 and oxidation state +5 is the most stable compared to the other congeners. The results also suggest that AgF6- is thermodynamically stable and, therefore, it might be feasable to synthesize this compound. For the copper fluorides we observe very large oscillations in the Møller-Plesset series up to the fourth order. Nonrelativistic calculations lead to the expected trend in the metal-fluorine bond distances for the MF2- compounds, CuF2-

Novel catalytic properties of quadruple perovskites

PubMed Central

Yamada, Ikuya

2017-01-01

ABSTRACT Quadruple perovskite oxides AA′3 B 4O12 demonstrate a rich variety of structural and electronic properties. A large number of constituent elements for A/A′/B-site cations can be introduced using the ultra-high-pressure synthesis method. Development of novel functional materials consisting of earth-abundant elements plays a crucial role in current materials science. In this paper, functional properties, especially oxygen reaction catalysis, for quadruple perovskite oxides CaCu3Fe4O12 and AMn7O12 (A = Ca, La) composed of earth-abundant elements are reviewed. PMID:28970864

Mechanical Mixing and Metamorphism of Mafic and Ultramafic Lithologies during Mylonisis at the ST. Paul Transform System, Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Adrião, Á.; Maia, M.; Hemond, C.; Kaczmarek, M. A.; Briais, A.; Vincent, C.; Brunelli, D.

2017-12-01

The St. Paul Transform System offsets by 630 km the Equatorial Mid Atlantic Ridge at 1° N. It consists of four major faults separating three intra transform ridge axes. This region shows a transition from a transpressive, hot spot affected, regional-scale shear zone to the North to a region dominated by a particular oceanic core complex spreading to the South (Vincent et al., this congress). Samples collected in the region during the COLMEIA cruise (Maia et al., 2016) were studied for textures and whole-rock major and trace element contents. All samples experienced pervasive deformation at ductile to brittle conditions overprinted by late low-T alteration. Mylonitic and ultramylonitic rocks can be grouped in three main types: peridotitic, gabbroic and talc-chlorite schist. Peridotitic ultramylonites preserve few opx, cpx and sp porphyroclasts; they have homogeneous nano-micro grain size groundmass, banded foliation and late amphibole and sulfide crystallization. Locally S-C fabric overprints the mylonitic texture. Micro cracks, filled with serpentine, chlorite and oxides are common, as well fluid inclusions trails in olivine and plagioclase crystals of peridotite and gabbros respectively. Major and trace element content of the peridotitic mylonites plot in the depleted field of the abyssal peridotites; however, they present marked LREE enrichment and Eu positive anomaly. Gabbroic and talc-chlorite mylonites display REE-enriched patterns (up to 100x CI) and variable Eu anomalies. Major elements show a remarkable linear trend in the talc-chlorite group suggesting mixing of pure talc and chlorite end-members. These compositional characteristics suggest variable assimilation of MORB and E-MORB during mylonisis or early melt-rock interaction and hydrothermal evolution at variable metamorphic conditions. Vincent et al., 2017. Particular Oceanic Core Complex evolution …; this congress Maia et al., 2016. Extreme mantle uplift and exhumation ... Nat. Geo. doi:10.1038/ngeo2759

Control of Sulfidogenesis Through Bio-oxidation of H 2S Coupled to (per)chlorate Reduction

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

Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G.

2014-04-04

Here, we investigate H 2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H 2S coupled to (per)chlorate reduction without sustaining growth. H 2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. We also propose a novel hybrid enzymatic-abiotic mechanism for H 2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

Mountain respiration: Rates and patterns of fossil organic carbon oxidation revealed using the trace element rhenium

NASA Astrophysics Data System (ADS)

Hilton, R. G.; Gaillardet, J.; Calmels, D.; Birck, J.

2013-12-01

Fossil organic carbon (OCfossil) from sedimentary rocks can contribute to the carbon stock within the deepest part of soil. OCfossil constitutes a vast stock of carbon that was sequestered from the atmosphere in the geological past, containing ~15x106 PgC, which is approximately 25,000 times the carbon content of the pre-industrial atmosphere. Oxidation of OCfossil during chemical weathering at Earth's surface is thought to be a major source of carbon dioxide (CO2) to the atmosphere. It has been proposed that OCfossil oxidation occurs when fresh sedimentary rocks are exposed to oxygenated water, with the rate of CO2 release controlled by the supply of OCfossil to react. As such, mountain belts where high rates of physical erosion provide an abundant supply of OCfossil to the soil critical zone should be locations where this CO2 source is most potent. However, the rates of OCfossil oxidation during weathering remain poorly constrained. Here we use the trace element rhenium (Re) to shed new light on the rates and patterns of OCfossil oxidation across the landscape. Re is known to be associated with organic matter in rocks and following oxidation forms a soluble anion which contributes to the dissolved load of rivers. Rivers can offer an integrated signal of chemical reactions occurring across the landscape, and so by quantifying the dissolved Re flux we are able to estimate the corresponding release of CO2 by OCfossil weathering. Using a set of mountain river catchments in Taiwan, where water and sediment fluxes are well quantified, we estimate that the rates of CO2 output by this process are significant, and encroach on values expected for net biome productivity. We find that OCfossil oxidation rates are strongly linked to physical erosion rate at the catchment-scale. This suggests that changes in the rates of surface processes may alter this CO2 output from deep soils. On longer timescales, our findings suggest that the total CO2 output by OCfossil weathering in Taiwan does not negate estimates of CO2 sequestration by erosion and sedimentary burial of recent organic matter. Our findings suggest that mountain building in the tropic can result in a net sink of organic carbon during erosion and weathering which acts to sequester atmospheric CO2.

Oxidative elemental cycling under the low O2 Eoarchean atmosphere

PubMed Central

Frei, Robert; Crowe, Sean A.; Bau, Michael; Polat, Ali; Fowle, David A.; Døssing, Lasse N.

2016-01-01

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3–2.9 Gyr ago. 3.8–3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth’s earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8–3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology. PMID:26864443

Acid Sulfate Alteration in Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Ming, D. W.; Catalano, J. G.

2016-01-01

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

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

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE PAGES

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.; ...

2017-03-20

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Extraterrestrial materials processing and construction

NASA Technical Reports Server (NTRS)

Criswell, D. R.

1978-01-01

Applications of available terrestrial skills to the gathering of lunar materials and the processing of raw lunar materials into industrial feed stock were investigated. The literature on lunar soils and rocks was reviewed and the chemical processes by which major oxides and chemical elements can be extracted were identified. The gathering of lunar soil by means of excavation equipment was studied in terms of terrestrial experience with strip mining operations on earth. The application of electrostatic benefication techniques was examined for use on the moon to minimize the quantity of materials requiring surface transport and to optimize the stream of raw materials to be transported off the moon for subsequent industrial use.

Recommended Values of the Thermophysical Properties of Eight Alloys, Major Constituents and Their Oxides

DTIC Science & Technology

1966-01-01

V & 1? MATERIALS 732 e a ja o 8 i 1* •ŗ •3V h Q £ u HO > HS MSB Q »H ELEMENTS...CO e - « « s M u I 2 H t- xti CO in eo N i o 7 o T-S T-1110 ""A ’ityAnonpuoo iBttueqx -•-■-■-- - ■ - ^ H.^’.^" V ...IO CO M i-t •O COCS O tr- lO CON I s e IO 05 w O Ü o Ü I g E 1_5I ,_uio JJBM ’AiAnonpuoo iBrajaqi i V

Using bromine gas to enhance mercury removal from flue gas of coal-fired power plants.

PubMed

Liu, Shou-Heng; Yan, Nai-Qiang; Liu, Zhao-Rong; Qu, Zan; Wang, H Paul; Chang, Shih-Ger; Miller, Charles

2007-02-15

Bromine gas was evaluated for converting elemental mercury (Hg0) to oxidized mercury, a form that can readily be captured by the existing air pollution control device. The gas-phase oxidation rates of Hg0 by Br2 decreased with increasing temperatures. SO2, CO, HCl, and H2O had insignificant effect, while NO exhibited a reverse course of effect on the Hg0 oxidation: promotion at low NO concentrations and inhibition at high NO concentrations. A reaction mechanism involving the formation of van der Waals clusters is proposed to accountfor NO's reverse effect. The apparent gas-phase oxidation rate constant, obtained under conditions simulating a flue gas without flyash, was 3.61 x 10(-17) cm3 x molecule(-1) x s(-1) at 410 K corresponding to a 50% Hg0 oxidation using 52 ppm Br2 in a reaction time of 15 s. Flyash in flue gas significantly promoted the oxidation of Hg0 by Br2, and the unburned carbon component played a major role in the promotion primarily through the rapid adsorption of Br2 which effectively removed Hg0 from the gas phase. At a typical flue gas temperature, SO2 slightly inhibited the flyash-induced Hg0 removal. Conversely, NO slightly promoted the flyash induced Hg0 removal by Br2. Norit Darco-Hg-LH and Darco-Hg powder activated carbons, which have been demonstrated in field tests, were inferred for estimating the flyash induced Hg0 oxidation by Br2. Approximately 60% of Hg0 is estimated to be oxidized with the addition of 0.4 ppm of gaseous Br2 into full scale power plant flue gas.

Critical Elements in Fly Ash from the Combustion of Bituminous Coal in Major Polish Power Plants

NASA Astrophysics Data System (ADS)

Bielowicz, Barbara; Botor, Dariusz; Misiak, Jacek; Wagner, Marian

2018-03-01

The concentration of critical elements, including such REE as Fe, Co, W, Zn, Cr, Ni, V, Mn, Ti, Ag, Ga, Ta, Sr, Li, and Cu, in the so-called fly ash obtained from the 9 Polish power plants and 1 thermal power station has been determined. The obtained values, compared with the global average concentration in bituminous coal ash and sedimentary rocks (Clarke values), have shown that the enrichment of fly ash in the specified elements takes place in only a few bituminous coal processing sites in Poland. The enrichment factor (EF) is only slightly higher (the same order of magnitude) than the Clarke values. The enrichment factor in relation to the Clarke value in the Earth's crust reached values above 10 in all of the examined ashes for the following elements: Cr, Ni, V, W, and, in some ash samples, also Cu and Zn. The obtained values are low, only slightly higher than the global average concentrations in sedimentary rocks and bituminous coal ashes. The ferromagnetic grains (microspheres) found in bituminous coal fly ashes seem to be the most economically prospective in recovery of selected critical elements. The microanalysis has shown that iron cenospheres and plerospheres in fly ash contain, in addition to enamel and iron oxides (magnetite and hematite), iron spinels enriched in Co, Cr, Cu, Mn, Ni, W, and Zn.

The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

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

Chan, Clara Sze-Yue

2015-07-02

Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Riflemore » aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles through the aquifer. Our work shows that microbial mineralization impacts in aquifers are dynamic, and that the fate and transport of biomineral-associated elements depend not only on geochemical conditions, but also physical pore-scale processes.« less

Petrogenesis of voluminous mid-Tertiary ignimbrites of the Sierra Madre Occidental, Chihuahua, Mexico

NASA Astrophysics Data System (ADS)

Cameron, Maryellen; Bagby, William C.; Cameron, Kenneth L.

1980-10-01

The mid-Tertiary ignimbrites of the Sierra Madre Occidental of western Mexico constitute the largest continuous rhyolitic province in the world. The rhyolites appear to represent part of a continental magmatic arc that was emplaced when an eastward-dipping subduction zone was located beneath western Mexico. In the Batopilas region of the northern Sierra Madre Occidental the mid-Tertiary Upper Volcanic sequence is composed predominantly of rhyolitic ignimbrites, but volumetrically minor lava flows as mafic as basaltic andesite are also present. The basaltic andesite to rhyolite series is calc-alkalic and contains ˜1% K2O at 60% SiO2. Trace element abundances of a typical ignimbrite with 73% SiO2 are Sr ˜ 225 ppm, Rb ˜130 ppm, Y ˜32 ppm, Th ˜12 ppm, Zr ˜200 ppm, and Nb ˜15 ppm. The entire series plots as coherent and continuous trends on variation diagrams involving major and trace elements, and the trends are distinct from those of geographicallyassociated rocks of other suites. We interpret these and other geochemical variations to indicate that the rocks are comagmatic. Mineral chemistry, Sr isotopic data, and REE modelling support this interpretation. Least squares calculations show that the major element variations are consistent with formation of the basaltic andesite to rhyolite series by crystal fractionation of observed phenocryst phases in approximate modal proportions. In addition, calculations modelling the behavior of Sr with the incompatible trace element Th favor a fractional crystallization origin over a crustal anatexis origin for the rock series. The fractionating minerals included plagioclase (> 50%), and lesser amounts of Fe-Ti oxides, pyroxenes, and/or hornblende. The voluminous ignimbrites represent no more than 20% of the original mass of a mantle-derived mafic parental magma.

Preliminary geochemical results of corals from the Puerto Morelos Reef, Southeastern Mexico

NASA Astrophysics Data System (ADS)

Marquez, N.; Kasper, J.

2012-04-01

A microprobe (MB), major, trace and rare earth elements (REE) analyses were carried out in three coral species Acropora palmata, Acropora cervicornis and Gorgonia ventalina at Puerto Morelos, Reef, Southeastern Mexico. This was done to assess the degree in which the corals developed under the different chemical-physical natural and artificial conditions. The corals were cut at the top and middle and based upon the observations by using the MB analysis, results showed the highest concentrations of Ag, Cu, Cr, Ni, S, Sr, Zn y Zr in Gorgonia Ventalina suggesting an impact coming from the industrial discharges and/or rusting of boats in the area. The results of X-ray fluorescence analysis for major and trace elements showed that the Fe , Sr and Zr increase their content in the skeletons of Acropora palmata y Gorgonia ventalina also asociated with the presence of human activity since the area is composed mainly by carbonate source sediments. The rare earth elements (REE) analysis showed that the negative anomaly of Ce suggests a well oxygenated, highly oxidative modern shallow waters, and high nutrients related to suspended matter for Acropora Palmata, Acropora cervicornis y Gorgonia ventalina, The Positive Eu anomaly in the corals are due to the development of the reef linked to the concentration of waters enriched in La. The Nd/Yb ratio indicates a shallow water development for the corals. This is also supported by the Ce/Ce* vs. Pr/Pr* ratios that indicate shallow marine waters in the development of the three corals studied (Ce*= 0.5La+0.5Pr and Pr*= 0.5Ce+0.5Nd). Enrichment of heavy rare earth elements (Gd-Lu) in the corals may be associated with high pH values and CO, OH- ions in the sea water.

Petrogenesis and tectonic association of rift-related basic Panjal dykes from the northern Indian plate, North-Western Pakistan: evidence of high-Ti basalts analogous to dykes from Tibet

NASA Astrophysics Data System (ADS)

Sajid, Muhammad; Andersen, Jens; Arif, Mohammad

2017-10-01

Rift related magmatism during Permian time in the northern margin of Indian plate is represented by basic dykes in several Himalayan terranes including north western Pakistan. The field relations, mineralogy and whole rock geochemistry of these basic dykes reveal significant textural, mineralogical and chemical variation between two major types (a) dolerite and (b) amphibolite. Intra-plate tectonic settings for both rock types have been interpreted on the basis of low Zr/Nb ratios (< 10), K/Ba ratios (20-40) and Hf-Ta-Th and FeO-MgO-Al2O3 discrimination diagrams. The compositional zoning in plagioclase and clinopyroxene, variation in olivine compositions and major elements oxide trends indicate a vital role of fractional crystallization in the evolution of dolerites, which also show depletion in rare earth elements (REEs) and other incompatible elements compared to the amphibolites. The equilibrium partial melting models from primitive mantle using Dy/Yb, La/Yb, Sm/Yb and La/Sm ratios show that amphibolite formed by smaller degrees (< 5%) of partial melting than the dolerites (< 10%). The trace elements ratios suggest the origination of dolerites from the subcontinental lithospheric mantle with some crustal contamination. This is consistent with a petrogenetic relationship with Panjal trap magmatism, reported from Kashmir and other parts of north western India. The amphibolites, in contrast, show affinity towards Ocean Island basalts (OIB) with a relatively deep asthenospheric mantle source and minimal crustal contribution and are geochemically similar to the High-Ti mafic dykes of southern Qiangtang, Tibet. These similarities combined with Permian tectonic restoration of Gondwana indicate the coeval origin for both dykes from distinct mantle source during continental rifting related to formation of the Neotethys Ocean.

Petrogenesis and tectonic association of rift-related basic Panjal dykes from the northern Indian plate, North-Western Pakistan: evidence of high-Ti basalts analogous to dykes from Tibet

NASA Astrophysics Data System (ADS)

Sajid, Muhammad; Andersen, Jens; Arif, Mohammad

2018-06-01

Rift related magmatism during Permian time in the northern margin of Indian plate is represented by basic dykes in several Himalayan terranes including north western Pakistan. The field relations, mineralogy and whole rock geochemistry of these basic dykes reveal significant textural, mineralogical and chemical variation between two major types (a) dolerite and (b) amphibolite. Intra-plate tectonic settings for both rock types have been interpreted on the basis of low Zr/Nb ratios (< 10), K/Ba ratios (20-40) and Hf-Ta-Th and FeO-MgO-Al2O3 discrimination diagrams. The compositional zoning in plagioclase and clinopyroxene, variation in olivine compositions and major elements oxide trends indicate a vital role of fractional crystallization in the evolution of dolerites, which also show depletion in rare earth elements (REEs) and other incompatible elements compared to the amphibolites. The equilibrium partial melting models from primitive mantle using Dy/Yb, La/Yb, Sm/Yb and La/Sm ratios show that amphibolite formed by smaller degrees (< 5%) of partial melting than the dolerites (< 10%). The trace elements ratios suggest the origination of dolerites from the subcontinental lithospheric mantle with some crustal contamination. This is consistent with a petrogenetic relationship with Panjal trap magmatism, reported from Kashmir and other parts of north western India. The amphibolites, in contrast, show affinity towards Ocean Island basalts (OIB) with a relatively deep asthenospheric mantle source and minimal crustal contribution and are geochemically similar to the High-Ti mafic dykes of southern Qiangtang, Tibet. These similarities combined with Permian tectonic restoration of Gondwana indicate the coeval origin for both dykes from distinct mantle source during continental rifting related to formation of the Neotethys Ocean.

Selective liquid chromatographic separation of yttrium from heavier rare earth elements using acetic acid as a novel eluent.

PubMed

Kifle, Dejene; Wibetoe, Grethe

2013-09-13

One of the major difficulties in the rare earth elements separation is purification of yttrium from heavy rare earth elements. Thus, an HPLC method using acetic acid as novel eluent was explored for selective separation of yttrium form the heavy rare earth elements. When acetic acid is used as a mobile phase yttrium eluted with the lighter lanthanides. This is contrary to its relative position amongst heavier lanthanides when eluents commonly used for separation of rare earth elements were employed. The shift in elution position of yttrium with acetic acid as eluent may reflect a relatively lower stability constant of the yttrium-AcOH complex (in the same order as for the lighter lanthanides) compared to the corresponding AcOH complexes with heavy lanthanides, enabling selective separation of yttrium from the latter. The method was successfully used for selective separation of yttrium in mixed rare earth sample containing about 80% of yttrium and about 20% of heavy rare earth oxides. Thus, the use of AcOH as eluent is an effective approach for separating and determining the trace amounts of heavy rare earth elements in large amounts of yttrium matrix. Separation was performed on C18 column by running appropriate elution programs. The effluent from the column was monitored with diode array detector at absorbance wavelength of 658nm after post column derivatization with Arsenazo III. Copyright © 2013 Elsevier B.V. All rights reserved.

Multiscale model of metal alloy oxidation at grain boundaries

NASA Astrophysics Data System (ADS)

Sushko, Maria L.; Alexandrov, Vitaly; Schreiber, Daniel K.; Rosso, Kevin M.; Bruemmer, Stephen M.

2015-06-01

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3-10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2-1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.

Multiscale model of metal alloy oxidation at grain boundaries

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

Sushko, Maria L., E-mail: maria.sushko@pnnl.gov; Alexandrov, Vitaly; Schreiber, Daniel K.

2015-06-07

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate thatmore » the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr{sub 2}O{sub 3}. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl{sub 2}O{sub 4}. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr{sub 2}O{sub 3} has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl{sub 2}O{sub 4} has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.« less

Distribution and origin of major and trace elements (particularly REE, U and Th) into labile and residual phases in an acid soil profile (Vosges Mountains, France)

NASA Astrophysics Data System (ADS)

Aubert, D.; Probst, A.; Stille, P.

2003-04-01

Physical and chemical weathering of rocks and minerals lead to soil formation and allow the removal of chemical elements from these systems to ground- or surface waters. But most of the time the determination of element concentrations in soils is not sufficient to estimate whether they are being accumulated or what is their ability to be released in the environment. Thus, the distribution and chemical binding for a given element is very important because it determines its mobility and potential bioavailability throughout a soil profile. Heavy metals and REE (Rare Earth Elements) are particularly of environmental concern because of their potential toxicity. For most of them, their chemical form strongly depends on the evolution of physico-chemical parameters like pH or redox conditions that will induce adsorption-desorption, complexation or co-precipitation phenomena in the material. The purpose of this study is to determine the distribution of several major and trace elements (especially REE, Th and U) in an acidic forested podzolic soil profile from the Vosges Mountains (France). To achieve this goal we use a 7 step sequential extraction procedure that allows determining precisely the origin and the behaviour of particular elements in the environment (Leleyter et al., 1999). In addition we performed leaching experiments using very dilute acetic and hydrochloric acid in order to establish the origin of REE in this soil. The results of the sequential extraction indicate that most of the metals, Th and U are mainly bound to Fe oxides. Organic matter appears also to be a great carrier of P, Ca, Fe and REE even if its content is very low in the deep horizons of the soil. Moreover, we show that in each soil horizon, middle REE (MREE) to heavy REE (HREE) are more labile than light REE (LREE). Leaching experiments using dilute acid solution further suggest that in the shallowest horizons REE largely derive from atmospheric deposition whereas at greater depth, weathering and particularly phosphate mineral weathering (apatite) is the main contributor to labile REE in the soil.

Igneous fractionation and subsolidus equilibration of diogenite meteorites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.

1993-01-01

Diogenites are coarse-grained orthopyroxenite breccias of remarkably uniform major element composition. Most diogenites contain homogeneous pyroxene fragments up to 5 cm across of Wo2En74Fs24 composition. Common minor constituents are chromite, olivine, trolite and metal, while silica, plagioclase, merrillite and diopside are trace phases. Diogenites are generally believed to be cumulates from the eucrite parent body, although their relationship with eucrites remains obscure. It has been suggested that some diogenites are residues after partial melting. I have performed EMPA and INAA for major, minor and trace elements on most diogenites, concentrating on coarse-grained mineral and lithic clasts in order to elucidate their igneous formation and subsequent metamorphic history. Major element compositions of diogenites are decoupled from minor and trace element compositions; the latter record an igneous fractionation sequence that is not preserved in the former. Low equilibration temperatures indicate that major element diffusion continued long after crystallization. Diffusion coefficients for trivalent and tetravalent elements in pyroxene are lower than those of divalent elements. Therefore, major element compositions of diogenites may represent means of unknown portions of a cumulate homogenized by diffusion, while minor and trace elements still yield information on their igneous history. The scale of major element equilibration is unknown, but is likely to be on the order of a few cm. Therefore, the diogenite precursors may have consisted largely of cm-sized, igneously zoned orthopyroxene grains, which were subsequently annealed during slow cooling, obliterating major element zoning but preserving minor and trace incompatible element zoning.

Major and trace-element analyses of acid mine waters in the Leviathan Mine drainage basin, California/Nevada; October, 1981 to October, 1982

USGS Publications Warehouse

Ball, J.W.; Nordstrom, D. Kirk

1985-01-01

Water issuing from the inactive Leviathan open-pit sulfur mine has caused serious degradation of the water quality in the Leviathan/Bryant Creek drainage basin which drains into the East Fork of the Carson River. As part of a pollution abatement project of the California Regional Water Quality Control Board, the U.S. Geological Survey collected hydrologic and water quality data for the basin during 1981-82. During this period a comprehensive sampling survey was completed to provide information on trace metal attenuation during downstream transport and to provide data for interpreting geochemical processes. This report presents the analytical results from this sampling survey. Sixty-seven water samples were filtered and preserved on-site at 45 locations and at 3 different times. Temperature, discharge, pH, and Eh and specific conductance were measured on-site. Concentrations of 37 major and trace constituents were determined later in the laboratory on preserved samples. The quality of the analyses was checked by using two or more techniques to determine the concentrations including d.c.-argon plasma emission spectrometry (DCP), flame and flameless atomic absorption spectrophotometry, UV-visible spectrophotometry, hydride-generation atomic absorption spectrophotometry and ion chromatography. Additional quality control was obtained by comparing measured to calculated conductance, comparing measured to calculated Eh (from Fe-2 +/Fe-3+ determinations), charge balance calculations and mass balance calculations for conservative constituents at confluence points. Leviathan acid mine waters contain mg/L concentrations of As, Cr, Co, Cu, Mn, Ni, T1, V and Zn, and hundreds to thousands of mg/L concentrations of Al, Fe, and sulfate at pH values as low as 1.8. Other elements including Ba, B, Be, Bi, Cd , Mo, Sb, Se and Te are elevated above normal background concentrations and fall in the microgram/L range. The chemical and 34 S/32 S isotopic analyses demonstrate that these acid waters are derived from pyrite oxidation and not from the oxidation of elemental sulfur. (Author 's abstract)

Spectroscopic geochemical study of vanadiferous marine sediments of the Gibellini claims, southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Böhlke, J.K.; Radtke, A.S.; Heropoulos, Chris; Lamothe, P.J.

1981-01-01

Samples of cuttings from three drill holes in the Gibellini claims were analyzed by emission spectroscopic techniques for a large suite of major and trace elements. Unoxidized siliceous "black shale" from drill hole NGA 7 is strongly enriched in Cd, Mo, Sb, Se, V, and Zn, and also contains relatively high concentrations of As, Ba, Cu, Ni, and Tl compared with nonmetalliferous shales. Analyses of 103 samples plotted against depth in drill holes NGA, NG31, and NGA7, and selected XRD data, show the following: 1. Groups of elements with distinct distribution patterns define most of major mineralogic components of the rocks. The "normal shale" component, which includes several detrital and authigenic phases, is indicated by covariations among Ti, Al, Fe, Na, Mg, K, B, Be, Co, Cr, Ga, La, Sc, Sr, and Zr. The shale component is diluted by varying amounts of the following minerals (and associated elements): silica (Si); dolomite (Mg, Ca, Mn, Sr); apatite (Ca, Be, Cr, La, Sr, Y); barite (Ba, Sr); sphalerite (Zn, Cd, Fe?); smithsonite (Cd, Co, Mn, Ni, Zn); bianchite (Cd, Ni, Zn) ; and bokite (V). Pyrite, gypsum, and jarosite were also identified.2. The highly siliceous kerogenous metalliferous Gibellini facies is underlain by argillaceous and (or) dolomitic rocks. The transition zone deduced from the chemical data is not well defined in all instances, but probably represents the bottom of the black shale deposit. 3. Oxidation has reached to variable depths up to at least 150 ft, and has caused profound changes in the distributions of the enriched metals. Molybdenum, Se, and V have been partially removed from the upper parts of the sections and are concentrated near or slightly above the base of the Gibellini facies. Cadmium, Ni, and Zn have been strongly leached and now occur at or below the base of the Gibellini facies. The variable depth of oxidation, the redistribution and separation of the metals, and the complex mineralogy of the deposit may make development of the claim complicated.

TRACE ELEMENT ANALYSES OF URANIUM MATERIALS

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

Beals, D; Charles Shick, C

The Savannah River National Laboratory (SRNL) has developed an analytical method to measure many trace elements in a variety of uranium materials at the high part-per-billion (ppb) to low part-per-million (ppm) levels using matrix removal and analysis by quadrapole ICP-MS. Over 35 elements were measured in uranium oxides, acetate, ore and metal. Replicate analyses of samples did provide precise results however none of the materials was certified for trace element content thus no measure of the accuracy could be made. The DOE New Brunswick Laboratory (NBL) does provide a Certified Reference Material (CRM) that has provisional values for a seriesmore » of trace elements. The NBL CRM were purchased and analyzed to determine the accuracy of the method for the analysis of trace elements in uranium oxide. These results are presented and discussed in the following paper.« less

Effect of processing conditions on microstructural features in Mn–Si sintered steels

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

Oro, Raquel, E-mail: raqueld@chalmers.se; Hryha, Eduard, E-mail: hryha@chalmers.se; Campos, Mónica, E-mail: campos@ing.uc3m.es

2014-09-15

Sintering of steels containing oxidation sensitive elements is possible if such elements are alloyed with others which present lower affinity for oxygen. In this work, a master alloy powder containing Fe–Mn–Si–C, specifically designed to create a liquid phase during sintering, has been used for such purpose. The effect of processing conditions such as sintering temperature and atmosphere was studied with the aim of describing the microstructural evolution as well as the morphology and distribution of oxides in the sintered material, evaluating the potential detrimental effect of such oxides on mechanical properties. Chemical analyses, metallography and fractography studies combined with X-raymore » photoelectron spectroscopy analyses on the fracture surfaces were used to reveal the main mechanism of fracture and their correlation with the chemical composition of the different fracture surfaces. The results indicate that the main mechanism of failure in these steels is brittle fracture in the surrounding of the original master alloy particles due to degradation of grain boundaries by the presence of oxide inclusions. Mn–Si oxide inclusions were observed on intergranular decohesive facets. The use of reducing atmospheres and high sintering temperatures reduces the amount and size of such oxide inclusions. Besides, high heating and cooling rates reduce significantly the final oxygen content in the sintered material. A model for microstructure development and oxide evolution during different stages of sintering is proposed, considering the fact that when the master alloy melts, the liquid formed can dissolve some of the oxides as well as the surface of the surrounding iron base particles. - Highlights: • Oxide distribution in steels containing oxidation-sensitive elements • Mn, Si introduced in a master alloy powder, mixed with a base iron powder • Selective oxidation of Mn and Si on iron grain boundaries • Decohesive fracture caused by degradation of grain boundaries by oxide inclusions • Reducing agents efficient at low temperatures critical for avoiding oxide inclusions.« less

Geochemistry of the Nsuta Mn deposit in Ghana: Implications for the Paleoproterozoic atmosphere and ocean chemistry

NASA Astrophysics Data System (ADS)

Goto, K. T.; Ito, T.; Suzuki, K.; Kashiwabara, T.; Takaya, Y.; Shimoda, G.; Nozaki, T.; Kiyokawa, S.; Tetteh, G. M.; Nyame, F. K.

2013-12-01

Oxygenation of the atmosphere and oceans has influenced the evolution of ocean chemistry and diversification of early life. A number of large manganese (Mn) deposits are distributed in the Paleoproterozoic sedimentary successions that were formed during the great oxidation event (GOE) around 2.4-2.2 Ga (Meynard, 2010). Due to the high redox potential of Mn, occurrences of Mn deposits have been regarded as important evidence for a highly oxidized environment during the Paleoproterozoic (Kirschvink et al., 2000). Furthermore, because Mn oxides strongly adsorb various elements, including bioessential elements such as Mo, formation of large Mn deposits may have affected the seawater chemical composition and ecology during the Paleoproterozoic. However, the genesis of each Mn deposit is poorly constrained, and the relationships among the formation of Mn deposits, the evolution of atmospheric and ocean chemistry, and the diversification of early life are still ambiguous. In this study, we report the Re-Os isotope compositions, rare earth element (REE) compositions, and abundance of manganophile elements in the Mn carbonate ore and host sedimentary rock samples collected from the Nsuta Mn deposit of the Birimian Supergroup, Ghana. The Nsuta deposit is one of the largest Paleoproterozoic Mn deposits, although its genesis remains controversial (Melcher et al., 1995; Mucke et al., 1999). The composite Re-Os isochron age (2149 × 130 Ma) of the Mn carbonate and sedimentary rock samples was consistent with the depositional age of the sedimentary rocks (~2.2 Ga) presumed from the U-Pb zircon age of volcanic rocks (Hirdes and Davis, 1998), suggesting that the timing of Mn ore deposition was almost equivalent to the host rock sedimentation. The PAAS-normalized REE pattern showed a positive Eu anomaly in all samples and a positive Ce anomaly only in the Mn carbonate ore. These REE patterns indicate the possible contribution of Eu-enriched fluids derived from hydrothermal activity and Ce enrichment due to the oxidation of Ce(III) by Mn(IV) during an ore formation. Among the manganophile elements, merely Mo is enriched in the Mn carbonate ore compared with the host sedimentary rocks. The profile of manganophile elements was similar to that of modern hydrothermal Mn oxide (Kuhn et al., 2003), although the exact Mo concentration was much lower. These geochemical lines of evidence provide the following plausible genetic model for the Nsuta deposits: (1) Mn(II) was derived from hydrothermal vents, (2) Mn(II) was oxidized to Mn(IV) oxide by the oxygenated seawater, (3) the precipitation of Mn oxide is almost concurrent with the deposition of the host sedimentary rocks, (4) Mn oxide was diagenetically transformed to be a Mn carbonate ore. The geochemical features of the Nsuta deposits suggest that, as in the present oxic oceans, Mn oxide was a potential sink for several trace elements in the Paleoproterozoic oceans. The low-Mo concentration in the Mn carbonate ore probably reflects the large difference between the chemical compositions of Paleoproterozoic and present seawater, implying the prevalence of reduced marine conditions even during the GOE (Scott et al., 2008)

Quantification of rare earth elements using laser-induced breakdown spectroscopy

DOE PAGES

Martin, Madhavi; Martin, Rodger C.; Allman, Steve; ...

2015-10-21

In this paper, a study of the optical emission as a function of concentration of laser-ablated yttrium (Y) and of six rare earth elements, europium (Eu), gadolinium (Gd), lanthanum (La), praseodymium (Pr), neodymium (Nd), and samarium (Sm), has been evaluated using the laser-induced breakdown spectroscopy (LIBS) technique. Statistical methodology using multivariate analysis has been used to obtain the sampling errors, coefficient of regression, calibration, and cross-validation of measurements as they relate to the LIBS analysis in graphite-matrix pellets that were doped with elements at several concentrations. Each element (in oxide form) was mixed in the graphite matrix in percentages rangingmore » from 1% to 50% by weight and the LIBS spectra obtained for each composition as well as for pure oxide samples. Finally, a single pellet was mixed with all the elements in equal oxide masses to determine if we can identify the elemental peaks in a mixed pellet. This dataset is relevant for future application to studies of fission product content and distribution in irradiated nuclear fuels. These results demonstrate that LIBS technique is inherently well suited for the future challenge of in situ analysis of nuclear materials. Finally, these studies also show that LIBS spectral analysis using statistical methodology can provide quantitative results and suggest an approach in future to the far more challenging multielemental analysis of ~ 20 primary elements in high-burnup nuclear reactor fuel.« less

[The bonding mechanisms of base metals for metal-ceramic crown microstructure analysis of bonding agent and gold bond between porcelain and base metals].

PubMed

Wang, C C; Hsu, C S

1996-06-01

The use of base metal alloys for porcelain fused to a metal crown and bridges has increased recently because of lower price, high hardness, high tensile strength and high elastic modulus. The addition of beryllium to base metal alloys increased fluidity and improved casting fitness. Beryllium also controlled surface oxidation and bonding strength. The bonding agent and gold bonding agent also affected the bonding strength between porcelain and metal alloys. Four commercially available ceramic base alloys were studied (two alloys contained beryllium element, another two did not). The purpose of this investigation was to study the microstructure between porcelain matrix, bonding agent and alloy matrix interfaces. A scanning electron micro-probe analyzer and energy dispersive X-ray spectroscopy (EDXS) were used to study the distribution of elements (Ni, Cr, Mo, Cu, O, Si, Sn, Al) in four base alloys. The following results were obtained: 1. The thickness of the oxidized layer of Rexillium III alloy and Unitbond alloy (contained beryllium) was thinner than Unibond alloy and Wiron 88 alloy (no beryllium). 2. The thickness of the oxidized layer of alloys in air (10 minutes and 30 minutes) was thinner in Unitbond (2.45 microns and 3.80 microns) and thicker in Wiron 88 (4.39 microns and 5.96 microns). 3. The thickness of the oxidized layer occurring for a duration of ten minutes (in vaccum) showed that the Rexillium III alloy was the thinnest (1.93 microns), and Wiron 88 alloy was the thickest (2.30 microns). But in thirty minutes (vacuum), Unitbond alloy was the thinnest (3.37 microns), and Wiron 88 alloy was the thickest (5.51 microns). 4. The intensity of Cr elements was increased obviously near the interface between Unitbond alloy, Wiron 88 alloy (no beryllium) and oxidized layer, but the intensity of Ni and Mo elements was slightly increased. The intensity of Cr element was not increased markedly between Rexillium III alloy, Unitbond alloy (beryllium) and oxidized layer. 5. A white-grayish oxidized layer appeared at the metal-ceramic interfaces but the thickness of oxidized layer was not obviously different. 6. The use of bonding agent at metal-ceramic interface leads to the deposition of many Sn elements at about 40 microns range within the porcelain surface. 7. Second interaction phases at the porcelain layer appeared when gold bonding agent was used, and a 50-100 microns microleakage occurred at the metal-ceramic interface.

Role of Nitric Oxide in the Regulation of Renin and Vasopressin Secretion

NASA Technical Reports Server (NTRS)

Reid, Ian A.

1994-01-01

Research during recent years has established nitric oxide as a unique signaling molecule that plays important roles in the regulation of the cardiovascular, nervous, immune, and other systems. Nitric oxide has also been implicated in the control of the secretion of hormones by the pancreas, hypothalamus, and anterior pituitary gland, and evidence is accumulating that it contributes to the regulation of the secretion of renin and vasopressin, hormones that play key roles in the control of sodium and water balance. Several lines of evidence have implicated nitric oxide in the control of renin secretion. The enzyme nitric oxide synthase is present in vascular and tubular elements of the kidney, particularly in cells of the macula densa, a structure that plays an important role in the control of renin secretion. Guanylyl cyclase, a major target for nitric oxide, is also present in the kidney. Drugs that inhibit nitric oxide synthesis generally suppress renin release in vivo and in vitro, suggesting a stimulatory role for the L-arginine/nitric oxide pathway in the control of renin secretion. Under some conditions, however, blockade of nitric oxide synthesis increases renin secretion. Recent studies indicate that nitric oxide not only contributes to the regulation of basal renin secretion, but also participates in the renin secretory responses to activation of the renal baroreceptor, macula densa, and beta adrenoceptor mechanisms that regulate renin secretion. Histochemical and immunocytochemical studies have revealed the presence of nitric oxide synthase in the supraoptic and paraventricular nuclei of the hypothalamus and in the posterior pituitary gland. Colocalization of nitric oxide synthase and vasopressin has been demonstrated in some hypothalamic neurons. Nitric oxide synthase activity in the hypothalamus and pituitary is increased by maneuvers known to stimulate vasopressin secretion, including salt loading and dehydration, Administration of L-arginine and nitric oxide donors in vitro and in vivo has variable effects on vasopressin secretion, but the most common one is inhibition. Blockade of nitric oxide synthesis has been reported to increase vasopressin secretion, but again variable results have been obtained. An attractive working hypothesis is that nitric oxide serves a neuromodulatory role as an inhibitor of vasopressin secretion.

Linking trace element variations with macronutrients and major cations in marine mussels Mytilus edulis and Perna viridis.

PubMed

Liu, Fengjie; Wang, Wen-Xiong

2015-09-01

Marine mussels have long been used as biomonitors of contamination of trace elements, but little is known about whether variation in tissue trace elements is significantly associated with those of macronutrients and major cations. The authors examined the variability of macronutrients and major cations and their potential relationships with bioaccumulation of trace elements. The authors analyzed the concentrations of macronutrients (C, N, P, S), major cations (Na, Mg, K, Ca), and trace elements (Al, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Pb) in the whole soft tissues of marine mussels Mytilus edulis and Perna viridis collected globally from 21 sites. The results showed that 12% to 84% of the variances in the trace elements was associated with major cations, and the tissue concentration of major cations such as Na and Mg in mussels was a good proxy for ambient seawater concentrations of the major cations. Specifically, bioaccumulation of most of the trace elements was significantly associated with major cations, and the relationships of major cations with trace cations and trace oxyanions were totally opposite. Furthermore, 14% to 69% of the variances in the trace elements were significantly associated with macronutrients. Notably, more than half of the variance in the tissue concentrations of As, Cd, V, Ba, and Pb was explained by the variance in macronutrients in one or both species. Because the tissue macronutrient concentrations were strongly associated with animal growth and reproduction, the observed coupling relationships indicated that these biological processes strongly influenced the bioaccumulation of some trace elements. The present study indicated that simultaneous quantification of macronutrients and major cations with trace elements can improve the interpretation of biomonitoring data. © 2015 SETAC.

Investigation of the Effect of Alloying Elements and Water Vapor Contents on the Oxidation and Decarburization of Transformation-Induced Plasticity Steels

NASA Astrophysics Data System (ADS)

Zhang, Z. T.; Sohn, I. R.; Pettit, F. S.; Meier, G. H.; Sridhar, S.

2009-08-01

The present research deals with an investigation of the effect of alloying element additions (Si, P, and Sb) and water vapor content ({{{{{P}}_{{{{H}}_{ 2} {{O}}}} } {{{P}}_{{{{H}}_{ 2} }} }}} = 0.01{{ to }}0.13}) on the oxidation and decarburization behavior of transformation-induced plasticity (TRIP) steels in a gas mixture of 95 vol pct argon and 5 vol pct hydrogen/steam, by thermogravimetry (TG). The oxidation proceeds primarily as an internal oxidation front in the TRIP steels, but a thin external scale on the order of a micrometer thickness exists and is comprised primarily of fayalite ((Mn,Fe)2SiO4) and ((MnO) x (FeO)1- x . The oxidation products are distributed near the surface and along grain boundaries. A comparison between calculated and measured oxidation curves indicated that the oxidation and decarburization are independent. The results for TRIP steels, both with and without an Sb addition, indicate that increasing Si and P contents accelerate, whereas Sb addition suppresses, both decarburization and oxidation rates. Water vapor content has no obvious effect on decarburization but has a pronounced effect on oxidation, and decreasing water vapor content decreases the oxidation rates.

Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

USGS Publications Warehouse

Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

2009-01-01

The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated with the fire had an OR of 1.091 (??0.003). Fire appears to be a major factor driving the soil C pool to higher oxidation states and lower OR values. Episodic fluxes caused by disturbances like fire may have substantially different ORs from ecosystem respiration fluxes and therefore should be better quantified to reduce uncertainties associated with our understanding of the global atmospheric carbon budget. Copyright 2009 by the American Geophysical Union.

Contaminants from Cretaceous Black Shale Part 1: Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

USGS Publications Warehouse

Tuttle, Michele L.W.; Fahy, Juli W.; Elliott, John G.; Grauch, Richard I.; Stillings, Lisa L.

2013-01-01

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na2SO4) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m−2) enriches soil moisture in Na and residual SO4. Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Catalysts for the selective oxidation of hydrogen sulfide to sulfur

DOEpatents

Srinivas, Girish; Bai, Chuansheng

2000-08-08

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

EXTRACTION AND QUANTITATIVE ANALYSIS OF ELEMENTAL SULFUR FROM SULFIDE MINERAL SURFACES BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY. (R826189)

EPA Science Inventory

A simple method for the quantitative determination of elemental sulfur on oxidized sulfide minerals is described. Extraction of elemental sulfur in perchloroethylene and subsequent analysis with high-performance liquid chromatography were used to ascertain the total elemental ...

Thiosulfate oxidation by Thiomicrospira thermophila: metabolic flexibility in response to ambient geochemistry

PubMed Central

Houghton, J.L.; Foustoukos, D.; Flynn, T.M.; Vetriani, C.; Bradley, A.S.; Fike, D.A.

2017-01-01

Summary Previous studies of the stoichiometry of thiosulfate oxidation by colorless sulfur bacteria have failed to demonstrate mass balance of sulfur, indicating that unidentified oxidized products must be present. Here we present reaction stoichiometry and kinetics under variable pH conditions during the growth of Thiomicrospira thermophila strain EPR85, isolated from diffuse hydrothermal fluids at the East Pacific Rise. At pH 8.0, thiosulfate is stoichiometrically converted to sulfate. At lower pH, the products of thiosulfate oxidation are extracellular elemental sulfur and sulfate. We were able to replicate previous experiments and identify the missing sulfur as tetrathionate, consistent with previous reports of the activity of thiosulfate dehydrogenase. Tetrathionate was formed under slightly acidic conditions. Genomic DNA from T. thermophila strain EPR85 contains genes homologous to those in the Sox pathway (soxAXYZBCDL), as well as rhodanese and thiosulfate dehydrogenase. No other sulfur oxidizing bacteria containing sox(CD)2 genes have been reported to produce extracellular elemental sulfur. If the apparent modified Sox pathway we observe in T. thermophila is present in marine Thiobacillus and Thiomicrospira species, production of extracellular elemental sulfur may be biogeochemically important in marine sulfur cycling. PMID:26914243

Thiosulfate oxidation by Thiomicrospira thermophila: Metabolic flexibility in response to ambient geochemistry

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

Houghton, J. L.; Foustoukos, D. I.; Flynn, T. M.

Previous studies of the stoichiometry of thiosulfate oxidation by colorless sulfur bacteria have failed to demonstrate mass balance of sulfur, indicating that unidentified oxidized products must be present. Here the reaction stoichiometry and kinetics under variable pH conditions during the growth of Thiomicrospira thermophila strain EPR85, isolated from diffuse hydrothermal fluids at the East Pacific Rise, is presented. At pH 8.0, thiosulfate was stoichiometrically converted to sulfate. At lower pH, the products of thiosulfate oxidation were extracellular elemental sulfur and sulfate. Here, we were able to replicate previous experiments and identify the missing sulfur as tetrathionate, consistent with previous reportsmore » of the activity of thiosulfate dehydrogenase. Tetrathionate was formed under slightly acidic conditions. Genomic DNA from T. thermophila strain EPR85 contains genes homologous to those in the Sox pathway ( soxAXYZBCDL), as well as rhodanese and thiosulfate dehydrogenase. No other sulfur oxidizing bacteria containing sox(CD)2 genes have been reported to produce extracellular elemental sulfur. If the apparent modified Sox pathway we observed in T. thermophila is present in marine Thiobacillus and Thiomicrospira species, production of extracellular elemental sulfur may be biogeochemically important in marine sulfur cycling.« less

Thiosulfate oxidation by Thiomicrospira thermophila: Metabolic flexibility in response to ambient geochemistry

DOE PAGES

Houghton, J. L.; Foustoukos, D. I.; Flynn, T. M.; ...

2016-03-21

Previous studies of the stoichiometry of thiosulfate oxidation by colorless sulfur bacteria have failed to demonstrate mass balance of sulfur, indicating that unidentified oxidized products must be present. Here the reaction stoichiometry and kinetics under variable pH conditions during the growth of Thiomicrospira thermophila strain EPR85, isolated from diffuse hydrothermal fluids at the East Pacific Rise, is presented. At pH 8.0, thiosulfate was stoichiometrically converted to sulfate. At lower pH, the products of thiosulfate oxidation were extracellular elemental sulfur and sulfate. Here, we were able to replicate previous experiments and identify the missing sulfur as tetrathionate, consistent with previous reportsmore » of the activity of thiosulfate dehydrogenase. Tetrathionate was formed under slightly acidic conditions. Genomic DNA from T. thermophila strain EPR85 contains genes homologous to those in the Sox pathway ( soxAXYZBCDL), as well as rhodanese and thiosulfate dehydrogenase. No other sulfur oxidizing bacteria containing sox(CD)2 genes have been reported to produce extracellular elemental sulfur. If the apparent modified Sox pathway we observed in T. thermophila is present in marine Thiobacillus and Thiomicrospira species, production of extracellular elemental sulfur may be biogeochemically important in marine sulfur cycling.« less

Grain-size distribution and selected major and trace element concentrations in bed-sediment cores from the Lower Granite Reservoir and Snake and Clearwater Rivers, eastern Washington and northern Idaho, 2010

USGS Publications Warehouse

Braun, Christopher L.; Wilson, Jennifer T.; Van Metre, Peter C.; Weakland, Rhonda J.; Fosness, Ryan L.; Williams, Marshall L.

2012-01-01

Fifty subsamples from 15 cores were analyzed for major and trace elements. Concentrations of trace elements were low, with respect to sediment quality guidelines, in most cores. Typically, major and trace element concentrations were lower in the subsamples collected from the Snake River compared to those collected from the Clearwater River, the confluence of the Snake and Clearwater Rivers, and Lower Granite Reservoir. Generally, lower concentrations of major and trace elements were associated with coarser sediments (larger than 0.0625 millimeter) and higher concentrations of major and trace elements were associated with finer sediments (smaller than 0.0625 millimeter).

The Concept of Oxidation States in Metal Complexes

ERIC Educational Resources Information Center

Steinborn, Dirk

2004-01-01

The concepts of oxidation numbers when applied means electrons that are shared between atoms in molecules are assigned to a specific atom. Oxidation numbers are assigned from the Lewis structure of a molecule, with knowledge of the electronegativities of elements.

ANSYS duplicate finite-element checker routine

NASA Technical Reports Server (NTRS)

Ortega, R.

1995-01-01

An ANSYS finite-element code routine to check for duplicated elements within the volume of a three-dimensional (3D) finite-element mesh was developed. The routine developed is used for checking floating elements within a mesh, identically duplicated elements, and intersecting elements with a common face. A space shuttle main engine alternate turbopump development high pressure oxidizer turbopump finite-element model check using the developed subroutine is discussed. Finally, recommendations are provided for duplicate element checking of 3D finite-element models.

Modern rather than Mesoarchaean oxidative weathering responsible for the heavy stable Cr isotopic signatures of the 2.95 Ga old Ijzermijn iron formation (South Africa)

NASA Astrophysics Data System (ADS)

Albut, Gülüm; Babechuk, Michael G.; Kleinhanns, Ilka C.; Benger, Manuela; Beukes, Nicolas J.; Steinhilber, Bernd; Smith, Albertus J. B.; Kruger, Stephanus J.; Schoenberg, Ronny

2018-05-01

Previously reported stable Cr isotopic fractionation in Archaean paleosols and iron formations (IFs) have been interpreted as a signature of oxidative weathering of Cr(III) to Cr(VI) in soils, and delivery of isotopically heavy Cr(VI) into the oceans. One of the oldest reported fingerprints of this process is isotopically heavy Cr preserved in the 2.95 Ga old Ijzermijn IF, Sinqeni Formation of the Mozaan Group (Pongola Supergroup), South Africa and could suggest that atmospheric free oxygen was present ca. 600 million years earlier than the Great Oxidation Event (GOE). However, fractionated stable Cr isotopic signatures have only been found to date in surface outcrop samples of the White Mfolozi Inlier exposed along the White Mfolozi River Gorge. In this study, the latter outcrop was resampled along with two drill cores of the Ijzermijn IF and a drill core of the Scotts Hill IF to represent multiple exposures of Mozaan Group IFs with different states of preservation. A detailed geochemical comparison on bulk samples of different units was undertaken using stable Cr isotopes coupled with trace and major elements. Outcrop iron-rich mudstones (Fe - lutites) show very low LOI [wt] %, and very low Fe(II)/Fetot ratios, and lower Ca and Mg relative to equivalent facies in drill cores, indicating the effects that oxidative recent surface weathering had on Fe/Mn-rich carbonate minerals of the IF. Overall rare earth element and yttrium (REE + Y) mixing models agree well with previous studies, confirming that they were minimally disturbed by weathering and are consistent with a high magnitude of continental solutes delivered in a near-shore depositional environment, with a minor contribution of hydrothermally derived fluids that upwelled into shallower depositional setting. Importantly, all drill core samples of this study revealed δ53/52Cr values within the igneous inventory, despite variable amounts of detrital Cr input that includes nearly detritus-free, chert/jasper-rich units. By contrast, a specific group of Fe-lutite samples near the base of White Mfolozi River outcrop bear fractionated Cr isotopic signatures with δ53/52Cr values up to 0.418‰. These outcrop samples also display unusually high U/Th ratios (max. 12.6) as well as enrichments of other elements (W, Tl, As, MREE) that far exceed that observed in correlative drill core units. These observations together with the lack of Cr isotopic fractionation in drill core samples lead us to propose that the heavy δ53/52Cr values of Fe-lutites from outcrop Ijzermijn IF samples reported here and in a previous study are the product of modern oxidative weathering rather than an indicator for Mesoarchaean oxidative weathering at ca. 2.95 Ga.

Acid pre-treatment method for in situ ore leaching

DOEpatents

Mallon, R.G.; Braun, R.L.

1975-10-28

An acid leaching method is described for the recovery of a desired element from a subterranean rubblized body of primary ore containing the element and also having associated therewith a carbonate mineral wherein the rubblized ore body is flooded with an aqueous acidic solution in order to release carbon dioxide from the associated carbonate mineral. After a substantial portion of the available carbon dioxide is released and removed from the ore body, as by venting to the atmosphere, an oxidizing gas is introduced into the flooded, rubblized ore to oxidize the ore and form an acid leach solution effective in the presence of the dissolved oxidizing gas to dissolve the ore and cause the desired element to go into solution. The leach solution is then circulated to the surface where the metal values are recovered therefrom.

Mercury Emission Measurement in Coal-Fired Boilers by Continuous Mercury Monitor and Ontario Hydro Method

NASA Astrophysics Data System (ADS)

Zhu, Yanqun; Zhou, Jinsong; He, Sheng; Cai, Xiaoshu; Hu, Changxin; Zheng, Jianming; Zhang, Le; Luo, Zhongyang; Cen, Kefa

2007-06-01

The mercury emission control approach attaches more importance. The accurate measurement of mercury speciation is a first step. Because OH method (accepted method) can't provide the real-time data and 2-week time for results attained, it's high time to seek on line mercury continuous emission monitors(Hg-CEM). Firstly, the gaseous elemental and oxidized mercury were conducted to measure using OH and CEM method under normal operation conditions of PC boiler after ESP, the results between two methods show good consistency. Secondly, through ESP, gaseous oxidized mercury decrease a little and particulate mercury reduce a little bit, but the elemental mercury is just the opposite. Besides, the WFGD system achieved to gaseous oxidized mercury removal of 53.4%, gaseous overall mercury and elemental mercury are 37.1% and 22.1%, respectively.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, V.K.; Deevi, S.C.; Fleischhauer, G.S.; Hajaligol, M.R.; Lilly, A.C. Jr.

1997-04-15

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, {<=}1% Cr and either {>=}0.05% Zr or ZrO{sub 2} stringers extending perpendicular to an exposed surface of the heating element or {>=}0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, {<=}2% Ti, {<=}2% Mo, {<=}1% Zr, {<=}1% C, {<=}0.1% B, {<=}30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, {<=}1% rare earth metal, {<=}1% oxygen, {<=}3% Cu, balance Fe. 64 figs.

Volatilization of oxides during oxidation of some superalloys at 1200 C

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1977-01-01

Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541 chromium was found to be the main metallic element in the oxide scales.

Volatilization of oxides during oxidation of some superalloys at 1200 C

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1977-01-01

Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541, chromium was found to be the main metallic element in the oxide scales.

Evidence that ferritin is associated with light production in the mucus of the marine worm Chaetopterus

PubMed Central

Rawat, Renu; Deheyn, Dimitri D.

2016-01-01

The blue glow of the mucus from Chaetopterus involves a photoprotein, iron and flavins. Identity and respective role of these components remain, however, largely unresolved today, likely because of viscosity issues and inhibition of this system by oxidizers conventionally used to track bioluminescence activity. Here, we used gentle centrifugation to obtain a mucus supernatant showing no inhibition to oxidizers, allowing for further analysis. We applied conventional chromatographic techniques to isolate major proteins associated with light emission. Luminescence ability of elutriate fractions was tested with hydrogen peroxide to track photoprotein and/or protein-bound chromophore. Fractions producing light contained few major proteins, one with similarity to ferritin. Addition to the mucus of elements with inhibitory/potentiary effect on ferritin ferroxidase activity induced corresponding changes in light production, emphasizing the possible role of ferritin in the worm bioluminescence. DNA of the protein was cloned, sequenced, and expressed, confirming its identity to a Chaetopterus Ferritin (ChF). Both ferric and ferrous iron were found in the mucus, indicating the occurrence of both oxidase and reductase activity. Biochemical analysis showed ChF has strong ferroxidase activity, which could be a source of biological iron and catalytic energy for the worm bioluminescence when coupled to a reduction process with flavins. PMID:27830745

Ubiquinol-10 supplementation activates mitochondria functions to decelerate senescence in senescence-accelerated mice.

PubMed

Tian, Geng; Sawashita, Jinko; Kubo, Hiroshi; Nishio, Shin-ya; Hashimoto, Shigenari; Suzuki, Nobuyoshi; Yoshimura, Hidekane; Tsuruoka, Mineko; Wang, Yaoyong; Liu, Yingye; Luo, Hongming; Xu, Zhe; Mori, Masayuki; Kitano, Mitsuaki; Hosoe, Kazunori; Takeda, Toshio; Usami, Shin-ichi; Higuchi, Keiichi

2014-06-01

The present study was conducted to define the relationship between the anti-aging effect of ubiquinol-10 supplementation and mitochondrial activation in senescence-accelerated mouse prone 1 (SAMP1) mice. Here, we report that dietary supplementation with ubiquinol-10 prevents age-related decreases in the expression of sirtuin gene family members, which results in the activation of peroxisome proliferator-activated receptor γ coactivator 1α (PGC-1α), a major factor that controls mitochondrial biogenesis and respiration, as well as superoxide dismutase 2 (SOD2) and isocitrate dehydrogenase 2 (IDH2), which are major mitochondrial antioxidant enzymes. Ubiquinol-10 supplementation can also increase mitochondrial complex I activity and decrease levels of oxidative stress markers, including protein carbonyls, apurinic/apyrimidinic sites, malondialdehydes, and increase the reduced glutathione/oxidized glutathione ratio. Furthermore, ubiquinol-10 may activate Sirt1 and PGC-1α by increasing cyclic adenosine monophosphate (cAMP) levels that, in turn, activate cAMP response element-binding protein (CREB) and AMP-activated protein kinase (AMPK). These results show that ubiquinol-10 may enhance mitochondrial activity by increasing levels of SIRT1, PGC-1α, and SIRT3 that slow the rate of age-related hearing loss and protect against the progression of aging and symptoms of age-related diseases.

Deconvolution of trace element (As, Cr, Mo, Th, U) sources and pathways to surface waters of a gold mining-influenced watershed.

PubMed

Grosbois, C; Schäfer, J; Bril, H; Blanc, G; Bossy, A

2009-03-01

The Upper Isle River (SW France) drains the second most productive gold-mining district of France. A high resolution survey during one hydrological year of As, Cl(-), Cr, Fe, Mn, Mo, SO(4)(2-), Th and U dissolved concentrations in surface water aimed to better understand pathways of trace element export to the river system downstream from the mining district. Dissolved concentrations of As (up to 35000 ng/L) and Mo (up to 292 ng/L) were about 3-fold higher than the regional dissolved background and showed a negative logarithmic relation with discharge. Dissolved concentrations of Cr (up to 483 ng/L), Th (up to 48 ng/L) and U (up to 184 ng/L) increased with discharge. Geochemical relationships between molar ratios in surface water, geochemical background as well as rain- and groundwater data were combined. The contrasting behavior of distinct element groups was explained by a scenario involving three seasonal components: (i) The high flow component is poorly concentrated in As and Mo but highly concentrated in Cr, Th, U. This has been attributed to diffuse sources such as water-soil interactions, atmospheric inputs, bedrock and bed sediment weathering. Although this component probably also includes a contribution by weathering of sulfide veins, this signal is masked by dilution. (ii) One low flow component presents high SO(4)(2-), Fe, As and Mo and moderate Cr, Th and U concentrations. This component has been attributed to point sources such as mine gallery effluents, mining waste weathering and groundwater inputs from natural and/or mining-induced sulfide oxidation in the ore deposit. (iii) A second low flow component showing high As plus Mo concentrations associated with very low SO(4)(2-), Fe, Cr, Th and U concentrations, probably reflects trace element scavenging by ferric oxyhydroxide formation in the adjacent aquifer. This is supported by the decrease of Fe, Cr, Th and U in surface waters. Flux estimates suggest contrasting element-specific impacts on annual dissolved fluxes. Runoff may account for the major part of annual dissolved As, Mo, Th and U fluxes in the Upper Isle River. Inputs related to sulfide oxidation respectively contributed approximately 30% and approximately 24% to annual As and Mo fluxes. The formation of ferric oxyhydroxides strongly retained Cr, Th and U during the low flow, limiting their dissolved concentrations in surface waters. If this process may eventually decrease As mobility, its impact on dissolved As concentrations in surface water may be limited or/and counterbalanced by As release during sulfide oxidation.

The environmental consequences of the oil shale utilization in Jordan: The effect of combustion processes

NASA Astrophysics Data System (ADS)

El-Hasan, Tayel

2015-04-01

The geochemical analysis of the upper Cretaceous organic rich oil shale of El-Lajjoun revealed that it contains considerable concentrations of trace element when compared to the average world shale. The aim of this study was to deduce the effect of various combustion processes on the geochemical and mineralogical characteristics of the produced ashes.The oil shale powder samples were burned under Aerobic Combustion Process (ACP) at 700˚C, 850˚C and 1000˚C respectively, beside the anaerobic (pyrolysis) combustion process (PCP) at 600, 650, 700, 750 and 800˚C respectively.The ashes produced from the (ACP) caused almost all major oxides contents to increase with increasing burning temperature, particularly SiO2 and CaO were nearly doubled at temperature 1000 ˚C. Moreover, trace elements showed the same trend where ashes at higher temperatures (i.e. 1000 ˚C) have doubled its contents of trace elements such as Cr, Ni, Zn, Cu and U. This was reflected through enrichment of calcite and quartz beside the anhydrite as the main mineral phases in the ACP ashes. As for the PCP ash show similar trend but relatively with lower concentrations as evident from its lowerEnrichment Factor (EF) values. This might be due to the higher organic matter remained in the PCP ashes compared with ACP ashes. However, PCP is more likely associated with toxic Cd and Asgasses as evident from their lowerconcentrations in the ashes.Moreover, recent results using the synchrotron-based XANES technique confirm that toxic elements are found in higher oxidation state due to ACP. The investigation was concerned on As and Cr. Thechromium in the original shales was in the form of Cr (III) and then it was converted to Cr(VI) in the ashes due of the ACP. Similarly, As (III) the XANES results showed that it was converted into As(V) too. These findingsare alarming and should be taken seriously. Because elements with higher oxidation states became more mobile, thus they can easily leached from the ash tailing into the nearby water resources. The most important species is Cr(VI) because itis easily leachable and very harmful species. It could cause pollution to surface and ground water resources.Therefore, allot of concerns should be paid on the ongoing oil shale utilization enterprises due to its pollution potential.Further investigation regarding the speciation of vanadium and cadmium are on the way.

Pseudopotentials for quantum Monte Carlo studies of transition metal oxides

DOE PAGES

Krogel, Jaron T.; Santana Palacio, Juan A.; Reboredo, Fernando A.

2016-02-22

Quantum Monte Carlo (QMC) calculations of transition metal oxides are partially limited by the availability of high-quality pseudopotentials that are both accurate in QMC and compatible with major plane-wave electronic structure codes. We have generated a set of neon-core pseudopotentials with small cutoff radii for the early transition metal elements Sc to Zn within the local density approximation of density functional theory. The pseudopotentials have been directly tested for accuracy within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (M) atoms and the binding curve of each M-O dimer. We find the ionization potentialsmore » to be accurate to 0.16(1) eV, on average, relative to experiment. The equilibrium bond lengths of the dimers are within 0.5(1)% of experimental values, on average, and the binding energies are also typically accurate to 0.18(3) eV. The level of accuracy we find for atoms and dimers is comparable to what has recently been observed for bulk metals and oxides using the same pseudopotentials. Our QMC pseudopotential results compare well with the findings of previous QMC studies and benchmark quantum chemical calculations.« less

Fucoxanthin enhances HO-1 and NQO1 expression in murine hepatic BNL CL.2 cells through activation of the Nrf2/ARE system partially by its pro-oxidant activity.

PubMed

Liu, Cheng-Ling; Chiu, Yu-Ting; Hu, Miao-Lin

2011-10-26

To determine whether fucoxanthin, a major carotenoid in brown sea algae, may activate cellular antioxidant enzymes via up-regulation of the Nrf2/antioxidant-response element (ARE) pathway, we incubated mouse hepatic BNL CL.2 cells with fucoxanthin (0.5-20 μM) for 0-24 h. We found that fucoxanthin (≥5 μM) significantly increased cellular reactive oxygen species (ROS) at 6 h of incubation, whereas preincubation with α-d-tocopherol (30 μM) significantly attenuated the increase of ROS, indicating the pro-oxidant nature of fucoxanthin. Fucoxanthin significantly increased the phosphorylation of ERK and p38 and markedly increased nuclear Nrf2 protein accumulation after incubation for 12 h. Moreover, fucoxanthin significantly enhanced binding activities of nuclear Nrf2 with ARE and increased mRNA and protein expression of HO-1 and NQO1 after incubation for 12 h. siRNA inhibition of Nrf2 led to markedly decreased HO-1 and NQO1 protein expression. Thus, fucoxanthin may exert its antioxidant activity, at least partly, through its pro-oxidant actions.

Uncertainties of Gaseous Oxidized Mercury Measurements Using KCl-Coated Denuders, Cation-Exchange Membranes, and Nylon Membranes: Humidity Influences.

PubMed

Huang, Jiaoyan; Gustin, Mae Sexauer

2015-05-19

Quantifying the concentration of gaseous oxidized mercury (GOM) and identifying the chemical compounds in the atmosphere are important for developing accurate local, regional, and global biogeochemical cycles. The major hypothesis driving this work was that relative humidity affects collection of GOM on KCl-coated denuders and nylon membranes, both currently being applied to measure GOM. Using a laboratory manifold system and ambient air, GOM capture efficiency on 3 different collection surfaces, including KCl-coated denuders, nylon membranes, and cation-exchange membranes, was investigated at relative humidity ranging from 25 to 75%. Recovery of permeated HgBr2 on KCl-coated denuders declined by 4-60% during spikes of relative humidity (25 to 75%). When spikes were turned off GOM recoveries returned to 60 ± 19% of permeated levels. In some cases, KCl-coated denuders were gradually passivated over time after additional humidity was applied. In this study, GOM recovery on nylon membranes decreased with high humidity and ozone concentrations. However, additional humidity enhanced GOM recovery on cation-exchange membranes. In addition, reduction and oxidation of elemental mercury during experiments was observed. The findings in this study can help to explain field observations in previous studies.

Tension-Compression Fatigue of an Oxide/Oxide Ceramic Matrix Composite at Elevated Temperature in Air and Steam Environments

DTIC Science & Technology

2015-03-26

method has been successfully used with several materials such as silicon carbide fiber - silicon carbide matrix ( SiC / SiC ) CMCs with carbon and boron...elements [14]. These advanced ceramics include oxides, nitrides and carbides of silicon , aluminum, titanium, and zirconium [12]. One of the most...oxides over silicon carbide and other non-oxide materials. In fact, it is the inherent stability of oxides in oxidizing environments which originally

Iron-oxide Aerogel and Xerogel Catalyst Formulations: Characterization by 57Fe Mössbauer and XAFS Spectroscopies

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

Huggins, F.; Bali, S; Huffman, G

2010-01-01

Iron in various iron-oxide aerogel and xerogel catalyst formulations ({ge}85% Fe{sub 2}O{sub 3}; {le}10% K, Co, Cu, or Pd) developed for possible use in Fischer-Tropsch synthesis (FTS) or the water-gas-shift (WGS) reaction has been examined by {sup 57}Fe Moessbauer spectroscopy. The seventeen samples consisted of both as-prepared and calcined aerogels and xerogels and their products after use as catalysts for FTS or the WGS reaction. Complementary XAFS spectra were obtained on the occurrence of the secondary elements in some of the same materials. A broad, slightly asymmetric, two-peak Moessbauer spectrum was obtained from the different as-prepared and calcined catalyst formulationsmore » in the majority of cases. Such spectra could only be satisfactorily fit with three quadrupole doublet components, but no systematic trends in the isomer shift and quadrupole splitting parameters and area ratios of the individual components could be discerned that reflected variations in the composition or preparation of the aerogel or xerogel materials. However, significant reductions were noted in the Moessbauer effective thickness (recoilless absorption effect per unit mass of iron) parameter, {chi}{sub eff}/g, determined at room temperature, for aerogels and xerogels compared to bulk iron oxides, reflecting the openness and lack of rigidity of the aerogel and xerogel structures. Moessbauer measurements for two aerogels over the range from 15 to 292 K confirmed the greatly diminished nature of this parameter at room temperature. Major increases in the effective thickness parameter were observed when the open structure of the aerogel or xerogel collapsed during calcination resulting in the formation of iron oxides (hematite, spinel ferrite). Similar structural changes were indicated by increases in this parameter after use of iron-oxide aerogels as catalysts for FTS or the WGS reaction, during which the iron-oxide aerogel was converted to a mixture of nonstoichiometric magnetite and the Haegg carbide, {chi}-Fe{sub 5}C{sub 2}, or nonstoichiometric magnetite, respectively.« less

Preliminary Geochemical and Rock Magnetic Study of a Stalagmite From Quintana Roo, Northeastern Yucatan Peninsula

NASA Astrophysics Data System (ADS)

Urrutia-Fucugauchi, J.; Perez-Cruz, L.; Zhao, X.; Rebolledo-Vieyra, M.; Rodriguez, A.

2012-04-01

We present the preliminary results of geochemical, stable isotopes and rock magnetic studies of a stalagmite from a cave in eastern Quintana Roo, northern Yucatan peninsula. In the past years, there has been increased interest in understanding the paleoclimatic and paleoenvironmental evolution of the Yucatan peninsula and northern Central America, investigating the relationships between climate variations and the development of the Maya civilization. In particular, the variations in regional precipitation and occurrence of several drought periods, which might have been related to the collapse of the Classic Maya period. Stable isotope data on speleothems from different sites in Yucatan and Central America have provided evidence on changes in precipitation, which have affected the Maya region. The stalagmite is ~47 cm long and about 4-5 cm wide at its base. It was collected from the Hilariós Well cave in Tulum, Quintana Roo. Magnetic susceptibility and geochemical analyses have been completed as part of the initial characterization of the stalagmite, with measurements taken every centimeter. Geochemical analyses have been carried out for x-ray fluorescence, with a Niton XRF analyzer. Magnetic susceptibility was determined with a Bartington MS2 instrument using the high resolution surface probe. Additional rock magnetic analyses include magnetic hysteresis loops and isothermal remanent magnetization (IRM) acquisition, and saturation IRM demagnetization, which have been measured with a MicroMag instrument. Hysteresis loops are diamagnetic, with small varying low-coercivity ferromagnetic components. The elemental compositions of major oxides and trace elements vary with depth. Calcium is the major element and displays a pattern of small amplitude fluctuations with a trend to lower values at the bottom, which are also shown in other elements such as barium. Silica and elements such as titanium and strontium are positively correlated and show an apparent cyclic pattern, with a trend to higher values towards the bottom.

Potential contaminants at a dredged spoil placement site, Charles City County, Virginia, as revealed by sequential extraction

PubMed Central

Tang, Jianwu; Whittecar, G Richard; Johannesson, Karen H; Daniels, W Lee

2004-01-01

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.

The hydrodynamic drag and the mobilisation of sediment into the water column of towed fishing gear components

NASA Astrophysics Data System (ADS)

O'Neill, F. G.; Summerbell, Keith David

2016-12-01

The hydrodynamic drag of towed fishing gears leads to direct impacts on the benthic environment, and can play a major role in the overall economic efficiency of the fishing operation and emissions of nitrogen oxides, sulphur oxides and greenhouse gases such as CO2. Here we investigate some of the underpinning processes which govern these issues and make direct hydrodynamic drag measurements and calculate the hydrodynamic drag coefficients for a range of well-defined gear components that, when fished, are in contact with the seabed. We measure the concentration and particle size distribution of the sediment mobilised into the water column in the wake of these gear elements, at a range of towing speeds, and demonstrate that as the hydrodynamic drag increases the amount of sediment mobilised also increases. We also vary the weight of the elements and show that this does not influence the amount of sediment put into the water column. These results provide a better understanding of the physical and mechanical processes that take place when a towed fishing gear interacts with the seabed. They will permit the development of more fuel efficient gears and gears of reduced benthic impact and will improve the empirical modelling of the sediment mobilised into the turbulent wake behind towed fishing gears which will lead to better assessments of the environmental and ecological impact of fishing gears.

DNA damage induced by coal dust, fly and bottom ash from coal combustion evaluated using the micronucleus test and comet assay in vitro.

PubMed

Matzenbacher, Cristina Araujo; Garcia, Ana Letícia Hilario; Dos Santos, Marcela Silva; Nicolau, Caroline Cardoso; Premoli, Suziane; Corrêa, Dione Silva; de Souza, Claudia Telles; Niekraszewicz, Liana; Dias, Johnny Ferraz; Delgado, Tânia Valéria; Kalkreuth, Wolfgang; Grivicich, Ivana; da Silva, Juliana

2017-02-15

Coal mining and combustion generating huge amounts of bottom and fly ash are major causes of environmental pollution and health hazards due to the release of polycyclic aromatic hydrocarbons (PAH) and heavy metals. The Candiota coalfield in Rio Grande do Sul, is one of the largest open-cast coal mines in Brazil. The aim of this study was to evaluate genotoxic and mutagenic effects of coal, bottom ash and fly ash samples from Candiota with the comet assay (alkaline and modified version) and micronucleus test using the lung fibroblast cell line (V79). Qualitative and quantitative analysis of PAH and inorganic elements was carried out by High Performance Liquid Chromatography (HPLC) and by Particle-Induced X-ray Emission (PIXE) techniques respectively. The samples demonstrated genotoxic and mutagenic effects. The comet assay modified using DNA-glicosilase formamidopirimidina (FPG) endonuclease showed damage related to oxidative stress mechanisms. The amount of PAHs was higher in fly ash followed by pulverized coal. The amount of inorganic elements was highest in fly ash, followed by bottom ash. It is concluded that the samples induce DNA damage by mechanisms that include oxidative stress, due to their complex composition, and that protective measures have to be taken regarding occupational and environmental hazards. Copyright © 2016 Elsevier B.V. All rights reserved.

Predicting Water Quality Problems Associated with Coal Fly Ash Disposal Facilities Using a Trace Element Partitioning Study

NASA Astrophysics Data System (ADS)

Bhattacharyya, S.; Donahoe, R. J.; Graham, E. Y.

2006-12-01

For much of the U.S., coal-fired power plants are the most important source of electricity for domestic and industrial use. Large quantities of fly ash and other coal combustion by-products are produced every year, the majority of which is impounded in lagoons and landfills located throughout the country. Many older fly ash disposal facilities are unlined and have been closed for decades. Fly ash often contains high concentrations of toxic trace elements such as arsenic, boron, chromium, molybdenum, nickel, selenium, lead, strontium and vanadium. Trace elements present in coal fly ash are of potential concern due to their toxicity, high mobility in the environment and low drinking water MCL values. Concern about the potential release of these toxic elements into the environment due to leaching of fly ash by acid rain, groundwater or acid mine drainage has prompted the EPA to develop national standards under the subtitle D of the Resource Conservation and Recovery Act (RCRA) to regulate ash disposal in landfills and surface impoundments. An attempt is made to predict the leaching of toxic elements into the environment by studying trace element partitioning in coal fly ash. A seven step sequential chemical extraction procedure (SCEP) modified from Filgueiras et al. (2002) is used to determine the trace element partitioning in seven coal fly ash samples collected directly from electric power plants. Five fly ash samples were derived from Eastern Bituminous coal, one derived from Western Sub-bituminous coal and the other derived from Northern Lignite. The sequential chemical extraction procedure gives valuable information on the association of trace elements: 1) soluble fraction, 2) exchangeable fraction, 3) acid soluble fraction, 4) easily reducible fraction, 5) moderately reducible fraction, 6) poorly reducible fraction and 7) oxidizable organics/sulfide fraction. The trace element partitioning varies with the composition of coal fly ash which is influenced by the type of coal burned. Preliminary studies show that in some fly ash samples, significant amounts of As, B, Mo, Se, Sr and V are associated with the soluble and exchangeable fraction, and thus would be highly mobile in the environment. Lead, on the other hand, is mainly associated with the amorphous Fe and Mn oxide fractions and would be highly immobile in oxidizing conditions, but mobile in reducing conditions. Ni and Cr show different associations in different fly ash samples. In most fly ash samples, significant amounts of the trace elements are associated with more stable fractions that do not threaten the environment. The study of trace element partitioning in coal fly ash thus helps us to predict their leaching behavior under various conditions.

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, Charles C.; Nelson, Paul A.; Dees, Dennis W.

1994-01-01

A solid oxide fuel cell having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed therebetween, and the anode, cathode and interconnect elements are comprised of substantially one material.

TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

EPA Science Inventory

Iron (hydr)oxides often control the mobility of inorganic contaminants in soils and sediments. A poorly ordered form of ferrihydrite is commonly produced during rapid oxidation of ferrous iron at sharp redox fronts encountered during discharge of anoxic/suboxic waters into terre...

Acute selenium selenite exposure effects on oxidative stress biomarkers and essential metals and trace-elements in the model organism zebrafish (Danio rerio).

PubMed

Hauser-Davis, R A; Silva, J A N; Rocha, Rafael C C; Saint'Pierre, Tatiana; Ziolli, R L; Arruda, M A Z

2016-01-01

Selenium (Se) is an essential trace-element that becomes toxic when present at high concentrations. Little is known regarding Se effects on parameters such as oxidative stress biomarkers. The aim of the present study was to investigate the effects of acute selenium exposure on oxidative stress biomarkers in a model organism, zebrafish (Danio rerio). Fish were exposed to selenium selenite at 1mgL(-1). Reduced glutathione (GSH), and metallothionein (MT) concentrations were determined in liver, kidney and brain, with MT also being determined in bile. Essential metals and trace-elements were also determined by inductively coupled mass spectrometry (ICP-MS) in order to verify possible metal homeostasis alterations. GSH concentrations in liver, kidney and brain increased significantly (1.05±0.03μmolg(-1) ww, 1.42±0.03μmolg(-1) ww and 1.64±0.03μmolg(-1) ww, respectively) in the Se-exposed group when compared to the controls (0.88±0.05μmolg(-1) ww, 0.80±0.04μmolg(-1) ww and 0.89±0.03μmolg(-1) ww for liver, kidney and brain, respectively). MT levels in Se-exposed liver (0.52±0.03μmolg(-1) ww) decreased significantly in comparison to the control group (0.64±0.02μmolg(-1) ww), while levels in bile increased, albeit non-significantly. This is in accordance with previous studies that indicate efficient biliary MT action, leading to a rapid metabolism and elimination of contaminants from the body. Levels in the brain increased significantly after Se-exposure (0.57±0.01μmolg(-1) ww) when compared to the control group (0.35±0.03μmolg(-1) ww) since this organ does not present a detoxification route as quick as the liver-gallbladder route. Several metal and trace-elements were altered with Se-exposure, indicating that excess of selenium results in metal dyshomeostasis. This is the first report on metal dyshomeostasis due to Se-exposure, which may be the first step in the mechanism of action of selenium toxicity, as is postulated to occur in certain major human pathophysiologies. Copyright © 2015 Elsevier GmbH. All rights reserved.

Role of alloying elements in adhesive transfer and friction of copper-base alloys

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

Sliding friction experiments were conducted in a vacuum with binary-copper alloy riders sliding against a conventional bearing-steel surface with normal residual oxides present. The binary alloys contained 1 atomic percent of various alloying elements. Auger spectroscopy analysis was used to monitor the adhesive transfer of the copper alloys to the bearing-steel surface. A relation was found to exist between adhesive transfer and the reaction potential and free energy of formation of the alloying element in the copper. The more chemically active the element and the more stable its oxide, the greater was the adhesive transfer and wear of the copper alloy. Transfer occurred in all the alloys except copper-gold after relatively few (25) passes across the steel surface.

Quantification of trace elements and speciation of iron in atmospheric particulate matter

NASA Astrophysics Data System (ADS)

Upadhyay, Nabin

Trace metal species play important roles in atmospheric redox processes and in the generation of oxidants in cloud systems. The chemical impact of these elements on atmospheric and cloud chemistry is dependent on their occurrence, solubility and speciation. First, analytical protocols have been developed to determine trace elements in particulate matter samples collected for carbonaceous analysis. The validated novel protocols were applied to the determination of trace elements in particulate samples collected in the remote marine atmosphere and urban areas in Arizona to study air pollution issues. The second part of this work investigates on solubility and speciation in environmental samples. A detailed study on the impact of the nature and strength of buffer solutions on solubility and speciation of iron lead to a robust protocol, allowing for comparative measurements in matrices representative of cloud water conditions. Application of this protocol to samples from different environments showed low iron solubility (less than 1%) in dust-impacted events and higher solubility (5%) in anthropogenically impacted urban samples. In most cases, Fe(II) was the dominant oxidation state in the soluble fraction of iron. The analytical protocol was then applied to investigate iron processing by fogs. Field observations showed that only a small fraction (1%) of iron was scavenged by fog droplets for which each of the soluble and insoluble fraction were similar. A coarse time resolution limited detailed insights into redox cycling within fog system. Overall results suggested that the major iron species in the droplets was Fe(1I) (80% of soluble iron). Finally, the occurrence and sources of emerging organic pollutants in the urban atmosphere were investigated. Synthetic musk species are ubiquitous in the urban environment (less than 5 ng m-3) and investigations at wastewater treatment plants showed that wastewater aeration basins emit a substantial amount of these species to the atmosphere.

Microwave-assisted wet digestion with H2O2 at high temperature and pressure using single reaction chamber for elemental determination in milk powder by ICP-OES and ICP-MS.

PubMed

Muller, Edson I; Souza, Juliana P; Muller, Cristiano C; Muller, Aline L H; Mello, Paola A; Bizzi, Cezar A

2016-08-15

In this work a green digestion method which only used H2O2 as an oxidant and high temperature and pressure in the single reaction chamber system (SRC-UltraWave™) was applied for subsequent elemental determination by inductively coupled plasma-based techniques. Milk powder was chosen to demonstrate the feasibility and advantages of the proposed method. Samples masses up to 500mg were efficiently digested, and the determination of Ca, Fe, K, Mg and Na was performed by inductively coupled plasma optical emission spectrometry (ICP-OES), while trace elements (B, Ba, Cd, Cu, Mn, Mo, Pb, Sr and Zn) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Residual carbon (RC) lower than 918mgL(-1) of C was obtained for digests which contributed to minimizing interferences in determination by ICP-OES and ICP-MS. Accuracy was evaluated using certified reference materials NIST 1549 (non-fat milk powder certified reference material) and NIST 8435 (whole milk powder reference material). The results obtained by the proposed method were in agreement with the certified reference values (t-test, 95% confidence level). In addition, no significant difference was observed between results obtained by the proposed method and conventional wet digestion using concentrated HNO3. As digestion was performed without using any kind of acid, the characteristics of final digests were in agreement with green chemistry principles when compared to digests obtained using conventional wet digestion method with concentrated HNO3. Additionally, H2O2 digests were more suitable for subsequent analysis by ICP-based techniques due to of water being the main product of organic matrix oxidation. The proposed method was suitable for quality control of major components and trace elements present in milk powder in consonance with green sample preparation. Copyright © 2016 Elsevier B.V. All rights reserved.

The potential leaching and mobilization of trace elements from FGD-gypsum of a coal-fired power plant under water re-circulation conditions.

PubMed

Córdoba, Patricia; Castro, Iria; Maroto-Valer, Mercedes; Querol, Xavier

2015-06-01

Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO2SO4, H2Se, and HAsO2 are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO4(2) in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe2 and MoSe2, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples. Copyright © 2015. Published by Elsevier B.V.

Effects of interferon-gamma and lipopolysaccharide on macrophage iron metabolism are mediated by nitric oxide-induced degradation of iron regulatory protein 2.

PubMed

Kim, S; Ponka, P

2000-03-03

Iron regulatory proteins (IRP-1 and IRP-2) control the synthesis of transferrin receptors (TfR) and ferritin by binding to iron-responsive elements, which are located in the 3'-untranslated region and the 5'-untranslated region of their respective mRNAs. Cellular iron levels affect binding of IRPs to iron-responsive elements and consequently expression of TfR and ferritin. Moreover, NO(*), a redox species of nitric oxide that interacts primarily with iron, can activate IRP-1 RNA binding activity resulting in an increase in TfR mRNA levels. Recently we found that treatment of RAW 264.7 cells (a murine macrophage cell line) with NO(+) (nitrosonium ion, which causes S-nitrosylation of thiol groups) resulted in a rapid decrease in RNA binding of IRP-2 followed by IRP-2 degradation, and these changes were associated with a decrease in TfR mRNA levels (Kim, S., and Ponka, P. (1999) J. Biol. Chem. 274, 33035-33042). In this study, we demonstrated that stimulation of RAW 264.7 cells with lipopolysaccharide (LPS) and interferon-gamma (IFN-gamma) increased IRP-1 binding activity, whereas RNA binding of IRP-2 decreased and was followed by a degradation of this protein. Moreover, the decrease of IRP-2 binding/protein levels was associated with a decrease in TfR mRNA levels in LPS/IFN-gamma-treated cells, and these changes were prevented by inhibitors of inducible nitric oxide synthase. Furthermore, LPS/IFN-gamma-stimulated RAW 264.7 cells showed increased rates of ferritin synthesis. These results suggest that NO(+)-mediated degradation of IRP-2 plays a major role in iron metabolism during inflammation.

Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

PubMed

Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

2015-04-01

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

FUSED REACTOR FUELS

DOEpatents

Mayer, S.W.

1962-11-13

This invention relates to a nuciear reactor fuel composition comprising (1) from about 0.01 to about 50 wt.% based on the total weight of said composition of at least one element selected from the class consisting of uranium, thorium, and plutonium, wherein said eiement is present in the form of at least one component selected from the class consisting of oxides, halides, and salts of oxygenated anions, with components comprising (2) at least one member selected from the class consisting of (a) sulfur, wherein the sulfur is in the form of at least one entity selected irom the class consisting of oxides of sulfur, metal sulfates, metal sulfites, metal halosulfonates, and acids of sulfur, (b) halogen, wherein said halogen is in the form of at least one compound selected from the class of metal halides, metal halosulfonates, and metal halophosphates, (c) phosphorus, wherein said phosphorus is in the form of at least one constituent selected from the class consisting of oxides of phosphorus, metal phosphates, metal phosphites, and metal halophosphates, (d) at least one oxide of a member selected from the class consisting of a metal and a metalloid wherein said oxide is free from an oxide of said element in (1); wherein the amount of at least one member selected from the class consisting of halogen and sulfur is at least about one at.% based on the amount of the sum of said sulfur, halogen, and phosphorus atom in said composition; and wherein the amount of said 2(a), 2(b) and 2(c) components in said composition which are free from said elements of uranium, thorium, arid plutonium, is at least about 60 wt.% based on the combined weight of the components of said composition which are free from said elements of uranium, thorium, and plutonium. (AEC)

Mycobacterium tuberculosis WhiB1 is an essential DNA-binding protein with a nitric oxide sensitive iron-sulphur cluster

PubMed Central

Smith, Laura J.; Stapleton, Melanie R.; Fullstone, Gavin J. M.; Crack, Jason C.; Thomson, Andrew J.; Le Brun, Nick E.; Hunt, Debbie M.; Harvey, Evelyn; Adinolfi, Salvatore; Buxton, Roger S.; Green, Jeffrey

2010-01-01

Mycobacterium tuberculosis is a major pathogen that has the ability to establish, and emerge from, a persistent state. Wbl family proteins are associated with developmental processes in actinomycetes, and M. tuberculosis has seven such proteins. Here it is shown that the M. tuberculosis H37Rv whiB1 gene is essential. The WhiB1 protein possesses a [4Fe-4S]2+ cluster that is stable in air but reacts rapidly with eight equivalents of nitric oxide to yield two dinuclear dinitrosyl-iron thiol complexes. The [4Fe-4S] form of WhiB1 did not bind whiB1 promoter DNA, but the reduced and oxidized apo-WhiB1, and nitric oxide-treated holo-WhiB1 did bind to DNA. Mycobacterium smegmatis RNA polymerase induced transcription of whiB1 in vitro; however in the presence of apo-WhiB1 transcription was severely inhibited, irrespective of the presence or absence of the CRP protein Rv3676, which is known to activate whiB1 expression. Footprinting suggested that autorepression of whiB1 is achieved by apo-WhiB1 binding at a region that overlaps the core promoter elements. A model incorporating regulation of whiB1 expression in response to nitric oxide and cAMP is discussed with implications for sensing two important signals in establishing M. tuberculosis infections. PMID:20929442

Protective effect and mechanism of glutaredoxin 1 on coronary arteries endothelial cells damage induced by high glucose.

PubMed

Li, Shuyan; Sun, Yan; Qi, Xiaodan; Shi, Yan; Gao, Han; Wu, Qi; Liu, Xiucai; Yu, Haitao; Zhang, Chunjing

2014-01-01

In recent years, diabetes and its associated complications have become a major public health concern. The cardiovascular risk increases significantly in diabetes patients. It is a complex disease characterized by multiple metabolic derangements and is known to impair cardiac function by disrupting the balance between pro-oxidants and antioxidants at the cellular level. The subsequent generation of reactive oxygen species (ROS) and accompanying oxidative stress are hallmarks of the molecular mechanisms responsible for cardiovascular disease. Protein thiols act as redox-sensitive switches and are believed to be a key element in maintaining the cellular redox balance. The redox state of protein thiols is regulated by oxidative stress and redox signaling and is important to cellular functions. The potential of the thiol-disulfide oxidoreductase enzymes (thioredoxin and glutaredoxin systems) in defense against oxidative stress has been noted previously. Increasing evidence demonstrates that glutaredoxin 1 (Grx1), a cytosolic enzyme responsible for the catalysis of protein deglutathionylation, plays distinct roles in inflammation and apoptosis by inducing changes in the cellular redox system. This study investigates whether and how Grx1 protects coronary artery vascular endothelial cells against high glucose (HG) induced damage. Results indicate that the activation of eNOS/NO system is regulated by Grx 1 and coupled with inhibition of JNK and NF-κB signaling pathway which could alleviate the oxidative stress and apoptosis damage in coronary arteries endothelial cells induced by HG.

Anatomy of a Nanoscale Conduction Channel Reveals the Mechanism of a High-Performance Memristor

NASA Astrophysics Data System (ADS)

Miao, Feng; Strachan, John Paul; Yang, J. Joshua; Yi, Wei; Goldfarb, Ilan; Zhang, M.-X.; Torrezan, Antonio C.; Eschbach, Peter; Kelley, Ronald D.; Medeiros-Ribeiro, Gilberto; Williams, R. Stanley

2012-02-01

Two major challenges for resistance memory devices (memristors) based on conductivity changes in oxide materials are better performance and understanding of the microscopic picture of the switching. After researchers' relentless pursuit for years, tantalum oxide-based memristors have rapidly risen to be the top candidate, showing fast speed, high endurance and excellent scalability. While the microscopic picture of these devices remains obscure, by employing a precise method for locating and directly visualizing the conduction channel, here we observed a nanoscale channel consisting of an amorphous Ta(O) solid solution surrounded by crystalline Ta2O5. Structural and chemical analyses of the channel combined with temperature dependent transport measurements revealed a unique resistance switching mechanism: the modulation of the channel elemental composition, and thus the conductivity, by the cooperative influence of drift, diffusion and thermophoresis, which seem to enable the high switching performance observed. (Miao*, Strachan*, Yang* et al., Advanced Materials. DOI: 10.1002/adma201103379 (2011))

Recalibration of the Mars Science Laboratory ChemCam instrument with an expanded geochemical database

DOE PAGES

Clegg, Samuel M.; Wiens, Roger C.; Anderson, Ryan; ...

2016-12-24

The ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) instrument onboard the Mars Science Laboratory (MSL) rover Curiosity has obtained > 300,000 spectra of rock and soil analysis targets since landing at Gale Crater in 2012, and the spectra represent perhaps the largest publicly-available LIBS datasets. The compositions of the major elements, reported as oxides, have been re-calibrated using a laboratory LIBS instrument, Mars-like atmospheric conditions, and a much larger set of standards (408) that span a wider compositional range than previously employed. The new calibration uses a combination of partial least squares (PLS1) and Independent Component Analysis (ICA) algorithms, together with amore » calibration transfer matrix to minimize differences between the conditions under which the standards were analyzed in the laboratory and the conditions on Mars. While the previous model provided good results in the compositional range near the average Mars surface composition, the new model fits the extreme compositions far better. Examples are given for plagioclase feldspars, where silicon was previously significantly over-estimated, and for calcium-sulfate veins, where silicon compositions near zero were inaccurate. Here, the uncertainties of major element abundances are described as a function of the abundances, and are overall significantly lower than the previous model, enabling important new geochemical interpretations of the data.« less

Recalibration of the Mars Science Laboratory ChemCam instrument with an expanded geochemical database

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

Clegg, Samuel M.; Wiens, Roger C.; Anderson, Ryan

The ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) instrument onboard the Mars Science Laboratory (MSL) rover Curiosity has obtained > 300,000 spectra of rock and soil analysis targets since landing at Gale Crater in 2012, and the spectra represent perhaps the largest publicly-available LIBS datasets. The compositions of the major elements, reported as oxides, have been re-calibrated using a laboratory LIBS instrument, Mars-like atmospheric conditions, and a much larger set of standards (408) that span a wider compositional range than previously employed. The new calibration uses a combination of partial least squares (PLS1) and Independent Component Analysis (ICA) algorithms, together with amore » calibration transfer matrix to minimize differences between the conditions under which the standards were analyzed in the laboratory and the conditions on Mars. While the previous model provided good results in the compositional range near the average Mars surface composition, the new model fits the extreme compositions far better. Examples are given for plagioclase feldspars, where silicon was previously significantly over-estimated, and for calcium-sulfate veins, where silicon compositions near zero were inaccurate. Here, the uncertainties of major element abundances are described as a function of the abundances, and are overall significantly lower than the previous model, enabling important new geochemical interpretations of the data.« less

Use of lectins to in situ visualize glycoconjugates of extracellular polymeric substances in acidophilic archaeal biofilms

PubMed Central

Zhang, R Y; Neu, T R; Bellenberg, S; Kuhlicke, U; Sand, W; Vera, M

2015-01-01

Biofilm formation and the production of extracellular polymeric substances (EPS) by meso- and thermoacidophilic metal-oxidizing archaea on relevant substrates have been studied to a limited extent. In order to investigate glycoconjugates, a major part of the EPS, during biofilm formation/bioleaching by archaea on pyrite, a screening with 75 commercially available lectins by fluorescence lectin-binding analysis (FLBA) has been performed. Three representative archaeal species, Ferroplasma acidiphilum DSM 28986, Sulfolobus metallicus DSM 6482T and a novel isolate Acidianus sp. DSM 29099 were used. In addition, Acidianus sp. DSM 29099 biofilms on elemental sulfur were studied. The results of FLBA indicate (i) 22 lectins bound to archaeal biofilms on pyrite and 21 lectins were binding to Acidianus sp. DSM 29099 biofilms on elemental sulfur; (ii) major binding patterns, e.g. tightly bound EPS and loosely bound EPS, were detected on both substrates; (iii) the three archaeal species produced various EPS glycoconjugates on pyrite surfaces. Additionally, the substratum induced different EPS glycoconjugates and biofilm structures of cells of Acidianus sp. DSM 29099. Our data provide new insights into interactions between acidophilic archaea on relevant surfaces and also indicate that FLBA is a valuable tool for in situ investigations on archaeal biofilms. PMID:25488256

Sulfide oxidation and acid mine drainage formation within two active tailings impoundments in the Golden Quadrangle of the Apuseni Mountains, Romania.

PubMed

Sima, Mihaela; Dold, Bernhard; Frei, Linda; Senila, Marin; Balteanu, Dan; Zobrist, Jurg

2011-05-30

Sulfidic mine tailings have to be classified as one of the major source of hazardous materials leading to water contamination. This study highlights the processes leading to sulfide oxidation and acid mine drainage (AMD) formation in the active stage of two tailings impoundments located in the southern part of the Apuseni Mountains, in Romania, a well-known region for its long-term gold-silver and metal mining activity. Sampling was undertaken when both impoundments were still in operation in order to assess their actual stage of oxidation and long-term behavior in terms of the potential for acid mine drainage generation. Both tailings have high potential for AMD formation (2.5 and 3.7 wt.% of pyrite equivalent, respectively) with lesser amount of carbonates (5.6 and 3.6 wt.% of calcite equivalent) as neutralization potential (ABA=-55.6 and -85.1 tCaCO(3)/1000 t ) and showed clear signs of sulfide oxidation yet during operation. Sequential extraction results indicate a stronger enrichment and mobility of elements in the oxidized tailings: Fe as Fe(III) oxy-hydroxides and oxides (transformation from sulfide minerals, leaching in oxidation zone), Ca mainly in water soluble and exchangeable form where gypsum and calcite are dissolved and higher mobility of Cu for Ribita and Pb for Mialu. Two processes leading to the formation of mine drainage at this stage could be highlighted (1) a neutral Fe(II) plume forming in the impoundment with ferrihydrite precipitation at its outcrop and (2) acid mine drainage seeping in the unsaturated zone of the active dam, leading to the formation of schwertmannite at its outcrop. Copyright © 2011 Elsevier B.V. All rights reserved.

Use of Carboxymethyl-beta-cyclodextrin (CMCD) as Flushing Agent for Remediation of Metal Contaminated Soil

NASA Astrophysics Data System (ADS)

Skold, M. E.; Thyne, G. D.; McCray, J. E.; Drexler, J. W.

2005-12-01

One of the major challenges in remediating soil and ground water is the presence of mixed organic and inorganic contaminants. Due to their very different behavior, research has to a large extent focused on remediation of either organic or inorganic contaminants rather than mixed waste. Cyclodextrins (CDs) are a group of non-toxic sugar based molecules that do not sorb to soil particles and do not experience pore size exclusion. Thus, they have good hydraulic properties. CDs enhance the solubility of organic compounds by forming inclusion complexes between organic contaminants and the non-polar cavity at the center of the CD. By substituting functional groups to the cyclodextrin molecule it can form complexes with heavy metals. Previous studies have shown that carboxymethyl-beta-cyclodextrin (CMCD) can simultaneously complex organic and inorganic contaminants. The aim of this study is to compare how strongly CMCD complexes several common heavy metals, radioactive elements and a common divalent cation. Results from batch experiments show that CMCD has the ability to complex a wide array of heavy metals and radioactive elements. The solubility of metal oxalates and metal oxides clearly increased in the presence of CMCD. Logarithmic conditional formation constants ranged from 3.5 to 6 for heavy metals and from 3 to 6 for radioactive elements. Calcium, which may compete for binding sites, has a logarithmic conditional formation constant of 3.1. Batch experiments performed at 10 and 25 degrees C showed little temperature effect on conditional formation constants. Results from batch experiments were compared to results from column experiments where Pb was sorbed onto hydrous ferric oxide coated sand and subsequently removed by a CMCD solution. The results indicate that CMCD is a potential flushing agent for remediation of mixed waste sites.

Oxides having high energy densities

DOEpatents

Ceder, Gerbrand; Kang, Kisuk

2013-09-10

Certain disclosed embodiments generally relate to oxide materials having relatively high energy and/or power densities. Various aspects of the embodiments are directed to oxide materials having a structure B.sub.i(M.sub.jY.sub.k)O.sub.2, for example, a structure Li.sub.j(Ni.sub.jY.sub.k)O.sub.2 such as Li(Ni.sub.0.5Mn.sub.0.5)O.sub.2. In this structure, Y represents one or more atoms, each independently selected from the group consisting of alkaline earth metals, transition metals, Group 14 elements, Group 15, or Group 16 elements. In some embodiments, such an oxide material may have an O3 crystal structure, and/or a layered structure such that the oxide comprises a plurality of first, repeating atomic planes comprising Li, and a plurality of second, repeating atomic planes comprising Ni and/or Y.

Electronically conductive perovskite-based oxide nanoparticles and films for optical sensing applications

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

Ohodnicki, Jr., Paul R; Schultz, Andrew M

2015-04-28

The disclosure relates to a method of detecting a change in a chemical composition by contacting a electronically conducting perovskite-based metal oxide material with a monitored stream, illuminating the electronically conducting perovskite-based metal oxide with incident light, collecting exiting light, monitoring an optical signal based on a comparison of the incident light and the exiting light, and detecting a shift in the optical signal. The electronically conducting perovskite-based metal oxide has a perovskite-based crystal structure and an electronic conductivity of at least 10.sup.-1 S/cm, where parameters are specified at the gas stream temperature. The electronically conducting perovskite-based metal oxide hasmore » an empirical formula A.sub.xB.sub.yO.sub.3-.delta., where A is at least a first element at the A-site, B is at least a second element at the B-site, and where 0.8« less

Analytical Transmission Electron Microscopy Studies on Copper-Alumina Interfaces.

DTIC Science & Technology

1999-06-01

association with alumina, such as, copper, aluminum, chromium, silver, and gold . In particular, copper has been chosen because of its excellent...similar results in variance. However, the oxide calculation program assumes that all elements are 100% oxidized with no monoatomic species or mixed oxide

Recovery of fissile materials from nuclear wastes

DOEpatents

Forsberg, Charles W.

1999-01-01

A process for recovering fissile materials such as uranium, and plutonium, and rare earth elements, from complex waste feed material, and converting the remaining wastes into a waste glass suitable for storage or disposal. The waste feed is mixed with a dissolution glass formed of lead oxide and boron oxide resulting in oxidation, dehalogenation, and dissolution of metal oxides. Carbon is added to remove lead oxide, and a boron oxide fusion melt is produced. The fusion melt is essentially devoid of organic materials and halogens, and is easily and rapidly dissolved in nitric acid. After dissolution, uranium, plutonium and rare earth elements are separated from the acid and recovered by processes such as PUREX or ion exchange. The remaining acid waste stream is vitrified to produce a waste glass suitable for storage or disposal. Potential waste feed materials include plutonium scrap and residue, miscellaneous spent nuclear fuel, and uranium fissile wastes. The initial feed materials may contain mixtures of metals, ceramics, amorphous solids, halides, organic material and other carbon-containing material.

Process for growing a film epitaxially upon an oxide surface and structures formed with the process

DOEpatents

McKee, Rodney Allen; Walker, Frederick Joseph

1998-01-01

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Process for growing a film epitaxially upon an oxide surface and structures formed with the process

DOEpatents

McKee, Rodney A.; Walker, Frederick J.

1995-01-01

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Three-dimensional flow and trace metal mobility in shallow Chalk groundwater, Dorset, United Kingdom

NASA Astrophysics Data System (ADS)

Schürch, Marc; Edmunds, W. Michael; Buckley, David

2004-06-01

The three-dimensional groundwater flow and the hydrogeochemical regime have been determined in the Bere Stream valley, North Dorset Downs, southern England. The dual porosity characteristics of the Portsdown Chalk have been established using geophysical and hydrochemical borehole logging. Chemical properties have been established using major and trace element analyses of depth samples and groundwaters. The study site is located at the unconfined-confined boundary of the Chalk aquifer, where it is overflowing in the observation boreholes. The Chalk dips locally at about 5 m/km to the south-east under Palaeogene confining beds and three distinctive flow horizons may be recognised. The Chalk groundwater is of Ca-HCO 3 type and three separate geochemical groundwater zones were also determined with depth, having different oxygen levels and trace element characteristics. (1) A shallow O 2-rich zone with around 80% dissolved O 2 and low trace element concentrations. (2) A mixing and transition zone with significant concentrations of trace elements and high trace metal concentrations at its base: manganese 29 μg/l, nickel 55 μg/l, cadmium 146 μg/l, and zinc 214 μg/l. (3) A deeper zone with depleted oxygen (5-20% dissolved O 2) and with longer water residence times shown by higher Mg/Ca and K/Na ratios as well as higher Sr and F. The groundwater geochemistry in the Chalk aquifer is dominated by incongruent reactions with the fine-grained carbonate sediments, which release trace element impurities to the water. Some of the metals are co-precipitated with Mn- and Fe-oxide phases on fissure surfaces, whilst producing a purer calcite. During subsequent recrystallisation to purer iron- and manganese-oxides on fissure surfaces under specific geochemical and hydrodynamic conditions, trace metals are released into the fissure water. The results demonstrate the need to monitor quality stratification and the changes in the groundwater baseline chemistry in areas close to the redox boundary which, in the dual porosity Chalk is likely to be a diffuse zone with exchange between oxygen poor matrix waters and more oxic water flowing through the fissures.

The role of herbometallic preparations in traditional medicine--a review on mica drug processing and pharmaceutical applications.

PubMed

Wijenayake, Apsara; Pitawala, Amarasooriya; Bandara, Ratnayake; Abayasekara, Charmalie

2014-09-11

Biotite mica enriched with Fe(2+) ions are widely used as a major mineral ingredient in traditional pharmaceutical science of alchemy (Rasashastra). Abhrak bhasma (mica ash), a pharmaceutical product containing treated mica, is utilized, for example, in Ayurvedic treatments for ailments such as gastritis, renal disease, skin disease and mainly in rejuvenation formulations. However, the untreated mica minerals may be harmful when used directly, as they carry considerably high amounts of trace-elements that can cause undesirable effects in the human body. In order to remove toxic factors and produce readily absorbable materials having high nutrient capacity, specific thermal and chemical treatments (purification, detoxification, particle size reduction and incineration) are performed during the preparation of Rasashastra. This review evaluates the chemical and pharmacological aspects of mica ash as well as the technological aspects of mica ash production. The detailed literature review on the chemistry and scientific basis of mica ash, its preparation techniques, mica alterations and pharmaceutical applications was carried out by using published Ayurvedic text books and research articles, available from Science Direct, on mica minerals, mica ash and their physico-chemical alteration processes and pharmacological applications. During the purification and detoxification procedures, heating followed by quenching (in ionic medium) influences the structural distortion and the development of stress-induced cracks and spallations of the micaceous plates. Thus, the efficient diffusion of the external medium takes place at successive heating and quenching steps. Acidic organic liquids and animal byproducts can enhance the cation exchange capacity and solubility of mica. Further, these natural compounds facilitate the removal of toxic-elements in the structure. When treated-mica and paddy husks are tied up in a cloth and squeezed, particle size reduction and further detoxification takes place. Leaching out of oxidized iron coatings is accelerated when the mixtures are immersed in acidic media, by which the filtrate is enriched with oxidized iron-silicate particles. These nano-oxide particles are converted into a more favorable oxidation form for human consumption when the herbometallic mixture is incinerated in closed vessels. Recent analytical data reveals that major and minor elements in mica ash are within the limits of pharmacopoeial standards for Ayurvedic formulations. Further, recent studies show that mica ash has hypoglycemic, hepatoprotective, anthelminthic and antimicrobial properties. Chemical and structural modifications in mica occur during mica-based drug preparation in traditional medicine. Purification steps particularly influence the structural distortion while heating and quenching can form nano-size particles. Carboxylic acids and other organic molecules present in quenching media serve as chemical modifiers of mica. At the same time the toxic elements are leached out from mica to the quenching media through an ion exchange process. Mica ash has been successfully used for treating liver, kidney and skin related ailments in traditional medicine, and mica ash alone or its herbo-metallic formulations have different applications. Further, the recent toxicological and analytical studies validate the traditional uses of mica ash and mica ash bearing products. Further scientific studies are needed to fully establish that mica-based pharmaceuticals are safe and devoid of toxic and long term side effects. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Biogeochemical redox processes and their impact on contaminant dynamics

USGS Publications Warehouse

Borch, Thomas; Kretzschmar, Ruben; Kappler, Andreas; Van Cappellen, Philippe; Ginder-Vogel, Matthew; Campbell, Kate M.

2010-01-01

Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

METHOD OF MAKING WIRE FUEL ELEMENTS

DOEpatents

Zambrow, J.L.

1960-08-01

A method is given for making a nuclear reactor fuel element in the form of a uranium-bearing wire clad with zirconium. A uranium bar is enclosed in a zirconium sheath which is coated with an oxide of magnesium, beryllium, or zirconium. The sheathed bar is then placed in a steel tube and reduced to the desired diameter by swaging at 800 to 900 deg C, after which the steel and oxide are removed.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

1997-01-01

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or ZrO.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B, .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

1999-01-01

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or ZrO.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B, .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

2001-01-01

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or ZrO.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B, .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Chemical Composition and Oxidation State of Iron-Containing Aerosol Particles Over West Antarctic Peninsula

NASA Astrophysics Data System (ADS)

Fan, S.; Yu, S.; Lai, B.; Gao, Y.

2017-12-01

Iron is a limiting micronutrient element critical for the marine ecosystem. In the extensive high-nutrient low-chlorophyll (HNLC) regions of the Southern Ocean, the activities of phytoplankton are partly controlled by iron (Fe) from different sources, including atmospheric deposition. Among important properties of atmospheric Fe are the elemental composition and Fe oxidation state of Fe-containing aerosol particles, as these properties affect aerosol Fe solubility. To explore these issues, aerosol samples were collected at Palmer Station in West Antarctic Peninsula. Samples were analyzed by submicron synchrotron-based X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) spectroscopy for the Fe oxidation state and elemental composition of aerosol particles. The morphological information of aerosol particles was also observed by the high-resolution fluorescence microscopy, revealing possible sources and formation processes of iron-containing particles. More detailed results will be discussed in this presentation.

Generalized trends in the formation energies of perovskite oxides.

PubMed

Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

2013-05-28

Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds.

High Temperature Oxidation Behavior of gamma-Ni+gamma'-Ni3Al Alloys and Coatings Modified with Pt and Reactive Elements

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

Mu, Nan

2007-12-01

Materials for high-pressure turbine blades must be able to operate in the high-temperature gases (above 1000 C) emerging from the combustion chamber. Accordingly, the development of nickel-based superalloys has been constantly motivated by the need to have improved engine efficiency, reliability and service lifetime under the harsh conditions imposed by the turbine environment. However, the melting point of nickel (1455 C) provides a natural ceiling for the temperature capability of nickel-based superalloys. Thus, surface-engineered turbine components with modified diffusion coatings and overlay coatings are used. Theses coatings are capable of forming a compact and adherent oxide scale, which greatly impedesmore » the further transport of reactants between the high-temperature gases and the underlying metal and thus reducing attack by the atmosphere. Typically, these coatings contain β-NiAl as a principal constituent phase in order to have sufficient aluminum content to form an Al 2O 3 scale at elevated temperatures. The drawbacks to the currently-used {beta}-based coatings, such as phase instabilities, associated stresses induced by such phase instabilities, and extensive coating/substrate interdiffusion, are major motivations in this study to seek next-generation coatings. The high-temperature oxidation resistance of novel Pt + Hf-modified γ-Ni + γ-Ni 3Al-based alloys and coatings were investigated in this study. Both early-stage and 4-days isothermal oxidation behavior of single-phase γ-Ni and γ'-Ni 3Al alloys were assessed by examining the weight changes, oxide-scale structures, and elemental concentration profiles through the scales and subsurface alloy regions. It was found that Pt promotes Al 2O 3 formation by suppressing the NiO growth on both γ-Ni and γ'Ni 3Al single-phase alloys. This effect increases with increasing Pt content. Moreover, Pt exhibits this effect even at lower temperatures (~970 C) in the very early stage of oxidation. It was also inferred that Pt enhances the diffusive flux of aluminum from the substrate to the scale/alloy interface. Relatively low levels of hafnium addition to Pt-free γ'-Ni 3Al increased the extent of external NiO formation due to non-protective HfO 2 formation. Accordingly, this effect intensified with increasing Hf content from 0.2 to 0.5 at.%.« less

Removal of titanium plates coated with anodic titanium oxide ceramic: retrospective study.

PubMed

Velich, Norbert; Németh, Zsolt; Suba, Csongor; Szabó, György

2002-09-01

Transformation of the surface of metallic titanium with titanium oxides prepared in various ways is a modern procedure. For more than 15 years, the authors have been utilizing fixing elements coated with titanium oxide ceramics, prepared by anodic oxidation and thermal treatment, for purposes of jawbone osteosynthesis. The aim of the authors' work was to assess the extent to which the titanium oxide ceramic coating influences the fate of the plates used for osteosynthesis within the human organism, in regard to the possible need for their removal. During a 5-year period, 108 of 1,396 plates coated with anodic titanium oxide had to be removed for various reasons: plate exposure (47), osteomyelitis (25), palpable swelling and tenderness (21), patient request for psychological reasons (13), or fracture of the plate (2). In none of these 108 cases was metallosis observed, which otherwise is reported relatively frequently in the vicinity of traditional titanium fixing elements, nor was any tissue damage connected with the surface of the plates. The results indicate the favorable properties of the titanium oxide ceramic surface.

Understanding complete oxidation of methane on spinel oxides at a molecular level

DOE PAGES

Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; ...

2015-08-04

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2Omore » 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3O with a following dehydrogenation to -CH 2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

PubMed Central

Thorup, Casper; Schramm, Andreas

2017-01-01

ABSTRACT This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus. Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. PMID:28720728

RECONDITIONING FUEL ELEMENTS

DOEpatents

Brandt, H.L.

1962-02-20

A process is given for decanning fuel elements that consist of a uranium core, an intermediate section either of bronze, silicon, Al-Si, and uranium silicide layers or of lead, Al-Si, and uranium silicide layers around said core, and an aluminum can bonded to said intermediate section. The aluminum can is dissolved in a solution of sodium hydroxide (9 to 20 wt%) and sodium nitrate (35 to 12 wt %), and the layers of the intermediate section are dissolved in a boiling sodium hydroxide solution of a minimum concentration of 50 wt%. (AEC) A method of selectively reducing plutonium oxides and the rare earth oxides but not uranium oxides is described which comprises placing the oxides in a molten solvent of zinc or cadmium and then adding metallic uranium as a reducing agent. (AEC)

Lithium metal oxide electrodes for lithium batteries

DOEpatents

Thackeray, Michael M [Naperville, IL; Kim, Jeom-Soo [Naperville, IL; Johnson, Christopher S [Naperville, IL

2008-01-01

An uncycled electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li.sub.(2+2x)/(2+x)M'.sub.2x/(2+x)M.sub.(2-2x)/(2+x)O.sub.2-.delta., in which 0.ltoreq.x<1 and .delta. is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

Ni/metal hydride secondary element

DOEpatents

Bauerlein, Peter

2005-04-19

A Ni/metal hydride secondary element having a positive nickel hydroxide electrode, a negative electrode having a hydrogen storage alloy, and an alkaline electrolyte, the positive electrode, provided with a three-dimensional metallic conductive structure, also contains an aluminum compound which is soluble in the electrolyte, in addition to nickel hydroxide and cobalt oxide. The aluminum compound is aluminum hydroxide and/or aluminum oxide, and the mass of the aluminum compound which is present in the positive bulk material mixture is 0.1 to 2% by weight relative to the mass of the nickel hydroxide which is present. In combination with aluminum hydroxide or aluminum oxide, the positive electrode further contains lanthanoid oxidic compounds Y.sub.2 O.sub.3, La.sub.2 O.sub.3 and Ca(OH).sub.2, as well as mixtures of these compounds.

Potential Application of Silica Mineral from Dieng Mountain in Agriculture Sector to Control the Release Rate of Fertilizer Elements

NASA Astrophysics Data System (ADS)

Solihin; Mursito, Anggoro Tri; Dida, Eki N.; Erlangga, Bagus D.; Widodo

2017-07-01

Silica mineral, which comes along with geothermal fluid in Dieng, is a product of erosion, decomposition and dissolution of silicon oxide based mineral, which is followed by precipitation to form silica mineral. This silica cell structure is non crystalline, and it contains 85,60 % silicon oxide, 6.49 volatile elements, and also other oxide elements. Among the direct potential application of this silica is as raw material in slow release fertilizer. Silica in compacted slow release fertilizer is able control the release rate of fertilizer elements. Two type of slow release fertilizer has been made by using silica as the matrix in these slow release fertilizer. The first type is the mixing of ordinary solid fertilizer with Dieng silica, whereas the second one is the mixing of disposal leach water with Dieng silica. The release test shows that both of these modified fertilizers have slow release fertilizer characteristic. The release rate of fertilizer elements (magnesium, potassium, ammonium, and phosphate) can be significantly reduced. The addition of kaolin in the first type of slow release fertilizer makes the release rate of fertilizer elements can be more slowed down. Meanwhile in the second type of slow release fertilizer, the release rate is determined by ratio of silica/hydrogel. The lowest release rate is achieved by sample that has highest ratio of silica/hydrogel.

Low-ω3 Fatty Acid and Soy Protein Attenuate Alcohol-Induced Fatty Liver and Injury by Regulating the Opposing Lipid Oxidation and Lipogenic Signaling Pathways

PubMed Central

Reyes-Gordillo, Karina; Shah, Ruchi; Varatharajalu, Ravi; Garige, Mamatha; Leckey, Leslie C.

2016-01-01

Chronic ethanol-induced downregulation of peroxisome proliferator-activated receptor gamma coactivator 1-alpha (PGC1α) and upregulation of peroxisome proliferator-activated receptor gamma coactivator 1-beta (PGC1β) affect hepatic lipid oxidation and lipogenesis, respectively, leading to fatty liver injury. Low-ω3 fatty acid (Low-ω3FA) that primarily regulates PGC1α and soy protein (SP) that seems to have its major regulatory effect on PGC1β were evaluated for their protective effects against ethanol-induced hepatosteatosis in rats fed with Lieber-deCarli control or ethanol liquid diets with high or low ω3FA fish oil and soy protein. Low-ω3FA and SP opposed the actions of chronic ethanol by reducing serum and liver lipids with concomitant decreased fatty liver. They also prevented the downregulation of hepatic Sirtuin 1 (SIRT1) and PGC1α and their target fatty acid oxidation pathway genes and attenuated the upregulation of hepatic PGC1β and sterol regulatory element-binding protein 1c (SREBP1c) and their target lipogenic pathway genes via the phosphorylation of 5′ adenosine monophosphate-activated protein kinase (AMPK). Thus, these two novel modulators attenuate ethanol-induced hepatosteatosis and consequent liver injury potentially by regulating the two opposing lipid oxidation and lipogenic pathways. PMID:28074114

Study of the antioxidant capacity in gills of the Pacific oyster Crassostrea gigas in link with its reproductive investment.

PubMed

Béguel, Jean-Philippe; Huvet, Arnaud; Quillien, Virgile; Lambert, Christophe; Fabioux, Caroline

2013-01-01

Energy allocation principle is a core element of life-history theory in which "the cost of reproduction" corresponds to an acceleration of senescence caused by an increase in reproductive investment. In the "theory of aging", senescence is mainly due to the degradation of lipids, proteins and DNA by reactive oxygen species (ROS), by-products of oxidative metabolism. Some studies have shown that oxidative stress susceptibility could be a cost of reproduction. The present study investigates the effect of reproductive investment on antioxidant capacity in the gills of a species with a very high reproductive investment, the Pacific oyster Crassostrea gigas. We used RNA interference targeting the oyster vasa-like gene (Oyvlg) to produce oysters with contrasted reproductive investment. Antioxidant capacity was studied by measuring the mRNA levels of genes encoding major antioxidant enzymes, and the activity of these enzymes. The highest reproductive investment was associated with the highest transcript levels for glutathione peroxidase and extra-cellular and mitochondrial superoxide dismutase. In contrast, lipid peroxidation did not show any sign of oxidative damage whatever the reproductive investment. Up-regulation of certain genes encoding enzymes involved in the first step of ROS detoxification could therefore be a part of the organism's strategy for managing the pro-oxidant species produced by heavy reproductive investment. Copyright © 2012 Elsevier Inc. All rights reserved.

Synthesis of high T.sub.C superconducting coatings and patterns by melt writing and oxidation of metallic precursor alloys

DOEpatents

Gao, Wei; Vander Sande, John B.

1998-01-01

A method is provided for fabrication of superconducting oxides and superconducting oxide composites and for joining superconductors to other materials. A coating of a molten alloy containing the metallic elements of the oxide is applied to a substrate surface and oxidized to form the superconducting oxide. A material can be contacted to the molten alloy which is subsequently oxidized joining the material to the resulting superconducting oxide coating. Substrates of varied composition and shape can be coated or joined by this method.

Synthesis of high {Tc} superconducting coatings and patterns by melt writing and oxidation of metallic precursor alloys

DOEpatents

Gao, W.; Vander Sande, J.B.

1998-07-28

A method is provided for fabrication of superconducting oxides and superconducting oxide composites and for joining superconductors to other materials. A coating of a molten alloy containing the metallic elements of the oxide is applied to a substrate surface and oxidized to form the superconducting oxide. A material can be contacted to the molten alloy which is subsequently oxidized joining the material to the resulting superconducting oxide coating. Substrates of varied composition and shape can be coated or joined by this method. 5 figs.

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, C.C.; Nelson, P.A.; Dees, D.W.

1994-07-19

A solid oxide fuel cell is described having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed there between, and the anode, cathode and interconnect elements are comprised of substantially one material. 9 figs.

PRACTICAL APPLICATIONS FROM OBSERVATIONS OF MERCURY OXIDATION AND BINDING MECHANISMS

EPA Science Inventory

This paper describes a bench-scale program at the U.S. EPA. The goals of this program are to (a) isolate individual mechanisms of elemental mercury oxidation and oxidized mercury capture, (b) compete these mechanisms over a broad temperature range to determine which are dominant...

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Terpstra, Robert L

2014-10-21

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. Bodies made from the dispersion strengthened solidified particles exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures.

Solid State Carbon Monoxide Sensor

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Wood, George M. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); DAmbrosia, Christine M. (Inventor)

1999-01-01

A means for detecting carbon monoxide which utilizes an un-heated catalytic material to oxidize carbon monoxide at ambient temperatures. Because this reaction is exothermic, a thermistor in contact with the catalytic material is used as a sensing element to detect the heat evolved as carbon monoxide is oxidized to carbon dioxide at the catalyst surface, without any heaters or external heating elements for the ambient air or catalytic element material. Upon comparison to a reference thermistor, relative increases in the temperature of the sensing thermistor correspond positively with an increased concentration of carbon monoxide in the ambient medium and are thus used as an indicator of the presence of carbon monoxide.

Compilation of gallium resource data for bauxite deposits

USGS Publications Warehouse

Schulte, Ruth F.; Foley, Nora K.

2014-01-01

Gallium (Ga) concentrations for bauxite deposits worldwide have been compiled from the literature to provide a basis for research regarding the occurrence and distribution of Ga worldwide, as well as between types of bauxite deposits. In addition, this report is an attempt to bring together reported Ga concentration data into one database to supplement ongoing U.S. Geological Survey studies of critical mineral resources. The compilation of Ga data consists of location, deposit size, bauxite type and host rock, development status, major oxide data, trace element (Ga) data and analytical method(s) used to derive the data, and tonnage values for deposits within bauxite provinces and districts worldwide. The range in Ga concentrations for bauxite deposits worldwide is

The New Element Curium (Atomic Number 96)

DOE R&D Accomplishments Database

Seaborg, G. T.; James, R. A.; Ghiorso, A.

1948-01-01

Two isotopes of the element with atomic number 96 have been produced by the helium-ion bombardment of plutonium. The name curium, symbol Cm, is proposed for element 96. The chemical experiments indicate that the most stable oxidation state of curium is the III state.

Trace element analysis of human urine collected after administration of Gd-based MRI contrast agents: characterizing spectral interferences using inorganic mass spectrometry

PubMed Central

Steuerwald, Amy J.; Parsons, Patrick J.; Arnason, John G.; Chen, Zhen; Peterson, C. Matthew; Louis, Germaine M. Buck

2013-01-01

Analysis of human urine is commonly used in biomonitoring studies to assess exposure to essential (e.g., Cu, Zn, Se) and non-essential (Pb, Cd, Pt) trace elements. These data are also used in epidemiological studies to evaluate potential associations between trace element exposure and various health outcomes within a population. Today most trace element analyses are typically performed using quadrupole-based inductively coupled plasma mass spectrometry (Q-ICP-MS). However, there is always the potential for spectral interferences with Q-ICP-MS instrumentation, especially when analyzing human specimens that may contain medications and other exogenous substances. Moreover, such xenobiotics may be unknown to the investigators. In a recent study focusing on environmental exposures and endometriosis: Endometriosis: Natural History, Diagnosis, and Outcomes (ENDO Study), urine specimens (n=619) were collected from participating women upon enrollment into the study or prior to surgery or pelvic magnetic resonance imaging (MRI), and analyzed for 21 trace elements by Q-ICP-MS. Here we report on some anomalous results observed for Se and Pt with elevated concentrations up to several orders of magnitude greater than what might be expected based on established reference intervals. Further investigations using Sector Field (SF-) ICP-MS instrumentation led to identification of doubly charged and polyatomic gadolinium (Gd) species traced to a Gd-based contrast agent that was administered to some subjects just prior to urine collection. Specifically, interferences from Gd2+ and several minor polyatomics were identified as interferences on all of the major isotopes of Se including 74Se, 76Se, 77Se, 78Se, 80Se, and 82Se. While trace amounts of Pt were present in the urine, a number of Gd-containing polyatomic species were also evident as major interferences on all isotopes of Pt (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt), including Gd-chlorides, Gd-argides, and Gd-oxides. These observations underscore the importance of considering potential isobaric interferences when interpreting unusual trace element results for clinical specimens. PMID:27397951

Petrographic and geochemical contrasts and environmentally significant trace elements in marine-influenced coal seams, Yanzhou mining area, China

USGS Publications Warehouse

Liu, Gaisheng; Yang, P.; Peng, Z.; Chou, C.-L.

2004-01-01

The Yanzhou mining area in west Shandong Province, China contains coals of Permian and Carboniferous age. The 31 and 32 seams of the Permian Shanxi Formation and seams 6, 15-17 of the Carboniferous Taiyuan Formation were analyzed for coal petrology, mineralogy and geochemical parameters. The parameters indicate that the coal is high volatile bituminous in rank. The coal is characterized by high vitrinite and low to medium inertinite and liptinite contents. These properties may be related to evolution of the coal forming environment from more reducing conditions in a marine influenced lower delta plain environment for the early Taiyuan coals to more oxidizing paleoenvironments in an upper delta plain for the upper Shanxi coal seams. The major mineral phases present in the coal are quartz, kaolinite, pyrite and calcite. Sulfur is one of the hazardous elements in coal. The major forms of sulfur in coal are pyritic, organic and sulfate sulfur. Pyritic and organic sulfur generally account for the bulk of the sulfur in coal. Elemental sulfur also occurs in coal, but only in trace to minor amounts. In this paper, the distribution and concentration of sulfur in the Yanzhou mining district are analyzed, and the forms of sulfur are studied. The sulfur content of the Taiyuan coal seams is considerably higher than that of the Shanxi coals. Organic sulfur content is positively correlated to total and pyritic sulfur. The vertical variation of Cu, Zn, Pb, As, Th, U and sulfur contents in coal seam 3 of the Shanxi Formation in the Xinglongzhuang mine show that all these trace elements, with the exception of Th, are enriched in the top and bottom plies of the seam, and that their concentrations are also relatively high in the dirt bands within the seam. The pyritic sulfur is positively correlated with total sulfur, and both are enriched in the top, bottom and parting plies of the seam. The concentrations of the trace elements are closely related to sulfur and ash contents. Most of the trace elements are correlated with the ash content, and may be associated with the mineral matter in the coal. ?? 2004 Elsevier Ltd. All rights reserved.

Prevention of sulfide oxidation in sulfide-rich waste rock

NASA Astrophysics Data System (ADS)

Nyström, Elsa; Alakangas, Lena

2015-04-01

The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

High Temperature Oxidation of Hot-Dip Aluminized T92 Steels

NASA Astrophysics Data System (ADS)

Abro, Muhammad Ali; Hahn, Junhee; Lee, Dong Bok

2018-03-01

The T92 steel plate was hot-dip aluminized, and oxidized in order to characterize the high-temperature oxidation behavior of hot-dip aluminized T92 steel. The coating consisted of Al-rich topcoat with scattered Al3Fe grains, Al3Fe-rich upper alloy layer with scattered (Al, Al5Fe2, AlFe)-grains, and Al5Fe2-rich lower alloy layer with scattered (Al5Fe2, AlFe)-grains. Oxidation at 800 °C for 20 h formed (α-Al2O3 scale)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer), while oxidation at 900 °C for 20 h formed (α-Al2O3 scale plus some Fe2O3)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer) from the surface. During oxidation, outward migration of all substrate elements, inward diffusion of oxygen, and back and forth diffusion of Al occurred according to concentration gradients. Also, diffusion transformed and broadened AlFe and AlFe3 layers dissolved with some oxygen and substrate alloying elements. Hot-dip aluminizing improved the high-temperature oxidation resistance of T92 steel through preferential oxidation of Al at the surface.

High Temperature Oxidation of Hot-Dip Aluminized T92 Steels

NASA Astrophysics Data System (ADS)

Abro, Muhammad Ali; Hahn, Junhee; Lee, Dong Bok

2018-05-01

The T92 steel plate was hot-dip aluminized, and oxidized in order to characterize the high-temperature oxidation behavior of hot-dip aluminized T92 steel. The coating consisted of Al-rich topcoat with scattered Al3Fe grains, Al3Fe-rich upper alloy layer with scattered (Al, Al5Fe2, AlFe)-grains, and Al5Fe2-rich lower alloy layer with scattered (Al5Fe2, AlFe)-grains. Oxidation at 800 °C for 20 h formed (α-Al2O3 scale)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer), while oxidation at 900 °C for 20 h formed (α-Al2O3 scale plus some Fe2O3)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer) from the surface. During oxidation, outward migration of all substrate elements, inward diffusion of oxygen, and back and forth diffusion of Al occurred according to concentration gradients. Also, diffusion transformed and broadened AlFe and AlFe3 layers dissolved with some oxygen and substrate alloying elements. Hot-dip aluminizing improved the high-temperature oxidation resistance of T92 steel through preferential oxidation of Al at the surface.

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Taylor, Howard E.; Kimball, B.A.

2004-01-01

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

Identification of Antimony- and Arsenic-Oxidizing Bacteria Associated with Antimony Mine Tailing

PubMed Central

Hamamura, Natsuko; Fukushima, Koh; Itai, Takaaki

2013-01-01

Antimony (Sb) is a naturally occurring toxic element commonly associated with arsenic (As) in the environment and both elements have similar chemistry and toxicity. Increasing numbers of studies have focused on microbial As transformations, while microbial Sb interactions are still not well understood. To gain insight into microbial roles in the geochemical cycling of Sb and As, soils from Sb mine tailing were examined for the presence of Sb- and As-oxidizing bacteria. After aerobic enrichment culturing with AsIII (10 mM) or SbIII (100 μM), pure cultures of Pseudomonas- and Stenotrophomonas-related isolates with SbIII oxidation activities and a Sinorhizobium-related isolate capable of AsIII oxidation were obtained. The AsIII-oxidizing Sinorhizobium isolate possessed the aerobic arsenite oxidase gene (aioA), the expression of which was induced in the presence of AsIII or SbIII. However, no SbIII oxidation activity was detected from the Sinorhizobium-related isolate, suggesting the involvement of different mechanisms for Sb and As oxidation. These results demonstrate that indigenous microorganisms associated with Sb mine soils are capable of Sb and As oxidation, and potentially contribute to the speciation and mobility of Sb and As in situ. PMID:23666539

Melatonin successfully rescues hippocampal bioenergetics and improves cognitive function following drug intoxication by promoting Nrf2-ARE signaling activity.

PubMed

Chen, Li-You; Renn, Ting-Yi; Liao, Wen-Chieh; Mai, Fu-Der; Ho, Ying-Jui; Hsiao, George; Lee, Ai-Wei; Chang, Hung-Ming

2017-09-01

Prolonged exposure to gamma-hydroxybutyric acid (GHB) would cause drug intoxication in which impaired cognitive function results from enhanced hippocampal oxidative stress may serve as a major symptom in this deficiency. Considering melatonin possesses significant anti-oxidative efficacy, this study aimed to determine whether melatonin would successfully promote the nuclear factor erythroid 2-related factor 2 and antioxidant responsive element (Nrf2-ARE) signaling, depress oxidative stress, and rescue hippocampal bioenergetics and cognitive function following drug intoxication injury. Adolescent rats subjected to 10 days of GHB were received melatonin at doses of either 10 or 100 mg/kg. Time-of-flight secondary ion mass spectrometry, biochemical assay, quantitative histochemistry, [ 14 C]-2-deoxyglucose analysis, together with Morris water maze were employed to detect the molecular signaling, oxidative status, bioenergetic level, as well as the cognitive performances, respectively. Results indicated that in GHB-intoxicated rats, enhanced oxidative stress, increased cholesterol level, and decreased anti-oxidative enzymes activities were detected in hippocampal regions. Intense oxidative stress paralleled well with reduced bioenergetics and poor performance in behavioral testing. However, in rats treated with melatonin following GHB intoxication, all above parameters and cognitive function were gradually returned to nearly normal levels. Melatonin also remarkably promoted the translocation of Nrf2 from cytoplasm to nucleus in a dose-dependent manner, thereby increased the Nrf2-ARE signaling-related downstream anti-oxidative enzymes activities. As melatonin effectively rescues hippocampal bioenergetics through depressing the oxidative stress by promoting Nrf2-ARE molecular machinery, this study thus highlights for the first time that clinical use of melatonin may serve as a therapeutic strategy to improve the cognitive function in unsuspecting victims suffered from GHB intoxication injury. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Ti-rich komatiites from northern Norway

NASA Astrophysics Data System (ADS)

Barnes, Sarah-Jane; Often, Morten

1990-06-01

Komatiites of the Karasjok Greenstone Belt, northern Norway, show two unusual features: they have certain compositional differences compared with other komatiites, and they are largely volcaniclastic in origin. Their geological setting suggests that the komatiites were crupted into shallow water, thus permitting phreatomagmatic eruption, in a small ocean basin that opened in the Baltic Shield. The major oxides (except for TiO2), the trace elements Y, Sc, V, heavy rare earth elements (HREE), Cr, Co, Ni and the platinum group elements (PGE) cover similar ranges to those observed in other komatiites, but TiO2, Sm, Zr and Hf (Ti-associated elements, TAE) are enriched compared with abundances commonly reported for komatiites. Thus, the Karasjok komatiites have interelement ratios 2 to 3 times greater than chondritic between the TAE and the HREE, PGE, Sc, V, Y, Al (HRE-associated elements, HAE). The light rare earth elements (LREE), Ta and Th are enriched in some samples relative to Ti, Sm, Zr, and Hf, but are depleted in others. One group of rocks that is similar to the Karasjok komatiites both in terms of geological setting and geochemistry is the Baffin Bay picrites. The reason for the high concentrations of TAE in the Karasjok komatiites could be that they formed at lower degrees of partial melting than most komatiites. The greater-than-chondritic TAE/HAE ratios indicate that garnet was a residual phase during their formation, requiring that the melt formed at a pressure greater than 40 kb. A model involving decompression melting of a mantle plume rising in a rifting environment, can explain the main features of the Karasjok komatiites.

Distribution and grain-size partitioning of metals in bovfom sediments of an experimentally acidified Wisconsin lake

USGS Publications Warehouse

Elder, John F.

2007-01-01

A study of concentrations and distribution of major and trace elements in surficial bottom sediments of Little Rock Lake in northern Wisconsin included examination of spatial variation and grain-size effects. No significant differences with respect to metal distribution in sediments were observed between the two basins of the lake, despite the experimental acidification of one of the basins from pH 6.1 to 4.6. The concentrations of most elements in the lake sediments were generally similar to soil concentrations in the area and were well below sediment quality criteria. Two exceptions were lead and zinc, whose concentrations in July 1990 exceeded the criteria of 50 μg/g and 100 μg/g, respectively, in both littoral and pelagic sediments. Concentrations of some elements, particularly Cu, Pb, and Zn, increased along transects from nearshore to midlake, following a similar gradient of sedimentary organic carbon. In contrast, Mn, Fe, and alkali/alkaline-earth elements were at maximum concentrations in nearshore sediments. These elements are less likely to partition to organic particles, and their distribution is more dependent on mineralogical composition, grain size, and other factors. Element concentrations varied among different sediment grain-size fractions, although a simple inverse relation to grain size was not observed. Fe, Mn, Pb, and Zn were more concentrated in a grain-size range 20–60 tm than in either the very fine or the coarse fractions, possibly because of the aggregation of smaller particles cemented together by organic and Fe/Mn hydrous-oxide coatings.

REE geochemistry of 3.2 Ga BIF from the Mapepe Formation, Barberton Greenstone Belt, South Africa

NASA Astrophysics Data System (ADS)

Yahagi, T. R.; Yamaguchi, K. E.; Haraguchi, S.; Sano, R.; Teraji, S.; Kiyokawa, S.; Ikehara, M.; Ito, T.

2012-12-01

Banded iron formations (BIFs) are chemical sediments interbedded with Fe- and Si-rich layers, characteristically present in the early history of the Earth. A popular hypothesis for the formation of BIFs postulates that dissolved oxygen produced by photosynthesizers such as cyanobacteria oxidized dissolved ferrous Fe supplied by submarine hydrothermal activities. During precipitation of Fe-oxide minerals, phosphorus and rare earth elements (REEs) were most likely adsorbed on their surface. Therefore, chemical compositions of REEs that adsorbed onto Fe-oxide have useful information on the seawater chemistry at the time of deposition. Especially, information on the redox state of seawater and the extent of the contribution of hydrothermal activity during BIF deposition are expected to have been recorded. Occurrence of BIF has been traditionally tied to the chemical evolution of the atmosphere. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 Ga ago. Contrary, however, some studies have suggested that such oxygenation could have occurred much earlier (e.g., Hoashi et al., 2009). In this study, we used 3.2 Ga old BIF from the Mapepe Formation at the bottom of the Fig Tree Group of the Swaziland Supergroup in the northeastern part of the Barberton Greenstone Belt, South Africa. We aimed to constrain the marine environment, and by inference atmospheric environment, at the time of BIF deposition from REE geochemistry. Major elements and REE compositions of 37 samples were measured using XRF and ICP-MS, respectively. Samples with less than 1.0 wt% Al2O3 are considered to be "pure" BIFs with minimal amount of continental contamination, and are expected to have inherited marine REE signatures. Abundance of REE normalized by C1 chondrite for the analyzed samples commonly exhibits positive Eu anomaly and LREE

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Crystal structure and DNA repair activities of the AP endonuclease from Leishmania major.

PubMed

Vidal, Antonio E; Harkiolaki, Maria; Gallego, Claribel; Castillo-Acosta, Victor M; Ruiz-Pérez, Luis M; Wilson, Keith; González-Pacanowska, Dolores

2007-11-02

Apurinic/apyrimidinic endonucleases initiate the repair of abasic sites produced either spontaneously, from attack of bases by reactive oxygen species or as intermediates during base excision repair. The catalytic properties and crystal structure of Leishmania major apurinic/apyrimidinic endonuclease are described and compared with those of human APE1 and bacterial exonuclease III. The purified enzyme is shown to possess apurinic/apyrimidinic endonuclease activity of the same order as eukaryotic and prokaryotic counterparts and an equally robust 3'-phosphodiesterase activity. Consistent with this, expression of the L. major endonuclease confers resistance to both methyl methane sulphonate and H2O2 in Escherichia coli repair-deficient mutants while expression of the human homologue only reverts methyl methane sulphonate sensitivity. Structural analyses and modelling of the enzyme-DNA complex demonstrates a high degree of conservation to previously characterized homologues, although subtle differences in the active site geometry might account for the high 3'-phosphodiesterase activity. Our results confirm that the L. major's enzyme is a key element in mediating repair of apurinic/apyrimidinic sites and 3'-blocked termini and therefore must play an important role in the survival of kinetoplastid parasites after exposure to the highly oxidative environment within the host macrophage.

Systematic variations in the spectral properties of bright regions on Mars

NASA Technical Reports Server (NTRS)

Murchie, Scott; Mustard, John; Bishop, Janice; Head, James; Pieters, Carle; Erard, Stephane

1992-01-01

The color and albedo of the martian surface define two basic surface units, dark gray material interpreted as relatively unaltered 'rock' and bright reddish material interpreted as weathered 'soil'. Understanding the processes contributing to soil formation first requires assessment of the soil's composition and compositional diversity. We report first results of an investigation of the character and variability of Fe- and water-bearing phases in bright reddish materials using ISM data. We also explore implications of these results for chemical evolution of martian soil. Information on the composition and distribution of bright reddish material comes from three major sources: Viking images, measurements by the XRF and GCMS instruments on the Viking Landers, and spectroscopic data. The XRF experiment found nearly identical, Fe-rich major-element compositions comparable to weathered basalt. Soil water, amounting to approximately 1-3 wt. percent as measured by the GCMS, was liberated mostly by heating to greater than or equal to 350 C, suggesting that it is present in a chemically bound form. Spectroscopic studies have detected ferric oxide, probably hematite, as well as molecular water. However, the identities of major silicate phases have been controversial, with conflicting evidence regarding phyllosilicates. Two main interpretations of this evidence have been proposed: Weathering of basaltic glasses by H2O and CO2 formed a mixture of oxides, salts, and metastable phyllosilicates such as montmorillonite and 'palagonite' formed when basaltic melt contacted ground ice or water. Palagonite is a hydrated basaltic glass containing dispersed ferric oxide, recrystallized in varying degrees to phyllosilicates. Typically it is aphanitic, although some examples contain phenocrysts. In either case, eolian redistribution is thought to have resulted in the material's global homogenization. Imaging spectroscopic data returned by the ISM instrument on Phobos 2 provide a powerful new basis for evaluating the composition and origin of martian soil because they are indicative of the presence and distribution of water- and Fe-bearing phases whose mineralogy is sensitive to the history of chemical weathering.

Major and trace element concentrations in samples from 72275 and 72255. [chemical composition of lunar rocks

NASA Technical Reports Server (NTRS)

Haskin, L. A.; Blanchard, D. P.; Korotev, R.; Jacobs, J. W.; Brannon, J. A.; Herrmann, A. G.

1974-01-01

Analytical data have been obtained for Co, Sc, Hf, Zn, Cr, Ga, Rb, Cs, Ni, major elements, and rare earth elements in eight samples from boulder 1. The data for trace elements were obtained by radiochemical neutron activation analysis. Major elements, except Na and Mn, were obtained by atomic absorption spectral photometry. Values for Na and Mn were obtained by neutron activation analysis of the same powder that was later dissolved to provide the atomic absorption analyses.

Chemical Reduction of SIM MOX in Molten Lithium Chloride Using Lithium Metal Reductant

NASA Astrophysics Data System (ADS)

Kato, Tetsuya; Usami, Tsuyoshi; Kurata, Masaki; Inoue, Tadashi; Sims, Howard E.; Jenkins, Jan A.

2007-09-01

A simulated spent oxide fuel in a sintered pellet form, which contained the twelve elements U, Pu, Am, Np, Cm, Ce, Nd, Sm, Ba, Zr,Mo, and Pd, was reduced with Li metal in a molten LiCl bath at 923 K. More than 90% of U and Pu were reduced to metal to form a porous alloy without significant change in the Pu/U ratio. Small fractions of Pu were also combined with Pd to form stable alloys. In the gap of the porous U-Pu alloy, the aggregation of the rare-earth (RE) oxide was observed. Some amount of the RE elements and the actinoides leached from the pellet. The leaching ratio of Am to the initially loaded amount was only several percent, which was far from about 80% obtained in the previous ones on simple MOX including U, Pu, and Am. The difference suggests that a large part of Am existed in the RE oxide rather than in the U-Pu alloy. The detection of the RE elements and actinoides in the molten LiCl bath seemed to indicate that they dissolved into the molten LiCl bath containing the oxide ion, which is the by-product of the reduction, as solubility of RE elements was measured in the molten LiCl-Li2O previously.

Catalyst for elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, Maria; Liu, Wei

1995-01-01

A catalytic reduction process for the direct recovery of elemental sulfur from various SO.sub.2 -containing industrial gas streams. The catalytic process provides high activity and selectivity, as well as stability in the reaction atmosphere, for the reduction of SO.sub.2 to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over a metal oxide composite catalyst having one of the following empirical formulas: [(OF.sub.2).sub.1-n (RO.sub.1)n].sub.1-k M.sub.k, [(FO.sub.2).sub.1-n (RO.sub.1.5).sub.n ].sub.1-k M.sub.k, or [Ln.sub.x Zr.sub.1-x O.sub.2-0.5x ].sub.1-k M.sub.k wherein FO.sub.2 is a fluorite-type oxide; RO represents an alkaline earth oxide; RO.sub.1.5 is a Group IIIB or rare earth oxide; Ln is a rare earth element having an atomic number from 57 to 65 or mixtures thereof; M is a transition metal or a mixture of transition metals; n is a number having a value from 0.0 to 0.35; k is a number having a value from 0.0 to about 0.5; and x is a number having a value from about 0.45 to about 0.55.

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

NASA Technical Reports Server (NTRS)

Smialek, James L.

1997-01-01

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Characterization and analyses of acid-extractable and leached trace elements in dental cements.

PubMed

Camilleri, J; Kralj, P; Veber, M; Sinagra, E

2012-08-01

Determination of the elemental constitution and investigation of the total and leachable arsenic, chromium and lead in Portland cement, pure tricalcium silicate, Biodentine, Bioaggregate and mineral trioxide aggregate (MTA) Angelus. The chemical composition of Portland cement, MTA Angelus, tricalcium silicate cement, Biodentine and Bioaggregate was determined using X-ray fluorescence (XRF). Measurements of arsenic, lead and chromium were taken with inductively coupled plasma-mass spectrometry (ICP-MS), following acid digestion on the hydrated material and on leachates of cements soaked in Hank's balanced salt solution (HBSS). All the cements investigated had a similar oxide composition with the main oxide being calcium and silicon oxide. Both the Portland cement and MTA Angelus had an additional aluminium oxide. The dental cements included a radiopacifying material. All the materials tested had higher acid-extractable arsenic content than the level set by ISO 9917-1 (2007) and an acceptable level of lead. Regardless these high levels of trace elements present in the materials, the leaching in HBSS was minimal for all the dental material tested in contrast to the high levels displayed by Portland cement. Dental materials based on tricalcium silicate cement and MTA Angelus release minimal quantities of trace elements when in contact with simulated body fluids. The results of acid extraction could be affected by nonspecific matrix effects by the cement. © 2012 International Endodontic Journal.

[Studies on high temperature oxidation of noble metal alloys for dental use. (III) On high temperature oxidation resistance of noble metal alloys by adding small amounts of alloying elements. (author's transl)].

PubMed

Ohno, H

1976-11-01

The previous report pointed out the undesirable effects of high temperature oxidation on the casting. The influence of small separate additions of Zn, Mg, Si, Be and Al on the high temperature oxidation of the noble metal alloys was examined. These alloying elements were chosen because their oxide have a high electrical resistivity and they have much higher affinity for oxygen than Cu. The casting were oxidized at 700 degrees C for 1 hour in air. The results obtained were as follows: 1. The Cu oxides are not observed on the as-cast surface of noble metal alloys containing small amounts of Zn, Mg, Si, Be, and Al. The castings have gold- or silver-colored surface. 2. After heating of the unpolished and polished castings, the additions of Si, Be and Al are effective in preventing oxidation of Cu in the 18 carats gold alloys. Especially the golden surface is obtained by adding Be and Al. But there is no oxidation-resistance on the polished castings in the alloys containing Zn and Mg. 3. The zinc oxide film formed on the as-cast specimen is effective in preventing of oxidation Cu in 18 carats gold alloys. 4. It seems that the addition of Al is most available in dental application.

Assessment of oxidative stress markers and concentrations of selected elements in the leaves of Cassia occidentalis growing wild on a coal fly ash basin.

PubMed

Love, Amit; Banerjee, B D; Babu, C R

2013-08-01

Assessment of oxidative stress levels and tissue concentrations of elements in plants growing wild on fly ash basins is critical for realistic hazard identification of fly ash disposal areas. Hitherto, levels of oxidative stress markers in plants growing wild on fly ash basins have not been adequately investigated. We report here concentrations of selected metal and metalloid elements and levels of oxidative stress markers in leaves of Cassia occidentalis growing wild on a fly ash basin (Badarpur Thermal Power Station site) and a reference site (Garhi Mandu Van site). Plants growing on the fly ash basin had significantly high foliar concentration of As, Ni, Pb and Se and low foliar concentration of Mn and Fe compared to the plants growing on the reference site. The plants inhabiting the fly ash basin showed signs of oxidative stress and had elevated levels of lipid peroxidation, electrolyte leakage from cells and low levels of chlorophyll a and total carotenoids compared to plants growing at the reference site. The levels of both protein thiols and nonprotein thiols were elevated in plants growing on the fly ash basin compared to plants growing on the reference site. However, no differences were observed in the levels of cysteine, reduced glutathione and oxidized glutathione in plants growing at both the sites. Our study suggests that: (1) fly ash triggers oxidative stress responses in plants growing wild on fly ash basin, and (2) elevated levels of protein thiols and nonprotein thiols may have a role in protecting the plants from environmental stress.

Low temperature chemical processing of graphite-clad nuclear fuels

DOEpatents

Pierce, Robert A.

2017-10-17

A reduced-temperature method for treatment of a fuel element is described. The method includes molten salt treatment of a fuel element with a nitrate salt. The nitrate salt can oxidize the outer graphite matrix of a fuel element. The method can also include reduced temperature degradation of the carbide layer of a fuel element and low temperature solubilization of the fuel in a kernel of a fuel element.

Characterization of Rare Earth Element Minerals in Coal Utilization Byproducts

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

Montross, Scott N.; Verba, Circe A.; Collins, Keith

The United States currently produces over 100 million tons of coal utilization byproducts (CUB) per year in the form of fly ash, bottom ash, slag, and flue gas (American Coal Ash Association (ACCA), 2015). But this “waste material” also contains potentially useful levels of rare earth elements (REE). Rare earth elements are crucial for many existing and emerging technologies, but the U.S. lacks a domestic, sustainable REE source. Our project explored the possibility of developing a supply of REEs for U.S. technologies by extracting REEs from CUBs. This work offers the potential to reduce our dependence on other countries formore » supply of these critical elements (NETL, REE 2016 Project Portfolio). Geologic and diagenetic history, industrial preparation methods, and the specific combustion process all play major roles in the composition of CUB. During combustion, inorganic mineral phases of coal particles are fluidized at temperatures higher than 1400oC, so inorganic mineral materials are oxidized, fused, disintegrated, or agglomerated into larger spherical and amorphous (non-crystalline) particles. The original mineralogy of the coal-containing rock and heating/cooling of the material significantly affects the composition and morphology of the particles in the combustion byproduct (Kutchko and Kim, 2006). Thus, different types of coal/refuse/ash must be characterized to better understand mineral evolution during the combustion process. Our research focused on developing a working model to address how REE minerals behave during the combustion process: this research should help determine the most effective engineering methods for extracting REEs from CUBs. We used multimodal imaging and image processing techniques to characterize six rock and ash samples from different coal power plants with respect to morphology, grain size, presence of mineral phases, and elemental composition. The results of these characterization activities provided thresholds for realizing the occurrence of REE mineral phases in CUB and allowed us to calculate structural and volumetric estimates of REE. Collectively, the rock and coal ash samples contained minerals such as quartz, kaolinite, muscovite/illite, iron oxide (as hematite or magnetite), mullite, and clinochlore. Trace minerals included pyrite, zircon, siderite, rutile, diopside, foresterite, gypsum, and barite. We identified REE phosphate minerals monazite (Ce,La,Nd,Th)(PO 4,SiO 4), xenotime (YPO 4,SiO 4), and apatite (Ca 5(PO 4) 3(F,Cl,OH) via SEM and electron microprobe analysis: these materials generally occurred as 1-10 μm-long crystals in the rock and ash samples. As has been shown in other studies, amorphous material-aluminosilicate glass or iron oxyhydroxide-are the major components of coal fly and bottom ash. Trace amounts of amorphous calcium oxide and mixed element (e.g., Al-Si-Ca-Fe) slag are also present. Quartz, mullite, hematite, and magnetite are the crystalline phases present. We found that REEs are present as monomineralic grains dispersed within the ash, as well as fused to or encapsulated by amorphous aluminosilicate glass particles. Monazite and xenotime have relatively high melting points (>1800 °C) compared to typical combustion temperatures; our observations indicate that the REE-phosphates, which presumably contribute a large percentage of REE to the bulk ash REE pool, as measured by mass spectroscopy, are largely unaltered by the combustion. Our study shows that conventional coal combustion processes sequester REE minerals into aluminosilicate glass phases, which presents a new engineering challenge for extracting REE from coal ash. The characterization work summarized in this report provides a semi-quantitative assessments of REE in coal-containing rock and CUB. The data we obtained from 2- and 3-D imaging, elemental mapping, volumetric estimates, and advanced high-resolution pixel classification successfully identified the different mineral phases present in CUB. Further, our characterization results can guide techniques for extracting REEs from CUB, or other geologic and engineered materials. Whilst, interpretations will inform future REE separation and extraction techniques and technologies practical for commercial utilization of combustion byproducts generated by power plants.« less

Bacterial Oxidation of Iron in Olivine: Implications for the Subsurface Biosphere, Global Chemical Cycles, and Life on Mars

NASA Astrophysics Data System (ADS)

Fisk, M. R.; Popa, R.; Smith, A. R.; Popa, R.; Boone, J.

2011-12-01

We isolated 21 species of bacteria from subseafloor and terrestrial basalt environments and which thrive on olivine at neutral pH. Cell numbers increase four to five orders of magnitude over three weeks in media where the only metabolic energy comes from the oxidation of Fe(II) in olivine. The subseafloor bacteria were isolated from a borehole on the flank of Juan de Fuca Ridge in the northeast Pacific basin where the temperature ranged from 4 up to 64 °C over four years. Terrestrial isolates originated from the basalt-ice boundary in a lava tube on the flank of Newberry Caldera in the Cascades of Oregon. The borehole water was either seawater or seawater plus subseafloor formation water and the lava tube ice was frozen meteoric or ground water. Although microorganisms capable of oxidizing iron for growth are known, microbes that oxidize iron from silicate minerals at neutral pH have not previously been cultured. The 21 species in this study are the first neutrophilic, iron-oxidizing bacteria (nFeOB) to be isolated and cultured that grow on olivine. These nFeOB are primary producers and we believe that they are a widespread component of the subsurface biosphere. In addition to their ability use iron from olivine, these microbes assimilate carbon from bicarbonate in solution and can grow when oxygen pressures are low. They also use nitrate as an alternative electron acceptor to oxygen in anaerobiosis. Since basalt is the most common rock in the Earth's crust and iron is the fourth most abundant element in the crust, we believe nFeOB are likely to be a significant portion of the subsurface biosphere. They are likely to affect, and perhaps in some environments control, the weathering rate of olivine and possibly of pyroxene and basalt glass. Olivine is a component of Mars's surface and it is present on other rocky bodies in the solar system. The ability of these bacteria to use Fe(II) from olivine, to assimilate carbon, to grow at low temperature, and to use low levels of oxygen and nitrate as oxidants would allow them to survive below the surface of Mars. These cultured organisms, which are the first known to oxidize iron from olivine at neutral pH, may be a major component of the subsurface biosphere, may affect global chemical cycles of elements in basalt, and could potentially, live in the Martian subsurface.

Contemporary Issues in Science. Implementation Manual.

ERIC Educational Resources Information Center

Staten Island Continuum of Education, NY.

Contemporary Issues in Science Program (CIIS) is designed to provide teachers and students with the necessary tools and strategies for bringing contemporary scientific issues into the classroom. Provided in this document are discussions of the three major elements in the program, support elements, and major activities. Major elements include the…

Model of Silicon Refining During Tapping: Removal of Ca, Al, and Other Selected Element Groups

NASA Astrophysics Data System (ADS)

Olsen, Jan Erik; Kero, Ida T.; Engh, Thorvald A.; Tranell, Gabriella

2017-04-01

A mathematical model for industrial refining of silicon alloys has been developed for the so-called oxidative ladle refining process. It is a lumped (zero-dimensional) model, based on the mass balances of metal, slag, and gas in the ladle, developed to operate with relatively short computational times for the sake of industrial relevance. The model accounts for a semi-continuous process which includes both the tapping and post-tapping refining stages. It predicts the concentrations of Ca, Al, and trace elements, most notably the alkaline metals, alkaline earth metal, and rare earth metals. The predictive power of the model depends on the quality of the model coefficients, the kinetic coefficient, τ, and the equilibrium partition coefficient, L for a given element. A sensitivity analysis indicates that the model results are most sensitive to L. The model has been compared to industrial measurement data and found to be able to qualitatively, and to some extent quantitatively, predict the data. The model is very well suited for alkaline and alkaline earth metals which respond relatively fast to the refining process. The model is less well suited for elements such as the lanthanides and Al, which are refined more slowly. A major challenge for the prediction of the behavior of the rare earth metals is that reliable thermodynamic data for true equilibrium conditions relevant to the industrial process is not typically available in literature.

Methods for separating oxygen from oxygen-containing gases

DOEpatents

Mackay, Richard; Schwartz, Michael; Sammells, Anthony F.

2000-01-01

This invention provides mixed conducting metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes. The materials of this invention have the general formula: A.sub.x A'.sub.x A".sub.2-(x+x') B.sub.y B'.sub.y B".sub.2-(y+y') O.sub.5+z ; where x and x' are greater than 0; y and y' are greater than 0; x+x' is less than or equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the f block lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides or Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof; and B' and B" are different elements and are independently selected from the group of elements Mg or the d-block transition elements. The invention also provides methods for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula. Examples of the materials used for the preparation of the membrane include A.sub.x Sr.sub.x' B.sub.y Fe.sub.y' Co.sub.2-(y+y') O.sub.5+z, where x is about 0.3 to about 0.5, x' is about 1.5 to about 1.7, y is 0.6, y' is between about 1.0 and 1.4 and B is Ga or Al.

In-situ XRD and EDS method study on the oxidation behaviour of Ni-Cu sulphide ore.

PubMed

Li, Guangshi; Cheng, Hongwei; Xiong, Xiaolu; Lu, Xionggang; Xu, Cong; Lu, Changyuan; Zou, Xingli; Xu, Qian

2017-06-12

The oxidation mechanism of sulfides is the key issue during the sulphide-metallurgy process. In this study, the phase transformation and element migration were clearly demonstrated by in-situ laboratory-based X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS), respectively. The reaction sequence and a four-step oxidation mechanism were proposed and identified. The elemental distribution demonstrated that at a low temperature, the Fe atoms diffused outward and the Ni/Cu atoms migrated toward the inner core, whereas the opposite diffusion processes were observed at a higher temperature. Importantly, the unique visual presentation of the oxidation behaviour provided by the combination of in-situ XRD and EDS might be useful for optimising the process parameters to improve the Ni/Cu extraction efficiency during Ni-Cu sulphide metallurgy.

METHOD FOR THE RECOVERY AND PURIFICATION OF BERKELIUM

DOEpatents

Hulet, E.K.

1959-10-20

A solvent extraction process is described for the separation of berkelium from a mixture of elements in the lanthanum and actinium series of the periodic table. In particular, the mixture of elements is dissolved in 1.0N nitric acid, and the resulting solution is extracted with n-tributyl phosphate containlng a stoichiometric excess of solid sodium bismuthate. The berkelium present in the nitric acid solution is oxidized to the IV oxidation state and is preferentially- extracted into the n-tributyl phosphate. The organic phase, containing berkelium in an oxidized state, is extracted with 0.1N hydrochloric acid solution containing a small quantity- of a reducing agent such as yvdrazine hydrochloride. The berkelium is reduced to the III oxidation state and is extracted into the aqueous phase. The berkelium is then recovered from the aqueous phase.

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

DOE PAGES

Evans, William J.

2016-09-15

A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Lastly, we present background information on the rare-earth and actinide elements, as well as the sequencemore » of events that led to these unexpected developments in the oxidation state chemistry of these metals.« less

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

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

Evans, William J.

A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Lastly, we present background information on the rare-earth and actinide elements, as well as the sequencemore » of events that led to these unexpected developments in the oxidation state chemistry of these metals.« less

34S/32S fractionation in sulfur cycles catalyzed by anaerobic bacteria

NASA Technical Reports Server (NTRS)

Fry, B.; Gest, H.; Hayes, J. M.

1988-01-01

Stable isotopic distributions in the sulfur cycle were studied with pure and mixed cultures of the anaerobic bacteria, Chlorobium vibrioforme and Desulfovibrio vulgaris. D. vulgaris and C. vibrioforme can catalyze three reactions constituting a complete anaerobic sulfur cycle: reduction of sulfate to sulfide (D. vulgaris), oxidation of sulfide to elemental sulfur (C. vibrioforme), and oxidation of sulfur to sulfate (C. vibrioforme). In all experiments, the first and last reactions favored concentration of the light 32S isotope in products (isotopic fractionation factor epsilon = -7.2 and -1.7%, respectively), whereas oxidation of sulfide favored concentration of the heavy 34S isotope in products (epsilon = +1.7%). Experimental results and model calculations suggest that elemental sulfur enriched in 34S versus sulfide may be a biogeochemical marker for the presence of sulfide-oxidizing bacteria in modern and ancient environments.

Effect of Sn on the oxide subscale structure formed on a 3% Si steel

NASA Astrophysics Data System (ADS)

Cesar, Maria das G. M. M.; Silveira, Carolina C.; Paolinelli, Sebastião C.; Cicale, Stefano

2018-04-01

Addition of tin in 3% Si steel is a method to improve magnetic properties since tin in steel is known as an element that segregates at grain boundaries, inhibits grain growth and has a dragging effect on grain boundary movement. However, tin is generally known as an element that has a harmful effect on surface coating properties. The oxide subscale formed on the decarburization annealing of a 3% Si steel containing tin was investigated by SEM, EDS, GDS and FTIR. The forsterite film was evaluated by SEM, EDS and GDS. The higher tin content decreased thickness, oxygen and fayalite/silica ratio in the subscale and resulted into a discontinuous forsterite film with poor oxidation resistance. After secondary coating the samples presented a reddish color due to the formation of iron oxide and poor dielectric property.

Efficient catalytic As(III) oxidation on the surface of ferrihydrite in the presence of aqueous Mn(II).

PubMed

Lan, Shuai; Ying, Hong; Wang, Xiaoming; Liu, Fan; Tan, Wenfeng; Huang, Qiaoyun; Zhang, Jing; Feng, Xionghan

2018-01-01

Arsenic is a carcinogenic element that exists primarily as arsenate [As(V)] and arsenite [As(III)] in the nature environment, with As(III) being more toxic and mobile of the two species. In addition, ferrihydrite, which is widely distributed in soils and aquatic environments, can catalyze the oxidation of Mn(II) and accelerate the formation of high-valence Mn, which can significantly influence the speciation, toxicity, and mobility of As when these species co-exist. In this context, we herein explored the mechanism of As(III) oxidation in the presence of ferrihydrite and Mn(II) using a kinetic approach combined with multiple spectroscopic techniques, including X-ray absorption near edge spectroscopy, in situ horizontal attenuated total-reflectance Fourier transform infrared spectroscopy, and in situ quick scanning X-ray absorption spectroscopy. Our results indicate that efficient As(III) oxidation by dissolved O 2 occurs on the surface of ferrihydrite in the presence of aqueous Mn(II). Compared with As(III) oxidation in the presence of ferrihydrite and Mn oxides (i.e., Mn oxides/hydroxides), the degree of As(III) oxidation in the ferrihydrite-Mn(II) system was significantly higher, and the majority of generated As(V) was adsorbed on the mineral (i.e., ferrihydrite) surface. Furthermore, As(III) oxidation was enhanced upon increasing both the molar ratio of Mn(II)/As(III) and the solution pH. The greater As(III) oxidation by O 2 in the ferrihydrite-Mn(II) system was mainly attributed to the formation of a strong oxidant of the instantaneous intermediate Mn(III) species via Mn(II) oxidation under catalysis by the ferrihydrite surface. Moreover, As(III) oxidation occurred mainly on the ferrihydrite surface and was accompanied by the regeneration of Mn(II), thereby rendering it recyclable. These results therefore provide new insights into the mechanism of As(III) oxidation on the surfaces of Fe oxides (i.e., Fe oxides/hydroxides) in the presence of aqueous Mn(II) as well as the new details regarding the electron transfer mechanisms between the As(III)-Mn(II, III)-O 2 species at the ferrihydrite surface, and could lead to novel approaches for As(III) contaminant remediation in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Associations between microvascular function and short-term exposure to traffic-related air pollution and particulate matter oxidative potential.

PubMed

Zhang, Xian; Staimer, Norbert; Tjoa, Tomas; Gillen, Daniel L; Schauer, James J; Shafer, Martin M; Hasheminassab, Sina; Pakbin, Payam; Longhurst, John; Sioutas, Constantinos; Delfino, Ralph J

2016-07-26

Short-term exposure to ambient air pollution has been associated with acute increases in cardiovascular hospitalization and mortality. However, causative chemical components and underlying pathophysiological mechanisms remain to be clarified. We hypothesized that endothelial dysfunction would be associated with mobile-source (traffic) air pollution and that pollutant components with higher oxidative potential to generate reactive oxygen species (ROS) would have stronger associations. We carried out a cohort panel study in 93 elderly non-smoking adults living in the Los Angeles metropolitan area, during July 2012-February 2014. Microvascular function, represented by reactive hyperemia index (RHI), was measured weekly for up to 12 weeks (N = 845). Air pollutant data included daily data from regional air-monitoring stations, five-day average PM chemical components and oxidative potential in three PM size-fractions, and weekly personal nitrogen oxides (NOx). Linear mixed-effect models estimated adjusted changes in microvascular function with exposure. RHI was inversely associated with traffic-related pollutants such as ambient PM2.5 black carbon (BC), NOx, and carbon monoxide (CO). An interquartile range change increase (1.06 μg/m(3)) in 5-day average BC was associated with decreased RHI, -0.093 (95 % CI: -0.151, -0.035). RHI was inversely associated with other mobile-source components/tracers (polycyclic aromatic hydrocarbons, elemental carbon, and hopanes), and PM oxidative potential as quantified in two independent assays (dithiothreitol and in vitro macrophage ROS) in accumulation and ultrafine PM, and transition metals. Our findings suggest that short-term exposures to traffic-related air pollutants with high oxidative potential are major components contributing to microvascular dysfunction.

Mineralogical and geochemical characteristics of BERYL (AQUAMARINE) from the Erongo Volcanic Complex, Namibia

NASA Astrophysics Data System (ADS)

Lum, Jullieta Enone; Viljoen, Fanus; Cairncross, Bruce; Frei, Dirk

2016-12-01

The granite hosted pegmatites of the Erongo Volcanic Complex in central Namibia are well known for the wide variety of minerals present, of considerable interest to mineral collectors. These include (amongst others) often spectacular, museum quality examples of beryl, schorl, jeremejevite, fluorite, quartz, goethite and cassiterite. The locality is particularly recognized for hosting a variety of beryl types, including green, yellow (heliodor), colorless (goshenite) and blue/greenish blue (aquamarine) variants. Comprehensive geochemical studies of the Erongo beryls are very limited. The present contribution serves to document the visual characteristics (colour, colour zoning, inclusion content) as well as the major and trace element chemistry of 42 blue, two green and one colorless beryl from Erongo, and to compare these with other localities worldwide. The beryls from Erongo are generally subhedral to euhedral with a well-formed prismatic habit. Idiomorphic crystals, characterised by strong hexagonal prisms, are common. Beryl is commonly associated with schorl, quartz, muscovite, alkali feldspar, plagioclase feldspar, iron oxides, foitite, rossmanite and cassiterite. Aquamarines range from pale blue to deep blue or greenish blue, with marked colour zoning seen in a number of samples. One of the two green beryls examined is of a medium green colour, and is heavily included, while the other specimen has a pale yellowish green colour. The goshenite sample is colourless, clear, and transparent. Numerous cracks are present in the samples examined, and these are usually filled by iron oxides. Inclusions species encountered in the beryl samples are schorl, quartz, muscovite, feldspar, iron oxides and cassiterite, clearly reflective of the host pegmatite mineralogy. Aquamarine and green beryl contain iron as the main chromophore while goshenite is devoid of chromophores. Fe contents in beryl increase with colour intensity, consistent with the known chromatic effects of Fe in blue, yellow and green beryl. Consistently low Cr contents in all studied beryls do not concur with Cr being a chromophore element for green beryl. Marked compositional zoning is present, with variable Fe (0.79-3.19 wt% FeOT), Na (0.09-0.35 wt% Na2O), Al (15.99-18.18 wt% Al2O3) in aquamarine. Zoning patterns range from simple core-to-rim transitions, to more complex sector and/or oscillatory zoning. Trace element contents vary amongst the beryl types examined, with the highest contents and most extreme variations observed in the aquamarines. This is probably partly due to sampling bias relating to the size of the sample set examined. Octahedral cation substitution is dominant, with Na incorporated (over Cs) at the channels, in order to maintain charge balance. Inferences based on charge balance arguments suggest that tetrahedral Be-Li substitution in these beryls may also be present. Cs, Sc, Ga and Mn are positively correlated with Rb, consistent with the incorporation of these elements at the octahedral site (Sc, Mn and minor Ga) or the channel site (Cs, Rb), in order to preserve charge balance. In contrast, Ca, Zn and Ti do not correlate with Rb, nor with Cs. This is unexpected, as Ti and Ca are known to substitute at the octahedral site in beryl, while Ca may also enter the 2a channel site of beryl. The major and trace element chemistry of the beryls are generally similar to other worldwide beryl deposits of similar colour and do not serve to distinguish beryls from Erongo.

Oxidative stress and age-related changes in T cells: is thalassemia a model of accelerated immune system aging?

PubMed

Ghatreh-Samani, Mahdi; Esmaeili, Nafiseh; Soleimani, Masoud; Asadi-Samani, Majid; Ghatreh-Samani, Keihan; Shirzad, Hedayatolah

2016-01-01

Iron overload in β-thalassemia major occurs mainly due to blood transfusion, an essential treatment for β-thalassemia major patients, which results in oxidative stress. It has been thought that oxidative stress causes elevation of immune system senescent cells. Under this condition, cells normally enhance in aging, which is referred to as premature immunosenescence. Because there is no animal model for immunosenescence, most knowledge on the immunosenescence pattern is based on induction of immunosenescence. In this review, we describe iron overload and oxidative stress in β-thalassemia major patients and how they make these patients a suitable human model for immunosenescence. We also consider oxidative stress in some kinds of chronic virus infections, which induce changes in the immune system similar to β-thalassemia major. In conclusion, a therapeutic approach used to improve the immune system in such chronic virus diseases, may change the immunosenescence state and make life conditions better for β-thalassemia major patients.

Oxidative stress and age-related changes in T cells: is thalassemia a model of accelerated immune system aging?

PubMed Central

Ghatreh-Samani, Mahdi; Esmaeili, Nafiseh; Soleimani, Masoud; Asadi-Samani, Majid; Ghatreh-Samani, Keihan

2016-01-01

Iron overload in β-thalassemia major occurs mainly due to blood transfusion, an essential treatment for β-thalassemia major patients, which results in oxidative stress. It has been thought that oxidative stress causes elevation of immune system senescent cells. Under this condition, cells normally enhance in aging, which is referred to as premature immunosenescence. Because there is no animal model for immunosenescence, most knowledge on the immunosenescence pattern is based on induction of immunosenescence. In this review, we describe iron overload and oxidative stress in β-thalassemia major patients and how they make these patients a suitable human model for immunosenescence. We also consider oxidative stress in some kinds of chronic virus infections, which induce changes in the immune system similar to β-thalassemia major. In conclusion, a therapeutic approach used to improve the immune system in such chronic virus diseases, may change the immunosenescence state and make life conditions better for β-thalassemia major patients. PMID:27095931

Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

DOEpatents

Rohrmann, Charles A.

1978-01-01

A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

Pack Cementation Aluminide Coatings on Superalloys: Codeposition of Cr and Reactive Elements (RE). Technical Report 1. Chromium and Reactive Element(RE)- Modified Aluminide Diffusion Coatings on Superalloys: Environmental Testing. Technical Report 2

DTIC Science & Technology

1992-11-01

Godlewska and K. Godlewski, Oxid. Met., 22 (1984) 117. 4. J.E. Restall, U.S. Patent #4,687,684 (1987). 5. P.N. Walsh, in Proceeding of the Fourth...McCarron, N.R. Lindblad, and D. Chatterji, Corrosion, 32 (1976) 476. 34 33. E. Godlewska and K. Godlewski, Oxid. Met., 22 (1984) 117. 34. B. Pieraggi

Trace element distribution in waters of the northern catchment area of Lake Linneret, northern Israel

NASA Astrophysics Data System (ADS)

Sandler, A.; Brenner, I. B.; Halicz, L.

1988-02-01

Waters of the northern watershed of Lake Kineret, sampled during the period 1978 1983, were analyzed for their major and trace element contents. The trace element concentrations of the major water sources of the watershed (the Dan and Banias springs) represent background values. After emergence, the waters are subjected to human activity. In crossing the populated and cultivated Hula Basin in man-made canals, the major and trace element contents increase. In comparison to the trace element concentrations, those of the major elements have narrow ranges and small temporal fluctuations. Trace element concentrations varied by 3 orders of magnitude, and temporal variations were large but not neccessarily seasonal. Point sources of trace elements were urban effluents, fish pond wastes, and peat soil drainage. The trace element concentrations decrease in the waters of the last segment of the Jordan River. All measured trace elements were below the criteria levels established by regulatory agencies. Several, however, were of the same order of magnitude. Addition of wastes from enhanced recycling, and morphologic modification of the final course of the Jordan River could result in increase in the trace element concentrations in the water.

Environmental Effects in Niobium Base Alloys and Other Selected Intermetallic Compounds

DTIC Science & Technology

1991-04-30

formation of this surface layer requires that the oxide be more stable than the lowest oxide of the base metal. Figure 2 indicates the free energies of...such requirements for temperatures beyond 10500C are aluminum and silicon. Both of these elements form oxides with large, negative free energies of...Nb-Si, and Ta-Si systems. In attempting to develop alloys in which aluminum or silicon is selectively oxidized, the standard free energies of oxides

Low cost, formable, high T(sub c) superconducting wire

NASA Technical Reports Server (NTRS)

Smialek, James L. (Inventor)

1991-01-01

A ceramic superconductivity part such as a wire is produced through the partial oxidation of a specially formulated copper alloy in the core. The alloys contain low level quantities of rare earth and alkaline earth dopant elements. Upon oxidation at high temperature, superconducting oxide phases are formed as a thin film.

Periodicity in the Acid-Base Behavior of Oxides and Hydroxides.

ERIC Educational Resources Information Center

Rich, Ronald L.

1985-01-01

Aqueous solubilities of many important hydrous oxides and hydroxides are displayed, for the various elements, as functions primarily of pH. These graphs are then arranged in groups to facilitate studies of the effects of oxidation state, electron structure, and position in the periodic table, along with size and coordination number. (JN)

Biogeochemical processes controlling the mobility of major ions and trace metals in aquitard sediments beneath an oil sand tailing pond: laboratory studies and reactive transport modeling.

PubMed

Holden, A A; Haque, S E; Mayer, K U; Ulrich, A C

2013-08-01

Increased production and expansion of the oil sand industry in Alberta are of great benefit to the economy, but they carry major environmental challenges. The volume of fluid fine tailings requiring storage is 840×10(6) m(3) and growing, making it imperative that we better understand the fate and transport of oil sand process-affected water (OSPW) seepage from these facilities. Accordingly, the current study seeks to characterize both a) the potential for major ion and trace element release, and b) the principal biogeochemical processes involved, as tailing pond OSPW infiltrates into, and interacts with, underlying glacial till sediments prior to reaching down gradient aquifers or surface waters. Objectives were addressed through a series of aqueous and solid phase experiments, including radial diffusion cells, an isotope analysis, X-ray diffraction, and sequential extractions. The diffusion cells were also simulated in a reactive transport framework to elucidate key reaction processes. The experiments indicate that the ingress and interaction of OSPW with the glacial till sediment-pore water system will result in: a mitigation of ingressing Na (retardation), displacement and then limited precipitation of exchangeable Ca and Mg (as carbonates), sulfate reduction and subsequent precipitation of the produced sulfides, as well as biodegradation of organic carbon. High concentrations of ingressing Cl (~375 mg L(-1)) and Na (~575 mg L(-1)) (even though the latter is delayed, or retarded) are expected to migrate through the till and into the underlying sand channel. Trace element mobility was influenced by ion exchange, oxidation-reduction, and mineral phase reactions including reductive dissolution of metal oxyhydroxides - in accordance with previous observations within sandy aquifer settings. Furthermore, although several trace elements showed the potential for release (Al, B, Ba, Cd, Mn, Pb, Si, Sr), large-scale mobilization is not supported. Thus, the present results suggest that in addition to the commonly cited naphthenic acids, remediation of OSPW-impacted groundwater will need to address high concentrations of major ions contributing to salinization. Copyright © 2013 Elsevier B.V. All rights reserved.

The content of trace element iron is a key factor for competition between anaerobic ammonium oxidation and methane-dependent denitrification processes.

PubMed

Lu, Yong-Ze; Fu, Liang; Li, Na; Ding, Jing; Bai, Ya-Nan; Samaras, Petros; Zeng, Raymond Jianxiong

2018-05-01

Coupling of anaerobic ammonium oxidation (Anammox) with denitrifying anaerobic methane oxidation (DAMO) is a sustainable pathway for nitrogen removal and reducing methane emissions from wastewater treatment processes. However, studies on the competitive relation between Anammox bacteria and DAMO bacteria are limited. Here, we investigated the effects of variations in the contents of trace element iron on Anammox and DAMO microorganisms. The short-term results indicated that optimal concentrations of iron, which obviously stimulated the activity of Amammox bacteria, DAMO bacteria and DAMO archaea, were 80, 20, and 80 μM, respectively. The activity of Amammox bacteria increased more significant than DAMO bacteria with increasing contents of trace element iron. After long-term incubation with high content of trace element iron of 160 μM in the medium, Candidatus Brocadia (Amammox bacteria) outcompeted Candidatus Methylomirabilis oxyfera (DAMO bacteria), and ANME-2d (DAMO archaea) remarkably increased in number and dominated the co-culture systems (64.5%). Meanwhile, with further addition of iron, the removal rate of ammonium and nitrate increased by 13.6 and 9.2 times, respectively, when compared with that noted in the control. As far as we know, this study is the first to explore the important role of trace element iron contents in the competition between Anammox bacteria and DAMO bacteria and further enrichment of DAMO archaea by regulating the contents of trace element iron. Copyright © 2018 Elsevier Ltd. All rights reserved.

Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

PubMed

Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

2015-06-16

Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a hydrogen absorption/desorption process as a trigger. Several atom percent replacements of Pd with Pt atoms resulted in a significantly enhanced hydrogen absorption capacity compared with Pd nanoparticles. AgxRh1-x and PdxRu1-x solid-solution alloy nanoparticles were also developed by nonequilibrium synthesis based on a polyol method. The AgxRh1-x nanoparticles demonstrated hydrogen storage properties, although pure metal nanoparticles of each constituent element do not adsorb hydrogen. AgxRh1-x is therefore considered to possess a similar electronic structure to Pd as a synthetic pseudo-palladium. The PdxRu1-x nanoparticles showed enhanced catalytic activity for CO oxidation, with the highest catalytic activity found using the equimolar Pd0.5Ru0.5 nanoparticles. The catalytic activity of the Pd0.5Ru0.5 nanoparticles exceeds that of the widely used and best-performing Ru catalysts for CO oxidation and is also higher than that of neighboring Rh on the periodic table. Our present work provides a guiding principle for the design of a suitable DOS shape according to the intended physical and/or chemical properties and a method for the development of novel solid-solution alloys.

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic-Resolution Electron Microscopy and Field Evaporation Simulation.

PubMed

Devaraj, Arun; Colby, Robert; Vurpillot, François; Thevuthasan, Suntharampillai

2014-04-17

Oxide-supported metal nanoparticles are widely used in heterogeneous catalysis. The increasingly detailed design of such catalysts necessitates three-dimensional characterization with high spatial resolution and elemental selectivity. Laser-assisted atom probe tomography (APT) is uniquely suited to the task but faces challenges with the evaporation of metal/insulator systems. Correlation of APT with aberration-corrected scanning transmission electron microscopy (STEM), for Au nanoparticles embedded in MgO, reveals preferential evaporation of the MgO and an inaccurate assessment of nanoparticle composition. Finite element field evaporation modeling is used to illustrate the evolution of the evaporation front. Nanoparticle composition is most accurately predicted when the MgO is treated as having a locally variable evaporation field, indicating the importance of considering laser-oxide interactions and the evaporation of various molecular oxide ions. These results demonstrate the viability of APT for analysis of oxide-supported metal nanoparticles, highlighting the need for developing a theoretical framework for the evaporation of heterogeneous materials.

Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

PubMed

Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

2014-02-15

The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Is Nitrate radical a major oxidant of elemental mercury in the atmosphere?

NASA Astrophysics Data System (ADS)

Luria, M.; Obrist, D.; Peleg, M.; Matveev, V.; Tas, E.

2012-12-01

Nitrate radicals (NO3) play a major role in the nighttime atmospheric oxidation of VOC. The radicals are produced throughout the reaction between O3 and NO2 and are removed via a sequence of homogeneous and heterogeneous reactions. Nitrate radicals reach significant levels only at night and mostly under conditions of low humidity (Asaf et al, 2009, 2010 and references therein). Because of its very high photolysis rate, daytime levels are extremely low, and thus are insignificant in atmospheric oxidation processes. The reaction of Hg with NO3 has not been sufficiently investigated; a value of 4x10-15 cm3 molec-1 s-1 (Sommar et al 1997) is most commonly used. Its importance for the atmospheric mercury chemistry was discussed by Mao el al., (2008) who examined the potential oxidation of mercury by the most common atmospheric oxidants applying the best available rate coefficients. According to their report, the uncertainty in the oxidation capacity of O3 is very large (a factor of 20). If the lower limit is applied, as suggested by Calvert and Lindberg (2005), oxidation by O3 is nearly negligible and, NO3 radicals, at typical nighttime levels, are responsible for the bulk of the Hg oxidation. Obviously this is true in the absence of reactive halogen compounds (RHC, Peleg et al., 2008). The most common method of measuring nitrate radicals is the differential optical absorption system (DOAS) technique. In a recent study performed at an urban semi arid site (Jerusalem, Israel; Asaf et al., 2009, 2010) it was found that nitrate levels could reach levels of up to 800 ppt, significantly higher than ever reported in the past. They further demonstrated that under the conditions prevailed; nitrate radicals are at least as important as the hydroxyl radicals in the overall oxidation capacity of VOC in the atmosphere. Side by side measurements of Nitrate radicals using the DOAS technique and speciated mercury compounds (Total, Particulate and Reactive gaseous) were performed during the summer months of 2012. Measurements took place at the same site and the same period were the highest levels of NO3 were earlier observed. Preliminary data indicated that RGM levels up to 100 pg/m3 were observed during the dark hours concurrent with NO3 concentrations higher than 200 ppt . First round model simulations using a 1-d model, the same model used for the simulations of Hg oxidation at the Dead Sea (Obrist et al., 2010) were also performed. The results indicated that for a 10 hour nighttime average of 50 ppt of nitrate radicals, the concentrations of RGM increase by a factor of more than three.

Automated Calibration of Atmospheric Oxidized Mercury Measurements.

PubMed

Lyman, Seth; Jones, Colleen; O'Neil, Trevor; Allen, Tanner; Miller, Matthieu; Gustin, Mae Sexauer; Pierce, Ashley M; Luke, Winston; Ren, Xinrong; Kelley, Paul

2016-12-06

The atmosphere is an important reservoir for mercury pollution, and understanding of oxidation processes is essential to elucidating the fate of atmospheric mercury. Several recent studies have shown that a low bias exists in a widely applied method for atmospheric oxidized mercury measurements. We developed an automated, permeation tube-based calibrator for elemental and oxidized mercury, and we integrated this calibrator with atmospheric mercury instrumentation (Tekran 2537/1130/1135 speciation systems) in Reno, Nevada and at Mauna Loa Observatory, Hawaii, U.S.A. While the calibrator has limitations, it was able to routinely inject stable amounts of HgCl 2 and HgBr 2 into atmospheric mercury measurement systems over periods of several months. In Reno, recovery of injected mercury compounds as gaseous oxidized mercury (as opposed to elemental mercury) decreased with increasing specific humidity, as has been shown in other studies, although this trend was not observed at Mauna Loa, likely due to differences in atmospheric chemistry at the two locations. Recovery of injected mercury compounds as oxidized mercury was greater in Mauna Loa than in Reno, and greater still for a cation-exchange membrane-based measurement system. These results show that routine calibration of atmospheric oxidized mercury measurements is both feasible and necessary.

Kinetics of Cyclic Oxidation and Cracking and Finite Element Analysis of MA956 and Sapphire/MA956 Composite System

NASA Technical Reports Server (NTRS)

Lee, Kang N.; Arya, Vinod K.; Halford, Gary R.; Barrett, Charles A.

1996-01-01

Sapphire fiber-reinforced MA956 composites hold promise for significant weight savings and increased high-temperature structural capability, as compared to unreinforced MA956. As part of an overall assessment of the high-temperature characteristics of this material system, cyclic oxidation behavior was studied at 1093 C and 1204 C. Initially, both sets of coupons exhibited parabolic oxidation kinetics. Later, monolithic MA956 exhibited spallation and a linear weight loss, whereas the composite showed a linear weight gain without spallation. Weight loss of the monolithic MA956 resulted from the linking of a multiplicity of randomly oriented and closely spaced surface cracks that facilitated ready spallation. By contrast, cracking of the composite's oxide layer was nonintersecting and aligned nominally parallel with the orientation of the subsurface reinforcing fibers. Oxidative lifetime of monolithic MA956 was projected from the observed oxidation kinetics. Linear elastic, finite element continuum, and micromechanics analyses were performed on coupons of the monolithic and composite materials. Results of the analyses qualitatively agreed well with the observed oxide cracking and spallation behavior of both the MA956 and the Sapphire/MA956 composite coupons.

Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

NASA Astrophysics Data System (ADS)

Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

2018-03-01

In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

Characterization of Representative Materials in Support of Safe, Long Term Storage of Surplus Plutonium in DOE-STD-3013 Containers

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

Narlesky, Joshua E.; Stroud, Mary Ann; Smith, Paul Herrick

2013-02-15

The Surveillance and Monitoring Program is a joint Los Alamos National Laboratory/Savannah River Site effort funded by the Department of Energy-Environmental Management to provide the technical basis for the safe, long-term storage (up to 50 years) of over 6 metric tons of plutonium stored in over 5,000 DOE-STD-3013 containers at various facilities around the DOE complex. The majority of this material is plutonium that is surplus to the nuclear weapons program, and much of it is destined for conversion to mixed oxide fuel for use in US nuclear power plants. The form of the plutonium ranges from relatively pure metalmore » and oxide to very impure oxide. The performance of the 3013 containers has been shown to depend on moisture content and on the levels, types and chemical forms of the impurities. The oxide materials that present the greatest challenge to the storage container are those that contain chloride salts. Other common impurities include oxides and other compounds of calcium, magnesium, iron, and nickel. Over the past 15 years the program has collected a large body of experimental data on 54 samples of plutonium, with 53 chosen to represent the broader population of materials in storage. This paper summarizes the characterization data, moisture analysis, particle size, surface area, density, wattage, actinide composition, trace element impurity analysis, and shelf life surveillance data and includes origin and process history information. Limited characterization data on fourteen nonrepresentative samples is also presented.« less

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

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Ubiquinol-10 Supplementation Activates Mitochondria Functions to Decelerate Senescence in Senescence-Accelerated Mice

PubMed Central

Tian, Geng; Sawashita, Jinko; Kubo, Hiroshi; Nishio, Shin-ya; Hashimoto, Shigenari; Suzuki, Nobuyoshi; Yoshimura, Hidekane; Tsuruoka, Mineko; Wang, Yaoyong; Liu, Yingye; Luo, Hongming; Xu, Zhe; Mori, Masayuki; Kitano, Mitsuaki; Hosoe, Kazunori; Takeda, Toshio; Usami, Shin-ichi

2014-01-01

Abstract Aim: The present study was conducted to define the relationship between the anti-aging effect of ubiquinol-10 supplementation and mitochondrial activation in senescence-accelerated mouse prone 1 (SAMP1) mice. Results: Here, we report that dietary supplementation with ubiquinol-10 prevents age-related decreases in the expression of sirtuin gene family members, which results in the activation of peroxisome proliferator-activated receptor γ coactivator 1α (PGC-1α), a major factor that controls mitochondrial biogenesis and respiration, as well as superoxide dismutase 2 (SOD2) and isocitrate dehydrogenase 2 (IDH2), which are major mitochondrial antioxidant enzymes. Ubiquinol-10 supplementation can also increase mitochondrial complex I activity and decrease levels of oxidative stress markers, including protein carbonyls, apurinic/apyrimidinic sites, malondialdehydes, and increase the reduced glutathione/oxidized glutathione ratio. Furthermore, ubiquinol-10 may activate Sirt1 and PGC-1α by increasing cyclic adenosine monophosphate (cAMP) levels that, in turn, activate cAMP response element-binding protein (CREB) and AMP-activated protein kinase (AMPK). Innovation and Conclusion: These results show that ubiquinol-10 may enhance mitochondrial activity by increasing levels of SIRT1, PGC-1α, and SIRT3 that slow the rate of age-related hearing loss and protect against the progression of aging and symptoms of age-related diseases. Antioxid. Redox Signal. 20, 2606–2620 PMID:24124769

Modeling of CMOS compatible ring resonator switch with intermediate vanadium oxide as the switching element

NASA Astrophysics Data System (ADS)

Singh, Mandeep; Datta, Arnab

2018-05-01

In this paper, silicon based dual ring resonator with hybrid plasmonic bus waveguides (Cu-SiO2-Si-SiO2-Cu) is investigated for achieving switching in the telecommunication C-band (λ = 1.54-1.553µm). The switch element uses vanadium oxide (VO2) as the switching medium when inserted between the rings in order to tailor transmission from one ring to the other through heating induced phase transition. In this manner, the proposed switch element uses one vanadium oxide medium instead of refractive index tailoring of the whole ring as in the prior reported works and achieves switching response. From two-dimensional finite element analysis we have found that, the proposed switch can achieve maximum extinction ratio of 2.72 dB at λ = 1.5434µm, exclusively by tailoring VO2 phase. Furthermore, impact of aperture width, and gap (separation between the bus waveguide and rings) are investigated to gain insight on the improvement of extinction ratio. From our numerical simulations, we find that free spectral range (FSR) and figure of merit (Q) for OFF and ON states are (173.36 nm, 92.63), and (173.58 nm, 65.39), respectively.

Quantitative ion beam analysis of M-C-O systems: application to an oxidized uranium carbide sample

NASA Astrophysics Data System (ADS)

Martin, G.; Raveu, G.; Garcia, P.; Carlot, G.; Khodja, H.; Vickridge, I.; Barthe, M. F.; Sauvage, T.

2014-04-01

A large variety of materials contain both carbon and oxygen atoms, in particular oxidized carbides, carbon alloys (as ZrC, UC, steels, etc.), and oxycarbide compounds (SiCO glasses, TiCO, etc.). Here a new ion beam analysis methodology is described which enables quantification of elemental composition and oxygen concentration profile over a few microns. It is based on two procedures. The first, relative to the experimental configuration relies on a specific detection setup which is original in that it enables the separation of the carbon and oxygen NRA signals. The second concerns the data analysis procedure i.e. the method for deriving the elemental composition from the particle energy spectrum. It is a generic algorithm and is here successfully applied to characterize an oxidized uranium carbide sample, developed as a potential fuel for generation IV nuclear reactors. Furthermore, a micro-beam was used to simultaneously determine the local elemental composition and oxygen concentration profiles over the first microns below the sample surface. This method is adapted to the determination of the composition of M?C?O? compounds with a sensitivity on elemental atomic concentrations around 1000 ppm.

Element mobilization from Bakken shales as a function of water chemistry.

PubMed

Wang, Lin; Burns, Scott; Giammar, Daniel E; Fortner, John D

2016-04-01

Waters that return to the surface after injection of a hydraulic fracturing fluid for gas and oil production contain elements, including regulated metals and metalloids, which are mobilized through interactions between the fracturing fluid and the shale formation. The rate and extent of mobilization depends on the geochemistry of the formation and the chemical characteristics of the fracturing fluid. In this work, laboratory scale experiments investigated the influence of water chemistry on element mobilization from core samples taken from the Bakken formation, one of the most productive shale oil plays in the US. Fluid properties were systematically varied and evaluated with regard to pH, oxidant level, solid:water ratio, temperature, and chemical additives. Element mobilization strongly depended on solution pH and redox conditions and to a lesser extent on the temperature and solid:water ratio. The presence of oxygen and addition of hydrogen peroxide or ammonium persulfate led to pyrite oxidation, resulting in elevated sulfate concentrations. Further, depending on the mineral carbonates available to buffer the system pH, pyrite oxidation could lower the system pH and enhance the mobility of several metals and metalloids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Petrogenesis of the Baishan granite stock, Eastern Tianshan, NW China: Geodynamic setting and implications for potential mineralization

NASA Astrophysics Data System (ADS)

Cao, MingJian; Qin, KeZhang; Li, GuangMing; Evans, Noreen J.; McInnes, Brent I. A.; Lu, WeiWei; Deng, Gang

2017-11-01

Located in a region rich in Cu-Ni and Mo mineralization, the Baishan granitic stock is barren for reasons that remain enigmatic. Whole rock elemental and Sr-Nd isotope analysis, major element analysis of a number of minerals, and zircon trace element, U-Pb and Hf isotope analysis were undertaken in order to reveal the petrogenesis of the granites. All granites show typical I-type characteristics including metaluminous to slightly peraluminous, calc-alkaline signatures with a strong depletion of Nb, Ta, Ti and P, enrichment of light rare earth elements and large ion lithophile elements (e.g., Cs, Rb, Th, U, K). In addition, a strong depletion in Ti and P, highly fractionated light rare earth element patterns and less fractionated heavy rare earth element patterns, and negative correlations between SiO2 and TiO2, Al2O3, MgO, FeOT, P2O5, Zr and Hf suggest significant fractional crystallization of amphibole, apatite, zircon and Ti-bearing minerals. Whole rock Sr-Nd and zircon Hf isotopic compositions show wide variations with (87Sr/86Sr)i values of 0.70358 to 0.70505, εNd (t) of 3.8 to 7.2, and εHf (t) of 2.4 to 12.2 indicating derivation from partial melting of juvenile lower crust with obvious addition of ancient crust. Zircon U-Pb ages indicate a formation age of 292 Ma, significantly older than the ore-forming granite porphyry and slightly older than the regional mafic-ultramafic, A-type and diabase magmatism of Eastern Tianshan. The granite stocks were likely derived during heating of ascending asthenospheric mantle above a mantle plume in the Early Permian. Mineral chemistry, saturation thermometry, mineral species and whole rock Fe2O3/FeO ratios indicate a crystallization temperature of > 980 to 665 °C, pressure of 1.6 kbar and oxygen fugacity of ≤ NNO for the granite stock. Comparing the geochemistry, magma source and crystallization environment for the Early Permian barren granite and Late Triassic ore-related granite porphyry, the low ratios of Sr/Y and low (La/Yb)N, and reduced oxidation state (≤ NNO) in the granitic stock are signatures of infertility for the Early Permian granite. This study implies high Mo mineralization potential for granitic rocks with high Sr/Y, (La/Yb)N and highly oxidized conditions.

Oxidative stress damage as a detrimental factor in preterm birth pathology.

PubMed

Menon, Ramkumar

2014-01-01

Normal term and spontaneous preterm births (PTB) are documented to be associated with oxidative stress (OS), and imbalances in the redox system (balance between pro- and antioxidant) have been reported in the maternal-fetal intrauterine compartments. The exact mechanism of labor initiation either at term or preterm by OS is still unclear, and this lack of understanding can partially be blamed for failure of antioxidant supplementation trials in PTB prevention. Based on recent findings from our laboratory, we postulate heterogeneity in host OS response. The physiologic (at term) and pathophysiologic (preterm) pathways of labor are not mediated by OS alone but by OS-induced damage to intrauterine tissues, especially fetal membranes of the placenta. OS damage affects all major cellular elements in the fetal cells, and this damage promotes fetal cell senescence (aging). The aging of the fetal cells is predominated by p38 mitogen activated kinase (p38MAPK) pathways. Senescing cells generate biomolecular signals that are uterotonic, triggering labor process. The aging of fetal cells is normal at term. However, aging is premature in PTB, especially in those PTBs complicated by preterm premature rupture of the membranes, where elements of redox imbalances and OS damage are more dominant. We postulate that fetal cell senescence signals generated by OS damage are likely triggers for labor. This review highlights the mechanisms involved in senescence development at term and preterm by OS damage and provides insight into novel fetal signals of labor initiation pathways.

Oxidative Stress Damage as a Detrimental Factor in Preterm Birth Pathology

PubMed Central

Menon, Ramkumar

2014-01-01

Normal term and spontaneous preterm births (PTB) are documented to be associated with oxidative stress (OS), and imbalances in the redox system (balance between pro- and antioxidant) have been reported in the maternal–fetal intrauterine compartments. The exact mechanism of labor initiation either at term or preterm by OS is still unclear, and this lack of understanding can partially be blamed for failure of antioxidant supplementation trials in PTB prevention. Based on recent findings from our laboratory, we postulate heterogeneity in host OS response. The physiologic (at term) and pathophysiologic (preterm) pathways of labor are not mediated by OS alone but by OS-induced damage to intrauterine tissues, especially fetal membranes of the placenta. OS damage affects all major cellular elements in the fetal cells, and this damage promotes fetal cell senescence (aging). The aging of the fetal cells is predominated by p38 mitogen activated kinase (p38MAPK) pathways. Senescing cells generate biomolecular signals that are uterotonic, triggering labor process. The aging of fetal cells is normal at term. However, aging is premature in PTB, especially in those PTBs complicated by preterm premature rupture of the membranes, where elements of redox imbalances and OS damage are more dominant. We postulate that fetal cell senescence signals generated by OS damage are likely triggers for labor. This review highlights the mechanisms involved in senescence development at term and preterm by OS damage and provides insight into novel fetal signals of labor initiation pathways. PMID:25429290

Coals of Hungary

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

Landis, E.R.; Rohrbacher, T.J.; Gluskoter, H.

1999-07-01

As part of the activities conducted under the U.S. Hungarian Science and Technology Fund, a total of 39 samples from five coal mines in Hungary were selected for standard coal analyses and major, minor and trace elements analysis. The mine areas sampled were selected to provide a spectrum of coal quality information for comparison with other coal areas in central Europe and worldwide. All of the areas are of major importance in the energy budget of Hungary. The five sample sites contain coal in rocks of Jurassic, Cretaceous, Eocene, Miocene, and Pliocene age. The coals, from four underground and onemore » surface mine, range in rank from high volatile bituminous to lignite B. Most of the coal produced from the mines sampled is used to generate electricity. Some of the power plants that utilize the coals also provide heat for domestic and process usage. The standard coal analysis program is based on tests performed in accordance with standards of the American Society for Testing and Materials (ASTM). Proximate and ultimate analyses were supplemented by determinations of the heating value, equilibrium moisture, forms of sulfur, free-swelling index, ash fusion temperatures (both reducing and oxidizing), apparent specific gravity and Hardgrove Grindability index. The major, minor and trace element analyses were performed in accordance with standardized procedures of the U.S. Geological Survey. The analytical results will be available in the International Coal Quality Data Base of the USGS. The results of the program provide data for comparison with test data from Europe and information of value to potential investors or cooperators in the coal industry of Hungary and Central Europe.« less

Hydrogen pickup mechanism of zirconium alloys

NASA Astrophysics Data System (ADS)

Couet, Adrien

Although the optimization of zirconium based alloys has led to significant improvements in hydrogen pickup and corrosion resistance, the mechanisms by which such alloy improvements occur are still not well understood. In an effort to understand such mechanisms, a systematic study of the alloy effect on hydrogen pickup is conducted, using advanced characterization techniques to rationalize precise measurements of hydrogen pickup. The hydrogen pick-up fraction is accurately measured for a specially designed set of commercial and model alloys to investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. Two different techniques to measure hydrogen concentrations were used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results indicate that hydrogen pickup varies not only from alloy to alloy but also during the corrosion process for a given alloy. For instance Zircaloy type alloys show high hydrogen pickup fraction and sub-parabolic oxidation kinetics whereas ZrNb alloys show lower hydrogen pickup fraction and close to parabolic oxidation kinetics. Hypothesis is made that hydrogen pickup result from the need to balance charge during the corrosion reaction, such that the pickup of hydrogen is directly related to (and indivisible of) the corrosion mechanism and decreases when the rate of electron transport or oxide electronic conductivity sigmao xe through the protective oxide increases. According to this hypothesis, alloying elements (either in solid solution or in precipitates) embedded in the oxide as well as space charge variations in the oxide would impact the hydrogen pick-up fraction by modifying sigmaox e, which drives oxidation and hydriding kinetics. Dedicated experiments and modelling were performed to assess and validate these hypotheses. In-situ electrochemical impedance spectroscopy (EIS) experiments were performed on Zircaloy-4 tubes to directly measure the evolution of sigma oxe as function of exposure time. The results show that sigmao xe decreases as function of exposure time and that its variations are directly correlated to the instantaneous hydrogen pickup fraction variations. The electron transport through the oxide layer is thus altered as the oxide grows, reasons for which are yet to be exactly determined. Preliminary results also show that sigma oxe of ZrNb alloys would be much higher compared with Zircaloy-4. Thus, it is confirmed that sigmaox e is a key parameter in the hydrogen and oxidation mechanism. Because the mechanism whereby alloying elements are incorporated into the oxide layer is critical to changing sigmao xe, the evolution of the oxidation state of two common alloying elements, Fe and Nb, when incorporated into the growing oxide layers is investigated using X-Ray Absorption Near-Edge Spectroscopy (XANES) using micro-beam synchrotron radiation on cross sectional oxide samples. The results show that the oxidation of both Fe and Nb is delayed in the oxide layer compared to that of Zr, and that this oxidation delay is related to the variations of the instantaneous hydrogen pick-up fraction with exposure time. The evolution of Nb oxidation as function of oxide depth is also compatible with space charge compensation in the oxide and with an increase in sigmaox e of ZrNb alloys compared to Zircaloys. Finally, various successively complex models from the well-known Wagner oxidation theory to the more complex effect of space charge on oxidation kinetics have been developed. The general purpose of the modeling effort is to provide a rationale for the sub-parabolic oxidation kinetics and demonstrate the correlation with hydrogen pickup fraction. It is directly demonstrated that parabolic oxidation kinetics is associated with high sigmao xe and low space charges in the oxide whereas sub-parabolic oxidation kinetics is associated with lower sigmaox e and higher space charge in the oxide. All these observations helped us to propose a general corrosion mechanism of zirconium alloys involving both oxidation and hydrogen pickup mechanism to better understand and predict the effect of alloying additions on the behavior of zirconium alloys.

Lithology and mineralogy recognition from geochemical logging tool data using multivariate statistical analysis.

PubMed

Konaté, Ahmed Amara; Ma, Huolin; Pan, Heping; Qin, Zhen; Ahmed, Hafizullah Abba; Dembele, N'dji Dit Jacques

2017-10-01

The availability of a deep well that penetrates deep into the Ultra High Pressure (UHP) metamorphic rocks is unusual and consequently offers a unique chance to study the metamorphic rocks. One such borehole is located in the southern part of Donghai County in the Sulu UHP metamorphic belt of Eastern China, from the Chinese Continental Scientific Drilling Main hole. This study reports the results obtained from the analysis of oxide log data. A geochemical logging tool provides in situ, gamma ray spectroscopy measurements of major and trace elements in the borehole. Dry weight percent oxide concentration logs obtained for this study were SiO 2 , K 2 O, TiO 2 , H 2 O, CO 2 , Na 2 O, Fe 2 O 3 , FeO, CaO, MnO, MgO, P 2 O 5 and Al 2 O 3 . Cross plot and Principal Component Analysis methods were applied for lithology characterization and mineralogy description respectively. Cross plot analysis allows lithological variations to be characterized. Principal Component Analysis shows that the oxide logs can be summarized by two components related to the feldspar and hydrous minerals. This study has shown that geochemical logging tool data is accurate and adequate to be tremendously useful in UHP metamorphic rocks analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

The role of Nrf2 transcription factor in viral infection.

PubMed

Ramezani, Ali; Nahad, Mehdi Parsa; Faghihloo, Ebrahim

2018-05-08

The nuclear factor erythroid 2 related factor 2 (Nrf2) is a major regulator of intracellular inducible defense systems against harmful endogenous and exogenous substances in the body. Under normal conditions Nrf2 is mainly binds to keap1 and located in the cytoplasm. However, in response to oxidative and electrophile stress, Nrf2 translocated to the nucleus and link to anti-oxidant response elements to induce the transcription of cytoprotective genes. Most viruses cause oxidative stress and increase the activity of radicals and reactive oxygen species (ROS), subsequently, the cellular protection system activates the Nrf2 and increases the expression of cytoprotective genes. However, in some cases, the activation of Nrf2 is not ROS-dependent, and is carried out directly via the ROS-independent pathway. Many viruses cause the activation of Nrf2, which is involved in the pathogenesis and the progression of the virus infection and even in its chronic form. However, some viruses inhibit the activation of Nrf2, in which case the virus also benefits of this mechanism to maintain the homeostasis of the cell. However, the challenge between the Nrf2/ARE signaling pathway of and viral infections is unknown in some cases, and in order to know more details in this regard, a more detailed seems necessary. © 2018 Wiley Periodicals, Inc.

Sensing temperature via downshifting emissions of lanthanide-doped metal oxides and salts. A review

NASA Astrophysics Data System (ADS)

Dramićanin, Miroslav D.

2016-12-01

Temperature is important because it has an effect on even the tiniest elements of daily life and is involved in a broad spectrum of human activities. That is why it is the most commonly measured physical quantity. Traditional temperature measurements encounter difficulties when used in some emerging technologies and environments, such as nanotechnology and biomedicine. The problem may be alleviated using optical techniques, one of which is luminescence thermometry. This paper reviews the state of luminescence thermometry and presents different temperature read-out schemes with an emphasis on those utilizing the downshifting emission of lanthanide-doped metal oxides and salts. The read-out schemes for temperature include those based on measurements of spectral characteristics of luminescence (band positions and shapes, emission intensity and ratio of emission intensities), and those based on measurements of the temporal behavior of luminescence (lifetimes and rise times). This review (with 140 references) gives the basics of the fundamental principles and theory that underlie the methods presented, and describes the methodology for the estimation of their performance. The major part of the text is devoted to those lanthanide-doped metal oxides and salts that are used as temperature probes, and to the comparison of their performance and characteristics.

Protection of human cultured cells against oxidative stress by Rhodiola rosea without activation of antioxidant defenses.

PubMed

Schriner, Samuel E; Avanesian, Agnesa; Liu, Yanxia; Luesch, Hendrik; Jafari, Mahtab

2009-09-01

Rhodiola rosea root has been long used in traditional medical systems in Europe and Asia as an adaptogen to increase an organism's resistance to physical stress. Recent research has demonstrated its ability to improve mental and physical stamina, to improve mood, and to help alleviate high-altitude sickness. We have also recently found that R. rosea is able to extend the life span of Drosophila melanogaster. The mode of action of R. rosea is currently unknown; it has been suggested by some to act as an antioxidant, whereas others have argued that it may actually be a pro-oxidant and act through a hormetic mechanism. We found that R. rosea supplementation could protect cultured cells against ultraviolet light, paraquat, and H(2)O(2). However, it did not alter the levels of the major antioxidant defenses nor did it markedly activate the antioxidant response element or modulate heme-oxygenase-1 expression levels at relevant concentrations. In addition, R. rosea extract was not able to significantly degrade H(2)O(2) in vitro. These results suggest that in human cultured cells R. rosea does not act as an antioxidant and that its mode of action cannot be sufficiently explained through a pro-oxidant hormetic mechanism.

Genetic Nature of Elemental Contents in Wheat Grains and Its Genomic Prediction: Toward the Effective Use of Wheat Landraces from Afghanistan

PubMed Central

Yamaoka, Shuhei; Yoshimura, Kazusa; Kondou, Youichi; Onogi, Akio; Matsui, Minami; Iwata, Hiroyoshi; Ban, Tomohiro

2017-01-01

Profiling elemental contents in wheat grains and clarifying the underlying genetic systems are important for the breeding of biofortified crops. Our objective was to evaluate the genetic potential of 269 Afghan wheat landraces for increasing elemental contents in wheat cultivars. The contents of three major (Mg, K, and P) and three minor (Mn, Fe, and Zn) elements in wheat grains were measured by energy dispersive X-ray fluorescence spectrometry. Large variations in elemental contents were observed among landraces. Marker-based heritability estimates were low to moderate, suggesting that the elemental contents are complex quantitative traits. Genetic correlations between two locations (Japan and Afghanistan) and among the six elements were estimated using a multi-response Bayesian linear mixed model. Low-to-moderate genetic correlations were observed among major elements and among minor elements respectively, but not between major and minor elements. A single-response genome-wide association study detected only one significant marker, which was associated with Zn, suggesting it will be difficult to increase the elemental contents of wheat by conventional marker-assisted selection. Genomic predictions for major elemental contents were moderately or highly accurate, whereas those for minor elements were mostly low or moderate. Our results indicate genomic selection may be useful for the genetic improvement of elemental contents in wheat. PMID:28072876

Mechanisms of Arsenic Mobilization and Attenuation in Subsurface Sediments

NASA Astrophysics Data System (ADS)

O'Day, P. A.; Illera, V.; Root, R.; Choi, S.; Vlassopoulos, D.

2007-12-01

This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited in labile or available S and/or Fe that remove As by precipitation or adsorption. In subsurface sediments with low labile S and Fe, laboratory experiments and spectroscopic studies suggest that sediment Mn minerals are important in the oxidation of sorbed As(III) to As(V), but that they have a limited oxidation capacity. Arsenic attenuation and mobilization in the subsurface are affected by seasonal variations when hydraulic conditions are influenced by surface infiltration, which may induce transitions from oxidized to reduced conditions (or vice versa) in porewater.

Markers of Oxidative Stress and Neuroprogression in Depression Disorder

PubMed Central

Vaváková, Magdaléna; Trebatická, Jana

2015-01-01

Major depression is multifactorial disorder with high prevalence and alarming prognostic in the nearest 15 years. Several mechanisms of depression are known. Neurotransmitters imbalance and imbalance between neuroprogressive and neuroprotective factors are observed in major depression. Depression is accompanied by inflammatory responses of the organism and consequent elevation of proinflammatory cytokines and increased lipid peroxidation are described in literature. Neuropsychiatric disorders including major depression are also associated with telomerase shortening, oxidative changes in nucleotides, and polymorphisms in several genes connected to metabolism of reactive oxygen species. Mitochondrion dysfunction is directly associated with increasing levels of oxidative stress. Oxidative stress plays significant role in pathophysiology of major depression via actions of free radicals, nonradical molecules, and reactive oxygen and nitrogen species. Products of oxidative stress represent important parameters for measuring and predicting of depression status as well as for determining effectiveness of administrated antidepressants. Positive effect of micronutrients, vitamins, and antioxidants in depression treatment is also reviewed. PMID:26078821

Inhibition of activated NR2B gene- and caspase-3 protein-expression by glutathione following traumatic brain injury in a rat model

PubMed Central

Arifin, Muhammad Zafrullah; Faried, Ahmad; Shahib, Muhammad Nurhalim; Wiriadisastra, Kahdar; Bisri, Tatang

2011-01-01

Background. Traumatic brain injury (TBI) remains a major cause of death and disability. Oxidative stress is an important element of the injury cascade following TBI. Progressive compromise of antioxidant defenses and free radical-mediated lipid peroxidation are one of the major mechanisms of secondary TBI. NR2B is a glutamate receptor and its activation is caused by TBI increasing a brain cell death, along with caspase-3 as a hall mark of apoptosis. Glutathione is a potent free radical scavenger that might prevent secondary TBI damage and inhibited apoptosis. Materials and Methods. In the present study, it aims to demonstrate the effect of glutathione on inhibition of brain oxidative damage in a TBI rat model. Results. In this study, the expressions of mRNA NR2B in placebo group and groups with glutathione administration at 0, 3, and 6 hours after TBI were 328.14, 229.90, 178.50, and 136.14, respectively (P<0.001). The highest caspase-3 expression was shown in placebo group with 66.7% showing strong positive results (>80%); as expected, glutathione administered in 0, 3, and 6 hours groups had lower strong positive results of 50%, 16.7%, and 16.7%, respectively, (P=0.025). Conclusion. In conclusion, this study showed that glutathione administration in a TBI rat model decreased NR2B gene- and caspase-3 protein-expression that lead to the inhibition of brain cell death. Our results suggest that glutathione, as a potent free radical scavenger, has a brain cell protective effect against oxidative damage and cell death induced by TBI in rat model. PMID:22347327

Elemental Zinc Is Inversely Associated with C-Reactive Protein and Oxidative Stress in Chronic Liver Disease.

PubMed

Uddin, Md Giash; Hossain, Mohammad Salim; Rahman, Md Atiqur; Uddin, A H M Mazbah; Bhuiyan, Md Shafiullah

2017-08-01

Chronic liver disease (CLD) is associated with the destruction of liver parenchyma cell. It is the main cause of morbidity and mortality in most of the developed countries. Oxidative stress and altered levels of different trace elements in serum have been documented for different diseases including inflammation and many liver diseases. This study aims to evaluate the serum level of malondialdehyde (MDA), nitric oxide (NO), antioxidant vitamin C, C-reactive protein (CRP), and zinc (Zn) in CLD patients and to establish a correlation among the study parameters with the severity of inflammatory conditions of CLD. In this study, CLD patients and healthy volunteers were recruited. Total cholesterol and triglyceride were determined by colorimeter using enzymatic method. Serum non-enzymatic antioxidant vitamin C, reactive oxygen species nitric oxide (NO), and malondialdehyde (MDA) were determined by UV-spectrophotometric method. Trace element (Zn) levels were determined by graphite furnace atomic absorption spectroscopy. Independent sample t test and Pearson's correlation test were performed for statistical analysis using the statistical software package SPSS, Version 20. Studies showed that the MDA (p < 0.001), NO (p < 0.001), and CRP levels were significantly higher in CLD patients than in control subjects. The antioxidant vitamin C (p < 0.001) and trace element zinc (p < 0.001) were comparatively lower in the CLD patients than in control subjects. Elemental Zn showed an inverse relationship with MDA, NO, and CRP but positively correlated with antioxidant capacity, whereas MDA showed a positive correlation with CRP level. Thus, we conclude that attenuated level of Zn and antioxidant in serum play an important role in the inflammatory status of CLD patients by elevating the concentration of MDA, NO, and CRP.

Bioflotation of sulfide minerals with Acidithiobacillus ferrooxidans in relation to copper activation and surface oxidation.

PubMed

Pecina-Treviño, E T; Ramos-Escobedo, G T; Gallegos-Acevedo, P M; López-Saucedo, F J; Orrantia-Borunda, E

2012-09-01

Surface oxidation of sulfides and copper (Cu) activation are 2 of the main processes that determine the efficiency of flotation. The present study was developed with the intention to ascertain the role of the phenomena in the biomodification of sulfides by Acidithiobacillus ferrooxidans culture (cells and growth media) and their impact in bioflotation. Surface characteristics of chalcopyrite, sphalerite, and pyrrhotite, alone and in mixtures, after interaction with A. ferrooxidans were evaluated. Chalcopyrite floatability was increased substantially by biomodification, while bacteria depressed pyrrhotite floatability, favoring separation. The results showed that elemental sulfur concentration increased because of the oxidation generated by bacterial cells, the effect is intensified by the Fe(III) left in the culture and by galvanic contact. Acidithiobacillus ferrooxidans culture affects the Cu activation of sphalerite. The implications of elemental sulfur concentration and Cu activation of sphalerite are key factors that must be considered for the future development of sulfide bioflotation processes, since the depressive effect of cells could be counteracted by elemental sulfur generation.

Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1978-01-01

The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

Thermo-electric modular structure and method of making same

DOEpatents

Freedman, N.S.; Horsting, C.W.; Lawrence, W.F.; Carrona, J.J.

1974-01-29

A method is presented for making a thermoelectric module wtth the aid of an insulating wafer having opposite metallized surfaces, a pair of similar equalizing sheets of metal, a hot-junction strap of metal, a thermoelectric element having hot- and cold-junction surfaces, and a radiator sheet of metal. The method comprises the following steps: brazing said equalizer sheets to said opposite metallized surfaces, respectively, of said insulating wafer with pure copper in a non-oxidizing ambient; brazing one surface of said hot-junction strap to one of the surfaces of said equalizing sheet with a nickel-gold alloy in a non- oxidizing ambient; and diffusion bonding said hot-junction surface of said thermoelectric element to the other surface of said hot-junction strap and said radiator sheet to said cold-junction surface of said thermoelectric element, said diffusion bonding being carried out in a non-oxidizing ambient, under compressive loading, at a temperature of about 550 deg C., and for about one-half hour. (Official Gazette)

Radioactive waste material disposal

DOEpatents

Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

1995-10-24

The invention is a process for direct conversion of solid radioactive waste, particularly spent nuclear fuel and its cladding, if any, into a solidified waste glass. A sacrificial metal oxide, dissolved in a glass bath, is used to oxidize elemental metal and any carbon values present in the waste as they are fed to the bath. Two different modes of operation are possible, depending on the sacrificial metal oxide employed. In the first mode, a regenerable sacrificial oxide, e.g., PbO, is employed, while the second mode features use of disposable oxides such as ferric oxide. 3 figs.

Radioactive waste material disposal

DOEpatents

Forsberg, Charles W.; Beahm, Edward C.; Parker, George W.

1995-01-01

The invention is a process for direct conversion of solid radioactive waste, particularly spent nuclear fuel and its cladding, if any, into a solidified waste glass. A sacrificial metal oxide, dissolved in a glass bath, is used to oxidize elemental metal and any carbon values present in the waste as they are fed to the bath. Two different modes of operation are possible, depending on the sacrificial metal oxide employed. In the first mode, a regenerable sacrificial oxide, e.g., PbO, is employed, while the second mode features use of disposable oxides such as ferric oxide.

Elemental mercury oxidation in an electrostatic precipitator enhanced with in situ soft X-ray irradiation.

PubMed

Jing, He; Wang, Xiaofei; Wang, Wei-Ning; Biswas, Pratim

2015-04-01

Corona discharge based techniques are promising approaches for oxidizing elemental mercury (Hg0) in flue gas from coal combustion. In this study, in-situ soft X-rays were coupled to a DC (direct current) corona-based electrostatic precipitator (ESP). The soft X-rays significantly enhanced Hg0 oxidation, due to generation of electrons from photoionization of gas molecules and the ESP electrodes. This coupling technique worked better in the positive corona discharge mode because more electrons were in the high energy region near the electrode. Detailed mechanisms of Hg0 oxidation are proposed and discussed based on ozone generation measurements and Hg0 oxidation behavior observations in single gas environments (O2, N2, and CO2). The effect of O2 concentration in flue gas, as well as the effects of particles (SiO2, TiO2, and KI) was also evaluated. In addition, the performance of a soft X-rays coupled ESP in Hg0 oxidations was investigated in a lab-scale coal combustion system. With the ESP voltage at +10 kV, soft X-ray enhancement, and KI addition, mercury oxidation was maximized. Mercury is a significant-impact atmospheric pollutant due to its toxicity. Coal-fired power plants are the primary emission sources of anthropogenic releases of mercury; hence, mercury emission control from coal-fired power plant is important. This study provides an alternative mercury control technology for coal-fired power plants. The proposed electrostatic precipitator with in situ soft X-rays has high efficiency on elemental mercury conversion. Effects of flue gas conditions (gas compositions, particles, etc.) on performance of this technology were also evaluated, which provided guidance on the application of the technology for coal-fired power plant mercury control.

CHEMICAL CHARACTERIZATION OF AMBIENT PARTICULATE MATTER NEAR THE WORLD TRADE CENTER: ELEMENTAL CARBON, ORGANIC CARBON, AND MASS RECONSTRUCTION

EPA Science Inventory

Concentrations of elemental carbon (EC), organic carbon matter (OM), particulate matter less than 2.5 um (PM2.5), and reconstructed soil, trace element oxides, and sulfate are reported from four locations near the World Trade Center (WTC) complex for airborne particulate matter (...

Application of Developed APCVD Transparent Conducting Oxides and Undercoat Technologies for Economical OLED Lighting

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

Martin Bluhm; James Coffey; Roman Korotkov

2011-01-02

Economics is a key factor for application of organic light emitting diodes (OLED) in general lighting relative to OLED flat panel displays that can handle high cost materials such as indium tin oxide (ITO) or Indium zinc oxide (IZO) as the transparent conducting oxide (TCO) on display glass. However, for OLED lighting to penetrate into general illumination, economics and sustainable materials are critical. The issues with ITO have been documented at the DOE SSL R&D and Manufacturing workshops for the last 5 years and the issue is being exacerbated by export controls from China (one of the major sources ofmore » elemental indium). Therefore, ITO is not sustainable because of the fluctuating costs and the United States (US) dependency on other nations such as China. Numerous alternatives to ITO/IZO are being evaluated such as Ag nanoparticles/nanowires, carbon nanotubes, graphene, and other metal oxides. Of these other metal oxides, doped zinc oxide has attracted a lot of attention over the last 10 years. The volume of zinc mined is a factor of 80,000 greater than indium and the US has significant volumes of zinc mined domestically, resulting in the ability for the US to be self-sufficient for this element that can be used in optoelectronic applications. The costs of elemental zinc is over 2 orders of magnitude less than indium, reflecting the relative abundance and availability of the elements. Arkema Inc. and an international primary glass manufacturing company, which is located in the United States, have developed doped zinc oxide technology for solar control windows. The genesis of this DOE SSL project was to determine if doped zinc oxide technology can be taken from the commodity based window market and translate the technology to OLED lighting. Thus, Arkema Inc. sought out experts, Philips Lighting, Pacific Northwest National Laboratories (PNNL) and National Renewable Research Laboratories (NREL), in OLED devices and brought them into the project. This project had a clear focus on economics and the work plan focused both on doped ZnO process and OLED device structure that would be consistent with the new TCO. The team successfully made 6 inch OLEDs with a serial construction. More process development is required to optimize commercial OLED structures. Feasibility was demonstrated on two different light extraction technologies: 1/4 lambda refractive index matching and high-low-high band pass filter. Process development was also completed on the key precursors for the TCO, which are ready for pilot-plant scale-up. Subsequently, Arkema has developed a cost of ownership model that is consistent with DOE SSL R&D Manufacturing targets as outlined in the DOE SSL R&D Manufacturing 2010 report. The overall outcome of this project was the demonstration that doped zinc oxide can be used for OLED devices without a drop-off in performance while gaining the economic and sustainable benefits of a more readily available TCO. The broad impact of this project, is the facilitation of OLED lighting market penetration into general illumination, resulting in significant energy savings, decreased greenhouse emissions, with no environmental impact issues such as mercury found in Fluorescent technology. The primary objective of this project was to develop a commercially viable process for 'Substrates' (Substrate/ undercoat/ TCO topcoat) to be used in production of OLED devices (lamps/luminaries/modules). This project focused on using Arkema's recently developed doped ZnO technology for the Fenestration industry and applying the technology to the OLED lighting industry. The secondary objective was the use of undercoat technology to improve light extraction from the OLED device. In optical fields and window applications, technology has been developed to mitigate reflection losses by selecting appropriate thicknesses and refractive indices of coatings applied either below or above the functional layer of interest. This technology has been proven and implemented in the fenestration industry for more than 15 years. Successful completion of this project would provide doped ZnO coated on inexpensive soda lime glass resulting in a significantly lower cost relative to the current ITO coated Flat Panel Display Glass substrates. Additional benefits will be a more consistent TCO that does not need an activation step with better optical performance. Clearly, this will serve to enhance penetration of OLED technologies into the lighting market.« less

Oxidation, carburization and/or sulfidation resistant iron aluminide alloy

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

2003-08-19

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or Zro.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B. .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Design of optimum solid oxide membrane electrolysis cells for metals production

DOE PAGES

Guan, Xiaofei; Pal, Uday B.

2015-12-24

Oxide to metal conversion is one of the most energy-intensive steps in the value chain for metals production. Solid oxide membrane (SOM) electrolysis process provides a general route for directly reducing various metal oxides to their respective metals, alloys, or intermetallics. Because of its lower energy use and ability to use inert anode resulting in zero carbon emission, SOM electrolysis process emerges as a promising technology that can replace the state-of-the-art metals production processes. In this paper, a careful study of the SOM electrolysis process using equivalent DC circuit modeling is performed and correlated to the experimental results. Finally, amore » discussion on relative importance of each resistive element in the circuit and on possible ways of lowering the rate-limiting resistive elements provides a generic guideline for designing optimum SOM electrolysis cells.« less

Proterozoic low-Ti iron-oxide deposits in New York and New Jersey: relation to Fe-oxide (Cu-U-Au-rare earth element) deposits and tectonic implications

USGS Publications Warehouse

Foose, M.P.; McLelland, J.M.

1995-01-01

Low-Ti iron-oxide deposits in exposed Grenville-age rocks of New York and New Jersey belong to a distinct class of iron-oxide (Cu-U-Au-rare earth element [REE]) deposits that includes similar iron deposits in southeastern Missouri and the Kiruna district of Sweden, the giant Olympic Dam U-Cu-Au-Ag deposit (Australia), and the Bayan Obo REE-Nb deposit (China). Most of the New York-New Jersey deposits exhibit features consistent with a hydrothermal origin and define a regionally significant metallogenic event that provides important clues to the evolution of this part of the Grenville orogen. In the Adirondacks, the tectonic setting of these deposits is consistent with postorogenic uplift and extensive crustal melting at 1070-1050 Ma that was accompanied by late tectonic to posttectonic deposition of iron. -Authors

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

NASA Astrophysics Data System (ADS)

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

1986-11-01

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

Selenite modulates the level of phenolics and nutrient element to alleviate the toxicity of arsenite in rice (Oryza sativa L.).

PubMed

Chauhan, Reshu; Awasthi, Surabhi; Tripathi, Preeti; Mishra, Seema; Dwivedi, Sanjay; Niranjan, Abhishek; Mallick, Shekhar; Tripathi, Pratibha; Pande, Veena; Tripathi, Rudra Deo

2017-04-01

Arsenic (As) contamination of paddy rice is a serious threat all over the world particularly in South East Asia. Selenium (Se) plays important role in protection of plants against various abiotic stresses including heavy metals. Moreover, arsenite (AsIII) and selenite (SeIV) can be biologically antagonistic due to similar electronic configuration and sharing the common transporter for their uptake in plant. In the present study, the response of oxidative stress, phenolic compounds and nutrient elements was analyzed to investigate Se mediated As tolerance in rice seedlings during AsIII and SeIV exposure in hydroponics. Selenite (25µM) significantly decreased As accumulation in plant than As (25µM) alone treated plants. Level of oxidative stress related parameters viz., reactive oxygen species (ROS), lipid peroxidation, electrical conductivity, nitric oxide and pro-oxidant enzyme (NADPH oxidase), were in the order of As>As+Se>control>Se. Selenium ameliorated As phytotoxicity by increased level of phenolic compounds particularly gallic acid, protocatechuic acid, ferulic acid and rutin and thiol metabolism related enzymes viz., serine acetyl transferase (SAT) and cysteine synthase (CS). Selenium supplementation enhanced the uptake of nutrient elements viz., Fe, Mn, Co, Cu, Zn, Mo, and improved plant growth. The results concluded that Se addition in As contaminated environment might be an important strategy to reduce As uptake and associated phytotoxicity in rice plant by modulation of phenolic compounds and increased uptake of nutrient elements. Copyright © 2016 Elsevier Inc. All rights reserved.

Chemical investigations of aquifers affected by pyrite oxidation in the Bitterfeld lignite district.

PubMed

Grützmacher, G; Hindel, R; Kantor, W; Wimmer, R

2001-01-01

In a large area around the former open-pit lignite mines near Bitterfeld, Germany, groundwater taken from wells was analyzed for the major cations, anions, and trace elements. Quaternary and Tertiary sediments were collected from aquifers exposed on the sides of the pits and from boreholes outside the mines and analyzed for major and trace elements, as well as for carbonate, pyritic sulfur and total organic carbon. The pH and electrical conductivity of the sediments in suspension were measured. Significant differences were determined between the Tertiary sediments of the aquifers that were exposed to atmospheric oxygen during the lowering of the groundwater table and those outside the cone of depression. The greatest differences were found in the pyrite content, the pH values, and the electrical conductivity. In order to map the degree to which the mining of the lignite has affected the quality of the groundwater in the study area, the water samples were divided into six classes on the basis of their sulfate content. The neutralization potential was calculated to estimate the potential for acidification. Prediction of future groundwater quality is based on both (i) the present composition of the groundwater, surface water, and Quaternary and Tertiary aquifer sediments and (ii) the present and future groundwater flow directions. These studies have shown which parameters are important for future groundwater monitoring.

A relatively reduced Hadean continental crust

NASA Astrophysics Data System (ADS)

Yang, Xiaozhi; Gaillard, Fabrice; Scaillet, Bruno

2014-05-01

Among the physical and chemical parameters used to characterize the Earth, oxidation state, as reflected by its prevailing oxygen fugacity (fO2), is a particularly important one. It controls many physicochemical properties and geological processes of the Earth's different reservoirs, and affects the partitioning of elements between coexisting phases and the speciation of degassed volatiles in melts. In the past decades, numerous studies have been conducted to document the evolution of mantle and atmospheric oxidation state with time and in particular the possible transition from an early reduced state to the present oxidized conditions. So far, it has been established that the oxidation state of the uppermost mantle is within ±2 log units of the quartz-fayalite-magnetite (QFM) buffer, probably back to ~4.4 billion years ago (Ga) based on trace-elements studies of mantle-derived komatiites, kimberlites, basalts, volcanics and zircons, and that the O2 levels of atmosphere were initially low and rose markedly ~2.3 Ga known as the Great Oxidation Event (GOE), progressively reaching its present oxidation state of ~10 log units above QFM. In contrast, the secular evolution of oxidation state of the continental crust, an important boundary separating the underlying upper mantle from the surrounding atmosphere and buffering the exchanges and interactions between the Earth's interior and exterior, has rarely been addressed, although the presence of evolved crustal materials on the Earth can be traced back to ~4.4 Ga, e.g. by detrital zircons. Zircon is a common accessory mineral in nature, occurring in a wide variety of igneous, sedimentary and metamorphic rocks, and is almost ubiquitous in crustal rocks. The physical and chemical durability of zircons makes them widely used in geochemical studies in terms of trace-elements, isotopes, ages and melt/mineral inclusions; in particular, zircons are persistent under most crustal conditions and can survive many secondary processes such as metamorphism, weathering and erosion. Thus, zircons in granites of shallow crust may record the chemical/isotopic composition of the deep crust that is otherwise inaccessible, and offer robust records of the magmatic and crust-forming events preserved in the continental crust. In fact, due to the absence of suitable rock records (in particular for periods older than ~4.0 Ga), studies in recent years concerning the nature, composition, growth and evolution of the continental crust, and especially the Hadean crust, have heavily relied on inherited/detrital zircons. Natural igneous zircons incorporate rare-earth elements (REE) and other trace elements in their structure at concentrations controlled by the temperature, pressure, fO2 and composition of their crystallization environment. Petrological observations and recent experiments have shown that the concentration of Ce relative to other REE in igneous zircons can be used to constrain the fO2 during their growth. By combining available trace-elements data of igneous zircons of crustal origin, we show that the Hadean continental crust was significantly more reduced than its modern counterpart and experienced progressive oxidation till ~3.6 billions years ago. We suggest that the increase in the oxidation state of the Hadean continental crust is related to the progressive decline in the intensity of meteorite impacts during the late veneer. Impacts of carbon- and hydrogen-rich materials during the formation of Hadean granitic crust must have favoured strongly reduced magmatism. The conjunction of cold, wet and reduced granitic magmatism during the Hadean implies the degassing of methane and water. When impacts ended, magma produced by normal decompression melting of the mantle imparted more oxidizing conditions to erupted lavas and the related crust.

Shielded regeneration heating element for a particulate filter

DOEpatents

Gonze, Eugene V [Pinckney, MI; Ament, Frank [Troy, MI

2011-01-04

An exhaust system includes a particulate filter (PF) that is disposed downstream from an engine. The PF filters particulates within an exhaust from the engine. A heating element heats particulate matter in the PF. A catalyst substrate or a flow converter is disposed upstream from said heating element. The catalyst substrate oxidizes the exhaust prior to reception by the heating element. The flow converter converts turbulent exhaust flow to laminar exhaust flow prior to reception by the heating element.