Hydrous iron oxide modified diatomite as an active filtration medium for phosphate capture.

Science.gov (United States)

Wang, Zhe; Lin, Yan; Wu, Deyi; Kong, Hainan

2016-02-01

A simple method to functionalize diatomite with hydrous iron oxide was attempted and its performance as a new active filtration material to remove and recover phosphate from water was investigated under varying solution conditions. The Langmuir phosphate adsorption capacity increased from 0.6 mgP/g for raw diatomite to 4.89, 14.71, 25.02 mgP/g for hydrous iron oxide modified diatomite (HIOMD), depending on the amount of iron loaded. Loading of hydrous iron oxide caused the increase in true and bulk density and a decline in filtration rate, but to a lesser extent. It was shown that the HIOMD product with suitable iron content could retain a good filtration performance with a greatly increased adsorption capacity for phosphate. The phosphate adsorption increased by decreasing pH and by increasing ionic strength at high pH levels. The adsorption process was interpreted by ligand exchange. Coexisting oxyanions of sulfate, nitrate, citrate, carbonate, silicate and humic acid showed different effects on phosphate fixation but it was presumed that their influence at their concentrations and pH levels commonly encountered in effluent or natural waters was limited, i.e., HIOMD had a reasonably good selectivity. Results in repeated adsorption, desorption and regeneration experiment showed that the adsorbed phosphate could be recovered and the material could be reused after regeneration. The column test showed that HIOMD could be potentially utilized as an adsorption filtration medium for phosphate removal and recovery from water. Copyright © 2015 Elsevier Ltd. All rights reserved.

Amorphous nanosized Al–Ti–Mn trimetal hydrous oxides: synthesis, characterization and enhanced performance in arsenic removal

Czech Academy of Sciences Publication Activity Database

Thanh, D. N.; Bastl, Zdeněk; Černá, K.; Ulbrich, P.; Lederer, J.

2016-01-01

Roč. 6, č. 103 (2016), s. 100732-100742 ISSN 2046-2069 Institutional support: RVO:61388955 Keywords : RAY PHOTOELECTRON-SPECTROSCOPY * BINARY MIXED-OXIDE * Al-Ti-Mn trimetal hydrous oxides * AQUEOUS-SOLUTION Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.108, year: 2016

Zirconium oxide crystal phase: The role of the pH and time to attain the final pH for precipitation of the hydrous oxide

International Nuclear Information System (INIS)

Srinivasan, R.; Harris, M.B.; Simpson, S.F.; De Angelis, R.J.; Davis, B.H.

1988-01-01

Precipitated hydrous zirconium oxide can be calcined to produce either a monoclinic or tetragonal product. It has been observed that the time taken to attain the final pH of the solution in contact with the precipitate plays a dominant role in determining the crystal structure of the zirconium oxide after calcination at 500 0 C. The dependence of crystal structure on the rate of precipitation is observed only in the pH range 7--11. Rapid precipitation in this pH range yields predominately monoclinic zirconia, whereas slow (8 h) precipitation produces the tetragonal phase. At pH of approximately 13.0, only the tetragonal phase is formed from both slowly and rapidly precipitated hydrous oxide. The present results, together with earlier results, show that both the pH of the supernatant liquid and the time taken to attain this pH play dominant roles in determining the crystal structure of zirconia that is formed after calcination of the hydrous oxide. The factors that determine the crystal phase are therefore imparted in a mechanism of precipitation that depends upon the pH, and it is inferred that it is the hydroxyl concentration that is the dominant factor

Sorption behaviour of uranium and thorium on hydrous tin oxide from aqueous and mixed-solvent HNO3 media

International Nuclear Information System (INIS)

Misak, N.Z.; Salama, H.N.; El-Naggar, I.M.

1983-01-01

In aqueous nitric acid, uranyl and thorium ions seem to be sorbed on hydrous tin oxide mainly by a cation exchange mechanism. In 10 - 3 M aqueous solutions, the hydrous oxide prefers thorium to uranium at the relative low pH values, while the reverse is true at the higher pH values. The exchange of uranium is particle diffusion controlled while that of thorium is chemically controlled, and the isotherms point to the presence of different-energy sites in the hydrous oxide. Except for the solutions containing 80% of methanol, ethanol, or acetone, cation exchange is probably still the main mechanism of sorption of uranium. Anionic sorption of thorium seems to occur in all the mixed-solvent solutions and is perhaps the main mechanism in 80% ethanol. The equilibrium distribution coefficient K sub (d) increases almost in all cases with organic solvent content, probably due to dehydration of sorbed ions and to increasing superposition on anionic sorption. Unlike the aqueous medium, large U/Th separation factors are achieved in many of the mixed-solvent solutions and separation schemes are suggested. (Authors)

Determination of Ideal Broth Formulations Needed to Prepare Hydrous Cerium Oxide Microspheres via the Internal Gelation Process

Energy Technology Data Exchange (ETDEWEB)

Collins, Jack Lee [ORNL; Chi, Anthony [ORNL

2009-02-01

A simple test tube methodology was used to determine optimum process parameters for preparing hydrous cerium oxide microspheres via the internal gelation process.1 Broth formulations of cerium ammonium nitrate [(NH4)2Ce(NO3)6], hexamethylenetetramine, and urea were found that can be used to prepare hydrous cerium oxide gel spheres in the temperature range of 60 to 90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations to be able to equate the test-tube gelation times to actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broth formulations.

Hydrous pyrolysis/oxidation process for in situ destruction of chlorinated hydrocarbon and fuel hydrocarbon contaminants in water and soil

Science.gov (United States)

Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.

2000-01-01

In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.

Evaluation of hydrous ferric oxide loaded activated carbon as a granular composite sorbent for radiostrontium

International Nuclear Information System (INIS)

Samanta, S.K.

1997-01-01

A composite sorbent was prepared in granular form by depositing hydrous ferric oxide inside the pores of activated carbon. The composite sorbent was found to show excellent sorption of radiostrontium in the presence of high sodium concentration under alkaline conditions. (author). 3 refs., 2 figs., 1 tab

Hydrous Ferric Oxides in Sediment Catalyze Formation of Reactive Oxygen Species during Sulfide Oxidation

Directory of Open Access Journals (Sweden)

Sarah A. Murphy

2016-11-01

Full Text Available Abstract: This article describes the formation of reactive oxygen species as a result of the oxidation of dissolved sulfide by Fe(III-containing sediments suspended in oxygenated seawater over the pH range 7.00 and 8.25. Sediment samples were obtained from across the coastal littoral zone in South Carolina, US, at locations from the beach edge to the forested edge of a Spartina dominated estuarine salt marsh and suspended in aerated seawater. Reactive oxygen species (superoxide and hydrogen peroxide production was initiated in sediment suspensions by the addition of sodium bisulfide. The subsequent loss of HS-, formation of Fe(II (as indicated by Ferrozine, and superoxide and hydrogen peroxide were monitored over time. The concentration of superoxide rose from the baseline and then persisted at an apparent steady state concentration of approximately 500 nanomolar at pH 8.25 and 200 nanomolar at pH 7.00 respectively until >97% hydrogen sulfide was consumed. Measured superoxide was used to predict hydrogen peroxide yield based on superoxide dismutation. Dismutation alone quantitatively predicted hydrogen peroxide formation at pH 8.25 but over predicted hydrogen peroxide formation at pH 7 by a factor of approximately 102. Experiments conducted with episodic spikes of added hydrogen peroxide indicated rapid hydrogen peroxide consumption could account for its apparent low instantaneous yield, presumably the result of its reaction with Fe(II species, polysulfides or bisulfite. All sediment samples were characterized for total Fe, Cu, Mn, Ni, Co and hydrous ferric oxide by acid extraction followed by mass spectrometric or spectroscopic characterization. Sediments with the highest loadings of hydrous ferric oxide were the only sediments that produced significant dissolved Fe(II species or ROS as a result of sulfide exposure.

Electrophoretic deposition (EPD) of hydrous ruthenium oxides with PTFE and their supercapacitor performances

International Nuclear Information System (INIS)

Jang, Jong H.; Machida, Kenji; Kim, Yuri; Naoi, Katsuhiko

2006-01-01

The effect of PTFE addition was investigated for the electrophoretic deposition (EPD) of hydrous ruthenium oxide electrodes. Mechanical stability of electrode layers, together with deposition yield, was enhanced by using hydrous ruthenium oxide/PTFE dispersions. High supercapacitor performance was obtained for the electrodes prepared with 2% PTFE and 10% water. When PTFE content was higher, the rate capability became poor with low electronic conductivity; higher water content than 10% resulted in non-uniform depositions with poor cycleability and power capability. When electrodes were heat treated at 200 deg. C for 10 h, the specific energy was as high as 17.6 Wh/kg based on single electrode (at 200 W/kg); while utilizable energy was lower with heat treatment time of 1 and 50 h, due to the high resistance and gradual crystallization, respectively. With PTFE addition and heat treatment at 200 deg. C for 10 h, the specific capacitance was increased by 31% (460 → 599 F/g at ca. 0.6 mg/cm 2 ) at 10 mV/s, and the deposition weight was increased up to 1.7 mg/cm 2 with initial capacitance of 350 F/g

Applications of x ray absorption fine structure to the in situ study of the effect of cobalt in nickel hydrous oxide electrodes for fuel cells and rechargeable batteries

Science.gov (United States)

Kim, Sunghyun; Tryk, Donald A.; Scherson, Daniel A.; Antonio, Mark R.

1993-01-01

Electronic and structural aspects of composite nickel-cobalt hydrous oxides have been examined in alkaline solutions using in situ X-ray absorption fine structure (XAFS). The results obtained have indicated that cobalt in this material is present as cobaltic ions regardless of the oxidation state of nickel in the lattice. Furthermore, careful analysis of the Co K-edge Extended X-ray absorption fine structure data reveals that the co-electrodeposition procedure generates a single phase, mixed metal hydrous oxide, in which cobaltic ions occupy nickel sites in the NiO2 sheet-like layers and not two intermixed phases each consisting of a single metal hydrous oxide.

Extraction of uranium (VI) from sea water using hydrous metalic oxide binded with hydrophilic polymers

International Nuclear Information System (INIS)

Shigetomi, Yasumasa; Kojima, Takehiro; Kamba, Hideaki

1978-01-01

In the past five years, many researches have been made to extract U(VI) from sea water. This is a report of the extraction of U(VI) from sea water using hydrous titanium oxide binded with hydrophilic polymers, the apparatus for the adsorption and the separation of U(VI) by means of ion exchange. (author)

Adsorption of arsenite and selenite using an inorganic ion exchanger based on Fe–Mn hydrous oxide

KAUST Repository

Szlachta, Małgorzata; Gerda, Vasyl; Chubar, Natalia

2012-01-01

The adsorption behaviour and mechanism of As(III) and Se(IV) oxyanion uptake using a mixed inorganic adsorbent were studied. The novel adsorbent, based on Fe(III)-Mn(III) hydrous oxides and manganese(II) carbonate, was synthesised using a hydrothermal precipitation approach in the presence of urea. The inorganic ion exchanger exhibited a high selectivity and adsorptive capacity towards As(III) (up to 47.6mg/g) and Se(IV) (up to 29.0mg/g), even at low equilibrium concentration. Although pH effects were typical for anionic species (i.e., the adsorption decreased upon pH increase), Se(IV) was more sensitive to pH changes than As(III). The rates of adsorption of both oxyanions were high. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) studies showed that the ion exchange adsorption of both anions took place via OH - groups, mainly from Fe(III) but also Mn(III) hydrous oxides. MnCO 3 did not contribute directly to As(III) and Se(IV) removal. A higher adsorptive capacity of the developed material towards As(III) was partly due to partial As(III) oxidation during adsorption. © 2011 Elsevier Inc.

Synthesis and characterization of tin(IV) antimonate and study of its ion-exchange equilibria

International Nuclear Information System (INIS)

Burham, N.; Abdel-Halim, S.H.; El-Shahat, M.F.

1995-01-01

Tin(IV) antimonate with different Sb/Sn molar ratios has been prepared. The characterization of the product materials was carried out using X-ray diffraction pattern, thermal analysis and infrared spectra. The saturation capacities of sodium and cesium were found to increase with Sb/Sn molar ratios. The K d values on thermal treatment of tin(IV) antimonate, as a cation exchanger, have been measured for some heavy metal ions in the temperature range of 50-400 deg C. The maximum adsorption of 10 -4 M of the metal ions studied was obtained at 400 deg C. The selectivity sequence was Eu 3+ > Co 2+ > Sr 2+ > Cs + for the sample heated up to 400 deg C. No adsorption was observed on the sample heated at 700 deg C because of the formation of SnO 2 and Sb 6 O 13 . (author) 9 refs.; 7 figs.; 5 tabs

A comparative study between the dissolution and the leaching methods for the separation of rare earths, uranium and thorium from hydrous metal oxide cake obtained by the alkaline digestion of monazite

International Nuclear Information System (INIS)

Chayavadhanangkur, C.; Busamongkol, A.; Hongsirinirachorn, S.; Rodthongkom, C.; Sirisena, K.

1986-12-01

Methods for the group-separation of rare-earths, thorium and uranium from hydrous metal oxide cake obtained by the alkaline digestion of monazite were studied. Leaching of the hydrous metal oxide cake at pH between 4-5 separates the elements under investigation into 3 major groups which are suitable to be used as feed materials for further purification. Total dissolution and gradient precipitation at pH 4-5 yields a poorer separation in comparison to the leaching method

χ{sup (3)} measurements of axial ligand modified high valent tin(IV) porphyrins using degenarete four wave mixing at 532nm

Energy Technology Data Exchange (ETDEWEB)

Narendran, N. K. Siji, E-mail: sijinarendran@gmail.com; Chandrasekharan, K. [Laser and nonlinear optics laboratory, Department of Physics, National Institute of Technology Calicut, Calicut-673601, Kerala (India); Soman, Rahul; Arunkumar, Chellaiah [Bioinorganic materials laboratory, Department of Chemistry, National Institute of Technology Calicut, Calicut-673601, Kerala (India); Sudheesh, P. [Department of Physics, VTM NSS College, Dhanuvachapuram, Thiruvananthapuram (India)

2014-10-15

Porphyrins and metalloporphyrins are unique class of molecules for Nonlinear Optical applications because of their unique structure of altering the central metal atom, large extended π-system, high thermal stability, tunable shape, symmetry and synthetic versatility Here, we report χ{sup (3)} Measurements of a simple phenyl porphyrins and its highvalent tin(IV) porphyrins with Bromination characterized by UV-Visible spectroscopic method. In this study, we employed the Degenerate Four Wave Mixing technique using forward Boxcar geometry with an Nd:YAG nano second pulsed laser as source and it was found that the tin(IV) porphyrin with Bromination exhibits good χ{sup (3)} value and figure of merit.

Solubilization of plutonium hydrous oxide by iron-reducing bacteria

International Nuclear Information System (INIS)

Rusin, P.A.; Quintana, L.; Brainard, J.R.; Strietelmeler, B.A.; Tait, C.D.; Ekberg, S.A.; Palmer, P.D.; Newton, T.W.; Clark, D.L.

1994-01-01

The removal of plutonium from soils id challenging because of its strong sorption to soils and limited solubility, Microbial reduction of metals is known to affect the speciation and solubility of sparingly soluble metals in the environment, notably iron and manganese. The similarity in reduction potential for α-FeOOH(s) and hydrous PuO 2 (s) suggests that iron-reducing bacteria may also reduce and solubilize plutonium. Bacillus strains were used to demonstrate that iron-reducing bacteria mediate the solubilization of hydrous PuO 2 (s) under anaerobic conditions. Up to ∼90% of the PuO 2 was biosolubilized in the presence of nitrilotriacetic acid (NTA) within 6-7 days. Biosolubilization occurred to a lesser extent (∼ 40%) in the absence of NTA. Little PuO 2 solubilization occurred in sterile culture media or in the presence of a non-iron-reducing Escherichia coli. These observations suggest a potentially attractive, environmentally benign strategy for the remediation of Pu-contaminated soils. 26 refs., 5 figs., 2 tabs

Dietary bioavailability of Cu adsorbed to colloidal hydrous ferric oxide

Science.gov (United States)

Cain, Daniel J.; Croteau, Marie-Noële; Fuller, Christopher C.

2013-01-01

The dietary bioavailability of copper (Cu) adsorbed to synthetic colloidal hydrous ferric oxide (HFO) was evaluated from the assimilation of 65Cu by two benthic grazers, a gastropod and a larval mayfly. HFO was synthesized, labeled with 65Cu to achieve a Cu/Fe ratio comparable to that determined in naturally formed HFO, and then aged. The labeled colloids were mixed with a food source (the diatom Nitzschia palea) to yield dietary 65Cu concentrations ranging from 211 to 2204 nmol/g (dry weight). Animals were pulse fed the contaminated diet and assimilation of 65Cu from HFO was determined following 1–3 days of depuration. Mass transfer of 65Cu from HFO to the diatom was less than 1%, indicating that HFO was the source of 65Cu to the grazers. Estimates of assimilation efficiency indicated that the majority of Cu ingested as HFO was assimilated (values >70%), implying that colloidal HFO potentially represents a source of dietary Cu to benthic grazers, especially where there is active formation and infiltration of these particles into benthic substrates.

Recovery of lithium from geothermal water by amorphous hydrous aluminium oxide

International Nuclear Information System (INIS)

Wada, Hideo; Kitamura, Takao; Ooi, Kenta; Katoh, Shunsaku

1984-01-01

Effects of chemical composition, temperature, and lithium concentration of geothermal water on lithium recovery by amorphous hydrous aluminium oxide (a-HAO) were investigated in order to evaluate the feasibility of this process. The results are summarized as follows: (1) Among various chemical consituents in geothermal water, silica interfered with the lithium adsorption. The lithium uptake decreased when silica concentration exceeded 73 mg/l under 100 mg/50 ml a-HAO to solution ratio. (2) The lithium uptake decreased with an increase of adsorption temperature and was not observed above 40 deg C. At higher temperature, the crystallization of a-HAO to bayerite occurred prior to lithium adsorption. (3) The lithium uptake increased with an increase of lithium concentration. Lithium uptake comparable with lithium contents in lithium ores was obtained at the lithium concentration of 30 mg/l at 20 deg C. These results show that a-HAO is applicable to collect lithium from geothermal water if silica can be removed before lithium adsorption. (author)

Hydrous manganese oxide-polyacrylonitrile (HMO-PAN) composite for the treatment of radioactive laundry wastewater

International Nuclear Information System (INIS)

Sanghwa Oh; Won Sik Shin; Sang-June Choi

2015-01-01

Hydrous manganese oxide-polyacrylonitrile (HMO-PAN) composite was applied for the removal of Co 2+ , Sr 2+ and Cs + from radioactive laundry wastewater. Single- and multi-solute competitive sorptions onto HMO-PAN were investigated. The maximum sorption capacity was in the order of Co 2+ (0.573) > Cs + (0.551) > Sr 2+ (0.310 mmol g -1 ). Sorption of the metals occurred via physical adsorption due to weak van der Waals force and ion exchange with Mn 2+ in HMO-PAN. Sorption behaviors were not related to the types of the surfactants. Among the tested surfactants, SDBS and SOBS remarkably increased the distribution coefficient of Co 2+ and Sr 2+ , respectively. (author)

Development of Surface Complexation Models of Cr(VI) Adsorption on Soils, Sediments and Model Mixtures of Kaolinite, Montmorillonite, γ-Alumina, Hydrous Manganese and Ferric Oxides and Goethite

Energy Technology Data Exchange (ETDEWEB)

Koretsky, Carla [Western Michigan University

2013-11-29

Hexavalent chromium is a highly toxic contaminant that has been introduced into aquifers and shallow sediments and soils via many anthropogenic activities. Hexavalent chromium contamination is a problem or potential problem in the shallow subsurface at several DOE sites, including Hanford, Idaho National Laboratory, Los Alamos National Laboratory and the Oak Ridge Reservation (DOE, 2008). To accurately quantify the fate and transport of hexavalent chromium at DOE and other contaminated sites, robust geochemical models, capable of correctly predicting changes in chromium chemical form resulting from chemical reactions occurring in subsurface environments are needed. One important chemical reaction that may greatly impact the bioavailability and mobility of hexavalent chromium in the subsurface is chemical binding to the surfaces of particulates, termed adsorption or surface complexation. Quantitative thermodynamic surface complexation models have been derived that can correctly calculate hexavalent chromium adsorption on well-characterized materials over ranges in subsurface conditions, such pH and salinity. However, models have not yet been developed for hexavalent chromium adsorption on many important constituents of natural soils and sediments, such as clay minerals. Furthermore, most of the existing thermodynamic models have been developed for relatively simple, single solid systems and have rarely been tested for the complex mixtures of solids present in real sediments and soils. In this study, the adsorption of hexavalent chromium was measured as a function of pH (3-10), salinity (0.001 to 0.1 M NaNO3), and partial pressure of carbon dioxide(0-5%) on a suite of naturally-occurring solids including goethite (FeOOH), hydrous manganese oxide (MnOOH), hydrous ferric oxide (Fe(OH)3), γ-alumina (Al2O3), kaolinite (Al2Si2O5(OH)4), and montmorillonite (Na3(Al, Mg)2Si4O10(OH)2-nH2O). The results show that all of these materials can bind substantial quantities of

Ion sorption onto hydrous ferric oxides: Effect on major element fluid chemistry at Aespoe, Sweden

International Nuclear Information System (INIS)

Bruton, C.J.; Viani, B.E.

1996-06-01

The observed variability of fluid chemistry at the Aespoe Hard Rock Laboratory is not fully described by conservative fluid mixing models. Ion exchange may account for some of the observed discrepancies. It is also possible that variably charged solids such as oxyhydroxides of Fe can serve as sources and sinks of anions and cations through surface complexation. Surface complexation reactions on hydrous ferric oxides involve sorption of both cations and anions. Geochemical modeling of the surface chemistry of hydrous ferric oxides (HFOs) in equilibrium with shallow HBH02 and deep KA0483A waters shows that HFOs can serve as significant, pH-sensitive sources and sinks for cations and anions. Carbonate sorption is favored especially at below-neutral pH. A greater mass of carbonate is sorbed onto HFO surfaces than is contained in the fluid when 10 g goethite, used as a proxy for HFOs, is in contact with 1 kg H 2 O. The masses of sorbent required to significantly impact fluid chemistry through sorption/desorption reactions seem to be reasonable when compared to the occurrences of HFOs at Aespoe. Thus, it is possible that small changes in fluid chemistry can cause significant releases of cations or anions from HFOs into the fluid phase or, alternately, result in uptake of aqueous species onto HFO surfaces. Simulations of the mixing of shallow HBH02 and native KA0483A waters in the presence of a fixed mass of goethite show that surface complexation does not cause the concentrations of Ca, Sr, and SO 4 to deviate from those that are predicted using conservative mixing models. Results for HCO 3 are more difficult to interpret and cannot be addressed adequately at this time

Effect of hot pressing additives on the leachability of hot pressed sodium hydrous titanium oxide

International Nuclear Information System (INIS)

Valentine, T.M.; Sambell, R.A.J.

1980-01-01

Sodium hydrous titanium oxide is an ion exchange resin which can be used for immobilizing medium level waste (MLW) liquors. When hot pressed, it undergoes conversion to a ceramic. Three low melting point materials (borax, bismuth trioxide, and a mixture of PbO/CuO) were added to the (Na)HTiO and the effect that each of these had on aiding densification was assessed. Hot pressing temperature, applied pressure, and percentage addition of hot pressing aid were varied. Percentage open porosity, flexural strength, and leachability were measured. There was a linear relationship between the percentage open porosity and the logarithm of the leach rate for a constant percentage addition of each additive

The collection of uranium from sea water with hydrous metal oxide, 2

International Nuclear Information System (INIS)

Yamashita, Hisao; Nakajima, Fumito; Ozawa, Yoshihiro; Murata, Toshifumi.

1980-01-01

The mechanism of uranium adsorption from sea water by hydrous titanium(IV) oxide was investigated. The uranium adsorption experiments were conducted using a solution containing NaCl, NaHCO 3 , and uranium. Thermochemical calculation showed that the tris(carbonato)dioxouranate(VI) ion (UO 2 (CO 3 ) 3 ) 4- found in sea water existed in the solution at pH 8 and 25 0 C. The uranium uptake varied with the pH of the solution, exhibiting a minimum value at pH 8. The enthalpy change, delta H, and the activation energy, E, of the uranium adsorption were found to be 23.6 kJ mol -1 and 52.7 kJ mol -1 respectively. The analysis of carbonate in the adsorbent showed that the carbonate ion in(UO 2 (CO 3 ) 3 ) 4- was released into the solution during the uranium adsorption. On the basis of the present experimental results, the mechanism of uranium adsorption was discussed. (author)

Uranium oxidation: characterization of oxides formed by reaction with water

International Nuclear Information System (INIS)

Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

1983-01-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

Spark Ignition Engine Combustion, Performance and Emission Products from Hydrous Ethanol and Its Blends with Gasoline

Directory of Open Access Journals (Sweden)

Musaab O. El-Faroug

2016-11-01

Full Text Available This paper reviews the serviceability of hydrous ethanol as a clean, cheap and green renewable substitute fuel for spark ignition engines and discusses the comparative chemical and physical properties of hydrous ethanol and gasoline fuels. The significant differences in the properties of hydrous ethanol and gasoline fuels are sufficient to create a significant change during the combustion phase of engine operation and consequently affect the performance of spark-ignition (SI engines. The stability of ethanol-gasoline-water blends is also discussed. Furthermore, the effects of hydrous ethanol, and its blends with gasoline fuel on SI engine combustion characteristics, cycle-to-cycle variations, engine performance parameters, and emission characteristics have been highlighted. Higher water solubility in ethanol‑gasoline blends may be obviously useful and suitable; nevertheless, the continuous ability of water to remain soluble in the blend is significantly affected by temperature. Nearly all published engine experimental results showed a significant improvement in combustion characteristics and enhanced engine performance for the use of hydrous ethanol as fuel. Moreover, carbon monoxide and oxides of nitrogen emissions were also significantly decreased. It is also worth pointing out that unburned hydrocarbon and carbon dioxide emissions were also reduced for the use of hydrous ethanol. However, unregulated emissions such as acetaldehyde and formaldehyde were significantly increased.

Transition of hydrated oxide layer for aluminum electrolytic capacitors

International Nuclear Information System (INIS)

Chi, Choong-Soo; Jeong, Yongsoo; Ahn, Hong-Joo; Lee, Jong-Ho; Kim, Jung-Gu; Lee, Jun-Hee; Jang, Kyung-Wook; Oh, Han-Jun

2007-01-01

A hydrous oxide film for the application as dielectric film is synthesized by immersion of pure aluminum in hot water. From a Rutherford backscattering analysis, the ratio of aluminum to oxygen atoms was found to be 3:2 in the anodized aluminum oxide film, and 2:1 in the hydrous oxide layer. Anodization of the hydrous oxide layer was more effective for the transition of amorphous anodic oxides to the crystalline aluminum oxides

Adsorption of lithium ion to amorphous hydrous aluminium oxide

International Nuclear Information System (INIS)

Wada, Hideo; Kitamura, Takao; Fujii, Ayako; Katoh, Shunsaku

1982-01-01

Adsorption process of lithium ion to amorphous hydrous aluminium oxide (a-HAO) was investigated by pH titration method with lithium chloride-lithium hydroxide mixed solution and X-ray diffraction analysis of a-HAO after pH titration. In the pH titration, the addition of hydroxide ion in amount from 0 to 4.0 mmol.g -1 gave no change to the pH of the solution and caused adsorption of lithium ion equivalent in amount to added hydroxide ion. X-ray diffraction analysis showed the formation of lithium hydrogenaluminate LiH (AlO 2 ) 2 .5H 2 O (LHA) in the a-HAO after pH titration. These results showed that adsorption of lithium ion by a-HAO was related to a reaction which consumed hydroxide ion and formed LHA. In order to elucidate detail process of the reaction, changes of pH, aluminium concentration and lithium concentration of the solution, respectively with time, were determined. The pH of the solution decreased in two stages. At the first stage of the pH decrease, the aluminium concentration increased whereas the lithium concentration did not change. At the second stage, the lithium concentration decreased together with the decrease of the aluminium concentration. It was inferred that adsorption of lithium ion proceeded through dissolution of a-HAO and precipitation of LHA. Theoretical adsorption capacity calculated from the above formula for LHA and aluminium content in a-HAO was 4.7 mmol.g -1 and agreed fairly well with observed value 4.0 mmol.g -1 . (author)

Synthesis, structure, and thermal properties of soluble hydrazinium germanium(IV) and tin(IV) selenide salts.

Science.gov (United States)

Mitzi, David B

2005-05-16

The crystal structures of two hydrazinium-based germanium(IV) and tin(IV) selenide salts are determined. (N(2)H(5))(4)Ge(2)Se(6) (1) [I4(1)cd, a = 12.708(1) Angstroms, c = 21.955(2) Angstroms, Z = 8] and (N(2)H(4))(3)(N(2)H(5))(4)Sn(2)Se(6) (2) [P, a = 6.6475(6) Angstroms, b = 9.5474(9) Angstroms, c = 9.8830(10) Angstroms, alpha = 94.110(2) degrees, beta = 99.429(2) degrees, gamma = 104.141(2) degrees, Z = 1] each consist of anionic dimers of edge-sharing metal selenide tetrahedra, M(2)Se(6)(4-) (M = Ge or Sn), separated by hydrazinium cations and, for 2, additional neutral hydrazine molecules. Substantial hydrogen bonding exists among the hydrazine/hydrazinium molecules as well as between the hydrazinium cations and the selenide anions. Whereas the previously reported tin(IV) sulfide system, (N(2)H(5))(4)Sn(2)S(6), decomposes cleanly to microcrystalline SnS(2) when heated to 200 degrees C in an inert atmosphere, higher temperatures (>300 degrees C) are required to dissociate selenium from 1 and 2 for the analogous preparations of single-phase metal selenides. The metal chalcogenide salts are highly soluble in hydrazine, as well as in a variety of amines and DMSO, highlighting the potential usefulness of these compounds as precursors for the solution deposition of the corresponding metal chalcogenide films.

Removal of aluminum(III)-based turbidity in water using hydrous titanium oxide dispersed in ion-exchange resins

International Nuclear Information System (INIS)

Venkataramani, B.; Karweer, S.B.; Iyer, R.K.; Phatak, G.M.; Iyer, R.M.

1988-01-01

An adsorber consisting of hydrous titanium oxide (HTiO) dispersed in a Dowex-type ion-exchange resin matrix (designated RT resins) has been developed which is capable of removing Al(III)-based colloidal dispersions in the neutral pH condition. The effect of resin crosslinking, particle size, HTiO loading, turbidity level, and flow rate on the turbidity removal efficiency of RT resins has been studied. It is demonstrated that a train of columns comprising RT resin, H + , and OH - form of resins could be used for large-scale purification operations at high flow rates. These columns, apart from removing turbidity and associated radioactivity, can effectively remove dissolved uranium present in ppb levels when used for water purification in nuclear reactors

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

Science.gov (United States)

Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

The role of alkenes produced during hydrous pyrolysis of a shale

Energy Technology Data Exchange (ETDEWEB)

Leif, R.N.; Simoneit, B.R.T. [Oregon State Univ., Corvallis, OR (United States). College of Oceanic and Atmospheric Sciences

2000-07-01

Hydrous pyrolysis experiments conducted on Messel shale with D{sub 2}O demonstrated that a large amount of deuterium becomes incorporated into the hydrocarbons generated from the shale kerogen. In order to understand the pathway of deuterium (and protium) exchange and the role of water during hydrous pyrolysis, we conducted a series of experiments using aliphatic compounds (1,13-tetradecadiene, 1-hexadecene, eicosane and dotriacontane) as probe molecules. These compounds were pyrolyzed in D{sub 2}O, shale/D{sub 2}O, and shale/H{sub 2}O and the products analyzed by GC-MS. In the absence of powdered shale, the incorporation of deuterium from D{sub 2}O occurred only in olefinic compounds via double bond isomerization. The presence of shale accelerated deuterium incorporation into the olefins and resulted in a minor amount of deuterium incorporation in the saturated n-alkanes. The pattern of deuterium substitution of the diene closely matched the deuterium distribution observed in the n-alkanes generated from the shale kerogen in the D{sub 2}O/shale pyrolyses. The presence of the shale also resulted in reduction (hydrogenation) of olefins to saturated n-alkanes with concomitant oxidation of olefins to ketones. These results show that under hydrous pyrolysis conditions, kerogen breakdown generates n-alkanes and terminal n-alkenes by free radical hydrocarbon cracking of the aliphatic kerogen structure. The terminal n-alkenes rapidly isomerize to internal alkenes via acid-catalyzed isomerization under hydrothermal conditions, a significant pathway of deuterium (and protium) exchange between water and the hydrocarbons. These n-alkenes simultaneously undergo reduction to n-alkanes (major) or oxidation to ketones (minor) via alcohols formed by the hydration of the alkenes. (Author)

The collection of uranium from sea water with hydrous metal oxide, 3

International Nuclear Information System (INIS)

Yamashita, Hisao; Nakajima, Fumito; Ozawa, Yoshihiro; Murata, Toshifumi.

1980-01-01

The effect of diverse ions present in sea water on the uranium adsorption is elucidated in the present paper. The uranium-adsorption experiments were conducted using sea water and a solution containing 0.72 mol dm -3 NaCl and 2.3 x 10 -3 mol dm -3 NaHCO 3 . The uranium uptake was about ten times larger from the NaCl-NaHCO 3 solution than from sea water. The ions which depressed the uranium uptake were the calcium, magnesium, and fluoride present in sea water. Among these ions, calcium had the largest effect on the uranium uptake. The analysis of calcium and carbonate in the adsorbent after the adsorption experiment has revealed that the molar ratio between calcium and carbonate was about one. It was considered that calcium carbonate was deposited on the adsorbent during the uranium adsorption. The specific surface area and the pore volume decreased after the deposition of calcium carbonate. It was supposed that the decrease in the uranium uptake was caused by the coverage of the surface of hydrous titanium(IV) oxide with calcium carbonate. Magnesium ions depressed the uranium uptake in the same manner as calcium ions. The effect of the magnesium ions, however, was relatively small compared with that of the calcium ions. (author)

Inorganic sorbents for removal of radioactivity from aqueous waste streams: 1. Development of seeded ultrafiltration. 2. Ion exchange properties of hydrous titanium oxide. 3. The novel absorber evaluation club

International Nuclear Information System (INIS)

Hooper, E.W.

1997-01-01

This report describes briefly three areas of work involving inorganic sorbents that have been carried out at AEA Technology, Harwell during the course of the Co-ordinated Research Programme (CRP). 1. Seed ultrafiltration, in which finely divided sodium nickel hexacyanoferrate (II), zirconium phosphate and a hydrous titanium oxide were used as a 'seed' cocktail, in combination with cross-flow membrane filtration, to decontaminate a simulate PWR primary coolant. All but one of the eight radionuclides present were reduced in concentration by a factor of ten or more. 2. Some data on the ion-exchange properties of hydrous titanium oxides are presented. These include the cation exchange capacity for barium (as a stand-in for radium), kinetics of sorption and Na:Ti ratio at different values of pH. 3. Some of the data collected from tests carried out by the Novel Absorber Evaluation Club are presented for a number of sorbents that have been examined during the period of this CRP. (author). 1 ref., 5 figs, 6 tabs

The mechanism of diffusion and ionic transport of alkali metal ions in the particles of tin(IV) antimonate

International Nuclear Information System (INIS)

El-Naggar, I.M.; El-Absy, M.A.; Aly, S.I.; Atomic Energy Establishment, Cairo

1992-01-01

The kinetics of exchange Li + , Na + , K + and Cs + ions of tin(IV) antimonate with H + form was studied under particle-diffusion-control conditions at different temperatures. The value of activation energy, diffusion coefficient and entropy of activation increase with the ionic mobilities and radii, and decrease with the hydration energy of the alkali metal ions. On the basis of the kinetic parameters, the exchange of alkali metal ions occurs in the unhydrated form. (author). 29 refs.; 4 figs.; 2 tabs

Thermochemistry of dense hydrous magnesium silicates

Science.gov (United States)

Bose, Kunal; Burnley, Pamela; Navrotsky, Alexandra

1994-01-01

Recent experimental investigations under mantle conditions have identified a suite of dense hydrous magnesium silicate (DHMS) phases that could be conduits to transport water to at least the 660 km discontinuity via mature, relatively cold, subducting slabs. Water released from successive dehydration of these phases during subduction could be responsible for deep focus earthquakes, mantle metasomatism and a host of other physico-chemical processes central to our understanding of the earth's deep interior. In order to construct a thermodynamic data base that can delineate and predict the stability ranges for DHMS phases, reliable thermochemical and thermophysical data are required. One of the major obstacles in calorimetric studies of phases synthesized under high pressure conditions has been limitation due to the small (less than 5 mg) sample mass. Our refinement of calorimeter techniques now allow precise determination of enthalpies of solution of less than 5 mg samples of hydrous magnesium silicates. For example, high temperature solution calorimetry of natural talc (Mg(0.99) Fe(0.01)Si4O10(OH)2), periclase (MgO) and quartz (SiO2) yield enthalpies of drop solution at 1044 K to be 592.2 (2.2), 52.01 (0.12) and 45.76 (0.4) kJ/mol respectively. The corresponding enthalpy of formation from oxides at 298 K for talc is minus 5908.2 kJ/mol agreeing within 0.1 percent to literature values.

Mineralogy of the Hydrous Lower Mantle

Science.gov (United States)

Shim, S. H.; Chen, H.; Leinenweber, K. D.; Kunz, M.; Prakapenka, V.; Bechtel, H.; Liu, Z.

2017-12-01

The hydrous ringwoodite inclusions found in diamonds suggest water storage in the mantle transition zone. However, water storage in the lower mantle remains unclear. Bridgmanite and magnesiowustite appear to have very little storage capacity for water. Here, we report experimental results indicating significant changes in the lower-mantle mineralogy under the presence of water. We have synthesized Mg2SiO4 ringwoodite with 2 wt% water in multi-anvil press at 20 GPa and 1573 K at ASU. The hydrous ringwoodite sample was then loaded to diamond anvil cells with Ar or Ne as a pressure medium. We heated the pure hydrous ringwoodite samples at lower-mantle pressure using a CO2 laser heating system at ASU. We measured X-ray diffraction patterns at the GSECARS sector of the Advanced Photon Source (APS) and 12.2.2 sector of the Advanced Light Source (ALS). For the separate Pt-mixed samples, we have conducted in situ heating at the beamlines using near IR laser heating systems. We measured the infrared spectra of the heated samples at high pressure and after pressure quench at 1.4.4 sector of ALS. In the in situ experiments with hydrous ringwoodite + Pt mixture as a starting material, we found formation of stishovite together with bridgmanite and periclase during heating with a near IR laser beams at 1300-2500 K and 35-66 GPa. However, some hydrous ringwoodite still remains even after a total of 45 min of heating. In contrast, the hydrous ringwoodite samples heated without Pt by CO2 laser beams are transformed completely to bridgmanite, periclase and stishovite at 31-55 GPa and 1600-1900 K. We have detected IR active OH mode of stishovite from the samples heated at lower-mantle pressures. The unit-cell volume of stishovite measured after pressure quench is greater than that of dry stishovite by 0.3-0.6%, supporting 0.5-1 wt% of H2O in stishovite in these samples. Stishovite is a thermodynamically forbidden phase in the dry lower mantle because of the existence of periclase and

Dynamically formed hydrous zirconium (IV) oxide-polyelectrolyte membranes. III: Poly(acrylic acid) and substituted poly(acrylic acid) homo, co and terpolymer membranes

International Nuclear Information System (INIS)

Van Reenen, A.J.; Sanderson, R.D.

1989-01-01

A series of acrylic acid and substituted acrylic acid homo, co and terpolymers was synthesised. These polymers were used as polyelectrolytes in dynamically formed hydrous zirconium (iv) oxide-polyelectrolyte membranes. Substitution of the acrylic acid α-hydrogen was done to increase the number of carboxylic acid groups per monomer unit and to change the acid strength of acrylic acid carboxylic acid group. None of these changes improved the salt rejection of these membranes over that of commercially used poly(acrylic acid). Improvement in rejection was found when a hydrophobic comonomer, vinyl acetate, was used in conjunction with acrylic acid in a copolymer dynamic membrane. 16 refs., 6 figs., 1 tab

Crystallization of biogenic hydrous amorphous silica

Science.gov (United States)

Kyono, A.; Yokooji, M.; Chiba, T.; Tamura, T.; Tuji, A.

2017-12-01

Diatom, Nitzschia cf. frustulum, collected from Lake Yogo, Siga prefecture, Japan was cultured in laboratory. Organic components of the diatom cell were removed by washing with acetone and sodium hypochlorite. The remaining frustules were studied by SEM-EDX, FTIR spectroscopy, and synchrotron X-ray diffraction. The results showed that the spindle-shaped morphology of diatom frustule was composed of hydrous amorphous silica. Pressure induced phase transformation of the diatom frustule was investigated by in situ Raman spectroscopic analysis. With exposure to 0.3 GPa at 100 oC, Raman band corresponding to quartz occurred at ν = 465 cm-1. In addition, Raman bands known as a characteristic Raman pattern of moganite was also observed at 501 cm-1. From the integral ratio of Raman bands, the moganite content in the probed area was estimated to be approximately 50 wt%. With the pressure and temperature effect, the initial morphology of diatom frustule was completely lost and totally changed to a characteristic spherical particle with a diameter of about 2 mm. With keeping the compression of 5.7 GPa at 100 oC, a Raman band assignable to coesite appeared at 538 cm-1. That is, with the compression and heating, the hydrous amorphous silica can be readily crystallized into quartz, moganite, and coesite. The first-principles calculations revealed that a disiloxane molecule stabilized in a trans configuration is twisted 60o and changed into the cis configuration with a close approach of water molecule. It is therefore a reasonable assumption that during crystallization of hydrous amorphous silica, the Si-O-Si bridging unit with the cis configuration would survive as a structural defect and then crystallized into moganite by keeping the geometry. This hypothesis is adaptable to the phase transformation from hydrous amorphous silica to coesite as well, because coesite has the four-membered rings and easily formed from the hydrous amorphous silica under high pressure and high

Preparation Effects on the Performance of Silica-Doped Hydrous Titanium Oxide (HTO:Si)-Supported Pt Catalysts for Lean-Burn NOx Reduction by Hydrocarbons; TOPICAL

International Nuclear Information System (INIS)

GARDNER, TIMOTHY J.; MCLAUGHLIN, LINDA I.; MOWERY, DEBORAH L.; SANDOVAL, RONALD S.

2002-01-01

This report describes the development of bulk hydrous titanium oxide (HTO)- and silica-doped hydrous titanium oxide (HTO:Si)-supported Pt catalysts for lean-burn NOx catalyst applications. The effects of various preparation methods, including both anion and cation exchange, and specifically the effect of Na content on the performance of Pt/HTO:Si catalysts, were evaluated. Pt/HTO:Si catalysts with low Na content ( and lt; 0.5 wt.%) were found to be very active for NOx reduction in simulated lean-burn exhaust environments utilizing propylene as the major reductant species. The activity and performance of these low Na Pt/HTO:Si catalysts were comparable to supported Pt catalysts prepared using conventional oxide or zeolite supports. In ramp down temperature profile test conditions, Pt/HTO:Si catalysts with Na contents in the range of 3-5 wt.% showed a wide temperature window of appreciable NOx conversion relative to low Na Pt/HTO:Si catalysts. Full reactant species analysis using both ramp up and isothermal test conditions with the high Na Pt/HTO:Si catalysts, as well as diffuse reflectance FTIR studies, showed that this phenomenon was related to transient NOx storage effects associated with NaNO(sub 2)/NaNO(sub 3) formation. These nitrite/nitrate species were found to decompose and release NOx at temperatures above 300 C in the reaction environment (ramp up profile). A separate NOx uptake experiment at 275 C in NO/N(sub 2)/O(sub 2) showed that the Na phase was inefficiently utilized for NOx storage. Steady state tests showed that the effect of increased Na content was to delay NOx light-off and to decrease the maximum NOx conversion. Similar results were observed for high K Pt/HTO:Si catalysts, and the effects of high alkali content were found to be independent of the sample preparation technique. Catalyst characterization (BET surface area, H(sub 2) chemisorption, and transmission electron microscopy) was performed to elucidate differences between the HTO- and HTO

Quantification of water in hydrous ringwoodite

Directory of Open Access Journals (Sweden)

Sylvia-Monique eThomas

2015-01-01

Full Text Available Ringwoodite, γ-(Mg,Fe2SiO4, in the lower 150 km of Earth’s mantle transition zone (410-660 km depth can incorporate up to 1.5-2 wt% H2O as hydroxyl defects. We present a mineral-specific IR calibration for the absolute water content in hydrous ringwoodite by combining results from Raman spectroscopy, secondary ion mass spectrometery (SIMS and proton-proton (pp-scattering on a suite of synthetic Mg- and Fe-bearing hydrous ringwoodites. H2O concentrations in the crystals studied here range from 0.46 to 1.7 wt% H2O (absolute methods, with the maximum H2O in the same sample giving 2.5 wt% by SIMS calibration. Anchoring our spectroscopic results to absolute H-atom concentrations from pp-scattering measurements, we report frequency-dependent integrated IR-absorption coefficients for water in ringwoodite ranging from 78180 to 158880 L mol-1cm-2, depending upon frequency of the OH absorption. We further report a linear wavenumber IR calibration for H2O quantification in hydrous ringwoodite across the Mg2SiO4-Fe2SiO4 solid solution, which will lead to more accurate estimations of the water content in both laboratory-grown and naturally occurring ringwoodites. Re-evaluation of the IR spectrum for a natural hydrous ringwoodite inclusion in diamond from the study of Pearson et al. (2014 indicates the crystal contains 1.43 ± 0.27 wt% H2O, thus confirming near-maximum amounts of H2O for this sample from the transition zone.

Hydrous Ruthenium Oxide Nanoparticles Anchored to Graphene and Carbon Nanotube Hybrid Foam for Supercapacitors

Science.gov (United States)

Wang, Wei; Guo, Shirui; Lee, Ilkeun; Ahmed, Kazi; Zhong, Jiebin; Favors, Zachary; Zaera, Francisco; Ozkan, Mihrimah; Ozkan, Cengiz S.

2014-01-01

In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO2) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO2 nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g−1, areal capacitance: 1.11 F cm−2) which leads to an exceptionally high energy density of 39.28 Wh kg−1 and power density of 128.01 kW kg−1. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications. PMID:24663242

Hydrous ruthenium oxide nanoparticles anchored to graphene and carbon nanotube hybrid foam for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei [Univ. of California, Riverside, CA (United States); Guo, S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lee, I. [Univ. of California, Riverside, CA (United States); Ahmed, K. [Univ. of California, Riverside, CA (United States); Zhong, J. [Univ. of California, Riverside, CA (United States); Favors, Z. [Univ. of California, Riverside, CA (United States); Zaera, F. [Univ. of California, Riverside, CA (United States); Ozkan, M. [Univ. of California, Riverside, CA (United States); Ozkan, C. S [Univ. of California, Riverside, CA (United States)

2014-03-25

In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO₂) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO₂ nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g⁻¹, areal capacitance: 1.11 F cm⁻²) which leads to an exceptionally high energy density of 39.28 Wh kg⁻¹ and power density of 128.01 kW kg⁻¹. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications.

Ion exchange characteristics of cerium (IV) and Tin(IV) antimonates and their use in rad waste treatment

Energy Technology Data Exchange (ETDEWEB)

Elnaggar, I M; Abdel Hamid, M M; Elabsy, M A; Aly, H F [Hot lab. centre, atomic energy authority, Cairo, (Egypt)

1995-10-01

Cerium (IV) and Tin(IV) antimonates cation exchangers have been synthesized. The products were characterized by powdered X-ray diffraction, thermal analysis and infrared spectrometry. The data of the distribution coefficients showed that the selectivity decreased in the order Eu{sup 3+}>Co{sup 2+}>Sr{sup 2+}>Cs{sup +} for both materials. Besides, the drying temperature of the matrices have a profound effect on their ion exchange capacities. Moreover, the obtained results of the effect of gamma radiation on the ion exchange behaviour of the samples showed that a slight decrease of the capacity and the distribution coefficient values with increasing the absorbed dose. 2 figs., 4 tabs.

Role of hydrous iron oxide formation in attenuation and diel cycling of dissolved trace metals in a stream affected by acid rock drainage

Science.gov (United States)

Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.

2007-01-01

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.

Sorption kinetics of cesium on hydrous titanium dioxide

International Nuclear Information System (INIS)

Altas, Y.; Tel, H.; Yaprak, G.

2003-01-01

Two types of hydrous titanium dioxide possessing different surface properties were prepared and characterized to study the sorption kinetics of cesium. The effect of pH on the adsorption capacity were determined in both type sorbents and the maximum adsorption percentage of cesium were observed at pH 12. To elucidate the kinetics of ion-exchange reaction on hydrous titanium dioxide, the isotopic exchange rates of cesium ions between hydrous titanium dioxides and aqueous solutions were measured radiochemically and compared with each other. The diffusion coefficients of Cs + ion for Type1 and Type2 titanium dioxides at pH 12 were calculated as 2.79 x 10 -11 m 2 s -1 and 1.52 x 10 -11 m 2 s -1 , respectively, under particle diffusion controlled conditions. (orig.)

Synthesis of hydrous zirconium oxide-impregnated chitosan beads and their application for removal of fluoride and lead

Energy Technology Data Exchange (ETDEWEB)

Cho, Dong-Wan [Department of Environment and Energy, Sejong University, Seoul 143-747 (Korea, Republic of); Jeon, Byong-Hun, E-mail: bhjeon@hanyang.ac.kr [Department of Natural Resources and Environmental Engineering, Hanyang University, 222 6 Wangsimni-ro, Seongdong-gu, Seoul, 133-791 (Korea, Republic of); Jeong, Yoojin [Department of Environment and Energy, Sejong University, Seoul 143-747 (Korea, Republic of); Nam, In-Hyun [Geologic Environment Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon (Korea, Republic of); Choi, Ui-Kyu [Mine reclamation corporation, Coal Center, 2 Segye-ro, Wonju, Gangwon-do, 16464 (Korea, Republic of); Kumar, Rahul [Department of Natural Resources and Environmental Engineering, Hanyang University, 222 6 Wangsimni-ro, Seongdong-gu, Seoul, 133-791 (Korea, Republic of); Song, Hocheol, E-mail: hcsong@sejong.ac.kr [Department of Environment and Energy, Sejong University, Seoul 143-747 (Korea, Republic of)

2016-05-30

A composite adsorbent capable of simultaneous removal of both cationic and anionic contaminants from aqueous solutions was developed by impregnating hydrous zirconium oxide (HZO) into chitosan beads (CB). The optimal mass ratio of chitosan to HZO was 2:2. The composite adsorbent (HZOCB) had the rugged surface (52.74 m{sup 2} g{sup −1}) with irregular cracks caused by HZO inclusion and amine functional groups. The rate of Pb{sup 2+} adsorption by HZOCB was relatively rapid. Most of Pb{sup 2+} (89%) was adsorbed within 2.5 h. A binary sorbate system was noticeably favorable for F{sup −} adsorption as compared to single sorbate system. Adsorption of F{sup −} and Pb{sup 2+} followed pseudo-second order kinetics. The maximum sorption capacities obtained from Langmuir isotherm model were 22.1 and 222.2 mg g{sup −1}, respectively. The study demonstrates that the developed composite could be a potential adsorbent for the simultaneous remediation of F{sup −} and Pb{sup 2+} contamination in water.

Fabrication of a Biomass-Based Hydrous Zirconium Oxide Nanocomposite for Preferable Phosphate Removal and Recovery.

Science.gov (United States)

Qiu, Hui; Liang, Chen; Zhang, Xiaolin; Chen, Mindong; Zhao, Yunxia; Tao, Tao; Xu, Zhengwen; Liu, Gang

2015-09-23

Advanced removal of phosphate by low-cost adsorbents from municipal wastewater or industrial effluents is an effective and economic way to prevent the occurrence of eutrophication. Here, we proposed a novel method to immobilize hydrous zirconium oxide nanoparticle within quaternary-aminated wheat straw, and obtained an inexpensive, eco-friendly nanocomposite Ws-N-Zr. The biomass-based Ws-N-Zr exhibited higher preference toward phosphate than commercial anion exchanger IRA-900 when competing sulfate ions coexisted at relatively high levels. Such excellent performance of Ws-N-Zr resulted from its specific hybrid structure, the quaternary ammonium groups bonded on the host favor the preconcentration of phosphate ions inside the wheat straw based on Donnan effect, and the encapsulated HZO nanoparticle exhibits preferable sequestration of phosphate ions through specific interaction, as further demonstrated by FTIR and X-ray photoelectron spectroscopy. Cycle adsorption and regeneration experiments demonstrated that Ws-N-Zr could be employed for repeated use without significant capacity loss, when the binary NaOH-NaCl solution was employed as the regenerant. The influence of solution pH and contact time was also examined. The results suggested that Ws-N-Zr has a great potential in efficient removal of phosphate in contaminated waters.

Crystallization of oxidized, moderately hydrous arc basalt at mid-to-lower crustal pressures

Science.gov (United States)

Blatter, D. L.; Sisson, T. W.; Hankins, W. B.

2012-12-01

Decades of experimental work show that dry, reduced, subalkaline basalts differentiate to produce tholeiitic (high Fe/Mg) daughter liquids, however the influences of H2O and oxidation on differentiation paths are not well established. Accordingly, we performed crystallization experiments on a relatively magnesian basalt (8.7 wt% MgO) typical of mafic lavas erupted in the Cascades magmatic arc near Mount Rainier, Washington. Starting material was synthesized with 3 wt% H2O and run in 2.54 cm piston-cylinder vessels at 900, 700, and 400 MPa and 1200 to 925 degrees C. Samples were contained in Au75Pd25 capsules pre-saturated with Fe by reaction with magnetite at controlled fO2. Oxygen fugacity was controlled during high-pressure syntheses by the double capsule method using Re-ReO2 plus H2O-CO2 vapor in the outer capsule, mixed to match the expected fH2O of the vapor-undersaturated sample. Crystallization was similar at all pressures with a high temperature interval consisting of augite + olivine + orthopyroxene + Cr-spinel (in decreasing abundance). With decreasing temperature, plagioclase crystallizes, FeTi-oxides replace spinel, olivine dissolves, and finally amphibole appears. Liquids at 900 MPa track along Miyashiro's (1974) tholeiitic vs. calc-alkaline boundary, whereas those at 700 and 400 MPa become calc-alkaline by ~57 wt% SiO2 and greater. Although these evolved liquids are similar in most respects to common calc-alkaline andesites, they differ in having low-CaO due to early and abundant crystallization of augite prior to plagioclase, with the result that they become peraluminous (ASI: Al/(Na+K+Ca)>1) by ~55 wt% SiO2, similar to liquids reported in other studies of the high-pressure crystallization of hydrous basalts (Müntener and Ulmer, 2006 and references therein). A compilation of >7000 analyses of volcanic and intrusive rocks from the Cascades and the Sierra Nevada batholith shows that ASI in arc magmas increases continuously and linearly with SiO2 from

Process for Making a Noble Metal on Tin Oxide Catalyst

Science.gov (United States)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Temperature impact on the primary radiolysis yields concerning the hydrous electron

International Nuclear Information System (INIS)

Baldacchino, G.; Vigneron, G.; Pommeret, St.

2005-01-01

We have studied the impact of temperature on the water radiolysis formation rate of the hydrous electron in presence of selenate di-anion SeO 4 2+ . We have used a high temperature (up to 500 Celsius degrees) optical cell coupled to the electron accelerator Alienor. It appears that the capture of the hydrous electron by selenate follows an Arrhenius law till the sub-critical range, beyond this range the kinetics of the reaction seems more erratic. We have also studied the capture of the hydrous electron by methyl-viologen (MV 2+ ) at 20 and 380 Celsius degrees. It seems that at high temperature more hydrous electrons are produced, it might be interpreted as a consequence of the shift toward the right of the following equilibrium reaction: OH - + H . ↔ e - (aq) + H 2 O. All these results need to be confirmed. (A.C.)

Tungstophosphoric acid supported onto hydrous zirconia ...

Indian Academy of Sciences (India)

Unknown

Hydrous zirconia; heteropolyacid; morphology; particle size; acidity. 1. Introduction. Catalysis by .... chemisorbed on the sample in every pulse was detected by a thermal ..... qualitative organic analysis (New York: Longman), Ch. 3,. 4th ed.

The application of Fe–Mn hydrous oxides based adsorbent for removing selenium species from water

KAUST Repository

Szlachta, Małgorzata

2013-02-01

In this study, the adsorptive removal of selenium(IV) and selenium(VI) from water by a newly developed ion exchange adsorbent, based on Fe(III) and Mn(III) hydrous oxides, was examined. This study was conducted to determine the influence of various operating parameters, such as initial anion concentration, contact time, adsorbent dose, pH, solution temperature, and the presence of competitive anions, on the treatment performance. The high Se(IV) adsorptive capacity of the adsorbent (up to 41.02. mg/g at pH 4) was due to its high affinity for selenite, as reflected in the fast rate of uptake (batch studies) and an efficient long-term removal (column experiments). Although adsorption of anions traditionally decreases as pH increases, the mixed adsorbent was capable of purifying large volumes of Se(IV)-containing water (at pH 7) to reach concentrations lower than 10 μg/L, which meets the European Commission standards. The presence of sulphate and carbonate did not influence Se(IV) adsorption. However, high phosphate and silicate concentrations may have decreased the removal efficiency of Se(IV). Data from the batch and column adsorption experiments were fitted with a number of approved models, which revealed the adsorption mechanism and allowed for a comparison of the results. © 2012 Elsevier B.V.

Novel approach to zinc removal from circum-neutral mine waters using pelletised recovered hydrous ferric oxide.

Science.gov (United States)

Mayes, William M; Potter, Hugh A B; Jarvis, Adam P

2009-02-15

Data are presented which evaluate the performance of a pilot-scale treatment system using pelletised hydrous ferric oxide (HFO; a waste stream from coal mine water treatment) as a high surface area sorbent for removing zinc (Zn) from a metal mine water discharge in the North Pennines Orefield, UK. Over a 10-month period the system removed Zn at mean area- and volume-adjusted removal rates of 3.7 and 8.1gm(-3)day(-1), respectively, with a mean treatment efficiency of 32% at a low mean residence time of 49min. There were seasonal effects in Zn removal owing to establishment and dieback of algae in the treatment tank. This led to increased Zn uptake in early summer months followed by slight Zn release upon algae senescence. In addition to these biosorptive processes, the principal sinks for Zn appear to be (1) sorption onto the HFO surface, and (2) precipitation with calcite-dominated secondary minerals. The latter were formed as a product of dissolution of portlandite in the cement binder and calcium recarbonation. Further optimisation of the HFO pelletisation process holds the possibility for providing a low-cost, low footprint treatment option for metal rich mine waters, in addition to a valuable after-use for recovered HFO from coal mine water treatment facilities.

Lean hydrous and anhydrous bioethanol combustion in spark ignition engine at idle

International Nuclear Information System (INIS)

Chuepeng, Sathaporn; Srisuwan, Sudecha; Tongroon, Manida

2016-01-01

Highlights: • Anhydrous ethanol burns fastest in uncalibrated engine at equal equivalence ratio. • The leaner hydrous ethanol combustion tends to elevate the COV in imep. • Hydrous ethanol consumption was 10% greater than anhydrous ethanol at ϕ = 0.67 limit. • Optimizing alternative fuel engine at idle for stability and emission is suggested. - Abstract: The applications of anhydrous bioethanol to substitute or replace gasoline fuel have shown to attain benefits in terms of engine thermal efficiency, power output and exhaust emissions from spark ignition engines. A hydrous bioethanol has also been gained more attention due to its energy and cost effectiveness. The main aim of this work is to minimize fuel quantity injected to the intake ports of a four-cylinder engine under idle condition. The engine running with hydrous ethanol undergoes within lean-burn condition as its combustion stability is analyzed using an engine indicating system. Coefficient of variation in indicated mean effective pressure is an indicator for combustion stability with hydrocarbon and carbon monoxide emission monitoring as a supplement. Anhydrous ethanol burns faster than hydrous ethanol and gasoline in the uncalibrated engine at the same fuel-to-air equivalence ratio under idle condition. The leaner hydrous ethanol combustion tends to elevate the coefficient of variation in indicated mean effective pressure. The experimental results have found that the engine consumes greater hydrous ethanol by 10% on mass basis compared with those of anhydrous ethanol at the lean limit of fuel-to-air equivalence ratio of 0.67. The results of exhaust gas analysis were compared with those predicted by chemical equilibrium analysis of the fuel-air combustion; the resemble trends were found. Calibrating the alternative fueled engine for fuel injection quantity should be accomplished at idle with combustion stability and emissions optimization.

Solubility product of tetravalent neptunium hydrous oxide and its ionic strength dependence

Energy Technology Data Exchange (ETDEWEB)

Fujiwara, K.; Mori, T. [Japan Nuclear Cycle Development Institute (JNC), 4-33, Muramatsu, Tokai-mura, Naka-gun, Ibaraki-ken, 319-1194 (Japan); Kohara, Y. [Inspection and Development Company, 4-33, Muramatsu, Tokaimura, Naka-gun, Ibaraki-ken, 319-1112 (Japan)

2005-07-01

Full text of publication follows: Solubility products (K{sub sp}) are key parameters in the context of reliable assessment of actinides migration in the repository conditions of high level radioactive waste. Neptunium (Np(IV)) is one of the most important actinide elements in the assessment, because of its inventory and the long half-life. A few previous data for Np(IV) solubility are varied widely due to experimental difficulties related to the extremely low solubility. We carried out batch-type experiments under nitrogen atmosphere using a glovebox. Np(V) was reduced to Np(III) by bubbling 0.5 ppm H{sub 2} / N{sub 2} gas through the solution for 30 days in the presence of platinum black as catalyst. After reducing treatment, the Np(III) converted to Np(IV) by auto-oxidation within approximately three days. The solubilities of the Np(IV) were measured in the pHc ranging from 2 to 4, at room temperature (23 {+-} 2 deg. C), in ionic strength(I) = 0.1, 0.5, 1.0 and 2.0 M NaClO{sub 4}. The equilibrium condition was confirmed by over-saturation and under-saturation method. After the equilibrium, the pH{sub c} and the E{sub h} value of the suspension were measured. The suspension was then filtered using a filter with a NMWL of 3000 (less than 2 nm{phi}). The Np radio activity in the filtrate was determined by alpha spectrometry and absorption spectra of Np(IV). The solubility decreased with increasing pHc and the hydrolysis species are predominantly formed. From the obtained results, the solubility products (K{sub sp}) of Np hydroxide, for the reaction, NpO{sub 2} . xH{sub 2}O {r_reversible} Np{sup 4+} + 4OH{sup -} + (x-2)H{sub 2}O, at I = 0.1, 0.5, 1.0 and 2.0 were determined by using formation constants ({beta}{sub n}(I)), which were determined for the reaction, Np{sup 4+} + nOH{sup -} {r_reversible} Np(OH){sub n}{sup (4-n)+}. By using the specific interaction theory (SIT), the solubility product of tetravalent Np hydrous oxide is calculated to be log K{sub sp}{sup 0

Static Compression of Hydrous Komatiite Liquid

Science.gov (United States)

Agee, C. B.

2005-12-01

High pressure sink/float experiments have been performed on komatiite with 3 and 10 wt% added H2O in order to investigate the effect of water on magma density at high pressure and to determine if density crossovers between equilibrium olivine and hydrous komatiite can exist in the upper mantle. The starting composition komatiite, from Munro Township, with MgO=28 wt%, has been previously studied using sink/float experiments under anhydrous conditions up to 9.3 GPa (Agee and Walker, 1988, 1993). In the present study the starting material mechanical mixtures consisted of powdered komatiite, brucite, fayalite, and reagent oxides of SiO2, Al203, and CaO. Samples were contained in compression-sealed molybdenum capsules. Sink/float marker spheres implemented were gem quality synthetic forsterite (Fo100) and San Carlos olivine (Fo90). Experimental run times were 30 seconds, thus minimizing sphere-liquid reactions and liquid reaction with capsule and pressure media. All experiments were carried out in a Walker multi-anvil apparatus at the Institute of Meteoritics, University of New Mexico. The komatiite + 3 wt% H2O liquid density was bracketed at 1900-1950°C by a float of Fo100 at 7 GPa and a sink at 6 GPa. Neutral buoyancy of Fo100 was observed at 6.4 GPa. An additional neutral buoyancy of Fo90 was observed at 9 GPa. These preliminary results suggest that a density crossover between equilibrium olivine (Fo93) and hydrous komatiite with up to 3 wt% H2O can exist in the mantle, thus lending support to the water filter hypothesis for the region above the 410 km discontinuity (Bercovici and Karato, 2003). Our results for static compression of komatiite + 3 wt% H2O are in good agreement with diamond sink/float observations by Sakamaki et al.(2005) on MORB + 2 wt% H2O. Our komatiite + 10 wt% H2O liquid density measurements are still in progress; however, flotation of Fo100 has not been observed in these experiments up to 9.2 GPa.

Energy, carbon dioxide and water use implications of hydrous ethanol production

International Nuclear Information System (INIS)

Saffy, Howard A.; Northrop, William F.; Kittelson, David B.; Boies, Adam M.

2015-01-01

Highlights: • We use a chemical refinery model and exergy analysis to determine the impact of hydrous ethanol. • The process is 70% efficient with 86% of the losses from fermentation, steam generation and drying. • We found that producing 86 wt% ethanol is optimal for thermal energy consumption. • Hydrous ethanol production can reduce energy costs and emissions by ∼8%. • Hydrous ethanol reduces water use by decreasing evaporation in cooling towers. - Abstract: Sub-azeotropic hydrous ethanol has been demonstrated as an effective diesel fuel replacement when used in dual-fuel compression ignition engines. Previous studies have also suggested that hydrous ethanol may be more efficient to produce from corn than anhydrous ethanol. In this study, we investigate corn ethanol production from a dry-mill, natural gas-fired corn ethanol refinery, producing ethanol with a range of ethanol concentrations from 58 wt% to 100 wt% to determine the effect on energy use, water consumption and greenhouse gas (GHG) emissions in the refining stage of the corn ethanol lifecycle. A second law (exergy) analysis of anhydrous ethanol refining revealed the overall process to be 70% efficient, whereby 86% of the exergy losses could be accounted for by three processes: fermentation (34%), steam generation (29%) and distiller’s grains and solubles drying (23%). We found that producing 86 wt% ethanol is optimal as thermal energy consumption decreases by a maximum of 10% (from 7.7 MJ/L to 6.9 MJ/L). These savings have the potential to reduce energy costs by approximately 8% ($0.34/L) and reduce refinery emissions by 8% (2 g CO 2 e/MJ). Production of hydrous ethanol reduced refinery water use due to decreased evaporative losses in the cooling towers, leading to water savings of between 3% and 6% at 86 wt% ethanol.

Preferable removal of phosphate from water using hydrous zirconium oxide-based nanocomposite of high stability.

Science.gov (United States)

Chen, Liang; Zhao, Xin; Pan, Bingcai; Zhang, Weixian; Hua, Ming; Lv, Lu; Zhang, Weiming

2015-03-02

In this study, we employed a new nanocomposite adsorbent HZO-201, which featured high stability under varying solution chemistry, for preferable removal of phosphate from synthetic solution and a real effluent. An anion exchange resin (D-201) was employed as the host of HZO-201, where nano-hydrous zirconium oxide (HZO) was encapsulated as the active species. D-201 binds phosphate through nonspecific electrostatic affinity, whereas the loaded HZO nanoparticles capture phosphate through formation of the inner-sphere complexes. Quantitative contribution of both species to phosphate adsorption was predicted based on the double-Langmuir model. Preferable removal of phosphate by HZO-201 was observed in the presence of the competing anions at higher levels (Cl(-), NO3(-), SO4(2-), HCO3(-)). Fixed-bed adsorption indicated that the effective volume capacity of a synthetic water (2.0 mg P-PO4(3-)/L) by using HZO-201 was ∼1600 BV in the first run (<0.5mg P-PO4(3-)/L), comparable to Fe(III)-based nanocomposite HFO-201 (∼1500 BV) and much larger than D-201 (<250 BV). The exhausted HZO-201 can be in situ regenerated by using a binary NaOH-NaCl solution for cyclic runs, whether fed with the synthetic solution or real effluent. In general, HZO-201 is a promising alternative to Fe(III)-based adsorbents for trace phosphate removal from effluent particularly at acidic pH. Copyright © 2014 Elsevier B.V. All rights reserved.

Cadmium, lead and silver adsorption in hydrous niobium oxide(V) prepared by precipitation in homogeneous solution method; Adsorcao de chumbo, cadmio e prata em oxido de niobio(V) hidratado preparado pelo metodo da precipitacao em solucao homogenea

Energy Technology Data Exchange (ETDEWEB)

Tagliaferro, Geronimo V.; Pereira, Paulo Henrique F.; Rodrigues, Liana Alvares; Silva, Maria Lucia Caetano Pinto da, E-mail: fernandes_eng@yahoo.com.b [Universidade de Sao Paulo (USP), Lorena, SP (Brazil). Escola de Engenharia. Dept. de Engenharia Quimica

2011-07-01

This paper describes the adsorption of heavy metals ions from aqueous solution by hydrous niobium oxide. Three heavy metals were selected for this study: cadmium, lead and silver. Adsorption isotherms were well fitted by Langmuir model. Maximum adsorption capacity (Q{sub 0}) for Pb{sup 2+}, Ag{sup +} and Cd{sup 2+} was found to be 452.5, 188.68 and 8.85 mg g{sup -1}, respectively. (author)

Plutonium(IV) hydrous polymer chemistry

International Nuclear Information System (INIS)

Toth, L.M.; Dodson, K.E.

1985-01-01

The hydrous polymer chemistry of Pu(IV) in aqueous nitric acid solutions has been a subject of considerable interest for several years. This interest stems mainly from the fact that most nuclear fuel reprocessing schemes based on the Purex process can be hampered by the occurrence of polymer. As a result, an understanding and control of the parameters that affect polymer formation during reprocessing are studied. 2 refs

Mercury (II) reduction and co-precipitation of metallic mercury on hydrous ferric oxide in contaminated groundwater.

Science.gov (United States)

Richard, Jan-Helge; Bischoff, Cornelia; Ahrens, Christian G M; Biester, Harald

2016-01-01

Mercury (Hg) speciation and sorption analyses in contaminated aquifers are useful for understanding transformation, retention, and mobility of Hg in groundwater. In most aquifers hydrous ferric oxides (HFOs) are among the most important sorbents for trace metals; however, their role in sorption or mobilization of Hg in aquifers has been rarely analyzed. In this study, we investigated Hg chemistry and Hg sorption to HFO under changing redox conditions in a highly HgCl2-contaminated aquifer (up to 870μgL(-1) Hg). Results from aqueous and solid phase Hg measurements were compared to modeled (PHREEQC) data. Speciation analyses of dissolved mercury indicated that Hg(II) forms were reduced to Hg(0) under anoxic conditions, and adsorbed to or co-precipitated with HFO. Solid phase Hg thermo-desorption measurements revealed that between 55 and 93% of Hg bound to HFO was elemental Hg (Hg(0)). Hg concentrations in precipitates reached more than 4 weight %, up to 7000 times higher than predicted by geochemical models that do not consider unspecific sorption to and co-precipitation of elemental Hg with HFO. The observed process of Hg(II) reduction and Hg(0) formation, and its retention and co-precipitation by HFO is thought to be crucial in HgCl2-contaminated aquifers with variable redox-conditions regarding the related decrease in Hg solubility (factor of ~10(6)), and retention of Hg in the aquifer. Copyright © 2015 Elsevier B.V. All rights reserved.

The density, compressibility and seismic velocity of hydrous melts at crustal and upper mantle conditions

Science.gov (United States)

Ueki, K.; Iwamori, H.

2015-12-01

Various processes of subduction zone magmatism, such as upward migration of partial melts and fractional crystallization depend on the density of the hydrous silicate melt. The density and the compressibility of the hydrous melt are key factors for the thermodynamic calculation of phase relation of the hydrous melt, and the geophysical inversion to predict physicochemical conditions of the melting region based on the seismic velocity. This study presents a new model for the calculations of the density of the hydrous silicate melts as a function of T, P, H2O content and melt composition. The Birch-Murnaghan equation is used for the equation of state. We compile the experimentally determined densities of various hydrous melts, and optimize the partial molar volume, compressibility, thermal expansibility and its pressure derivative, and K' of the H2O component in the silicate melt. P-T ranges of the calibration database are 0.48-4.29 GPa and 1033-2073 K. As such, this model covers the P-T ranges of the entire melting region of the subduction zone. Parameter set provided by Lange and Carmichael [1990] is used for the partial molar volume and KT value of the anhydrous silicate melt. K' of anhydrous melt is newly parameterized as a function of SiO2 content. The new model accurately reproduces the experimentally determined density variations of various hydrous melts from basalt to rhyolite. Our result shows that the hydrous melt is more compressive and less dense than the anhydrous melt; with the 5 wt% of H2O in melt, density and KT decrease by ~10% and ~30% from those of the anhydrous melt, respectively. For the application of the model, we calculated the P-wave velocity of the hydrous melt. With the 5 wt% of H2O, P-wave velocity of the silicate melt decreases by >10%. Based on the melt P-wave velocity, we demonstrate the effect of the melt H2O content on the seismic velocity of the partially molten zone of the subduction zone.

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Science.gov (United States)

Oba, Y.; Naraoka, H.

2009-08-01

A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y-791198, Y-793321, A-881280, A-881334, A-881458 and B-7904) as well as Murchison IOM residues after hydrous pyrolysis at 270-330 °C for 72 h. Isotopic compositions of bulk carbon (δ13Cbulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from -15.1 to -7.6‰ and +133 to +986‰, respectively. Intramolecular carboxyl carbon (δ13CCOOH) is more enriched in 13C by 7.5 -11‰ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13Cbulk, δ13CCOOH, and δD values decrease by up to 0.31, 3.5‰, 5.5‰, and 961‰, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13Cbulk- δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A-881280, A-881458, Y-791198 and B-7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A-881334 and Y-793321 consist of another distinct isotope group. A δ13Cbulk-δ13CCOOH cross-plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.

The Role of Hydrogen Bonds Of The Azeotropic Hydrous Ethanol Fuel Composition To The Exhaust Emissions

Science.gov (United States)

Made Suarta, I.; Nyoman Gede Baliarta, I.; Sopan Rahtika, I. P. G.; Wijaya Sunu, Putu

2018-01-01

In this study observed the role of hydrogen bonding to the composition of exhaust emissions which is produced hydrous ethanol fuel (95.5% v). Testing is done by using single cylinder four stroke motor engine. The composition of exhaust gas emissions is tested using exhaust gas analyzer on lean and stoichiometry mixer. The exhaust emissions produced by anhydrous ethanol were also tested. The composition of emissions produced by that two fuels is compared. The results showed CO emissions levels produced by hydrous ethanol are slightly higher than anhydrous ethanol in stoichiometric mixtures. But the composition of CO hydrous ethanol emissions is lower in the lean mix. If lean the mixer the different in the composition of emissions is increasing. On hydrous ethanol emission CO2 content little bit lower on the stoichiometric mixer and higher on the lean mixture. Exhaust emissions of ethanol fuel also produce O2. O2 hydrous ethanol emissions is higher than anhydrous ethanol fuel.

Hydrous mineral dehydration around heat-generating nuclear waste in bedded salt formations.

Science.gov (United States)

Jordan, Amy B; Boukhalfa, Hakim; Caporuscio, Florie A; Robinson, Bruce A; Stauffer, Philip H

2015-06-02

Heat-generating nuclear waste disposal in bedded salt during the first two years after waste emplacement is explored using numerical simulations tied to experiments of hydrous mineral dehydration. Heating impure salt samples to temperatures of 265 °C can release over 20% by mass of hydrous minerals as water. Three steps in a series of dehydration reactions are measured (65, 110, and 265 °C), and water loss associated with each step is averaged from experimental data into a water source model. Simulations using this dehydration model are used to predict temperature, moisture, and porosity after heating by 750-W waste canisters, assuming hydrous mineral mass fractions from 0 to 10%. The formation of a three-phase heat pipe (with counter-circulation of vapor and brine) occurs as water vapor is driven away from the heat source, condenses, and flows back toward the heat source, leading to changes in porosity, permeability, temperature, saturation, and thermal conductivity of the backfill salt surrounding the waste canisters. Heat pipe formation depends on temperature, moisture availability, and mobility. In certain cases, dehydration of hydrous minerals provides sufficient extra moisture to push the system into a sustained heat pipe, where simulations neglecting this process do not.

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

Science.gov (United States)

Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

2011-12-28

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

Coordination Nature of 4-Mercaptoaniline to Sn(II Ion: Formation of a One Dimensional Coordination Polymer and Its Decomposition to a Mono Nuclear Sn(IV Complex

Directory of Open Access Journals (Sweden)

Eon S. Burkett

2014-12-01

Full Text Available The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. However, when submerged in a solution saturated with oxygen, the compound oxidizes to a mononuclear tin(IV complex. Both the compounds were characterized by single crystal X-ray diffraction studies. Although the structure of the tin(IV complex was previously reported, crystal structure of this compound was redetermined.

High-pressure synchrotron x-ray diffraction and infrared microspectroscopy: applications to dense hydrous phases

CERN Document Server

Liu, Z; Yang, H; Mao Ho Kwang; Hemley, R J

2002-01-01

Synchrotron x-ray diffraction (XRD) and infrared (IR) absorption spectra of hydrous and 'anhydrous' forms of phase X were measured to 30 GPa at room temperature. Three OH stretching modes were found in the hydrous phase, and surprisingly one sharp OH mode was observed in the previously characterized anhydrous phase. All OH stretching modes soften and broaden with increasing pressure and become very weak above approx 20 GPa. XRD indicates that the crystal structure remains stable up to 30 GPa. Combining IR absorption and XRD results, the behaviour is attributed to pressure-induced distortion of the Si sub 2 O sub 7 groups and disorder of the hydrogen atoms. The bulk moduli of the hydrous and 'anhydrous' phases are in the region of 74 GPa.

Dietary uptake of Cu sorbed to hydrous iron oxide is linked to cellular toxicity and feeding inhibition in a benthic grazer

Science.gov (United States)

Cain, Daniel J.; Croteau, Marie-Noele; Fuller, Christopher C.; Ringwood, Amy H.

2016-01-01

Whereas feeding inhibition caused by exposure to contaminants has been extensively documented, the underlying mechanism(s) are less well understood. For this study, the behavior of several key feeding processes, including ingestion rate and assimilation efficiency, that affect the dietary uptake of Cu were evaluated in the benthic grazer Lymnaea stagnalis following 4–5 h exposures to Cu adsorbed to synthetic hydrous ferric oxide (Cu–HFO). The particles were mixed with a cultured alga to create algal mats with Cu exposures spanning nearly 3 orders of magnitude at variable or constant Fe concentrations, thereby allowing first order and interactive effects of Cu and Fe to be evaluated. Results showed that Cu influx rates and ingestion rates decreased as Cu exposures of the algal mat mixture exceeded 104 nmol/g. Ingestion rate appeared to exert primary control on the Cu influx rate. Lysosomal destabilization rates increased directly with Cu influx rates. At the highest Cu exposure where the incidence of lysosomal membrane damage was greatest (51%), the ingestion rate was suppressed 80%. The findings suggested that feeding inhibition was a stress response emanating from excessive uptake of dietary Cu and cellular toxicity.

Surface complexation modeling of Cu(II adsorption on mixtures of hydrous ferric oxide and kaolinite

Directory of Open Access Journals (Sweden)

Schaller Melinda S

2008-09-01

Full Text Available Abstract Background The application of surface complexation models (SCMs to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO, pure kaolinite (from two sources and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples.

Preferable removal of phosphate from water using hydrous zirconium oxide-based nanocomposite of high stability

International Nuclear Information System (INIS)

Chen, Liang; Zhao, Xin; Pan, Bingcai; Zhang, Weixian; Hua, Ming; Lv, Lu; Zhang, Weiming

2015-01-01

Highlights: • The nanocomposite HZO-201 was stable under varying solution chemistry. • HZO-201 exhibited preferable phosphate removal over other ubiquitous anions. • Selective sorption mechanism was probed and discussed. • HZO-201 could be regenerated for cyclic use with constant efficiency. - Abstract: In this study, we employed a new nanocomposite adsorbent HZO-201, which featured high stability under varying solution chemistry, for preferable removal of phosphate from synthetic solution and a real effluent. An anion exchange resin (D-201) was employed as the host of HZO-201, where nano-hydrous zirconium oxide (HZO) was encapsulated as the active species. D-201 binds phosphate through nonspecific electrostatic affinity, whereas the loaded HZO nanoparticles capture phosphate through formation of the inner-sphere complexes. Quantitative contribution of both species to phosphate adsorption was predicted based on the double-Langmuir model. Preferable removal of phosphate by HZO-201 was observed in the presence of the competing anions at higher levels (Cl − , NO 3 − , SO 4 2− , HCO 3 − ). Fixed-bed adsorption indicated that the effective volume capacity of a synthetic water (2.0 mg P-PO 4 3− /L) by using HZO-201 was ∼1600 BV in the first run (<0.5 mg P-PO 4 3− /L), comparable to Fe(III)-based nanocomposite HFO-201 (∼1500 BV) and much larger than D-201 (<250 BV). The exhausted HZO-201 can be in situ regenerated by using a binary NaOH–NaCl solution for cyclic runs, whether fed with the synthetic solution or real effluent. In general, HZO-201 is a promising alternative to Fe(III)-based adsorbents for trace phosphate removal from effluent particularly at acidic pH

Arsenic Removal from Water Using Various Adsorbents: Magnetic Ion Exchange Resins, Hydrous Ion Oxide Particles, Granular Ferric Hydroxide, Activated Alumina, Sulfur Modified Iron, and Iron Oxide-Coated Microsand

KAUST Repository

Sinha, Shahnawaz

2011-09-30

The equilibrium and kinetic adsorption of arsenic on six different adsorbents were investigated with one synthetic and four natural types (two surface and two ground) of water. The adsorbents tested included magnetic ion exchange resins (MIEX), hydrous ion oxide particles (HIOPs), granular ferric hydroxide (GFH), activated alumina (AA), sulfur modified iron (SMI), and iron oxide-coated mic - rosand (IOC-M), which have different physicochemical properties (shape, charge, surface area, size, and metal content). The results showed that adsorption equilibriums were achieved within a contact period of 20 min. The optimal doses of adsorbents determined for a given equilibrium concentration of C eq = 10 μg/L were 500 mg/L for AA and GFH, 520–1,300 mg/L for MIEX, 1,200 mg/L for HIOPs, 2,500 mg/L for SMI, and 7,500 mg/L for IOC-M at a contact time of 60 min. At these optimal doses, the rate constants of the adsorbents were 3.9, 2.6, 2.5, 1.9, 1.8, and 1.6 1/hr for HIOPs, AA, GFH, MIEX, SMI, and IOC-M, respectively. The presence of silicate significantly reduced the arsenic removal efficiency of HIOPs, AA, and GFH, presumably due to the decrease in chemical binding affinity of arsenic in the presence of silicate. Additional experiments with natural types of water showed that, with the exception of IOC-M, the adsorbents had lower adsorption capacities in ground water than with surface and deionized water, in which the adsorption capacities decreased by approximately 60–95 % .

Visible-near infrared spectra of hydrous carbonates, with implications for the detection of carbonates in hyperspectral data of Mars

Science.gov (United States)

Harner, Patrick L.; Gilmore, Martha S.

2015-04-01

We present visible-near infrared (VNIR, 0.35-5 μm) spectra for a suite of hydrous carbonates that may be relevant to the surface of Mars. This includes VNIR spectra for ikaite, nesquehonite, synthetic monohydrocalcite and lansfordite over the 0.35-2.5 μm range that are new to the literature. The spectral features of the hydrous carbonates are dominated by absorptions at ∼1.0, 1.2, 1.4-1.5, 1.9 and 2.8 μm that are due to overtones and combinations of fundamental water and hydroxyl vibrations. Absorptions due to (CO3)2-, Mg-OH, Fe-OH, and/or water are seen at ∼2.3-2.5, 3.4, and 3.9 μm in hydrous Mg and Mg-Fe3+ carbonates containing hydroxyl groups, but are weaker than in the common anhydrous carbonates. When present in the hydrous carbonates, the positions of the centers of the 2.3 μm and/or 2.5 μm absorptions are often shifted relative to the anhydrous carbonates, which may be diagnostic. Some or all of the (CO3)2- absorptions typical of anhydrous carbonates are weak to absent in the hydrous carbonates, and thus this group may be difficult to distinguish from other hydrous minerals like sulfates, phyllosilicates or chlorides in Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) data using standard spectral search parameters for anhydrous carbonates. We present strategies for recognizing hydrous carbonates in CRISM data using combinations of spectral parameters that measure the intensity and shape of the water-related absorptions in these minerals.

The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

Science.gov (United States)

Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovič, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

2007-09-01

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron

Solubilities of some hydrous REE phosphates with implications for diagenesis and sea water concentrations

International Nuclear Information System (INIS)

Jonasson, R.G.; Bancroft, G.M.; Nesbitt, H.W.

1985-01-01

Solubility product determinations suggest that the hydrous phosphates of the rare earths, REPO 4 .xH 2 O, are important in controlling the sea water REE concentrations. Two of these solids, rhabdophane, (P6 2 22) and 'hydrous xenotime', (I4 1 /amd), have been synthesized at 100 C via the acid hydrolysis of the respective REE pyrophosphate. The solubility products at infinite dilution were determined to be pK 0 = 24.5, (La at 25 C); 26.0, (Pr at 100 C); 25.7, (Nd at 100 C); and 25.5, (Er at 100 C). On the basis of calculations involving the reaction of Re 3+ with apatite to form the hydrous phosphate, the lanthanum concentration in sea water is predicted to be about 140 pmol/L. Laboratory experiments support the hypothesis that apatite is a substrate for reactions with dissolved REE. (author)

Structural and optical studies of 100 MeV Au irradiated thin films of tin oxide

Science.gov (United States)

Jaiswal, Manoj Kumar; Kanjilal, D.; Kumar, Rajesh

2013-11-01

Thin films of tin(IV) oxide (SnO2) of 100 nm thickness were grown on silicon (1 0 0) matrices by electron beam evaporation deposition technique under high vacuum. The thicknesses of these films were monitored by piezo-sensor attached to the deposition chamber. Nanocrystallinity is achieved in these thin films by 100 MeV Au8+ using 1 pnA current at normal incidence with ion fluences varying from 1 × 1011 ions/cm2 to 5 × 1013 ions/cm2. Swift Heavy Ion beam irradiation was carried out by using 15 UD Pelletron Accelerator at IUAC, New Delhi, India. Optical studies of pristine and ion irradiated thin films were characterized by UV-Visible spectroscopy and Fourier Transform Infrared (FTIR) spectroscopy. Prominent peak at 610 cm-1 in FTIR spectrum confirmed the O-Sn-O bonding of tin(IV) oxide. For Surface topographical studies and grain size calculations, these films were characterized by Atomic Force Microscope (AFM) using Nanoscope III-A. Crystallinity and phase transformation due to irradiation of pristine and irradiated films were characterized by Glancing Angle X-ray Diffraction (GAXRD) using Brucker-D8 advance model. GAXRD results show improvement in crystallinity and phase transformation due to swift heavy ion irradiation. Grain size distribution was verified by AFM and GAXRD results. Swift heavy ion induced modifications in thin films of SnO2 were confirmed by the presence of prominent peaks at 2θ values of 30.65°, 32.045°, 43.94°, 44.96° and 52.36° in GAXRD spectrum.

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

Science.gov (United States)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

The impact of dissolved fluorine on bubble nucleation in hydrous rhyolite melts

Science.gov (United States)

Gardner, James E.; Hajimirza, Sahand; Webster, James D.; Gonnermann, Helge M.

2018-04-01

Surface tension of hydrous rhyolitic melt is high enough that large degrees of supersaturation are needed to homogeneously nucleate H2O bubbles during eruptive magma ascent. This study examines whether dissolved fluorine lowers surface tension of hydrous rhyolite, and thus lowers the supersaturation required for bubble nucleation. Fluorine was targeted because it, like H2O, changes melt properties and is highly soluble, unlike all other common magmatic volatiles. Rhyolite melts were saturated at Ps = 245 MPa with H2O fluid that contained F, generating rhyolite with 6.7 ± 0.4 wt.% H2O and 1.1-1.3 wt.% F. When these melts were decompressed rapidly to Pf = 149-202 MPa and quenched after 60 s, bubbles nucleated at supersaturations of ΔP = Ps - Pf ≥52 MPa, and reached bubble number densities of NB = 1012-13 m-3 at ΔP = 78-101 MPa. In comparison, rhyolite saturated with 6.34 ± 0.09 wt.% H2O, but only 0.25 wt.% F, did not nucleate bubbles until ΔP ≥ 100-116 MPa, and even then, at significantly lower NB (<1010 m-3). Numerical modeling of bubble nucleation and growth was used to estimate the values of surface tension required to generate the observed values of NB. Slight differences in melt compositions (i.e., alkalinity and H2O content), H2O diffusivity, or melt viscosity cannot explain the observed differences in NB. Instead, surface tension of F-rich rhyolite must be lower by approximately 4% than that of F-poor rhyolite. This difference in surface tension is significant and, for example, exceeds that found between hydrous basaltic andesite and hydrous rhyolite. These results suggest that is likely that surface tension for F-rich magmas, such as topaz rhyolite, is significantly lower than for F-poor magmas.

Stepwise fluorination - a useful approach for the isotopic analysis of hydrous minerals

Energy Technology Data Exchange (ETDEWEB)

Haimson, M; Knauth, L P [Arizona State Univ., Tempe (USA). Dept. of Geology

1983-09-01

Analytical uncertainties in oxygen isotopic studies of hydrous silica have been investigated using a partial fluorination procedure in which fractional oxygen yields are achieved by reducing the amount of fluorine. Stepwise reaction of opaline silica results in a set of sequential oxygen fractions which show a wide range of delta/sup 18/O values due to variable amounts of water, organic matter, and other impurities. Delta-values for successive fractions in non-biogenic opal systematically increase as water is reacted away and then remain constant to within +- 0.2 per thousand as the remaining silica reacts. Delta-values in biogenic silica increase similarly but then decrease when low /sup 18/O oxide impurities begin to react. The troublesome water component in opal is readily removed by stepwise fluorination. This technique allows more precise oxygen isotope analysis of non-biogenic opal-A, and may improve the analytical precision for biogenic silica and any silicate mineral containing a significant water component.

Thermal stability of thiophene biomarkers as studied by hydrous pyrolysis

NARCIS (Netherlands)

Sinninghe Damsté, J.S.; Koopmans, M.P.; Lewan, M.D.; Leeuw, J.W. de

1995-01-01

An immature (Ro = 0.25%) sulphur-rich calcareous shale from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) was artificially matured by hydrous pyrolysis at constant temperatures ranging from 160 to 330°C for 72 h to study the applicability of alkylthiophenes

Megafans as Hydrous Environments

Science.gov (United States)

Wilkinson, M. Justin; Miller, R. McG.; Allen, C. C.; Kreslavsky, M. H.; Eckardt, F.

2009-01-01

The mesoscale sedimentary environment known as the megafan, is a low-angle, partial cone of fluvial sediment generated where a river enters an unconfined basin where it begins the process of avulsing over wide areas. In shifting to different positions, the river lays down a partial cone of sediment and establishes a characteristic radial pattern of paleo courses. The apparent paucity of sedimentary bodies obviously tied to martian outflow channels may also relate to the difficulty of recognition due to their sheer size and featurelessness. However, the existence of megafans on Mars is being examined now that their ubiquity and characteristics on Earth are better understood. Accordingly we suggest two likely candidates on Mars: Maja Valles fluvial cone and Amazonis Planitia fluvial sedimentary bodies. Two cryptic examples from Amazonis Planitia may be important for understanding subsurface hydrous accumulation. For at least some of its history, discharges from Mangala Valles likely resulted in megafans. Distances from the end of Mangala Valles to the northern (low) margin of the planitia are very large, a fact that has suggested that fluvial emplacement was unlikely. However, the megafan model shows that long megafan radii are indeed feasible. It has been suggested further that discharge from Labou Vallis (8.5S 154.5W) must have led to fluvial sedimentation in the planitia. We suggest that during locally non-lacustrine/ocean phases, this sedimentation would have occurred in the form of megafans. However, the megafan model shows that long megafan radii are indeed feasible. It has been suggested further that discharge from Labou Vallis (8.5S 154.5W) must have led to fluvial sedimentation in the planitia. We suggest that during locally non-lacustrine/ocean phases, this sedimentation would have occurred in the form of megafans. Megafans emanating from Marte, Mangala and Labou valles have probably contributed to hydrous near-subsurface environments--in their distal

Structural and optical studies of 100 MeV Au irradiated thin films of tin oxide

Energy Technology Data Exchange (ETDEWEB)

Jaiswal, Manoj Kumar [University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110 078 (India); Kanjilal, D. [Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110 067 (India); Kumar, Rajesh, E-mail: rajeshkumaripu@gmail.com [University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110 078 (India)

2013-11-01

Thin films of tin(IV) oxide (SnO{sub 2}) of 100 nm thickness were grown on silicon (1 0 0) matrices by electron beam evaporation deposition technique under high vacuum. The thicknesses of these films were monitored by piezo-sensor attached to the deposition chamber. Nanocrystallinity is achieved in these thin films by 100 MeV Au{sup 8+} using 1 pnA current at normal incidence with ion fluences varying from 1 × 10{sup 11} ions/cm{sup 2} to 5 × 10{sup 13} ions/cm{sup 2}. Swift Heavy Ion beam irradiation was carried out by using 15 UD Pelletron Accelerator at IUAC, New Delhi, India. Optical studies of pristine and ion irradiated thin films were characterized by UV–Visible spectroscopy and Fourier Transform Infrared (FTIR) spectroscopy. Prominent peak at 610 cm{sup −1} in FTIR spectrum confirmed the O–Sn–O bonding of tin(IV) oxide. For Surface topographical studies and grain size calculations, these films were characterized by Atomic Force Microscope (AFM) using Nanoscope III-A. Crystallinity and phase transformation due to irradiation of pristine and irradiated films were characterized by Glancing Angle X-ray Diffraction (GAXRD) using Brucker-D8 advance model. GAXRD results show improvement in crystallinity and phase transformation due to swift heavy ion irradiation. Grain size distribution was verified by AFM and GAXRD results. Swift heavy ion induced modifications in thin films of SnO{sub 2} were confirmed by the presence of prominent peaks at 2θ values of 30.65°, 32.045°, 43.94°, 44.96° and 52.36° in GAXRD spectrum.

Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide

International Nuclear Information System (INIS)

Shinomiya, Takuya; Gupta, Vinay; Miura, Norio

2006-01-01

The amorphous nano-structured manganese oxide was electrochemically deposited onto a stainless-steel electrode. The structure and surface morphology of the obtained manganese oxide were studied by means of X-ray diffraction analysis and scanning electron microscopy. The capacitive characteristics of the manganese oxide electrodes were investigated by means of cyclic voltammetry and constant current charge-discharge cycling. The morphological and capacitive characteristics of the hydrous manganese oxide was found to be strongly influenced by the electrochemical deposition conditions. The highest specific capacitance value of ca. 410 F g -1 and the specific power of ca. 54 kW kg -1 were obtained at 400 mV s -1 sweep rate of potentiodynamic deposition condition. The cyclic-life data showed that the specific capacitance was highly stable up to 10,000 cycles examined. This suggests the excellent cyclic stability of the obtained amorphous hydrous manganese oxide for supercapacitor application

Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide

Energy Technology Data Exchange (ETDEWEB)

Shinomiya, Takuya; Gupta, Vinay; Miura, Norio [Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580 (Japan)

2006-06-01

The amorphous nano-structured manganese oxide was electrochemically deposited onto a stainless-steel electrode. The structure and surface morphology of the obtained manganese oxide were studied by means of X-ray diffraction analysis and scanning electron microscopy. The capacitive characteristics of the manganese oxide electrodes were investigated by means of cyclic voltammetry and constant current charge-discharge cycling. The morphological and capacitive characteristics of the hydrous manganese oxide was found to be strongly influenced by the electrochemical deposition conditions. The highest specific capacitance value of ca. 410Fg{sup -1} and the specific power of ca. 54kWkg{sup -1} were obtained at 400mVs{sup -1} sweep rate of potentiodynamic deposition condition. The cyclic-life data showed that the specific capacitance was highly stable up to 10,000 cycles examined. This suggests the excellent cyclic stability of the obtained amorphous hydrous manganese oxide for supercapacitor application. (author)

Water and Slabs in the Transition Zone - Hydrous Ringwoodite in Diamond

Science.gov (United States)

Pearson, D. G.; Brenker, F. E.; Nestola, F.; McNeill, J.; Nasdala, L.; Hutchison, M.; Matveev, S.; Mather, K.; Vincze, L.; Schmitz, S.; Vekemens, B.

2014-12-01

Theory and experiments have shown that the Earth's Transition Zone (TZ) could be a major repository for water, due to the ability of the higher-pressure polymorphs of olivine - wadsleyite and ringwoodite - to host up to ~2.5wt. % H2O. Despite experimental demonstration of the water-bearing capacity of these phases, geophysical probes such as electrical conductivity have provided conflicting results, and the issue of whether the TZ contains abundant water remains highly controversial. We report X-ray diffraction, Raman and infra-red spectroscopic evidence for the first terrestrial occurrence of any higher pressure polymorph of olivine: ringwoodite, included in a diamond from Juína, Brazil. The ringwoodite occurs with a Ca-walstromite phase that we interpret to be retrogressed Ca-silicate perovskite. The most likely interpretation of this two-phase assemblage is that it represents a partially retrogressed portion of a somewhat Fe-rich peridotitic mantle, in which hydrous ringwoodite, and former CaSiO3- perovskite co-existed above 15GPa. The ringwoodite has a Mg# of ~ 75, suggesting that it may be mantle hybrised with a more fertile component such as subducted oceanic crust. The water-rich nature of this inclusion (~1.5 wt%), along with the preservation of ringwoodite, is the first direct evidence that, at least locally, the TZ is hydrous, to about 1 wt%. As well as being in agreement with recent magnetotelluric estimates of the TZ water content, this amount of water helps to reconcile measured TZ seismic velocities with those predicted from lab experiments. The finding also indicates that some kimberlites must have their primary sources in this deep mantle region. The high water content of the ringwoodite suggests that it was not close to the mantle geotherm when trapped in the diamond. This may be an indication that the the assemblage was part of a water-rich subducted slab out of thermal equilibrium, within the transition zone. The water-rich nature of the

Single-crystal structure determination of hydrous minerals and insights into a wet deep lower mantle

Science.gov (United States)

Zhang, L.; Yuan, H.; Meng, Y.; Popov, D.

2017-12-01

Water enters the Earth's interior through hydrated subducting slabs. How deep within the lower mantle (670-2900 km depth) can water be transported down and stored depends upon the availability of hydrous phases that is thermodynamically stable under the high P-T conditions and have a sufficiently high density to sink through the lower mantle. Phase H [MgSiH2O4] (1) and the δ-AlOOH (2) form solid solutions that are stable in the deep lower mantle (3), but the solid solution phase is 10% lighter than the corresponding lower mantle. Recent experimental discoveries of the pyrite (Py) structured FeO2 and FeOOH (4-6) suggest that these Fe-enriched phases can be transported to the deepest lower mantle owing to their high density. We have further discovered a very dense hydrous phase in (Fe,Al)OOH with a previously unknown hexagonal symmetry and this phase is stable relative to the Py-phase under extreme high P-T conditions in the deep lower mantle. Through in situ multigrain analysis (7) and single-crystal structure determination of the hydrous minerals at P-Tconditions of the deep lower mantle, we can obtain detailed structure information of the hydrous phases and therefore provide insights into the hydration mechanism in the deep lower mantle. These highly stable hydrous minerals extend the water cycle at least to the depth of 2900 km. 1. M. Nishi et al., Nature Geoscience 7, 224-227 (2014). 2. E. Ohtani, K. Litasov, A. Suzuki, T. Kondo, Geophysical Research Letters 28, 3991-3993 (2001). 3. I. Ohira et al., Earth and Planetary Science Letters 401, 12-17 (2014). 4. Q. Hu et al., Proceedings of the National Academy of Sciences of the United States of America 114, 1498-1501 (2017). 5. M. Nishi, Y. Kuwayama, J. Tsuchiya, T. Tsuchiya, Nature 547, 205-208 (2017). 6. Q. Hu et al., Nature 534, 241-244 (2016). 7. L. Zhang et al., American Mineralogist 101, 231-234 (2016).

The Role of Hydrogen Bonding on Laminar Burning Velocity of Hydrous and Anhydrous Ethanol Fuel with Small Addition of n-Heptane

Directory of Open Access Journals (Sweden)

I Made Suarta

2016-01-01

Full Text Available The molecular structure of mixed hydrous and anhydrous ethanol with up to 10% v n-heptane had been studied. The burning velocity was examined in a cylindrical explosion combustion chamber. The result showed that the burning velocity of hydrous ethanol is higher than anhydrous ethanol and n-heptane at stoichiometric, rich, and very rich mixtures. The burning velocity of hydrous ethanol with n-heptane drops drastically compared to the burning velocity of anhydrous ethanol with n-heptane. It is caused by two reasons. Firstly, there was a composition change of azeotropic hydrous ethanol molecules within the mixture of fuel. Secondly, at the same volume the number of ethanol molecules in hydrous ethanol was less than in anhydrous ethanol at the same composition of the n-heptane in the mixture. At the mixture of anhydrous ethanol with n-heptane, the burning velocity decreases proportionally to the addition of the n-heptane composition. The burning velocity is between the velocities of anhydrous ethanol and n-heptane. It shows that the burning velocity of anhydrous ethanol mixed with n-heptane is only influenced by the mixture composition.

Hydrogen-isotopic composition of some hydrous manganese minerals

International Nuclear Information System (INIS)

Hariya, Y.; Tsutsumi, M.

1981-01-01

Initial data on the hydrogen-isotopic compositions in hydrous Mn minerals from various occurrences fall in a wide range from -298 to -84per thousand, relative to SMOW. deltaD-values of todorokite and cryptomelane from Tertiary deposits show -89 and -150per thousand. 10 A-manganite and delta-MnO 2 from deep-sea nodules have relatively restricted deltaD-values ranging from -96 to -84per thousand. The deltaD-values for manganese bog ores from recent hot springs show almost -105per thousand. It is recognized that the isotopic values obtained for the deep-sea nodules and recent bog ores are slightly different ranged. Manganite and groutite are unique in their hydrogen-isotopic compositions, having the most depleted deltaD-values ranging from -298 to -236per thousand. MnO(OH) minerals are more deuterium-depleted hydrous minerals than any other hydrothermal minerals from various ore deposits. Hydrogen-isotope fractionation factors between manganite and water were experimentally determined to be 0.7894, 0.7958 and 0.8078 at 150 0 , 200 0 and 250 0 C respectively. The present experimental results indicate that if manganites were formed at temperatures below 250 0 C, under isotopic equilibrium conditions most of the manganite mineralization in the Tertiary manganese deposits must have precipitated from meteoric hydrothermal solutions. (Auth.)

Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

International Nuclear Information System (INIS)

Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

2009-01-01

Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

Fixation of Selenium by Clay Minerals and Iron Oxides

DEFF Research Database (Denmark)

Hamdy, A. A.; Nielsen, Gunnar Gissel

1977-01-01

In studying Se fixation, soil components capable of retaining Se were investigated. The importance of Fe hydrous oxides in the fixation of Se was established. The clay minerals common to soils, such as kaolinite, montmorillonite and vermiculite, all exhibited Se fixation, but greater fixation occ...

Ir/Sn dual-reagent catalysis towards highly selective alkylation of ...

Indian Academy of Sciences (India)

Wintec

Organometallic; bimetallic; catalysis; alkylation; benzyl alcohol; iridium, tin. 1. Introduction ... cording to our proposal, the oxidative addition of tin(IV) halides across a ..... 33. 4. Conclusion. In summary, we have demonstrated here an Ir/Sn.

Natural rubber, a potential alternative source for the synthesis of renewable fuels via Hydrous Pyrolysis

Science.gov (United States)

Ahmad, N.; Dayana, S. A. S.; Abnisa, F.; Mohd, W. A. W. D.

2018-03-01

Natural rubber is a humid agricultural harvest, which mostly contains hydrocarbon cis-1, 4-Poly isoprene. Through depolymerisation technology, the natural rubber can be changed into liquid product, and then it can be subsequently utilized as a fuel or chemical feedstock. This article aims to provide an outlook on the natural rubber and its sources, which are available globally. Numerous depolymerisation processes, which include pyrolysis, gasification, chemical degradation, catalytic cracking and hydrogenation, were introduced in this paper, while the focus of discussion was emphasized on the hydrous pyrolysis process. Many studies have shown that the use of hydrous pyrolysis able to improve the depolymerisation process, e.g. the raw material can be feed without drying, the process can be carried out at lower temperature, only the water is used as the reaction medium, and it is easy to separate the water from oil product. The effect of operating parameters such as temperature, water to rubber mass ratio, reaction time and type of gases on the product yield and composition were reviewed in this paper. In addition, this paper also highlighted the eco-friendly and economic viability of the hydrous pyrolysis process.

Ianthinite: A rare hydrous uranium oxide mineral from Akkavaram ...

Indian Academy of Sciences (India)

In the area of ianthinite occurrence (figure 1), the basement ... Akkavaram area, from where ianthinite is reported. (figure 1), falls in ... feldspar grains from separated yellowish material .... oxidizing environment and its relevance to the disposal.

Supercapacitive performance of hydrous ruthenium oxide (RuO2 ...

Indian Academy of Sciences (India)

gel method have been employed to prepare ruthenium oxide thin films. Recently ... the potentiostat (263A EG&G, Princeton Applied Research. Potentiostat). .... is a mixed conductor that conducts protons and electrons in acidic solution (as ...

An investigation on the preparation of nanocrystalline hydrous zirconia from zirconium tungstate

Science.gov (United States)

Antunes, M.; Perottoni, C. A.; Gouvêa, D.; Machado, G.; Zorzi, J. E.

2018-02-01

Hydrous nanocrystalline zirconia was prepared from an unusual precursor—the bimetallic oxide zirconium tungstate (ZrW2O8)—in alkaline medium. Different experimental conditions (NaOH concentration, time and temperature) were used to investigate the effects on crystallographic, morphological, chemical and thermal characteristics of the products. The resulting materials are composed of particles with a crystal structure similar to that of cubic ZrO2 (or a mixture of tetragonal and cubic phases, depending on the synthesis conditions), with particle size around 5 nm and crystallites around 3 nm in diameter. These particles form high surface area agglomerates, exhibiting mesoporosity and capacity for adsorption of water and carbon dioxide. The synthesis mechanism appears to be constituted, first, by a chemical substitution reaction between the WO4 tetrahedra and hydroxyl ions, with subsequent solubilization of the structure. Indeed, excess hydroxyls in the medium form colloidal zirconium ions which polymerize/condense, generating crystalline nuclei in a process facilitated by heterogeneous nucleation and supersaturation. The presence of residual tungsten in all samples appears to be a key element for stabilizing the size and crystalline structure of the materials produced.

[Removal and Recycle of Phosphor from Water Using Magnetic Core/Shell Structured Fe₃O₄ @ SiO₂Nanoparticles Functionalized with Hydrous Aluminum Oxide].

Science.gov (United States)

Lai, Li; Xie, Qiang; Fang, Wen-kan; Xing, Ming-chao; Wu, De-yi

2016-04-15

A novel magnetic core/shell structured nano-particle Fe₃O₄@ SiO₂phosphor-removal ahsorbent functionalized with hydrous aluminum oxides (Fe₃O₄@ SiO₂@ Al₂O₃· nH₂O) was synthesized. Fe₃O₄@ SiO₂@ Al₂O₃· nH₂O was characterized by XRD, TEM, VSM and BET nitrogen adsorption experiment. The XRD and TEM results demonstrated the presence of the core/shell structure, with saturated magnetization and specific surface area of 56.00 emu · g⁻¹ and 47.27 m² · g⁻¹, respectively. In batch phosphor adsorption experiment, the Langmuir adsorption maximum capacity was 12.90 mg · g⁻¹ and nearly 96% phosphor could be rapidly removed within a contact time of 40 mm. Adsorption of phosphor on Fe₃O₄@ SiO₂@ Al₂O₃ · nH₂O was highly dependent on pH condition, and the favored pH range was 5-9 in which the phosphor removal rate was above 90%. In the treatment of sewage water, the recommended dosage was 1.25 kg · t⁻¹. In 5 cycles of adsorption-regeneration-desorption experiment, over 90% of the adsorbed phosphor could be desorbed with 1 mol · L⁻¹ NaOH, and Fe₃O₄@ SiO₂@ Al₂O₃· nH₂O could be reused after regeneration by pH adjustment with slightly decreased phosphor removal rate with increasing recycling number, which proved the recyclability of Fe₃O₄@ SiO₂@ Al₂O₃· nH₂O and thereby its potential in recycling of phosphor resources.

Thermal-maturity limit for primary thermogenic-gas generation from humic coals as determined by hydrous pyrolysis

Science.gov (United States)

Lewan, Michael; Kotarba, M.J.

2014-01-01

Hydrous-pyrolysis experiments at 360°C (680°F) for 72 h were conducted on 53 humic coals representing ranks from lignite through anthracite to determine the upper maturity limit for hydrocarbon-gas generation from their kerogen and associated bitumen (i.e., primary gas generation). These experimental conditions are below those needed for oil cracking to ensure that generated gas was not derived from the decomposition of expelled oil generated from some of the coals (i.e., secondary gas generation). Experimental results showed that generation of hydrocarbon gas ends before a vitrinite reflectance of 2.0%. This reflectance is equivalent to Rock-Eval maximum-yield temperature and hydrogen indices (HIs) of 555°C (1031°F) and 35 mg/g total organic carbon (TOC), respectively. At these maturity levels, essentially no soluble bitumen is present in the coals before or after hydrous pyrolysis. The equivalent kerogen atomic H/C ratio is 0.50 at the primary gas-generation limit and indicates that no alkyl moieties are remaining to source hydrocarbon gases. The convergence of atomic H/C ratios of type-II and -I kerogen to this same value at a reflectance of indicates that the primary gas-generation limits for humic coal and type-III kerogen also apply to oil-prone kerogen. Although gas generation from source rocks does not exceed vitrinite reflectance values greater than , trapped hydrocarbon gases can remain stable at higher reflectance values. Distinguishing trapped gas from generated gas in hydrous-pyrolysis experiments is readily determined by of the hydrocarbon gases when a -depleted water is used in the experiments. Water serves as a source of hydrogen in hydrous pyrolysis and, as a result, the use of -depleted water is reflected in the generated gases but not pre-existing trapped gases.

Effect of glycerol ethoxylate as an ignition improver on injection and combustion characteristics of hydrous ethanol under CI engine condition

International Nuclear Information System (INIS)

Munsin, R.; Laoonual, Y.; Jugjai, S.; Matsuki, M.; Kosaka, H.

2015-01-01

Highlights: • Glycerol ethoxylate (GE) shows the similar results as the commercial additive. • GE decreases injection rate, but increases injection delay and duration of ethanol. • GE shortens ignition delay and decreases heat released in premixed burn of ethanol. • GE has a minor effect on flame temperature of ethanol. • KL factor and soot of ethanol are sensitive to both GE and the commercial additive. - Abstract: This paper investigates the effects of glycerol ethoxylate as an ignition improver on injection and combustion characteristics of hydrous ethanol under a CI engine condition. Injection characteristics were investigated by an in-house injection rate measurement device based on the Zeuch method, while spray combustion has been performed in the rapid compression and expansion machine (RCEM). The CI engine condition indicated as density, pressure and temperature of compressed synthetic gas, consisting of 80% argon and 20% oxygen, at fuel injection timing in RCEM of 21 kg/m 3 , 4.4 MPa and 900 K, respectively. This condition is equivalent to the isentropic compression of air of the actual CI engine with compression ratio of 22. Hydrous ethanol without ignition improver (Eh95) and the ethanol dedicated for heavy duty vehicles (ED95: composed of hydrous ethanol with the commercial additive for ED95) are reference fuels representing low and high quality ethanol fuel for CI engines, respectively. All test fuels are injected at constant heat input. The results indicate that the additional ignition improvers change injection characteristics, i.e. injection delay, injection rate and discharge coefficient of hydrous ethanol. The maximum injection rates at fully opened needle for the ethanol dedicated for heavy duty vehicles (ED95) and hydrous ethanol with 5% glycerol ethoxylate (5%GE) are lower than that of hydrous ethanol without ignition improver (Eh95) by approximately 10%. Additional injection duration is required for ED95 and 5%GE to maintain a

Studies of the hydrous titanium oxide ion exchanger. 4. Rate of the isotopic exchange of sodium ions between the exchanger in the Na+ form and aqueous solution

International Nuclear Information System (INIS)

Inoue, Yasushi; Yamazaki, Hiromichi; Kasuga, Fuminori

1995-01-01

The isotopic exchange rate of Na + between hydrous titanium(IV) oxides, precipitated at pH 6 and 13, in the Na + form and aqueous solution of sodium salt was determined radiochemically. The rate in the exchanger precipitated at pH 6 is controlled by the diffusion of Na + in the exchanger particles (particle diffusion). The diffusion coefficient and its activation energy are 1.9 x 10 -11 m 2 s -1 (pH 12, 5.0degC) and 29 kJ mol -1 (pH 12), respectively. The rate in the exchanger precipitated at pH 13 is also controlled by the particle diffusion. The rate is much slower than that in the other; this can be explained by assuming the existence of two kinds of independently diffusing ions (fast and slow species) in the exchanger. The diffusion coefficients are of the order of 10 -12 and 10 -13 m 2 s -1 for the fast and the slow species, respectively. Their activation energies are 48-60 kJ mol -1 at pH 12. The marked difference in kinetics between two exchanges was interpreted in terms of the difference in the acid-base property and in the microstructure of the matrix. (author)

Analysis of Mineral Assemblages Containing Unstable Hydrous Phases

Science.gov (United States)

Vaniman, D. T.; Wilson, S. A.; Bish, D. L.; Chipera, S.

2011-12-01

Minerals in many environments can be treated as durable phases that preserve a record of their formation. However many minerals, especially those with hydrogen-bonded H2O molecules as part of their structure, are ephemeral and are unlikely to survive disturbance let alone removal from their environment of formation. Minerals with exceptionally limited stability such as meridianiite (Mg-sulfate 11 hydrate), ikaite (Ca-carbonate 6 hydrate), and mirabilite (Na-sulfate 10 hydrate) are very susceptible to destabilization during analysis, and even modest changes in temperature or relative humidity can lead to change in hydration state or deliquescence. The result may be not only loss of the salt hydrate but dissolution of other salts present, precipitation of new phases, and ion exchange between the concentrated solution and otherwise unaffected phases. Exchange of H2O molecules can also occur in solid-vapor systems without any liquid involvement; moreover, recent work has shown that cation exchange between smectite and sulfate hydrates can occur without any liquid phase present other than a presumed thin film at the salt-silicate interface. Among hydrous silicates, clay minerals are susceptible to cation exchange and similar alteration can be expected for zeolites, palagonite, and possibly other hydrous silicate alteration products. Environmentally sensitive phases on Mars, such as meridianiite, may occur at higher latitudes or in the subsurface where permafrost may be present. Accurate determination of the presence and paragenesis of such minerals will be important for understanding the near-surface hydrogeology of Mars, and in situ analysis may be the only way to obtain this information. Access to the subsurface may be required, yet the act of exposure by excavation or drilling can itself lead to rapid degradation as the sample is exposed or brought to the surface for analysis. Mars is not the only body with which to be concerned, for similar concerns can be raised

Catalytic combustion of particulate matter Catalysts of alkaline nitrates supported on hydrous zirconium

International Nuclear Information System (INIS)

Galdeano, N.F.; Carrascull, A.L.; Ponzi, M.I.; Lick, I.D.; Ponzi, E.N.

2004-01-01

In order to explore a method to remove particulate matter, catalysts of different alkaline nitrates (Li, K and Cs) supported on hydrous zirconium were prepared by the method of incipient humidity and tested as catalysts for particulate matter combustion. The catalytic activity was determined by using the temperature programmed oxidation technique (TPO), utilizing two equipments, a thermogravimetric reactor and other of fixed bed. In the first case the particulate matter/catalyst mixture was milled carefully in a mortar (tight contact) while in the second case more realistic operative conditions were used, particulate matter/catalyst mixture was made with a spatula (loose contact). All prepared catalysts showed good activity for the particulate matter combustion. The cesium catalyst was the one that presented higher activity, decreasing the combustion temperature between 200 and 250 deg. C with respect to the combustion without catalyst. The catalyst with lithium nitrate became active at higher temperature than its melting point and the same occurred with the potassium catalyst. This did not occur for the catalyst containing cesium nitrate that melts at 407 deg. C and became active from 350 deg. C

Methane production by treating vinasses from hydrous ethanol using a modified UASB reactor

Science.gov (United States)

2012-01-01

Background A modified laboratory-scale upflow anaerobic sludge blanket (UASB) reactor was used to obtain methane by treating hydrous ethanol vinasse. Vinasses or stillage are waste materials with high organic loads, and a complex composition resulting from the process of alcohol distillation. They must initially be treated with anaerobic processes due to their high organic loads. Vinasses can be considered multipurpose waste for energy recovery and once treated they can be used in agriculture without the risk of polluting soil, underground water or crops. In this sense, treatment of vinasse combines the elimination of organic waste with the formation of methane. Biogas is considered as a promising renewable energy source. The aim of this study was to determine the optimum organic loading rate for operating a modified UASB reactor to treat vinasse generated in the production of hydrous ethanol from sugar cane molasses. Results The study showed that chemical oxygen demand (COD) removal efficiency was 69% at an optimum organic loading rate (OLR) of 17.05 kg COD/m3-day, achieving a methane yield of 0.263 m3/kg CODadded and a biogas methane content of 84%. During this stage, effluent characterization presented lower values than the vinasse, except for potassium, sulfide and ammonia nitrogen. On the other hand, primers used to amplify the 16S-rDNA genes for the domains Archaea and Bacteria showed the presence of microorganisms which favor methane production at the optimum organic loading rate. Conclusions The modified UASB reactor proposed in this study provided a successful treatment of the vinasse obtained from hydrous ethanol production. Methanogen groups (Methanobacteriales and Methanosarcinales) detected by PCR during operational optimum OLR of the modified UASB reactor, favored methane production. PMID:23167984

Methane production by treating vinasses from hydrous ethanol using a modified UASB reactor

Directory of Open Access Journals (Sweden)

España-Gamboa Elda I

2012-11-01

Full Text Available Abstract Background A modified laboratory-scale upflow anaerobic sludge blanket (UASB reactor was used to obtain methane by treating hydrous ethanol vinasse. Vinasses or stillage are waste materials with high organic loads, and a complex composition resulting from the process of alcohol distillation. They must initially be treated with anaerobic processes due to their high organic loads. Vinasses can be considered multipurpose waste for energy recovery and once treated they can be used in agriculture without the risk of polluting soil, underground water or crops. In this sense, treatment of vinasse combines the elimination of organic waste with the formation of methane. Biogas is considered as a promising renewable energy source. The aim of this study was to determine the optimum organic loading rate for operating a modified UASB reactor to treat vinasse generated in the production of hydrous ethanol from sugar cane molasses. Results The study showed that chemical oxygen demand (COD removal efficiency was 69% at an optimum organic loading rate (OLR of 17.05 kg COD/m3-day, achieving a methane yield of 0.263 m3/kg CODadded and a biogas methane content of 84%. During this stage, effluent characterization presented lower values than the vinasse, except for potassium, sulfide and ammonia nitrogen. On the other hand, primers used to amplify the 16S-rDNA genes for the domains Archaea and Bacteria showed the presence of microorganisms which favor methane production at the optimum organic loading rate. Conclusions The modified UASB reactor proposed in this study provided a successful treatment of the vinasse obtained from hydrous ethanol production. Methanogen groups (Methanobacteriales and Methanosarcinales detected by PCR during operational optimum OLR of the modified UASB reactor, favored methane production.

Methane production by treating vinasses from hydrous ethanol using a modified UASB reactor.

Science.gov (United States)

España-Gamboa, Elda I; Mijangos-Cortés, Javier O; Hernández-Zárate, Galdy; Maldonado, Jorge A Domínguez; Alzate-Gaviria, Liliana M

2012-11-21

A modified laboratory-scale upflow anaerobic sludge blanket (UASB) reactor was used to obtain methane by treating hydrous ethanol vinasse. Vinasses or stillage are waste materials with high organic loads, and a complex composition resulting from the process of alcohol distillation. They must initially be treated with anaerobic processes due to their high organic loads. Vinasses can be considered multipurpose waste for energy recovery and once treated they can be used in agriculture without the risk of polluting soil, underground water or crops. In this sense, treatment of vinasse combines the elimination of organic waste with the formation of methane. Biogas is considered as a promising renewable energy source. The aim of this study was to determine the optimum organic loading rate for operating a modified UASB reactor to treat vinasse generated in the production of hydrous ethanol from sugar cane molasses. The study showed that chemical oxygen demand (COD) removal efficiency was 69% at an optimum organic loading rate (OLR) of 17.05 kg COD/m3-day, achieving a methane yield of 0.263 m3/kg CODadded and a biogas methane content of 84%. During this stage, effluent characterization presented lower values than the vinasse, except for potassium, sulfide and ammonia nitrogen. On the other hand, primers used to amplify the 16S-rDNA genes for the domains Archaea and Bacteria showed the presence of microorganisms which favor methane production at the optimum organic loading rate. The modified UASB reactor proposed in this study provided a successful treatment of the vinasse obtained from hydrous ethanol production.Methanogen groups (Methanobacteriales and Methanosarcinales) detected by PCR during operational optimum OLR of the modified UASB reactor, favored methane production.

Quantitative XRD analysis: tools to investigate link between hydrous strain and clay mineral CEC

International Nuclear Information System (INIS)

Oueslati, W.; Ammar, M.; Ben Rhaiem, H.; Ben Haj Amara, A.

2012-01-01

Document available in extended abstract form only. This work aims at examining, by quantitative XRD analysis, the effect of an applied hydrous strain in the cationic exchange process of a di-octahedral smectite (Na-rich montmorillonite SWy-2). The hydrous constraint was created by a continuous, in situ, hydration-dehydration cycles using a variation of the %RH rate. Respectively, The starting, the intermediate and the final stressed samples was deposed in contact with saturated Me 2+ (i.e. Cd 2+ , Co 2+ , Zn 2+ and Ni 2+ ) chloride solutions respectively in order to examine the effect of the retained materials stress on the CEC of the host materials. An XRD profile modelling approach is adopted to describe all structural changes created by the environmental evolution of the %RH rate. This investigation allowed us to determine several structural parameters related to the nature, abundance, size, position and organization of exchangeable cation and water molecule in the inter-lamellar space along the c* axis. The obtained qualitative results show a considerable change in the hydration behaviour, versus the number of hydration - dehydration cycle, from homogeneous '2W' to heterogeneous '1W-2W' hydration state indicating an interstratified hydration phases and due probably to a new organization of the inter-lamellar space content. Quantitatively, the theoretical Mixed Layer Structure MLS suggest the coexistence of more one 'crystallite' species. Which are saturated by more than one exchangeable cations, indicating a partial saturation of all exchangeable sites. Using optimum structural parameter values, deduced from XRD modelling profile approach, some equations which described the evolution of exchangeable cation amount versus the applied hydrous strain were derived. (authors)

Geochemical characterization of the hydrous pyrolysis products from a recent cyanobacteria-dominated microbial mat

Energy Technology Data Exchange (ETDEWEB)

Franco, N.; Mendoça-Filho, J.G.; Silva, T.F.; Stojanovic, K.; Fontana, L.F.; Carvalhal-Gomes, S.B.V.; Silva, F.S.; Furukawa, G.G.

2016-07-01

Hydrous pyrolysis experiments were performed on a recent microbial mat sample from Lagoa Vermelha, Brazil, to determine whether crude oil can be generated and expelled during artificial maturation of the Organic Matter (OM). The experiments were conducted at 280ºC, 330ºC and 350ºC during 20h. Two types of liquid pyrolysis products, assigned as free oil and bitumen, were isolated and analyzed. Free oil represents free organic phase released by hydrous pyrolysis, whereas bitumen was obtained by extraction from the solid pyrolysis residue with dichloromethane. Changes in the OM maturity were determined using Rock-Eval parameters and biomarker maturity ratios of original sample and pyrolysis products. Biomarker compositions of original sample extract and liquid pyrolysates were used for determination of dominant bacterial source. The yields of free oil and bitumen showed that a microbial mat OM has a high liquid hydrocarbons generation potential. Rock-Eval maturity parameters, biopolymer and biomarker compositions indicate a significant increase of the OM maturity during hydrous pyrolysis. At 280ºC the release of free, adsorbed and occluded compounds was observed; however, without a cracking of the OM. At 330ºC the generation of bitumen and free oil is mostly related to the OM cracking. The highest yield of free oil was recorded at this temperature. Distribution of biomarkers in the extract of original sample and liquid pyrolysates confirms cyanobacteria-dominated microbial mats, whereas the identification of long chain n-alkane series, with maximum at C26, and prominent C30 hop-17(21)-ene additionally suggest the presence of sulfate reducing bacteria. (Author)

Sol-gel processed thin-layer ruthenium oxide/carbon black supercapacitors: A revelation of the energy storage issues

Energy Technology Data Exchange (ETDEWEB)

Panic, V.V.; Dekanski, A.B.; Stevanovic, R.M. [Institute of Chemistry, Technology and Metallurgy, Department of Electrochemistry, University of Belgrade, Njegoseva 12, Belgrade 125213 (RS)

2010-07-01

Hydrous ruthenium oxide/carbon black nanocomposites were prepared by impregnation of the carbon blacks by differently aged inorganic RuO{sub 2} sols, i.e. of different particle size. Commercial Black Pearls 2000 {sup registered} (BP) and Vulcan {sup registered} XC-72 R (XC) carbon blacks were used. Capacitive properties of BP/RuO{sub 2} and XC/RuO{sub 2} composites were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in H{sub 2}SO{sub 4} solution. Capacitance values and capacitance distribution through the composite porous layer were found different if high- (BP) and low- (XC) surface-area carbons are used as supports. The aging time (particle size) of Ru oxide sol as well as the concentration of the oxide solid phase in the impregnating medium influenced the capacitive performance of prepared composites. While the capacitance of BP-supported oxide decreases with the aging time, the capacitive ability of XC-supported oxide is promoted with increasing oxide particle size. The increase in concentration of the oxide solid phase in the impregnating medium caused an improvement of charging/discharging characteristics due to pronounced pseudocapacitance contribution of the increasing amount of inserted oxide. The effects of these variables in the impregnation process on the energy storage capabilities of prepared nanocomposites are envisaged as a result of intrinsic way of population of the pores of carbon material by hydrous Ru oxide particle. (author)

Effects of selected metal oxide nanoparticles on Artemia salina larvae: evaluation of mortality and behavioural and biochemical responses.

Science.gov (United States)

Gambardella, Chiara; Mesarič, Tina; Milivojević, Tamara; Sepčić, Kristina; Gallus, Lorenzo; Carbone, Serena; Ferrando, Sara; Faimali, Marco

2014-07-01

The aim was to investigate the toxicity of selected metal oxide nanoparticles (MO-NPs) on the brine shrimp Artemia salina, by evaluating mortality and behavioural and biochemical responses. Larvae were exposed to tin(IV) oxide (stannic oxide (SnO2)), cerium(IV) oxide (CeO2) and iron(II, III) oxide (Fe3O4) NPs for 48 h in seawater, with MO-NP suspensions from 0.01 to 1.0 mg/mL. Mortality and behavioural responses (swimming speed alteration) and enzymatic activities of cholinesterase, glutathione-S-transferase and catalase were evaluated. Although the MO-NPs did not induce any mortality of the larvae, they caused changes in behavioural and biochemical responses. Swimming speed significantly decreased in larvae exposed to CeO2 NPs. Cholinesterase and glutathione-S-transferase activities were significantly inhibited in larvae exposed to SnO2 NPs, whereas cholinesterase activity significantly increased after CeO2 NP and Fe3O4 NP exposure. Catalase activity significantly increased in larvae exposed to Fe3O4 NPs. In conclusion, swimming alteration and cholinesterase activity represent valid endpoints for MO-NP exposure, while glutathione-S-transferase and catalase activities appear to be NP-specific.

The evolution of hydrous magmas in the Tongariro Volcanic Centre : the 10 ka Pahoka-Mangamate eruptions

International Nuclear Information System (INIS)

Auer, A.; Palin, J.M.; White, J.D.L.; Nakagawa, M.; Stirling, C.

2015-01-01

The majority of arc-type andesites in the Tongariro Volcanic Centre are highly porphyritic, hornblende-free, two-pyroxene andesites. An exception is tephras from the c. 10,000 ka Pahoka-Mangamate event. Magmas of these Plinian eruptions bypassed the extensive crustal mush columns under the central volcanoes and sequentially derived a series of almost aphyric rocks spanning a compositional range from dacite to basaltic andesite. Mineral composition, trace element and isotopic data suggest that this eruptive series tapped a mid-crustal magma reservoir, resulting in the initial eruption of an hydrous dacitic magma and several following eruptions characterised by less-evolved and less-hydrous compositions at progressively higher temperatures and substantially lower 87 Sr/ 86 Sr ratios. Systematic changes in magma chemistry are also reflected in a sequential change in phenocryst content starting with an early hornblende-plagioclase-dominated assemblage to a late olivine-plagioclase-dominated assemblage. (author).

Conversion electron Moessbauer spectroscopic studies on the chemical states of surface layers of corroded tin plates and tin-coated iron plates

International Nuclear Information System (INIS)

Kato, Akinori; Endo, Kazutoyo; Sano, Hirotoshi

1980-01-01

By means of the conversion electron Moessbauer spectroscopy (CEMS), we studied surface layers of ''tin'' plates and tin-coated iron plates corroded by various acids. Transmission Moessbauer spectra and X-ray diffraction patterns were also measured. Metastannic acid was formed, when the ''tin'' plate was corroded by nitric acid solution. In corrosion by phosphoric acid solution, the X-ray diffractometry revealed the formation of tin(IV) pyrophosphate. In corrosion by various organic acid solutions, the formation of oxides was identified by the 119 Sn CEMS, but not by the X-ray diffractometry because of the too thin corrosion layer. In corrosion of tin-coated iron plates, maleic acid, malonic acid, formic acid, and oxalic acid were used. It was determined by CEMS that the corrosion products caused by these acids were tin(IV) oxides, although they could not be identified by the X-ray diffractometry. CEMS also confirmed that the surface of uncorroded tin-coated iron plate was already oxidized by air. Colorimetric determinations of Sn and Fe dissolved from tin-coated iron plates to various acid solutions confirmed that maleic acid had the strongest corrosion effect among the organic acids studied. (author)

Evaluating Re-Os systematics in organic-rich sedimentary rocks in response to petroleum generation using hydrous pyrolysis experiments

Science.gov (United States)

Rooney, A.D.; Selby, D.; Lewan, M.D.; Lillis, P.G.; Houzay, J.-P.

2012-01-01

Successful application of the 187Re–187Os geochronometer has enabled the determination of accurate and precise depositional ages for organic-rich sedimentary rocks (ORS) as well as establishing timing constraints of petroleum generation. However, we do not fully understand the systematics and transfer behaviour of Re and Os between ORS and petroleum products (e.g., bitumen and oil). To more fully understand the behaviour of Re–Os systematics in both source rocks and petroleum products we apply hydrous pyrolysis to two immature hydrocarbon source rocks: the Permian Phosphoria Formation (TOC = 17.4%; Type II-S kerogen) and the Jurassic Staffin Formation (TOC = 2.5%; Type III kerogen). The laboratory-based hydrous pyrolysis experiments were carried out for 72 h at 250, 300, 325 and 350 °C. These experiments provided us with whole rock, extracted rock and bitumen and in some cases expelled oil and asphaltene for evaluation of Re–Os isotopic and elemental abundance. The data from these experiments demonstrate that the majority (>95%) of Re and Os are housed within extracted rock and that thermal maturation does not result in significant transfer of Re or Os from the extracted rock into organic phases. Based on existing thermodynamic data our findings suggest that organic chelating sites have a greater affinity for the quadravalent states of Re and Os than sulphides. Across the temperature range of the hydrous pyrolysis experiments both whole rock and extracted rock 187Re/188Os ratios show small variations (3.3% and 4.7%, for Staffin, respectively and 6.3% and 4.9% for Phosphoria, respectively). Similarly, the 187Os/188Os ratios show only minor variations for the Staffin and Phosphoria whole rock and extracted rock samples (0.6% and 1.4% and 1.3% and 2.2%). These isotopic data strongly suggest that crude oil generation through hydrous pyrolysis experiments does not disturb the Re–Os systematics in ORS as supported by various studies on natural systems. The

Use of hydrous titanium dioxide as potential sorbent for the removal of manganese from water

Directory of Open Access Journals (Sweden)

Ramakrishnan Kamaraj

2014-12-01

Full Text Available This research article deals with an electrosynthesis of hydrous titanium dioxide by anodic dissolution of titanium sacrificial anodes and their application for the adsorption of manganese from aqueous solution. Titanium sheet was used as the sacrificial anode and galvanized iron sheet was used as the cathode. The optimization of different experimental parameters like initial ion concentration, current density, pH, temperature, etc., on the removal efficiency of manganese was carried out. The maximum removal efficiency of 97.55 % was achieved at a current density of 0.08 A dm-2 and pH of 7.0. The Langmuir, Freundlich and Redlich Peterson isotherm models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The adsorption of manganese preferably followed the Langmuir adsorption isotherm. The adsorption kinetics was modelled by first- and second- order rate models and the adsorption kinetic studies showed that the adsorption of manganese was best described using the second-order kinetic model. Thermodynamic parameters indicate that the adsorption of manganese on hydrous titanium dioxide was feasible, spontaneous and exothermic.

Reactions of metal oxides with molten NaPO3 + NaCl mixtures

International Nuclear Information System (INIS)

Kovarskaya, E.N.; Mityakhina, V.S.; Rodionov, Yu.I.; Silin, M.Yu.

1988-01-01

We consider the dissolution mechanism for iron (III), europium(III), and tin(IV) oxides in molten NaPO 3 + NaCl that are responsible for the peak solubilities. We chose Fe 2 O 3 as the basic material since this occurs in large amounts around damaged metal structures in rock salt mines in a proposed zone for storing vitrified radioactive wastes. Solubility measurement and paper chromatography show that Fe 2 O 3 dissolves in molten NaPO 3 + NaCl in air by reaction with the solvent to give double iron and sodium diphosphates and monophosphates in accordance with the initial solution-in-the-melt composition, the degree of equilibration, and the temperature. The elevated solubilities for initial NaCl contents close to 30 mole % are due to sodium triphosphates and tricyclophosphates present in these melts. Moessbauer spectroscopy confirms that double iron, europium and tin diphosphates and monophosphates containing sodium occur in these chloride-polyphosphate melts

The kinetics of sterane biological marker release and degradation processes during the hydrous pyrolysis of vitrinite kerogen

Science.gov (United States)

Abbott, G. D.; Wang, G. Y.; Eglinton, T. I.; Home, A. K.; Petch, G. S.

1990-09-01

The hydrous pyrolysis of a mineral-free vitrinite kerogen (Dinantian coal Lower Carboniferous, North East England) has been carried out at four temperatures (270, 300, 330, and 350°C) for heating times ranging from 2 to 648 h. No significant differences in the epimer-based maturation parameters 20S/(20S + 20R)-5α(H),14α(H),17α(H) C 29 non-rearranged steranes and 22S/(22S+22R)-17α(H), 21β(H) homohopanes were found for a comparison between "expelled oil" and "bitumen" fractions in the resulting pyrolysates. A deuterated model compound ((20R)-5α(H),14α(H),17α(H)-[2,2,4,4-d 4] cholestane) was added to a number of preextracted kerogens (vitrinite, Kimmeridge, Messel and Monterey) and the mixtures were heated under typical hydrous pyrolysis conditions. These experiments showed that direct chiral isomerisation at C-20 in the non-rearranged steranes appears to be relatively unimportant during hydrous pyrolysis which has also been suggested by other recent studies on geological samples.A kinetic model comprising consecutive release and degradation processes was derived to measure first-order rate coefficients from the bi-exponential concentration-time functions of both the (20R)-and (20S)-5α(H),14α(H),17α(H) C 29 "free" steranes in the vitrinite kerogen pyrolysates. This data was then used to calculate preliminary Arrhenius parameters for release ((20S): ΔEa = 125 ± 30 kJ mol -1, A ≈ 4.7 × 10 5 s -1;(20R): ΔEa = 151 ± 39 kJ mol -1, A ≈ 2.7 × 10 9 s -1) and degradation ((20S): ΔEa = 104 ± 22 kJ mol -1, A ≈ 5.8 × 10 3 s -1; (20R): Δa = 87 ± 6 kJ mol -1, A ≈ 2.2 × 10 2 s -1) of the above individual isomers and the values were found to be consistent with a free-radical chain mechanism. This work helps in the greater understanding of the important biomarker reactions that prevail in hydrous pyrolysis experiments.

Effect of Flowing Water on Sr Sorption Changes of Hydrous Sodium Titanate

OpenAIRE

Youko Takahatake; Atsuhiro Shibata; Kazunori Nomura; Tsutomu Sato

2017-01-01

Radioactive contaminated water has been generated at the Fukushima Daiichi Nuclear Power station (F1NPS). Hydrous sodium titanate (SrTreat®) is able to remove radioactive Strontium (Sr) from this water. Knowing the amount of radioactive nuclides in the used as-received SrTreat® is important for effective disposal and deposition of the F1NPS waste. This study investigated changes in the ability of SrTreat® to sorb Sr, and to understand the causes of changes in the sorbing. An investigation of ...

Redox substoichiometry in isotope dilution analysis Pt. 4

International Nuclear Information System (INIS)

Kambara, T.; Yoshioka, H.; Ugai, Y.

1980-01-01

The oxidation reaction of antimony(III) with potassium dichromate has been investigated radiometrically. The quantitative oxidation of antimony(III) was found to be not disturbed even in large amounts of tin(IV). On the basis of these results the redox substoichiometric isotope dilution analysis using potassium dichromate as the oxidizing agent was proposed for the determination of antimony in metallic tin. An antimony content of 1.22+-0.05 μg in metallic tin (10 mg) was determined without separation of the matrix element. (author)

Separation of radionuclides from water by magnesium oxide adsorption

International Nuclear Information System (INIS)

Tseng, Chia-Lian; Lo, Jem-Mau; Yeh, Si-Jung

1987-01-01

Adsorption by magnesium oxide of more than forty radionuclides in respective ionic species in water was observed. Generally, the radionuclides in di-valent and/or multi-valent cations are favorably adsorbed by magnesium oxide; but not for the those in mono-valent cations. In addition, the adsorption by magnesium oxide was not effective to most of the radionuclides in negative ionic species. From the observations, the adsorption mechanism is more prominently by the ion exchange of the di- or multi-valent cation species with the hydrous magnesium oxide. Separation of the radionuclides related to the corrosion products possibly produced in a nuclear power plant from natural seawater was attempted by the magnesium oxide adsorption method. It should be emphasized that the adsorption method was found to be practical for separating radionuclides from a large quantity of natural seawater with high recovery and high reproducibility. (author)

Enhanced rate performance of mesoporous Co3O4 nanosheet supercapacitor electrodes by hydrous RuO2 nanoparticle decoration

KAUST Repository

Baby, Rakhi Raghavan; Ché n, Wěi; Hedhili, Mohamed N.; Cha, Dong Kyu; Alshareef, Husam N.

2014-01-01

-dimensional network with exceptional supercapacitor performance in standard two electrode configuration. Dramatic improvement in the rate capacity of the Co3O4 nanosheets is achieved by electrodeposition of nanocrystalline, hydrous RuO 2 nanoparticles dispersed

Differentiation of pre-existing trapped methane from thermogenic methane in an igneous-intruded coal by hydrous pyrolysis

Science.gov (United States)

Dias, Robert F.; Lewan, Michael D.; Birdwell, Justin E.; Kotarba, Maciej J.

2014-01-01

So as to better understand how the gas generation potential of coal changes with increasing rank, same-seam samples of bituminous coal from the Illinois Basin that were naturally matured to varying degrees by the intrusion of an igneous dike were subjected to hydrous pyrolysis (HP) conditions of 360 °C for 72 h. The accumulated methane in the reactor headspace was analyzed for δ13C and δ2H, and mol percent composition. Maximum methane production (9.7 mg/g TOC) occurred in the most immature samples (0.5 %Ro), waning to minimal methane values at 2.44 %Ro (0.67 mg/g TOC), and rebounding to 3.6 mg/g TOC methane in the most mature sample (6.76 %Ro). Methane from coal with the highest initial thermal maturity (6.76 %Ro) shows no isotopic dependence on the reactor water and has a microbial δ13C value of −61‰. However, methane from coal of minimal initial thermal maturity (0.5 %Ro) shows hydrogen isotopic dependence on the reaction water and has a δ13C value of −37‰. The gas released from coals under hydrous pyrolysis conditions represents a quantifiable mixture of ancient (270 Ma) methane (likely microbial) that was generated in situ and trapped within the rock during the rapid heating by the dike, and modern (laboratory) thermogenic methane that was generated from the indigenous organic matter due to thermal maturation induced by hydrous pyrolysis conditions. These findings provide an analytical framework for better assessment of natural gas sources and for differentiating generated gas from pre-existing trapped gas in coals of various ranks.

A Brillouin scattering study of hydrous basaltic glasses: the effect of H2O on their elastic behavior and implications for the densities of basaltic melts

Science.gov (United States)

Wu, Lei; Yang, De-Bin; Liu, Jun-Xiu; Hu, Bo; Xie, Hong-Sen; Li, Fang-Fei; Yu, Yang; Xu, Wen-Liang; Gao, Chun-Xiao

2017-06-01

Hydrous basalt glasses with water contents of 0-6.82% were synthesized using a multi-anvil press at 1.0-2.0 GPa and 1200-1400 °C. The starting materials were natural Mesozoic basalts from the eastern North China Craton (NCC). Their sound velocities and elastic properties were measured by Brillouin scattering spectroscopy. The longitudinal ( V P) and shear ( V S) wave velocities decreased with increasing water content. Increasing the synthesis pressure resulted in the glass becoming denser, and finally led to an increase in V P. As the degree of depolymerization increased, the V P, V S, and shear and bulk moduli of the hydrous basalt glasses decreased, whereas the adiabatic compressibility increased. The partial molar volumes of water (ν) under ambient conditions were independent of composition, having values of 11.6 ± 0.8, 10.9 ± 0.6 and 11.5 ± 0.5 cm3/mol for the FX (Feixian), FW (Fuxin), and SHT (Sihetun) basalt glasses, respectively. However, the {{V}_{{{{H}}_{{2}}}{O}}} values measured at elevated temperatures and pressures are increasing with increasing temperature or decreasing pressure. The contrasting densities of these hydrous basalt melts with those previously reported for mid-ocean ridge basalt and preliminary reference Earth model data indicate that hydrous basalt melts may not maintain gravitational stability at the base of the upper mantle.

Proton NMR relaxation in hydrous melts

International Nuclear Information System (INIS)

Braunstein, J.; Bacarella, A.L.; Benjamin, B.M.; Brown, L.L.; Girard, C.

1976-01-01

Pulse and continuous wave NMR measurements are reported for protons in hydrous melts of calcium nitrate at temperatures between -4 and 120 0 C. Although measured in different temperature ranges, spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation times appear to be nearly equal to each other and proportional to the self-diffusion coefficients of solute metal cations such as Cd 2+ . At temperatures near 50 0 C, mean Arrhenius coefficients Δ H/sub T 1 / (kcal/mol) are 7.9, 7.3, and 4.8, respectively, for melts containing 2.8, 4.0, and 8.0 moles of water per mole of calcium nitrate, compared to 4.6 kcal/mol for pure water. Temperature dependence of T 1 and T 2 in Ca(NO 3 ) 2 -2.8 H 2 O between -4 and 120 0 C are non-Arrhenius and can be represented by a Fulcher-type equation with a ''zero mobility temperature'' (T 0 ) of 225 0 K, close to the value of T 0 for solute diffusion, electrical conductance and viscosity. Resolution of the relaxation rates into correlation times for intramolecular (rotational) and intermolecular (translational) diffusional motion is discussed in terms of the Bloembergen-Purcell-Pound and more recent models for dipolar relaxation

Effect of annealing temperature on optical properties of binary zinc tin oxide nano-composite prepared by sol-gel route using simple precursors: structural and optical studies by DRS, FT-IR, XRD, FESEM investigations.

Science.gov (United States)

Habibi, Mohammad Hossein; Mardani, Maryam

2015-02-25

Binary zinc tin oxide nano-composite was synthesized by a facile sol-gel method using simple precursors from the solutions consisting of zinc acetate, tin(IV) chloride and ethanol. Effect of annealing temperature on optical and structural properties was investigated using X-ray diffraction (XRD), diffuse reflectance spectra (DRS), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). XRD results revealed the existence of the ZnO and SnO2 phases. FESEM results showed that binary zinc tin oxide nano-composites ranges from 56 to 60 nm in diameter at 400°C and 500°C annealing temperatures respectively. The optical band gap was increased from 2.72 eV to 3.11 eV with the increasing of the annealing temperature. FTIR results confirmed the presence of zinc oxide and tin oxide and the broad absorption peaks at 3426 and 1602 cm(-1) can be ascribed to the vibration of absorptive water, and the absorption peaks at 546, 1038 and 1410 cm(-1) are due to the vibration of Zn-O or Sn-O groups in binary zinc tin oxide. Copyright © 2014 Elsevier B.V. All rights reserved.

Geological Sequestration of CO2 by Hydrous Carbonate Formation with Reclaimed Slag

Energy Technology Data Exchange (ETDEWEB)

Von L. Richards; Kent Peaslee; Jeffrey Smith

2008-02-06

The concept of this project is to develop a process that improves the kinetics of the hydrous carbonate formation reaction enabling steelmakers to directly remove CO2 from their furnace exhaust gas. It is proposed to bring the furnace exhaust stream containing CO2 in contact with reclaimed steelmaking slag in a reactor that has an environment near the unit activity of water resulting in the production of carbonates. The CO2 emissions from the plant would be reduced by the amount sequestered in the formation of carbonates. The main raw materials for the process are furnace exhaust gases and specially prepared slag.

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

NARCIS (Netherlands)

Sinninghe Damsté, J.S.; Putchew, A.; Schaeffer-Reiss, C.; Schaeffer, P.; Koopmans, M.P.; Leeuw, J.W. de; Lewan, M.D.

1998-01-01

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons

Effect of process parameters on removal and recovery of Cd(II) and Cu(II) from electroplating wastewater by fixed-bed column of nano-dimensional titanium (IV) oxide agglomerates

CSIR Research Space (South Africa)

Debnath, S

2014-01-01

Full Text Available Removal performances of Cd(II) and Cu(II) from water was investigated using agglomerated nanoparticle of hydrous titanium(IV) oxide (NTO) packed fixed bed. The parameters varied were the bed depth, flow rate and feed solution concentrations...

The Role of Molecule Clustering by Hydrogen Bond in Hydrous Ethanol on Laminar Burning Velocity

Directory of Open Access Journals (Sweden)

I Made Suarta

2016-01-01

Full Text Available The role of hydrogen bond molecule clustering in laminar burning velocities was observed. The water in hydrous ethanol can change the interaction between water-ethanol molecules. A certain amount of water can become oxygenated which increases the burning velocity. The hydrogen bond interaction pattern of ethanol and water molecules was modeled. Based on the molecular model, azeotropic behavior emerges from ethanol-water hydrogen bond, which is at a 95.1%v composition. The interaction with water molecule causes the ethanol molecule to be clustered with centered oxygenated compound. So, it supplies extra oxygen and provides intermolecular empty spaces that are easily infiltrated by the air. In the azeotropic composition, the molecular bond chain is the shortest, so hypothetically the burning velocity is anticipated to increase. The laminar burning velocity of ethanol fuel was tested in a cylindrical explosion bomb in lean, stoichiometric, and rich mixtures. The experimental result showed that the maximum burning velocity occurred at hydrous ethanol of 95.5%v composition. This discrepancy is the result of the addition of energy from 7.7% free ethanol molecules that are not clustered. At the rich mixture, the burning velocity of this composition is higher than that of anhydrous ethanol.

Hydrothermal synthesis of hydrous ruthenium oxide/graphene sheets for high-performance supercapacitors

International Nuclear Information System (INIS)

Lin, Na; Tian, Jianhua; Shan, Zhongqiang; Chen, Kuan; Liao, Wenming

2013-01-01

Ruthenium oxide particles were supported on graphene sheets (GS) by hydrothermal and low temperature annealing process. The GS was prepared from graphene oxide by an expansion process and different expanding temperatures were studied and polystyrene sulfonate sodium was used as dispersion agent of hydrophobic GS. Different Ru content of the RuO 2 /GS composites on the influence of the electrochemical properties was studied. Atomic force microscope analysis was applied to test the layers of GS. The morphology of GS and RuO 2 /GS composites were confirmed by field emission transmission electron microscopy analysis. X-ray diffraction, Raman spectroscopy and liquid-nitrogen cryosorption were used to characterize the structure and morphology of the GS and RuO 2 /GS. The RuO 2 /GS (Ru:40 wt%) composites used as electrode materials of supercapacitors exhibited a specific capacitance of 551 F/g at 1 A/g in 1 M H 2 SO 4 electrolyte. Besides, both the rate capability and cycle performance of RuO 2 /GS composites had a great improvement compared with GS

Iron oxides in acid mine drainage environments and their association with bacteria

Energy Technology Data Exchange (ETDEWEB)

Ferris, F G; Tazaki, K; Fyfe, W S

1989-01-20

A variety of iron oxides were identified by X-ray diffraction in sediments receiving acid drainage from mine tailing and coal refuse impoundments. Small amounts of goethite and hematite were found in the sediment samples. However, the major iron oxide species was ferrihydrite which gave diffuse diffraction bands at angles corresponding to d2.5, 2.2 and 1.5 Angstrom. Main core line binding energies in Fe (2p) and O (1s) X-ray photoelectron spectra were consistent with the hydrous nature and predominance of ferrihydrite. Electron microscopy and energy-dispersive X-ray spectroscopy also showed that individual bacterial cells promoted the development of iron oxide mineralization. The bacterial associated iron oxides were similar to those in the bulk sediment samples, and exhibited structures conforming to the presence of chemisorbed sulfate or silicate anions. 23 refs., 3 figs.

Intraplate mantle oxidation by volatile-rich silicic magmas

Energy Technology Data Exchange (ETDEWEB)

Martin, Audrey M.; Médard, Etienne; Righter, Kevin; Lanzirotti, Antonio

2017-11-01

The upper subcontinental lithospheric mantle below the French Massif Central is more oxidized than the average continental lithosphere, although the origin of this anomaly remains unknown. Using iron oxidation analysis in clinopyroxene, oxybarometry, and melt inclusions in mantle xenoliths, we show that widespread infiltration of volatile (HCSO)-rich silicic melts played a major role in this oxidation. We propose the first comprehensive model of magmatism and mantle oxidation at an intraplate setting. Two oxidizing events occurred: (1) a 365–286 Ma old magmatic episode that produced alkaline vaugnerites, potassic lamprophyres, and K-rich calc-alkaline granitoids, related to the N–S Rhenohercynian subduction, and (2) < 30 Ma old magmatism related to W–E extension, producing carbonatites and hydrous potassic trachytes. These melts were capable of locally increasing the subcontinental lithospheric mantle fO2 to FMQ + 2.4. Both events originate from the melting of a metasomatized lithosphere containing carbonate + phlogopite ± amphibole. The persistence of this volatile-rich lithospheric source implies the potential for new episodes of volatile-rich magmatism. Similarities with worldwide magmatism also show that the importance of volatiles and the oxidation of the mantle in intraplate regions is underestimated.

Effects of smectite on the oil-expulsion efficiency of the Kreyenhagen Shale, San Joaquin Basin, California, based on hydrous-pyrolysis experiments

Science.gov (United States)

Lewan, Michael D.; Dolan, Michael P.; Curtis, John B.

2014-01-01

The amount of oil that maturing source rocks expel is expressed as their expulsion efficiency, which is usually stated in milligrams of expelled oil per gram of original total organic carbon (TOCO). Oil-expulsion efficiency can be determined by heating thermally immature source rocks in the presence of liquid water (i.e., hydrous pyrolysis) at temperatures between 350°C and 365°C for 72 hr. This pyrolysis method generates oil that is compositionally similar to natural crude oil and expels it by processes operative in the subsurface. Consequently, hydrous pyrolysis provides a means to determine oil-expulsion efficiencies and the rock properties that influence them. Smectite in source rocks has previously been considered to promote oil generation and expulsion and is the focus of this hydrous-pyrolysis study involving a representative sample of smectite-rich source rock from the Eocene Kreyenhagen Shale in the San Joaquin Basin of California. Smectite is the major clay mineral (31 wt. %) in this thermally immature sample, which contains 9.4 wt. % total organic carbon (TOC) comprised of type II kerogen. Compared to other immature source rocks that lack smectite as their major clay mineral, the expulsion efficiency of the Kreyenhagen Shale was significantly lower. The expulsion efficiency of the Kreyenhagen whole rock was reduced 88% compared to that of its isolated kerogen. This significant reduction is attributed to bitumen impregnating the smectite interlayers in addition to the rock matrix. Within the interlayers, much of the bitumen is converted to pyrobitumen through crosslinking instead of oil through thermal cracking. As a result, smectite does not promote oil generation but inhibits it. Bitumen impregnation of the rock matrix and smectite interlayers results in the rock pore system changing from water wet to bitumen wet. This change prevents potassium ion (K+) transfer and dissolution and precipitation reactions needed for the conversion of smectite to

Influence of Fe content on the creep properties of olivine under anhydrous and hydrous conditions

Science.gov (United States)

Trimmer, M. B.; Zhao, Y.; Zimmerman, M. E.; Kohlstedt, D. L.

2007-12-01

High-temperature, high-pressure compressive creep experiments were performed on both wet and dry aggregates of Fa75 in a gas-medium deformation apparatus. The results from these experiments are compared with those for San Carlos olivine, Fa10, and our previous results on Fa30 and Fa50 in order to provide a basis for comparing convection models for the mantle of Earth with those for the more iron-rich mantle of Mars. Samples were fabricated from powders of Fa75 that were synthesized from mixtures of Fe2O3 and SiO2 combined with San Carlos olivine. The Fa75 powders were cold-pressed into Fe capsules and then hot-pressed at 300 MPa, 1473 K for 3 h. The average grain size of the resultant hot-pressed samples was ~40 μm. For experiments under hydrous conditions, three drops of deionized water were added before sealing the sample within telescoping Fe cans for deformation. Water bubbles were present both within olivine grains and along grain boundaries, demonstrating that the samples were water-saturated. Triaxial compressive creep experiments were carried out in a servo-controlled, internally heated gas-medium apparatus at 50 K intervals between 1273 and 1423 K and a confining pressure of 300 MPa with differential stress of 10 to 300 MPa. For each sample, creep tests were performed at several differential stresses at a constant temperature to determine the stress exponent or at several temperatures to determine the activation energy for creep. Under anhydrous conditions the viscosity of samples of Fa75 is more than a factor of 10 lower than the viscosity of Fa50. Previous experiments showed a similar relationship between Fa50 and Fa30 and Fa30 and Fa10. Under hydrous conditions the viscosity of samples of Fa75 are about a factor of 5 lower than the viscosity of Fa50, which is less than that observed between Fa50 and Fa30 or Fa30 and Fa10. The viscosity of a sample of a specific Fe:Mg ratio deformed under hydrous conditions is a factor of 10 lower than its counterpart

A hydrous Ca-bearing magnesium carbonate from playa lake sediments, Salines Lake, Spain

Science.gov (United States)

Queralt, I.; Julia, R.; Plana, F.; Bischoff, J.L.

1997-01-01

Sediments of playa Lake Salines, SE, Spain, contain a carbonate mineral characterized by X-ray diffraction peaks very similar to, but systematically shifted from those of pure magnesite. Analyses (SEM, IR and Raman spectroscopy, DTA, TGA, and ICP) indicate the mineral is a hydrous Ca-bearing magnesium carbonate with the chemical formula (Mg0.92,Ca0.08)CO3??3H2O. Thermal characteristics of the mineral are similar to those of other known hydrated magnesium carbonates. X-ray and electron diffraction data suggests a monoclinic system (P21/n space group) with unit-cell parameters of a = 6.063(6), b = 10.668(5), and c = 6.014(4) A?? and ?? = 107.28??.

Stress-Induced Proton Disorder in Hydrous Ringwoodite

Science.gov (United States)

Koch-Müller, M.; Rhede, D.; Mrosko, M.; Speziale, S.; Schade, U.

2008-12-01

The system (Fe,Mg)2SiO4 with its modifications olivine, wadsleyite and ringwoodite has been the subject of numerous studies in the past to determine the maximum solubility of hydrogen in their structures (e.g., Kudoh et al., 2000). Nowadays experimental work is focused on the effect of the water content on the physical, structural and thermodynamic properties. Camorro Perez et al. (2006) studied hydrous (1 and 1.7 wt % water) Mg-ringwoodite by in-situ high-pressure IR spectroscopy up to 30 GPa using Neon as pressure medium and reported a second-order phase transition at pressures of about 25 GPa with sudden disappearance of the prominent OH band centred at 3150 cm-1. To study this phenomenon in the whole system (Fe,Mg)2SiO4 we synthesized Fe- rich hydrated ringwoodite of different compositions ranging from xFe = 1.0 to xFe = 0.40. The samples were investigated by electron microprobe, secondary ion mass spectrometry (SIMS), conventional and synchrotron FTIR spectroscopy at ambient condition and to 30 GPa in situ in the diamond anvil cell (DAC). Water determination using SIMS in combination with IR spectroscopy yielded concentrations ranging from 0.6 wt % for the Fe- endmember to 2.5 wt % for the Mg-richest sample. Several DAC experiments were performed with ringwoodite of compositions xFe = 0.4, 0.5 and 0.6 in a Megabar diamond anvil cell. We performed the high pressure measurements in different pressure transmitting environments. In the experiments performed using CsI powder, or cryogenically loaded liquid Argon, between 10 and 12 GPa, the prominent OH-stretching suddenly disappears, and the lattice vibrations show discontinuities, independent of composition. In another set of experiments cryogenically loaded liquid Argon was annealed for one hour at 8.6 GPa to 120° C before further increasing the pressure to ensure more hydrostatic conditions (Wittlinger et al. 1997). In these experiments the OH stretching vibrations as well as lattice vibrations could be

Actinide speciation bound to hydrous ferric oxide colloids in the near-field conditions of the waste pond at 'Mayak' facility (Russia)

International Nuclear Information System (INIS)

Kalmykov, St.; Khasanova, A.; Kriventsov, V.; Teterin, Y.; Novikov, A.

2007-01-01

Full text of publication follows: 'Mayak' facility is a nuclear waste and spent nuclear fuel reprocessing plant located in Ural Mountains, Russia. The opened pond, Karachay Lake, was used for several decades for the discharge of low- and intermediate level waste solutions containing fission products and traces of actinides. Due to high salt concentration and high density of waste solutions, they are penetrating into the groundwater system that is represented by oxic Eh conditions. The speciation of actinides in groundwater samples collected close to Karachay Lake was studied by successive micro- and ultra-filtrations with subsequent SEM, TEM, nano-SIMS, membrane extraction and other techniques. It was established that U and Np were found in soluble fraction (pass through 10 kD ultra-filter) in the form of their bi- and tri-carbonate complexes that was supported by chemical thermodynamic calculations. In contrast, Pu and Am were bound to nano-colloids 10 kD - 50 nm in size. The SEM and TEM data indicate the presence of variety of different colloidal particles which relative concentration decrease in the row: hydrous ferric oxides (HFO) >> clays ≅ calcite > rutile ≅ hematite ≅ barite ≅ MnO 2 > monazite > other phases. The SIMS with submicron resolution (Cameca nanoSIMS-50) was used to study local concentration of actinides. According to the obtained data among different colloids detected in the sample actinides were preferentially bound to HFO and MnO 2 while other phases did not sorb actinides. In order to determine actinide speciation bound to HFO colloids XPS and An L 3 edge XAFS measurements were done at Siberian Synchrotron Radiation Centre. The storage ring VEPP-3 with electron beam energy of 2 GeV and an average stored current of 80 mA was used as the source of radiation. Since the concentration of actinides in actual samples was too low for XAFS, the samples for measurements were prepared by contacting about 10 -5 M solutions of Np(V) and Pu(V) with

Enhanced rate performance of mesoporous Co3O4 nanosheet supercapacitor electrodes by hydrous RuO2 nanoparticle decoration

KAUST Repository

Baby, Rakhi Raghavan

2014-03-26

Mesoporous cobalt oxide (Co3O4) nanosheet electrode arrays are directly grown over flexible carbon paper substrates using an economical and scalable two-step process for supercapacitor applications. The interconnected nanosheet arrays form a three-dimensional network with exceptional supercapacitor performance in standard two electrode configuration. Dramatic improvement in the rate capacity of the Co3O4 nanosheets is achieved by electrodeposition of nanocrystalline, hydrous RuO 2 nanoparticles dispersed on the Co3O4 nanosheets. An optimum RuO2 electrodeposition time is found to result in the best supercapacitor performance, where the controlled morphology of the electrode provides a balance between good conductivity and efficient electrolyte access to the RuO2 nanoparticles. An excellent specific capacitance of 905 F/g at 1 A/g is obtained, and a nearly constant rate performance of 78% is achieved at current density ranging from 1 to 40 A/g. The sample could retain more than 96% of its maximum capacitance even after 5000 continuous charge-discharge cycles at a constant high current density of 10 A/g. Thicker RuO2 coating, while maintaining good conductivity, results in agglomeration, decreasing electrolyte access to active material and hence the capacitive performance. © 2014 American Chemical Society.

EXPERIMENTAL INVESTIGATION OF IRRADIATION-DRIVEN HYDROGEN ISOTOPE FRACTIONATION IN ANALOGS OF PROTOPLANETARY HYDROUS SILICATE DUST

Energy Technology Data Exchange (ETDEWEB)

Roskosz, Mathieu; Remusat, Laurent [IMPMC, CNRS UMR 7590, Sorbonne Universités, Université Pierre et Marie Curie, IRD, Muséum National d’Histoire Naturelle, CP 52, 57 rue Cuvier, Paris F-75231 (France); Laurent, Boris; Leroux, Hugues, E-mail: mathieu.roskosz@mnhn.fr [Unité Matériaux et Transformations, Université Lille 1, CNRS UMR 8207, Bâtiment C6, F-59655 Villeneuve d’Ascq (France)

2016-11-20

The origin of hydrogen in chondritic components is poorly understood. Their isotopic composition is heavier than the solar nebula gas. In addition, in most meteorites, hydrous silicates are found to be lighter than the coexisting organic matter. Ionizing irradiation recently emerged as an efficient hydrogen fractionating process in organics, but its effect on H-bearing silicates remains essentially unknown. We report the evolution of the D/H of hydrous silicates experimentally irradiated by electrons. Thin films of amorphous silica, amorphous “serpentine,” and pellets of crystalline muscovite were irradiated at 4 and 30 keV. For all samples, irradiation leads to a large hydrogen loss correlated with a moderate deuterium enrichment of the solid residue. The entire data set can be described by a Rayleigh distillation. The calculated fractionation factor is consistent with a kinetically controlled fractionation during the loss of hydrogen. Furthermore, for a given ionizing condition, the deuteration of the silicate residues is much lower than the deuteration measured on irradiated organic macromolecules. These results provide firm evidence of the limitations of ionizing irradiation as a driving mechanism for D-enrichment of silicate materials. The isotopic composition of the silicate dust cannot rise from a protosolar to a chondritic signature during solar irradiations. More importantly, these results imply that irradiation of the disk naturally induces a strong decoupling of the isotopic signatures of coexisting organics and silicates. This decoupling is consistent with the systematic difference observed between the heavy organic matter and the lighter water typically associated with minerals in the matrix of most carbonaceous chondrites.

Partitioning of Trace Elements Between Hydrous Minerals and Aqueous Fluids : a Contribution to the Chemical Budget of Subduction Zones

Science.gov (United States)

Daniel, I.; Koga, K. T.; Reynard, B.; Petitgirard, S.; Chollet, M.; Simionovici, A.

2006-12-01

Subduction zones are powerful chemical engines where the downgoing lithosphere reacts with asthenospheric mantle and produces magmas. Understanding this deep recycling system is a scientific challenge requiring multiple approaches. Among those, it appears that we lack basic information on the composition of the fluid that begins the process of material transfer in subduction zones. Indeed, no pristine fluid sample has yet been collected from this particular environment. Albeit challenging, the alternative would be experimental study of fluids under the appropriate conditions. Consequently, we developed an experimental protocol to measure the concentration of aqueous fluids equilibrated with minerals up to pressures (P) of 5 GPa, at least and temperatures (T) of 550 C. This includes syntheses at high-P and -T conditions, and determination of the fluid composition. Syntheses were performed in a large volume belt-type press at the conditions, 2-5 GPa and ca. 550 C. Oxides or minerals were loaded with water in a gold capsule sealed afterwards. Presence of free fluid during experiments could be confirmed by direct observation of fluid release from the sealed capsule upon puncturing. The composition in trace elements of the fluids that were equilibrated at high-P and -T with minerals was reconstructed from that of the precipitates deposited at the surface of minerals after evaporation of the capsule. The precipitates were dissolved and analyzed by a leaching technique detailed in Koga et al. (2005). Two hydrous minerals of prime interest for subductions were sofar investigated: the high-pressure variety of serpentine, antigorite, and talc. The partitioning coefficients of a series of trace-elements will be presented, as well as their evolution as a function of pressure. Consequences for the composition of the fluids released during the dehydration of hydrous metamorphic minerals will be drawn. Those measurements are unlikely to be feasible at pressures in excess of 5 GPa

Elevated naturally occurring arsenic in a semiarid oxidizing system, Southern High Plains aquifer, Texas, USA

International Nuclear Information System (INIS)

Scanlon, B.R.; Nicot, J.P.; Reedy, R.C.; Kurtzman, D.; Mukherjee, A.; Nordstrom, D.K.

2009-01-01

High groundwater As concentrations in oxidizing systems are generally associated with As adsorption onto hydrous metal (Al, Fe or Mn) oxides and mobilization with increased pH. The objective of this study was to evaluate the distribution, sources and mobilization mechanisms of As in the Southern High Plains (SHP) aquifer, Texas, relative to those in other semiarid, oxidizing systems. Elevated groundwater As levels are widespread in the southern part of the SHP (SHP-S) aquifer, with 47% of wells exceeding the current EPA maximum contaminant level (MCL) of 10 μg/L (range 0.3-164 μg/L), whereas As levels are much lower in the north (SHP-N: 9% ≥ As MCL of 10 μg/L; range 0.2-43 μg/L). The sharp contrast in As levels between the north and south coincides with a change in total dissolved solids (TDS) from 395 mg/L (median north) to 885 mg/L (median south). Arsenic is present as arsenate (As V) in this oxidizing system and is correlated with groundwater TDS (Spearman's ρ = 0.57). The most likely current source of As is sorbed As onto hydrous metal oxides based on correlations between As and other oxyanion-forming elements (V, ρ = 0.88; Se, ρ = 0.54; B, ρ = 0.51 and Mo, ρ = 0.46). This source is similar to that in other oxidizing systems and constitutes a secondary source; the most likely primary source being volcanic ashes in the SHP aquifer or original source rocks in the Rockies, based on co-occurrence of As and F (ρ = 0.56), oxyanion-forming elements and SiO 2 (ρ = 0.41), which are found in volcanic ashes. High groundwater As concentrations in some semiarid oxidizing systems are related to high evaporation. Although correlation of As with TDS in the SHP aquifer may suggest evaporative concentration, unenriched stable isotopes (δ 2 H: -65 to -27; δ 18 O: -9.1 to -4.2) in the SHP aquifer do not support evaporation. High TDS in the SHP aquifer is most likely related to upward movement of saline water from the underlying Triassic Dockum aquifer. Mobilization

The effects of hydrous ethanol gasoline on combustion and emission characteristics of a port injection gasoline engine

OpenAIRE

Xiaochen Wang; Zhenbin Chen; Jimin Ni; Saiwu Liu; Haijie Zhou

2015-01-01

Comparative experiments were conducted on a port injection gasoline engine fueled with hydrous ethanol gasoline (E10W), ethanol gasoline (E10) and pure gasoline (E0). The effects of the engine loads and the additions of ethanol and water on combustion and emission characteristics were analyzed deeply. According to the experimental results, compared with E0, E10W showed higher peak in-cylinder pressure at high load. Increases in peak heat release rates were observed for E10W fuel at all the op...

Structural, morphological, and optical properties of tin(IV) oxide nanoparticles synthesized using Camellia sinensis extract: a green approach

Science.gov (United States)

Selvakumari, J. Celina; Ahila, M.; Malligavathy, M.; Padiyan, D. Pathinettam

2017-09-01

Tin oxide (SnO2) nanoparticles were cost-effectively synthesized using nontoxic chemicals and green tea ( Camellia sinensis) extract via a green synthesis method. The structural properties of the obtained nanoparticles were studied using X-ray diffraction, which indicated that the crystallite size was less than 20 nm. The particle size and morphology of the nanoparticles were analyzed using scanning electron microscopy and transmission electron microscopy. The morphological analysis revealed agglomerated spherical nanoparticles with sizes varying from 5 to 30 nm. The optical properties of the nanoparticles' band gap were characterized using diffuse reflectance spectroscopy. The band gap was found to decrease with increasing annealing temperature. The O vacancy defects were analyzed using photoluminescence spectroscopy. The increase in the crystallite size, decreasing band gap, and the increasing intensities of the UV and visible emission peaks indicated that the green-synthesized SnO2 may play future important roles in catalysis and optoelectronic devices.

In situ study at high pressure and temperature of the environment of water in hydrous Na and Ca aluminosilicate melts and coexisting aqueous fluids

Science.gov (United States)

Le Losq, Charles; Dalou, Célia; Mysen, Bjorn O.

2017-07-01

The bonding and speciation of water dissolved in Na silicate and Na and Ca aluminosilicate melts were inferred from in situ Raman spectroscopy of the samples, in hydrothermal diamond anvil cells, while at crustal temperature and pressure conditions. Raman data were also acquired on Na silicate and Na and Ca aluminosilicate glasses, quenched from hydrous melts equilibrated at high temperature and pressure in a piston cylinder apparatus. In the hydrous melts, temperature strongly influences O-H stretching ν(O-H) signals, reflecting its control on the bonding of protons between different molecular complexes. Pressure and melt composition effects are much smaller and difficult to discriminate with the present data. However, the chemical composition of the melt + fluid system influences the differences between the ν(O-H) signals from the melts and the fluids and, hence, between their hydrogen partition functions. Quenching modifies the O-H stretching signals: strong hydrogen bonds form in the glasses below the glass transition temperature Tg, and this phenomenon depends on glass composition. Therefore, glasses do not necessarily record the O-H stretching signal shape in melts near Tg. The melt hydrogen partition function thus cannot be assessed with certainty using O-H stretching vibration data from glasses. From the present results, the ratio of the hydrogen partition functions of hydrous silicate melts and aqueous fluids mostly depends on temperature and the bulk melt + fluid system chemical composition. This implies that the fractionation of hydrogen isotopes between magmas and aqueous fluids in water-saturated magmatic systems with differences in temperature and bulk chemical composition will be different.

Diffusion of hydrous species in model basaltic melt

Science.gov (United States)

Zhang, Li; Guo, Xuan; Wang, Qinxia; Ding, Jiale; Ni, Huaiwei

2017-10-01

Water diffusion in Fe-free model basaltic melt with up to 2 wt% H2O was investigated at 1658-1846 K and 1 GPa in piston-cylinder apparatus using both hydration and diffusion couple techniques. Diffusion profiles measured by FTIR are consistent with a model in which both molecular H2O (H2Om) and hydroxyl (OH) contribute to water diffusion. OH diffusivity is roughly 13% of H2Om diffusivity, showing little dependence on temperature or water concentration. Water diffusion is dominated by the motion of OH until total H2O (H2Ot) concentration reaches 1 wt%. The dependence of apparent H2Ot diffusivity on H2Ot concentration appears to be overestimated by a previous study on MORB melt, but H2Ot diffusivity at 1 wt% H2Ot in basaltic melt is still greater than those in rhyolitic to andesitic melts. The appreciable contribution of OH to water diffusion in basaltic melt can be explained by enhanced mobility of OH, probably associated with the development of free hydroxyl bonded with network-modifying cations, as well as higher OH concentration. Calculation based on the Nernst-Einstein equation demonstrates that OH may serve as an effective charge carrier in hydrous basaltic melt, which could partly account for the previously observed strong influence of water on electrical conductivity of basaltic melt.

Sorption behaviour of uranium and thorium on cryptomelane-type hydrous manganese dioxide from aqueous solution

International Nuclear Information System (INIS)

El-Naggar, I.M.; El-Absy, M.A.; Abdel-Hamid, M.M.; Aly, H.F.

1993-01-01

The kinetics of sorption of uranium and thorium from aqueous nitrate solutions on cryptomelane-type hydrous manganese dioxide (CRYMO) was studied. The exchange of uranium is particle diffusion controlled while that of thorium is chemical reaction at the exchange sites. Sorption of uranium and thorium by CRYMO has been also studied as a function of metal concentrations and temperature. The sorption of both cations is found to be an endothermic process and increases markedly with temperature between 30 and 60 degree C. The sorption results have been analysed by the langmuir adsorption isotherm over the entire range of uranium and thorium concentrations investigated. 35 refs., 8 figs., 5 tabs

Metal ion binding to iron oxides

Science.gov (United States)

Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

2006-06-01

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

Science.gov (United States)

Yu, Na; Klepov, Vladislav V.; Villa, Eric M.; Bosbach, Dirk; Suleimanov, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.; Alekseev, Evgeny V.

2014-07-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O (α-, β-RbUAs) and the anhydrous phase Rb[UO2(AsO3OH)(AsO2(OH)2)] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions.

Elasticity of Pargasite Amphibole: A Hydrous Phase at Mid Lithospheric Discontinuity

Science.gov (United States)

Peng, Y.; Mookherjee, M.

2017-12-01

Mid Lithospheric Discontinuity (MLD) is characterized by a low shear wave velocity ( 3 to 10 %). In cratons, the depth of MLD varies between 80 and 100 km. The reduction of the shear wave velocity at MLD is similar to what is observed in the lithosphere-asthenosphere boundary (LAB). Such low velocity at MLD could be caused by partial melting, temperature induced grain boundary sliding, changes in the elastic anisotropy, and/or metasomatism which may lead to the formation of hydrous phases including mica and amphibole. Thus, it is clear that in order to assess the role of metasomatism at MLD, we need better constraints on the elasticity of hydrous phases. However, such elasticity data are scarce. In this study, we explore elasticity of pargasite amphibole [NaCa2(Mg4Al)(Si6Al2)O22(OH)2] using density functional theory (DFT) with local density approximation (LDA) and generalized gradient approximation (GGA). We find that the pressure-volume results can be adequately described by a finite strain equation with the bulk modulus, K0 being 102 and 85 GPa for LDA and GGA respectively. We also determined the full elastic constant tensor (Cij) using the finite difference method. The bulk modulus, K0 determined from the full elastic constant tensor is 104 GPa for LDA and 87 GPa for GGA. The shear modulus, G0 determined from the full elastic constant tensor is 64 GPa for LDA and 58 GPa for GGA. The bulk and shear moduli predicted with LDA are 5 and 1 % stiffer than the recent results [1]. In contrast, the bulk and shear moduli predicted with GGA are 12 and 10 % softer compared to the recent results [1]. The full elastic constant tensor for pargasite shows significant anisotropy. For instance, LDA predicts compressional (AVP) and shear (AVS) wave anisotropy of 22 and 20 % respectively. At higher pressure, elastic moduli stiffen. However, temperature is likely to have an opposite effect on the elasticity and this remains largely unknown for pargasite. Compared to the major mantle

Discovery of Ni-smectite-rich saprolite at Loma Ortega, Falcondo mining district (Dominican Republic): geochemistry and mineralogy of an unusual case of "hybrid hydrous Mg silicate - clay silicate" type Ni-laterite

Science.gov (United States)

Tauler, Esperança; Lewis, John F.; Villanova-de-Benavent, Cristina; Aiglsperger, Thomas; Proenza, Joaquín A.; Domènech, Cristina; Gallardo, Tamara; Longo, Francisco; Galí, Salvador

2017-10-01

Hydrous Mg silicate-type Ni-laterite deposits, like those in the Falcondo district, Dominican Republic, are dominated by Ni-enriched serpentine and garnierite. Recently, abundant Ni-smectite in the saprolite zone have been discovered in Loma Ortega, one of the nine Ni-laterite deposits in Falcondo. A first detailed study on these Ni-smectites has been performed (μXRD, SEM, EPMA), in addition to a geochemical and mineralogical characterisation of the Loma Ortega profile (XRF, ICP-MS, XRD). Unlike other smectite occurrences in laterite profiles worldwide, the Loma Ortega smectites are trioctahedral and exhibit high Ni contents never reported before. These Ni-smectites may be formed from weathering of pyroxene and olivine, and their composition can be explained by the mineralogy and the composition of the Al-depleted, olivine-rich parent ultramafic rock. Our study shows that Ni-laterites are mineralogically complex, and that a hydrous Mg silicate ore and a clay silicate ore can be confined to the same horizon in the weathering profile, which has significant implications from a recovery perspective. In accordance, the classification of "hybrid hydrous Mg silicate - clay silicate" type Ni-laterite deposit for Loma Ortega would be more appropriate.

Structural and optical properties of electrodeposited molybdenum oxide thin films

International Nuclear Information System (INIS)

Patil, R.S.; Uplane, M.D.; Patil, P.S.

2006-01-01

Electrosynthesis of Mo(IV) oxide thin films on F-doped SnO 2 conducting glass (10-20/Ω/□) substrates were carried from aqueous alkaline solution of ammonium molybdate at room temperature. The physical characterization of as-deposited films carried by thermogravimetric/differential thermogravimetric analysis (TGA/DTA), infrared spectroscopy and X-ray diffraction (XRD) showed the formation of hydrous and amorphous MoO 2 . Scanning electron microscopy (SEM) revealed a smooth but cracked surface with multi-layered growth. Annealing of these films in dry argon at 450 deg. C for 1 h resulted into polycrystalline MoO 2 with crystallites aligned perpendicular to the substrate. Optical absorption study indicated a direct band gap of 2.83 eV. The band gap variation consistent with Moss rule and band gap narrowing upon crystallization was observed. Structure tailoring of as-deposited thin films by thermal oxidation in ambient air to obtain electrochromic Mo(VI) oxide thin films was exploited for the first time by this novel route. The results of this study will be reported elsewhere

Developing the photovoltaic performance of dye-sensitized solar cells (DSSCs) using a SnO2-doped graphene oxide hybrid nanocomposite as a photo-anode

Science.gov (United States)

Sasikumar, Ragu; Chen, Tse-Wei; Chen, Shen-Ming; Rwei, Syang-Peng; Ramaraj, Sayee Kannan

2018-05-01

Tin(IV) oxide nanoparticles (SnO2 NPs) doped on the surface of graphene oxide (GO) sheets for application in Dye-Sensitized Solar Cells (DSSCs). The effective incorporation of SnO2 on the surface of GO sheets were confirmed by powder X-ray diffraction (PXRD), Fourier transform infra-red spectroscopy (FT-IR), thermogravimetric analysis (TGA), electrochemical impedance spectroscopy (EIS), and Raman spectroscopy. The morphology of the GO/SnO2 hybrid nanocomposite was confirmed by field emission scanning electron microscopy (FE-SEM) analysis. This current study involvement with the effect of different photo-anodes such as GO, SnO2, and GO/SnO2 hybrid nanocomposite on the power conversion efficiency (PCE) of the triiodide electrolyte based DSSCs. Remarkably, GO/SnO2 hybrid nanocomposite based photo-anode for DSSC observed PCE of 8.3% and it is about 12% higher than that of un-doped TiO2 photo-anode. The equivalent short-circuit photocurrent density (Jsc) of 16.67 mA cm-2, open circuit voltage (Voc) of 0.77 V, and fill factor (FF) of 0.65 respectively. The achieved results propose that the hybrid nanocomposite is an appropriate photo-anodic material for DSSCs applications.

Application of uniaxial confining-core clamp with hydrous pyrolysis in petrophysical and geochemical studies of source rocks at various thermal maturities

Science.gov (United States)

Lewan, Michael D.; Birdwell, Justin E.; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

2013-01-01

Understanding changes in petrophysical and geochemical parameters during source rock thermal maturation is a critical component in evaluating source-rock petroleum accumulations. Natural core data are preferred, but obtaining cores that represent the same facies of a source rock at different thermal maturities is seldom possible. An alternative approach is to induce thermal maturity changes by laboratory pyrolysis on aliquots of a source-rock sample of a given facies of interest. Hydrous pyrolysis is an effective way to induce thermal maturity on source-rock cores and provide expelled oils that are similar in composition to natural crude oils. However, net-volume increases during bitumen and oil generation result in expanded cores due to opening of bedding-plane partings. Although meaningful geochemical measurements on expanded, recovered cores are possible, the utility of the core for measuring petrophysical properties relevant to natural subsurface cores is not suitable. This problem created during hydrous pyrolysis is alleviated by using a stainless steel uniaxial confinement clamp on rock cores cut perpendicular to bedding fabric. The clamp prevents expansion just as overburden does during natural petroleum formation in the subsurface. As a result, intact cores can be recovered at various thermal maturities for the measurement of petrophysical properties as well as for geochemical analyses. This approach has been applied to 1.7-inch diameter cores taken perpendicular to the bedding fabric of a 2.3- to 2.4-inch thick slab of Mahogany oil shale from the Eocene Green River Formation. Cores were subjected to hydrous pyrolysis at 360 °C for 72 h, which represents near maximum oil generation. One core was heated unconfined and the other was heated in the uniaxial confinement clamp. The unconfined core developed open tensile fractures parallel to the bedding fabric that result in a 38 % vertical expansion of the core. These open fractures did not occur in the

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

Science.gov (United States)

Putschew, A.; Schaeffer-Reiss, C.; Schaeffer, P.; Koopmans, M.P.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.; Maxwell, J.R.

1998-01-01

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330??C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAIH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis-GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260??C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak Carbon-heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220??C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.

Study of Pd-Sn/Al{sub 2}O{sub 3} catalysts prepared by an oxide colloidal route; Etude de catalyseurs Pd-Sn/Al{sub 2}O{sub 3} prepares par voie colloidale oxyde

Energy Technology Data Exchange (ETDEWEB)

Verdier, St.

2001-09-01

The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the oxide particles. To synthesize oxide bimetallic sols, three strategies were defined. Copolymerization (formation of a mixed oxide nano-sol by cross condensation of both metals) does not lead to a mixed oxide Pd-Sn phase. Surface precipitation (neutralization of the second metal in the presence of the first oxide sol) yields nano-particles of both oxides in close interaction. Adsorption (adsorption of the second metal onto the first oxide sol) significantly occurs when contacting tin with a basic PdO sol (hydrolytic adsorption). The characterization and the assessment of the catalytic properties (selective hydrogenation of buta-1,3-diene) of the catalysts prepared by deposition of oxide bimetallic sols showed that the oxide colloidal route allows the control of the properties of the supported bimetallic phase. Moreover, our results display that both Pd-Sn alloy formation and,aggregation of the metallic particles contribute to increase the selectivity for this reaction. (author)

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

Science.gov (United States)

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

2018-05-01

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

Elevated naturally occurring arsenic in a semiarid oxidizing system, Southern High Plains aquifer, Texas, USA

Science.gov (United States)

Scanlon, Bridget R.; Nicot, J.-P.; Reedy, R.C.; Kurtzman, D.; Mukherjee, A.; Nordstrom, D. Kirk

2009-01-01

High groundwater As concentrations in oxidizing systems are generally associated with As adsorption onto hydrous metal (Al, Fe or Mn) oxides and mobilization with increased pH. The objective of this study was to evaluate the distribution, sources and mobilization mechanisms of As in the Southern High Plains (SHP) aquifer, Texas, relative to those in other semiarid, oxidizing systems. Elevated groundwater As levels are widespread in the southern part of the SHP (SHP-S) aquifer, with 47% of wells exceeding the current EPA maximum contaminant level (MCL) of 10 μg/L (range 0.3–164 μg/L), whereas As levels are much lower in the north (SHP-N: 9% ⩾ As MCL of 10 μg/L; range 0.2–43 μg/L). The sharp contrast in As levels between the north and south coincides with a change in total dissolved solids (TDS) from 395 mg/L (median north) to 885 mg/L (median south). Arsenic is present as arsenate (As V) in this oxidizing system and is correlated with groundwater TDS (Spearman’s ρ = 0.57). The most likely current source of As is sorbed As onto hydrous metal oxides based on correlations between As and other oxyanion-forming elements (V, ρ = 0.88; Se, ρ = 0.54; B, ρ = 0.51 and Mo, ρ = 0.46). This source is similar to that in other oxidizing systems and constitutes a secondary source; the most likely primary source being volcanic ashes in the SHP aquifer or original source rocks in the Rockies, based on co-occurrence of As and F (ρ = 0.56), oxyanion-forming elements and SiO2 (ρ = 0.41), which are found in volcanic ashes. High groundwater As concentrations in some semiarid oxidizing systems are related to high evaporation. Although correlation of As with TDS in the SHP aquifer may suggest evaporative concentration, unenriched stable isotopes (δ2H: −65 to −27; δ18O: −9.1 to −4.2) in the SHP aquifer do not support evaporation. High TDS in the SHP aquifer is most likely related to upward movement of saline water from the underlying

Determination of thermal stability of specific biomarker lipids of the freshwater fern Azolla through hydrous pyrolysis

Science.gov (United States)

Sap, Merel; Speelman, Eveline N.; Lewan, Michael D.; Sinninghe Damsté, Jaap S.; Reichart, Gert-Jan

2010-05-01

Enormous blooms of the free-floating freshwater fern Azolla occurred within the Arctic Basin during an extended period of ~1.2 Ma during the middle Eocene (Brinkhuis et al. 2006; Speelman et al., GB, 2009). The sustained growth of Azolla, currently ranking among the fastest growing plants on Earth, in a major anoxic basin may have substantially contributed to decreasing atmospheric CO2 levels by burial of Azolla-derived organic matter. Speelman et al. (OG, 2009) reported biomarkers for Azolla (1,w20 C32 - C36 diols, structurally related C29 ω20,ω21 diols, C29 1,20,21 triols, C29 dihydroxy fatty acids as well as a series of wax esters containing these mono- and dihydroxy lipids), which can be used to reconstruct palaeo-environmental conditions. Here we assess the thermal stability of these compounds, to extend their biomarker potential. We specifically focused on the thermal stability of the Azolla biomarkers using hydrous pyrolysis in order to determine which burial conditions allow reconstruction of past occurrences of Azolla. In addition, hydrous pyrolysis was also performed on samples from the Eocene Arctic Ocean (ACEX core), to test if and how the biomarkers change under higher temperatures and pressures in situ. During hydrous pyrolysis, the biomass was heated under high pressure at temperatures ranging between 220 and 365°C for 72 hours. Four experiments were also run using different durations to explore the kinetics of biomarker degradation at specific temperatures. First results indicate that the Azolla specific diols are still present at 220°C, while the corresponding wax esters are already absent. At 300°C all Azolla specific biomarkers are destroyed. More specific determination of the different biomarkers' stability and kinetics would potentially allow the reconstruction of the temperature and pressure history of Azolla deposits. Literature: • Brinkhuis, H., Schouten, S., Collinson, M. E., Sluijs, A., Sinninghe Damste, J. S., Dickens, G. R., Huber

Ion-exchange behaviour of hydrous zirconia in mixed solvents: capacity and kinetics of exchange

International Nuclear Information System (INIS)

Misak, N.Z.; Ghoneimy, H.F.

1982-01-01

The capacity of the Li + form of hydrous zirconia for Na + and Cs + increases in the presence of methanol. This may be due to the greater stability of Li + in methanol/water than in pure water and to dehydration of Na + and Cs + and their stronger interaction with the exchange sites, which may facilitate their replacing Li + . The ion-exchange capacity of zirconia for NO 3 - , Cl - and Br - is almost the same in aqueous solution and is not affected by addition of up to 90% (v/v) methanol, which probably shows that these anions are electrostatically bound in zirconia without specific interactions. The internal diffusion coefficients of the Na + /H + and Cl - /OH - systems decrease in the presence of alcohol: the decrease is highest with methanol and similar for ethanol and propan-2-ol. This is discussed in the light of ion solvation and alcohol penetration inside zirconia. (author)

Lubrication of dislocation glide in MgO by hydrous defects

Science.gov (United States)

Skelton, Richard; Walker, Andrew M.

2018-02-01

Water-related defects, principally in the form of protonated cation vacancies, are potentially able to weaken minerals under high-stress or low-temperature conditions by reducing the Peierls stress required to initiate dislocation glide. In this study, we use the Peierls-Nabarro (PN) model to determine the effect of protonated Mg vacancies on the 1/2{110} and 1/2{100} slip systems in MgO. This PN model is parameterized using generalized stacking fault energies calculated using plane-wave density functional theory, with and without protonated Mg vacancies present at the glide plane. It found that these defects increase dislocation core widths and reduce the Peierls stress over the entire pressure range 0-125 GPa. Furthermore, 1/2{110} slip is found to be more sensitive to the presence of protonated vacancies which increases in the pressure at which {100} becomes the easy glide plane for 1/2 screw dislocations. These results demonstrate, for a simple mineral system, that water-related defects can alter the deformation behavior of minerals in the glide-creep regime by reducing the stress required to move dislocations by glide. (Mg, Fe)O is the most anisotropic mineral in the Earth's lower mantle, so the differential sensitivity of the major slip systems in MgO to hydrous defects has potential implications for the interpretation of the seismic anisotropy in this region.

Perform Tests and Document Results and Analysis of Oxide Layer Effects and Comparisons

Energy Technology Data Exchange (ETDEWEB)

Collins, E. D. [ORNL; DelCul, G. D. [ORNL; Spencer, B. B. [ORNL; Hunt, R. D. [ORNL; Ausmus, C. [ORNL

2014-08-30

During the initial feasibility test using actual used nuclear fuel (UNF) cladding in FY 2012, an incubation period of 30–45 minutes was observed in the initial dry chlorination. The cladding hull used in the test had been previously oxidized in a dry air oxidation pretreatment prior to removal of the fuel. The cause of this incubation period was attributed to the resistance to chlorination of an oxide layer imparted by the dry oxidation pretreatment on the cladding. Subsequently in 2013, researchers at the Korea Atomic Energy Institute (KAERI) reported on their chlorination study [R1] on ~9-gram samples of unirradiated ZirloTM cladding tubes that had been previously oxidized in air at 500oC for various time periods to impart oxide layers of varying thickness. In early 2014, discussions with Indefinite Delivery, Indefinite Quantity (IDIQ) contracted technical consultants from Westinghouse described their previous development (and patents) [R2] on methods of chemical washing to remove some or all of the hydrous oxide layer imparted on UNF cladding during irradiation in light water reactors (LWRs) . Thus, the Oak Ridge National Laboratory (ORNL) study, described herein, was planned to extend the KAERI study on the effects of anhydrous oxide layers, but on larger ~100-gram samples of unirradiated zirconium alloy cladding tubes, and to investigate the effects of various methods of chemical pretreatment prior to chlorination with 100% chlorine on the average reaction rates and Cl2 usage efficiencies.

Mechanically activated synthesis of PZT and its electromechanical properties

Energy Technology Data Exchange (ETDEWEB)

Liu, X.; Akdogan, E.K.; Safari, A.; Riman, R.E. [Rutgers the State University of New Jersey, Department of Ceramic and Materials Engineering, Piscataway, NJ (United States)

2005-08-01

Mechanical activation was successfully used to synthesize nanostructured phase-pure Pb(Zr{sub 0.7}Ti{sub 0.3})O{sub 3} (PZT) powders. Lead-zirconium-titanium (PbZrTi) hydrous oxide precursor, synthesized from chemical co-precipitation, was mechanically activated in a NaCl matrix. The synthesized PZT particles were characterized by using X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, laser-light diffraction, and nitrogen adsorption. Thermogravimetric analysis and differential thermal analysis were used to monitor dehydration and phase transformation of PbZrTi hydrous oxide precursor during mechanical activation. The best mechanical activation conditions corresponded to mechanically activating PbZrTi hydrous oxide precursor in a NaCl matrix with a NaCl/precursor weight ratio of 4:1 for 8 h. These conditions resulted in a dispersible phase-pure PZT powder with a median secondary-particle size of {proportional_to}110 nm. The properties of PZT 70/30 from mechanically activated powder, as measured on discs sintered at 1150 C for 2 h, were found to be in close conformity to those obtained by a conventional mixed oxide solid state reaction route. (orig.)

Mechanically activated synthesis of PZT and its electromechanical properties

Science.gov (United States)

Liu, X.; Akdogan, E. K.; Safari, A.; Riman, R. E.

2005-08-01

Mechanical activation was successfully used to synthesize nanostructured phase-pure Pb(Zr0.7Ti0.3)O3 (PZT) powders. Lead zirconium titanium (PbZrTi) hydrous oxide precursor, synthesized from chemical co-precipitation, was mechanically activated in a NaCl matrix. The synthesized PZT particles were characterized by using X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, laser-light diffraction, and nitrogen adsorption. Thermogravimetric analysis and differential thermal analysis were used to monitor dehydration and phase transformation of PbZrTi hydrous oxide precursor during mechanical activation. The best mechanical activation conditions corresponded to mechanically activating PbZrTi hydrous oxide precursor in a NaCl matrix with a NaCl/precursor weight ratio of 4:1 for 8 h. These conditions resulted in a dispersible phase-pure PZT powder with a median secondary-particle size of ˜110 nm. The properties of PZT 70/30 from mechanically activated powder, as measured on discs sintered at 1150 °C for 2 h, were found to be in close conformity to those obtained by a conventional mixed oxide solid state reaction route.

Invasion of Hydrous Fluids Predates Kimberlite Formation

Science.gov (United States)

Kopylova, M. G.; Wang, Q.; Smith, E. M.

2017-12-01

Petrological observations on diamonds and peridotite xenoliths in kimberlites point towards an influx of hydrous metasomatic fluids shortly predating kimberlite formation. Diamonds may grow at different times within the same segment of the cratonic mantle, and diamonds that form shortly before (diamonds typically contain 10-25 wt.% water in fluid inclusions, while older octahedrally-grown diamonds host "dry" N2-CO2 fluids. Our recent studies of fluids in diamond now show that many different kinds of diamonds can contain fluid inclusions. Specifically, we found a new way to observe and analyze fluids in octahedrally-grown, non-fibrous diamonds by examining healed fractures. This is a new textural context for fluid inclusions that reveals a valuable physical record of infiltrating mantle fluids, that postdate diamond growth, but equilibrate within the diamond stability field at depths beyond 150 km. Another sign of the aqueous fluids influx is the formation of distinct peridotite textures shortly predating the kimberlite. Kimberlites entrain peridotite xenoliths with several types of textures: older coarse metamorphic textures and younger, sheared textures. The preserved contrast in grain sizes between porphyroclasts and neoblasts in sheared peridotites constrain the maximum duration of annealing. Experimental estimates of the annealing time vary from 7x107 sec (2 years) to 106 years (1 My) depending on olivine hydration, strain rate, pressure, temperature and, ultimately, the annealing mechanism. Kimberlite sampling of sheared peridotites from the lithosphere- asthenosphere boundary (LAB) implies their formation no earlier than 1 My prior to the kimberlite ascent. Water contents of olivine measured by FTIR spectrometry using polarized light demonstrated contrasting hydration of coarse and sheared samples. Olivine from sheared peridotite samples has the average water content of 78±3 ppm, in contrast to the less hydrated coarse peridotites (33±6 ppm). LAB hydration

Laboratory simulation studies of uranium mobility in natural waters

International Nuclear Information System (INIS)

Giblin, A.M.; Swaine, D.J.; Batts, B.D.

1981-01-01

The effects of imposed variations of pH and Eh on aqueous uranium mobility at 25 0 C have been studied in three simulations of natural water systems. Constituents tested for their effect on uranium mobility were: (a) hydrous ferric oxide, to represent adsorptive solids which precipitate or dissolve in response to variations in pH and Eh; (b) kaolinite, representing minerals which, although modified by pH and Eh changes, are present as solids over the pH-Eh range of natural waters; and (c) carbonate, to represent a strong uranium-complexing species. Uranium mobility measurements from each simulation were regressed against pH and Eh within a range appropriate to natural waters. Hydrous ferric oxide and kaolinite each affected uranium mobility, but in separate pH-Eh domains. Aqueous carbonate increased mobility of uranium, and adsorption of UO 2 (CO 3 ) 3 4- caused colloidal dispersion of hydrous ferric oxide, possibly explaining the presence of 'hydrothermal hematite' in some uranium deposits. Enhanced uranium mobility observed in the pH-Eh domains of thermodynamically insoluble uranium oxides could be explained if the oxides were present as colloids. Uranium persisting as a mobile species, even after reduction, has implications for the near surface genesis of uranium ores. (author)

Elasticity of phase-Pi (Al3Si2O7(OH)3) - A hydrous aluminosilicate phase

Science.gov (United States)

Peng, Ye; Mookherjee, Mainak; Hermann, Andreas; Bajgain, Suraj; Liu, Songlin; Wunder, Bernd

2017-08-01

Phase-Pi (Al3Si2O7(OH)3) is an aluminosilicate hydrous mineral and is likely to be stable in hydrated sedimentary layers of subducting slabs. Phase-Pi is likely to be stable between the depths of 60 and 200 km and is likely to transport water into the Earth's interior. Here, we use first principles simulations based on density functional theory to explore the crystal structure at high-pressure, equation of state, and full elastic stiffness tensor as a function of pressure. We find that the pressure volume results could be described by a finite strain fit with V0 , K0 , and K0‧ being 310.3 Å3, 133 GPa, and 3.6 respectively. At zero pressure, the full elastic stiffness tensor shows significant anisotropy with the diagonal principal components C11 , C22 , and C33 being 235, 292, 266 GPa respectively, the diagonal shear C44 , C55 , and C66 being 86, 92, and 87 GPa respectively, and the off-diagonal stiffness C12 , C13 , C14 ,C15 , C16 , C23 , C24 , C25 , C26 , C34 , C35 , C36 , C45 , C46 , and C56 being 73, 78, 6, -30, 15, 61, 17, 2, 1, -13, -15, 6, 3, 1, and 3 GPa respectively. The zero pressure, shear modulus, G0 and its pressure derivative, G0 ‧ are 90 GPa and 1.9 respectively. Upon compression, hydrogen bonding in phase-Pi shows distinct behavior, with some hydrogen bonds weakening and others strengthening. The latter eventually undergo symmetrization, at pressure greater (>40 GPa) than the thermodynamic stability of phase-Pi. Full elastic constant tensors indicate that phase-Pi is very anisotropic with AVP ∼22.4% and AVS ∼23.7% at 0 GPa. Our results also indicate that the bulk sound velocity of phase-Pi is slower than that of the high-pressure hydrous aluminosilicate phase, topaz-OH.

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

Science.gov (United States)

Sossi, Paolo A.; Prytulak, Julie; O'Neill, Hugh St. C.

2018-04-01

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities ({f_{{{O}2}}}), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V3+ and V4+ in magnetite, and a mixture of IV- and VI-fold V5+ and V4+ in the melt. The magnitude of the fractionation factor systematically increases with increasing log{f_{{{O}2}}} relative to the Fayalite-Magnetite-Quartz buffer (FMQ), from Δ51Vmag-gl = - 0.63 ± 0.09‰ at FMQ - 1 to - 0.92 ± 0.11‰ (SD) at ≈ FMQ + 5, reflecting constant V3+/V4+ in magnetite but increasing V5+/V4+ in the melt with increasing log{f_{{{O}2}}}. These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.

As(III) oxidation by MnO2 during groundwater treatment.

Science.gov (United States)

Gude, J C J; Rietveld, L C; van Halem, D

2017-03-15

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

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Hongbin Dai

2017-02-01

Full Text Available The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine (N2H4·H2O as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO2 matrix. The Ni-Ir/CeO2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N2H4·H2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.

Stability of oxidized iron species and the redox budget of slab-derived fluids

Science.gov (United States)

Sanchez-Valle, C.; Hin, R.; Testemale, D.; Borca, C.; Grolimund, D.

2017-12-01

The high oxidation state of subduction zone magmas compared to magmas from other locations might result from the influx of oxidized fluid from the subducted oceanic plate into the mantle wedge. However, the nature of the chemical agent(s) and the mechanism responsible for the transfer of the oxidized signature from the slab to the mantle wedge remains poorly understood. In this contribution, we will discuss the oxidizing capacity of slab-derived fluids in the light of experimental results of the solubility and speciation of iron in high-pressure fluids that mimic the slab flux. Iron-bearing mineral assemblages were equilibrated with chlorinated aqueous fluids and hydrous granitic melts at different oxygen fugacities relevant for the present day crust/mantle. The concentration of iron and the distribution of stability of oxidized iron species were monitored up to 2.5 GPa and 800 °C using a combination of diamond trap experiments and XANES measurements in diamond anvil cells. The results illustrate the role of coordination chemistry involving halogen and polymerized species in the stability of oxidized iron in the fluids. The concentration of Fe3+ in the fluids progressively decreases as temperature increases, regardless of fluid composition and pressure. This implies that the fluid capacity to transport Fe3+ at high temperature may be limited, even at the redox conditions relevant for the present day crust and mantle. With the new experimental results, we place constrains on the oxidizing capacity of Fe-bearing metasomatic fluids and discuss the transfer of the oxidizing signature and the conditions for the genesis of oxidized arc magmas.

The impact of pre-oxidation with potassium permanganate on cyanobacterial organic matter removal by coagulation.

Science.gov (United States)

Naceradska, Jana; Pivokonsky, Martin; Pivokonska, Lenka; Baresova, Magdalena; Henderson, Rita K; Zamyadi, Arash; Janda, Vaclav

2017-05-01

The study investigates the effect of permanganate pre-oxidation on the coagulation of peptides/proteins of Microcystis aeruginosa which comprise a major proportion of the organic matter during cyanobacterial bloom decay. Four different permanganate dosages (0.1, 0.2, 0.4 and 0.6 mg KMnO 4 mg -1 DOC) were applied prior to coagulation by ferric sulphate. Moreover, changes in sample characteristics, such as UV 254 , DOC content and molecular weight distribution, after pre-oxidation were monitored. The results showed that permanganate pre-oxidation led to a reduction in coagulant dose, increased organic matter removals by coagulation (by 5-12% depending on permanganate dose), microcystin removal (with reductions of 91-96%) and a shift of the optimum pH range from 4.3 to 6 without to 5.5-7.3 with pre-oxidation. Degradation of organic matter into inorganic carbon and adsorption of organic matter onto hydrous MnO 2 are suggested as the main processes responsible for coagulation improvement. Moreover, permanganate prevented the formation of Fe-peptide/protein complexes that inhibit coagulation at pH about 6.2 without pre-oxidation. The study showed that carefully optimized dosing of permanganate improves cyanobacterial peptide/protein removal, with the benefit of microcystin elimination. Copyright © 2017 Elsevier Ltd. All rights reserved.

Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

Science.gov (United States)

Evans, K.; Ferris, F.

2009-05-01

At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the

Setting constraints on the nature and origin of the two major hydrous sulfates on Mars: Monohydrated and polyhydrated sulfates

Science.gov (United States)

Wang, Alian; Jolliff, Bradley L.; Liu, Yang; Connor, Kathryn

2016-04-01

Monohydrated Mg sulfate (MgSO4·H2O) and polyhydrated sulfate are the most common and abundant hydrous sulfates observed thus far on Mars. They are widely distributed and coexist in many locations. On the basis of results from two new sets of experiments, in combination with past experimental studies and the subsurface salt mineralogy observed at a saline playa (Dalangtan, DLT) in a terrestrial analogue hyperarid region on the Tibet Plateau, we can now set new constraints on the nature and origin of these two major Martian sulfates. Starkeyite (MgSO4·4H2O) is the best candidate for polyhydrated sulfate. MgSO4·H2O in the form of "LH-1w," generated from dehydration of Mg sulfates with high degrees of hydration, is the most likely mineral form for the majority of Martian monohydrated Mg sulfate. Two critical properties of Mg sulfates are responsible for the coexistence of these two phases that have very different degrees of hydration: (1) the metastability of a substructural unit in starkeyite at relatively low temperatures, and (2) catalytic effects attributed to coprecipitated species (sulfates, chlorides, oxides, and hydroxides) from chemically complex brines that help overcome the metastability of starkeyite. The combination of these two properties controls the coexistence of the LH-1w layer and starkeyite layers at many locations on Mars, which sometimes occur in an interbedded stratigraphy. The structural H2O held by these two broadly distributed sulfates represents a large H2O reservoir at the surface and in the shallow subsurface on current Mars.

A bench-scale study on the removal and recovery of phosphate by hydrous zirconia-coated magnetite nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhe; Fang, Wenkan; Xing, Mingchao; Wu, Deyi, E-mail: dywu@sjtu.edu.cn

2017-02-15

Owing to the easy magnetic separation from water for reuse, magnetic nanoparticles have drawn great interest as adsorbents. Herein hydrous zirconia-coated magnetite nanoparticles (Fe{sub 3}O{sub 4}@ZrO{sub 2}) were created by a facile method and a bench–scale study was undertaken to evaluate its effectiveness and mechanism to remove phosphate at low concentrations. Results indicated that phosphate removal by Fe{sub 3}O{sub 4}@ZrO{sub 2} was fast (95% of phosphate removal within 10 min) and nearly complete removal could be achieved at the adsorbent dosage >0.6 g/L. In tap water or wastewater where competitive anions coexist, regulation of pH was found to be quite effective to augment the performance of phosphate removal. In pH–lowered adsorption systems, phosphate removal followed a good pattern similarly to pure water, i.e., a continuous high efficiency removal followed by a rapid saturation. Adsorption–desorption–regeneration studies showed that Fe{sub 3}O{sub 4}@ZrO{sub 2} could be repeatedly used for phosphate removal and adsorbed phosphate could be stripped for recovery. The fractionation of adsorbed phosphorus suggested that NaOH-P fraction was dominant. We also found that the adsorption reaction of phosphate with Fe{sub 3}O{sub 4}@ZrO{sub 2} shifted the isoelectric point of Fe{sub 3}O{sub 4}@ZrO{sub 2} from ~9.0 to ~3.0. FTIR measurements further showed the direct coordination of phosphate onto zirconium by replacement of hydroxyl groups. The formation of the monodentate (ZrO)PO{sub 2}(OH) complex was proposed. - Highlights: • Hydrous zirconia–coated magnetite was used for phosphate capture. • Regulation of pH was able to enhance P removal in the presence of coexisting ions. • Phosphate was coordinated onto zirconium by replacement of hydroxyl groups. • The material could be easily separated from water for reuse by a magnet. • Desorption of phosphate from the material could be achieved with NaOH treatment.

Diffusion coefficients for Tl, Pb, Cd, In, Zn, Bi, As, Mo and Sb in hydrous rhyolite at 100-200 MPa

Science.gov (United States)

Berlo, Kim; Brooker, Richard; Wilke, Max

2014-05-01

A series of experiments have been conducted to determine the diffusivities of Tl, Pb, Cd, In, Zn, Bi, As, Mo and Sb in hydrous rhyolitic melt. Diffusion experiments used two adjoining glass cylinder of the same hydrous composition, one doped with the elements of interest at ~ 100 ppm. These couples were rapidly heated to 850, 1000 and 1150°C at 100-200 MPa for a few hours. After quenching the sectioned charges were analyzed by both synchrotron XRF (The Diamond Light Source) and LA-ICP-MS (University of Oxford). The data shows excellent correlation between these two techniques. The diffusion profiles were fitted to a 1-D diffusion couple equation to determine the diffusivities and fitting to the different temperature runs defined the Arrhenius parameters. We find that for 850°C the diffusion coefficients follow the trend Tl>Pb>Cd>Zn>In>Bi>As>Sb>Mo. Additional experiments were performed with either S or Cl added (to both sides of the diffusion couple). In general S increases the diffusion rate of all metals except Mo and Sb, which diffuse slower in the presence of S. Chlorine also speeds up the diffusion of metals with the exception of In, Mo and Sb. The systematic change in diffusivities of these metals and their different behaviour in the presence of the ligands that are also observed to be significant in volcanic gases, are important in determining the distribution of these metals during degassing (e.g. MacKenzie and Canil, 2008). This is particularly important in a dynamic environment such as a volcanic conduit. There are also implications for economic exploration and well as hazard mitigation.

Effect of Flowing Water on Sr Sorption Changes of Hydrous Sodium Titanate

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Youko Takahatake

2017-12-01

Full Text Available Radioactive contaminated water has been generated at the Fukushima Daiichi Nuclear Power station (F1NPS. Hydrous sodium titanate (SrTreat® is able to remove radioactive Strontium (Sr from this water. Knowing the amount of radioactive nuclides in the used as-received SrTreat® is important for effective disposal and deposition of the F1NPS waste. This study investigated changes in the ability of SrTreat® to sorb Sr, and to understand the causes of changes in the sorbing. An investigation of the Sr sorption ability of SrTreat® is important for calculating the initial radioactive inventory of used SrTreat®. This study carries out Sr sorption studies with acid-base titrations and X-ray photoelectron spectroscopy (XPS to characterize the properties. After exposure to simulated treated water for 99 h, the surface structure of the SrTreat® was changed, and the percentage of sorbed Sr and the buffer capacity for protons decreased. When the amount of radioactive nuclides contained in the used SrTreat® is calculated from the sorption data of the as-received SrTreat®, the radioactive Sr content will be overestimated with a concomitant increase in the deposition and disposal costs of the used SrTreat®.

Phosphate dynamics in an acidic mountain stream: Interactions involving algal uptake, sorption by iron oxide, and photoreduction

Science.gov (United States)

Tate, Cathy M.; Broshears, Robert E.; McKnight, Diane M.

1995-01-01

Acid mine drainage streams in the Rocky Mountains typically have few algal species and abundant iron oxide deposits which can sorb phosphate. An instream injection of radiolabeled phosphate (32P0,) into St. Kevin Gulch, an acid mine drainage stream, was used to test the ability of a dominant algal species, Ulothrix sp., to rapidly assimilate phosphate. Approximately 90% of the injected phosphate was removed from the water column in the 175-m stream reach. When shaded stream reaches were exposed to full sunlight after the injection ended, photoreductive dissolution of iron oxide released sorbed 32P, which was then also removed downstream. The removal from the stream was modeled as a first-order process by using a reactive solute transport transient storage model. Concentrations of 32P mass-’ of algae were typically lo-fold greater than concentrations in hydrous iron oxides. During the injection, concentrations of 32P increased in the cellular P pool containing soluble, low-molecular-weight compounds and confirmed direct algal uptake of 32P0, from water. Mass balance calculations indicated that algal uptake and sorption on iron oxides were significant in removing phosphate. We conclude that in stream ecosystems, PO, sorbed by iron oxides can act as a dynamic nutrient reservoir regulated by photoreduction.

Studies on treatment of low level radioactive liquid waste for removal of anionic species of 125Sb, 99Tc and 106Ru. Contributed Paper RD-14

International Nuclear Information System (INIS)

Shivakamy, K.; Chitra, S.; Rao, S.V.S.; Paul, Biplob

2014-01-01

The treatment of intermediate level waste at Waste Immobilization Plant generates low level radioactive waste which would require further management before discharge to sea. This waste is expected to contain polymeric oxo anions of 125 Sb, 99 Tc, 106 Ru in addition to cationic species like 137 Cs, 90 Sr etc. Chemical treatment takes care of the major contributors to radioactivity viz 137 Cs, 90 Sr etc but traces of activity due to anionic species remain in the treated waste effluent. Novel composite anionic exchanger namely Polyurethane foam coated with Hydrous Zirconium Oxide was developed for removal of these anionic species. This material was successfully employed for removal of anionic 1 25S b from radioactive waste effluent at Waste Management Division, Trombay. Based on our experience with Sb removal using the above material it was decided to assess the ability of the exchanger in removal of other anionic species bearing Ru and Tc. It was observed that in addition to complete removal of Sb, 50% Ru removal and 40% Tc could also be removed using this material from radioactive waste effluents. In lab experiments, similar results were obtained with simulated low level waste bearing inactive Ru. Among several hydrous oxides tried in a batch study, Hydrous Zirconium Oxide showed a maximum removal of 40% for Tc in actual waste generated from reprocessing plant. Based on the above it has been planned to set up an anion exchange column with Hydrous Zirconium Oxide coated Polyurethane foam for final treatment of chemically treated waste effluent prior to discharge as a prime step towards achieving our goal of minimum discharge to Sea. (author)

Cyclic voltammetric study of electro-oxidation of methanol on platinum electrode in acidic and neutral media

International Nuclear Information System (INIS)

Khan, A.S.A.; Ahmed, R.; Mirza, M.L.

2007-01-01

The electro-oxidation of methanol on electrochemically treated platinum foil was investigated in acidic and neutral media for comparison of cyclic voltammetric characteristics and elucidation of mechanism of electro-oxidation of methanol. The surface area and roughness factor of platinum electrode was calculated. The electro-oxidation of mathanol is an irreversible process giving. anodic peaks in both anodic and cathodic sweep. The characteristic peaks of electrooxidation of methanol appeared at almost the same potential region in both acidic and neutral media. In neutral medium, certain additional cathodic/anodic peaks appeared which were confirmed to arise by the reduction/oxidation of hydrogen ions. The exchange current density and heterogeneous electron transfer rate constant was higher in neutral medium as. compared with acidic medium. The thermodynamic parameters delta H, delta S, and delta G/sub 298/ were calculated. The values of delta H and delta G/sub 298/were positive which indicated that the process of electro-oxidation of methanol is an endothermic and nonspontaneous. The mechanism of electro-oxidation of methanol was same in both acidic and neutral media involving the formation of various adsorbed intermediate species through dissociative adsorption steps leading to the formation of Co adsorbed radicals, which are removed. during interaction with adsorbed hydrous oxides provided by the oxidation of adsorbed water molecules. The higher rate of electro-oxidation of methanol in neutral medium was interpreted in the tight of electrochemical mechanism and was attributed to the presence of comparatively small amount of hydrogen ions only along the surface of working electrode, which are produced during electro-oxidation of methanol. (author)

Crystal structure, equation of state, and elasticity of hydrous aluminosilicate phase, topaz-OH (Al2SiO4(OH)2) at high pressures

Science.gov (United States)

Mookherjee, Mainak; Tsuchiya, Jun; Hariharan, Anant

2016-02-01

We examined the equation of state and high-pressure elasticity of the hydrous aluminosilicate mineral topaz-OH (Al2SiO4(OH)2) using first principles simulation. Topaz-OH is a hydrous phase in the Al2O3-SiO2-H2O (ASH) ternary system, which is relevant for the mineral phase relations in the hydrated sedimentary layer of subducting slabs. Based on recent neutron diffraction experiments, it is known that the protons in the topaz-OH exhibit positional disorder with half occupancy over two distinct crystallographic sites. In order to adequately depict the proton environment in the topaz-OH, we examined five crystal structure models with distinct configuration for the protons in topaz-OH. Upon full geometry optimization we find two distinct space group, an orthorhombic Pbnm and a monoclinic P21/c for topaz-OH. The topaz-OH with the monoclinic P21/c space group has a lower energy compared to the orthorhombic Pbmn space group symmetry. The pressure-volume results for the monoclinic topaz-OH is well represented by a third order Birch-Murnaghan formulation, with V0mon = 348.63 (±0.04) Å3, K0mon = 164.7 (±0.04) GPa, and K0mon = 4.24 (±0.05). The pressure-volume results for the orthorhombic topaz-OH is well represented by a third order Birch-Murnaghan formulation, with V0orth = 352.47 (±0.04) Å3, K0orth = 166.4 (±0.06) GPa, and K0orth = 4.03 (±0.04). While the bulk moduli are very similar for both the monoclinic and orthorhombic topaz-OH, the shear elastic constants and the shear moduli are very sensitive to the position of the proton, orientation of the O-H dipole, and the space group symmetry. The S-wave anisotropy for the orthorhombic and monoclinic topaz-OH are also quite distinct. In the hydrated sedimentary layer of subducting slabs, transformation of a mineral assemblage consisting of coesite (SiO2) and diaspore (AlOOH) to topaz-OH (Al2SiO4(OH)2) is likely to be accompanied by an increase in density, compressional velocity, and shear wave velocity. However

Preparation of iron molybdate catalysts for methanol to formaldehyde oxidation based on ammonium molybdoferrate(II precursor

Directory of Open Access Journals (Sweden)

N.V. Nikolenko

2018-03-01

Full Text Available It was demonstrated that iron molybdate catalysts for methanol oxidation can be prepared using Fe(II as a precursor instead of Fe(III. This would allow for reduction of acidity of preparation solutions as well as elimination of Fe(III oxide impurities which are detrimental for the process selectivity. The system containing Fe(II and Mo(VI species in aqueous solution was investigated using UV–Vis spectroscopy. It was demonstrated that three types of chemical reactions occur in the Fe(II–Mo(VI system: (i formation of complexes between Fe(II and molybdate(VI ions, (ii inner sphere oxidation of coordinated Fe(II by Mo(VI and (iii decomposition of the Fe–Mo complexes to form scarcely soluble Fe(III molybdate, Mo(VI hydrous trioxide and molybdenum blue. Solid molybdoferrate(II prepared by interaction of Fe(II and Mo(VI in solution was characterized by EDXA, TGA, DTA and XRD and a scheme of its thermal evolution proposed. The iron molybdate catalyst prepared from Fe(II precursor was tested in methanol-to-formaldehyde oxidation in a continuous flow fixed-bed reactor to show similar activity and selectivity to the conventional catalyst prepared with the use of Fe(III.

Boosting water oxidation layer-by-layer.

Science.gov (United States)

Hidalgo-Acosta, Jonnathan C; Scanlon, Micheál D; Méndez, Manuel A; Amstutz, Véronique; Vrubel, Heron; Opallo, Marcin; Girault, Hubert H

2016-04-07

Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(III)/Ir(IV) and Ir(IV)-Ir(IV)/Ir(IV)-Ir(V) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology.

The solubility of Pd and Au in hydrous intermediate silicate melts: The effect of oxygen fugacity and the addition of Cl and S

Science.gov (United States)

Sullivan, Neal A.; Zajacz, Zoltan; Brenan, James M.

2018-06-01

The solubilities of Pd and Au in a hydrous trachyandesitic melt were experimentally determined at 1000 °C and 200 MPa at oxygen fugacity (ƒO2) from 0.45 log units below to 6.55 log units above the Ni-NiO buffer (NNO). The effect of adding metal-binding ligands (i.e. Cl and S) to the silicate melt was also studied. The solubility of Au increases from 0.15 ± 0.1 to 3.85 ± 1.48 ppm in Cl- and S-free melts with ƒO2 increasing from NNO-0.45 to NNO+6.55 with a slope that suggests that it is present in 1+ oxidation state over the entire studied ƒO2 range. On the other hand, Pd solubility, shows a more moderate increase with ƒO2, especially in the lower half of the studied range, increasing from 2.66 ± 0.25 ppm at NNO-0.45 to only 3.62 ± 0.38 ppm at NNO+1.72 in Cl- and S-free melts. Overall, the variation in Pd solubility as a function of ƒO2 indicates Pd being dissolved in the silicate melt in both zero and 1+ oxidation state, with the former being dominant below NNO+4.5. At NNO-0.45 to +3.48, the addition of 3170-4060 ppm Cl to the silicate melt increased the solubility of Au by an average factor of 1.5, in comparison to Cl-free melts. However, at NNO+6.55, Au solubility increased by a factor of 2.5. The addition of Cl had a negligible effect on the solubility of Pd except for a large increase (factor of 2.4) at NNO+6.55. At reducing conditions (NNO-0.45), the addition of 170 ppm S to the silicate melt increased the solubility of Au by a factor of ∼4 but did not change the solubility of Pd in comparison to S-free melts. The observation that Pd is dominantly present as Pd0 at NNO one may expect similar behavior in fluids degassing from magmas at depth, the lack of oxidized Pd species could be an important factor behind the scarcity of economically viable Pd-rich magmatic-hydrothermal deposits observed in nature.

Electrocatalytic oxidation of alcohols on single gold particles in highly ordered SiO2 cavities

International Nuclear Information System (INIS)

Li, Na; Zhou, Qun; Tian, Shu; Zhao, Hong; Li, Xiaowei; Adkins, Jason; Gu, Zhuomin; Zhao, Lili; Zheng, Junwei

2013-01-01

In the present work, we report a new and simple approach for preparing a highly ordered Au (1 1 1) nanoparticle (NP) array in SiO 2 cavities on indium-doped tin oxide (ITO) electrodes. We fabricated a SiO 2 cavity array on the surface of an ITO electrode using highly ordered self-assembly of polystyrene spheres as a template. Gold NPs were electrodeposited at the bottom of the SiO 2 cavities, and single gold NPs dominated with (1 1 1) facets were generated in each cavity by annealing the electrode at a high temperature. Such (1 1 1) facets were the predominate trait of the single gold particle which exhibited considerable electrocatalytic activity toward oxidation of methanol, ethanol, and glycerol. This has been attributed to the formation of incipient hydrous oxides at unusually low potential on the specific (1 1 1) facet of the gold particles. Moreover, each cavity of the SiO 2 possibly behaves as an independent electrochemical cell in which the methanol molecules are trapped; this produces an environment advantageous to catalyzing electrooxidation. The oxidation of methanol on the electrodes is a mixed control mechanism (both by diffusion and electrode kinetics). This strategy both provided an approach to study electrochemical reactions on a single particle in a microenvironment and may supply a way to construct alcohols sensors

Study of Dronino Iron Meteorite Weathering in Clay Sand Using Mössbauer Spectroscopy

Directory of Open Access Journals (Sweden)

Grigoriy A. Yakovlev

2016-06-01

Full Text Available Weathering products of two fragments of Dronino iron ungrouped meteorite found in the wet and drier clay sand were studied using X-ray diffraction and Mössbauer spectroscopy with a high velocity resolution. The products of metal oxidation in the internal and external surface layers were different for both fragments. The weathering products in fragment found in the wet clay sand contain magnetite (Fe3O4, maghemite (γ-Fe2O3, goethite (α-FeOOH and probably ferrihydrite (5Fe2O3∙9H2O while those in fragment found in drier clay sand contained ferric hydrous oxides (FeOOH and siderite (FeCO3 mainly. Concretions found near the first fragment contain ferric hydrous oxides (FeOOH mainly. This work is licensed under a Creative Commons Attribution 4.0 International License.

A Hydrous Seismogenic Fault Rock Indicating A Coupled Lubrication Mechanism

Science.gov (United States)

Okamoto, S.; Kimura, G.; Takizawa, S.; Yamaguchi, H.

2005-12-01

In the seismogenic subduction zone, the predominant mechanisms have been considered to be fluid induced weakening mechanisms without frictional melting because the subduction zone is fundamentally quite hydrous under low temperature conditions. However, recently geological evidence of frictional melting has been increasingly reported from several ancient accretionary prisms uplifted from seismogenic depths of subduction zones (Ikesawa et al., 2003; Austrheim and Andersen, 2004; Rowe et al., 2004; Kitamura et al., 2005) but relationship between conflicting mechanisms; e.g. thermal pressurization of fluid and frictional melting is still unclear. We found a new exposure of pseudotachylyte from a fossilized out-of-sequence thrust (OOST) , Nobeoka thrust in the accretionary complex, Kyushu, southwest Japan. Hanging-wall and foot-wall are experienced heating up to maximum temperature of about 320/deg and about 250/deg, respectively. Hanging-wall rocks of the thrust are composed of shales and sandstones deformed plastically. Foot-wall rocks are composed of shale matrix melange with sandstone and basaltic blocks deformed in a brittle fashion (Kondo et al, 2005). The psudotachylyte was found from one of the subsidiary faults in the hanging wall at about 10 m above the fault core of the Nobeoka thrust. The fault is about 1mm in width, and planer rupture surface. The fault maintains only one-time slip event because several slip surfaces and overlapped slip textures are not identified. The fault shows three deformation stages: The first is plastic deformation of phyllitic host rocks; the second is asymmetric cracking formed especially in the foot-wall of the fault. The cracks are filled by implosion breccia hosted by fine carbonate minerals; the third is frictional melting producing pseudotachylyte. Implosion breccia with cracking suggests that thermal pressurization of fluid and hydro-fracturing proceeded frictional melting.

Filamentous hydrous ferric oxide biosignatures in a pipeline carrying acid mine drainage at Iron Mountain Mine, California

Science.gov (United States)

Williams, Amy J.; Alpers, Charles N.; Sumner, Dawn Y.; Campbell, Kate M.

2017-01-01

A pipeline carrying acidic mine effluent at Iron Mountain, CA, developed Fe(III)-rich precipitate caused by oxidation of Fe(II)aq. The native microbial community in the pipe included filamentous microbes. The pipe scale consisted of microbial filaments, and schwertmannite (ferric oxyhydroxysulfate, FOHS) mineral spheres and filaments. FOHS filaments contained central lumina with diameters similar to those of microbial filaments. FOHS filament geometry, the geochemical environment, and the presence of filamentous microbes suggest that FOHS filaments are mineralized microbial filaments. This formation of textural biosignatures provides the basis for a conceptual model for the development and preservation of biosignatures in other environments.

Determination of the hydrogen isotopic compositions of organic materials and hydrous minerals using thermal combustion laser spectroscopy.

Science.gov (United States)

Koehler, Geoff; Wassenaar, Leonard I

2012-04-17

Hydrogen isotopic compositions of hydrous minerals and organic materials were measured by combustion to water, followed by optical isotopic analysis of the water vapor by off-axis integrated cavity output spectroscopy. Hydrogen and oxygen isotopic compositions were calculated by numerical integration of the individual isotopologue concentrations measured by the optical spectrometer. Rapid oxygen isotope exchange occurs within the combustion reactor between water vapor and molecular oxygen so that only hydrogen isotope compositions may be determined. Over a wide range in sample sizes, precisions were ±3-4 per mil. This is comparable but worse than continuous flow-isotope ratio mass spectroscopy (CF-IRMS) methods owing to memory effects inherent in water vapor transfer. Nevertheless, the simplicity and reduced cost of this analysis compared to classical IRMS or CF-IRMS methods make this an attractive option to determine the hydrogen isotopic composition of organic materials where the utmost precision or small sample sizes are not needed.

Adsorption of zinc(II) on hydrous iron oxides

International Nuclear Information System (INIS)

Music, S.; Ristic, M.

1992-01-01

The adsorption of Zn 2+ ions on amorphous Fe(OH 3 ) and α-Fe 2 O 3 , as a function of pH, has been investigated. In the pH region corresponding to the formation of positively charged Zn-hydroxy complexes, an abrupt increase in adsorption was observed. The influence of EDTA and glycine on the adsorption of Zn 2+ by α-Fe 2 O 3 has also been investigated. Strong suppression of the adsorption of Zn 2+ was observed for high [EDTA or Gly]/[Zn 2+ ] concentration ratios. The results of the adsorption of Zn 2+ in the presence of an organic ligand were explained by the formation of Zn-EDTA or Zn-glycine complexes and also by the occupation of adsorption sites by the free organic ligand. (author) 26 refs.; 6 figs

Effect of agglomeration during coprecipitation: Delayed ...

Indian Academy of Sciences (India)

Administrator

Department of Ceramic Technology, Government College of Engineering and Ceramic Technology,. Kolkata 700 ... Different wet chemical routes have been developed in the recent ..... magnesium with hydrous aluminium oxide, Ph D Thesis,.

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

Science.gov (United States)

Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.

2017-01-01

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

International Nuclear Information System (INIS)

Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

2009-01-01

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

Energy Technology Data Exchange (ETDEWEB)

Wen, Xiao-Ping; Dai, Hong-Bin, E-mail: mshbdai@scut.edu.cn; Wu, Lin-Song; Wang, Ping, E-mail: mspwang@scut.edu.cn

2017-07-01

Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N{sub 2}H{sub 4} electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N{sub 2}H{sub 4} as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

International Nuclear Information System (INIS)

Wen, Xiao-Ping; Dai, Hong-Bin; Wu, Lin-Song; Wang, Ping

2017-01-01

Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N_2H_4 electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N_2H_4 as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

Characterization of natural microporous metal-oxides: the case of todorokite ([Mn2+,Ca,Mg]Mn4+3O7.H2O)

International Nuclear Information System (INIS)

Godelitsas, A.; Misaelides, P; Katranas, T.; Klewe-Nebenius, H.; Triantafyllidis, C.; Pavlidou, E.; Anousis, I.

1998-01-01

Todorokite is a naturally occurring hydrous Mn-oxide exhibiting a complicated chemical composition. It shows a referred unusual crystal structure characterized by the presence of micropores (tunnels) with a free aperture of 0.69 x 0.69 nm and therefore exceptional physicochemical properties. In order to define the compositional and structural characteristics of the mineral and especially its physicochemical properties. For this purpose a number of characterization techniques were used including XRD, SEM-EDS, XRF, AAS, FT-IR, XPS, TPD, Z-potential measurements and TG/TDA combined with micro-porosimetry. The obtained results were compared to relevant ones concerning other natural microporous materials (e.g. clays, zeolites, micas) and were used to predict potential applications of the material.(author)

Association of radionuclides with streambed sediments in White Oak Creek watershed

International Nuclear Information System (INIS)

Spalding, B.P.; Cerling, T.E.

1979-09-01

Radionuclides are found in much higher concentrations on streambed sediment than in the water of White Oak Creek. Selective extraction of sediments demonstrates that 60 Co is immobilized in a nonexchangeable form in the ferromanganese hydrous oxide coatings on the sediments; 90 Sr occurs predominantly in an exchangeable form on clay, iron oxides, and ferromanganese hydrous oxides; 137 Cs occurs in a nonexchangeable and strongly bound form on clays which compose the dominant rock (Conasauga shale) in the watershed. The fine-gravel to coarse-sand size fraction of streambed sediments is the most suitable fraction for radionuclide analysis because of its abundance in the sediment and its high concentration of radionuclides compared to larger and smaller size fractions. A preliminary survey of all major tributes in White Oak Creek shows that radionuclide analysis of streambed sediments is a very useful technique to locate sources of radioactive contamination

BaSnF4 fast ion conductor: Variations versus the method of preparation and anomalous temperature variation of the quadrupole splitting

International Nuclear Information System (INIS)

Hantash, Jamil; Bartlett, Alan; Denes, Georges; Muntasar, Abdualhafeed; Oldfield, Philip

2005-01-01

A new method of preparation of high performance fluoride ion conductor, BaSnF 4 , by water leaching of newly discovered barium tin(II) chloride fluorides, has been designed, and the materials have been studied and compared to the solid prepared by the usual dry method. The unit-cell parameters and crystallite dimensions were found to vary with the method of preparation. In addition, the crystallite dimensions were found to be highly anisotropic for the samples obtained by the wet method. The Moessbauer spectrum is made of a large tin(II) quadrupole doublet, and a broad tin(IV) oxide peak due to surface oxidation. The tin(II) spectrum is in agreement with covalently bonded tin(II) having a strongly stereoactive lone pair. An unusually high dependence of the quadrupole splitting at low temperatures was observed (5.8 times larger than for α-SnF 2 ).

Environmental applications of chemically pure natural ferrihydrite

Czech Academy of Sciences Publication Activity Database

Filip, J.; Zbořil, R.; Schneeweiss, Oldřich; Zeman, J.; Černík, M.; Kvapil, P.; Otyepka, M.

2007-01-01

Roč. 41, č. 12 (2007), s. 4367-4374 ISSN 0013-936X R&D Projects: GA MŠk 1M0512 Institutional research plan: CEZ:AV0Z20410507 Keywords : hydrous ferric-oxide * acid - mine drainage * iron-oxide Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.363, year: 2007

Far infrared extinction coefficients of minerals of interest for astronomical observations

International Nuclear Information System (INIS)

Hasegawa, H.

1984-01-01

Far infrared extinction coefficients of mineral grains of interest for astronomical observations have been measured. The measured mineral species are: amorphous carbon, high temperature magnesium silicates, hydrous silicates, iron oxides, and amorphous silicates. (author)

seasonal variation in chromium hexavalent and copper

African Journals Online (AJOL)

Admin

Seasonal variation in heavy metal contamination of groundwater in the Jimeta- Yola area ... animal feedlots, industrial waste and food processing ...... and conservation of groundwater quality; a) ... significant role of hydrous Mn and Fe oxides.

New inorganic (an)ion exchangers with a higher affinity for arsenate and a competitive removal capacity towards fluoride, bromate, bromide, selenate, selenite, arsenite and borate

KAUST Repository

Chubar, Natalia

2011-01-01

Highly selective materials and effective technologies are needed to meet the increasingly stronger drinking water standards for targeted ionic species. Inorganic ion exchangers based on individual and mixed-metal hydrous oxides (or mixed adsorbents

Low temperature {sup 57}Fe Moessbauer study of cucumber root

Energy Technology Data Exchange (ETDEWEB)

Kovacs, K; Kuzmann, E; Homonnay, Z; Vertes, A [Institute of Chemistry, Eoetvoes Lorand University, PO Box 32, 1512 Budapest (Hungary); Fodor, F [Department of Plant Physiology and Molecular Plant Biology, Eoetvoes Lorand University, PO Box 32, 1512 Budapest (Hungary); Machala, L, E-mail: kkriszti@chem.elte.h [Centre for Nanomaterial Research, Palacky University, Svobody 26, Olomouc 771 46 (Czech Republic)

2010-03-01

Iron uptake and distribution in cucumber root were studied with the help of {sup 57}Fe Moessbauer spectroscopy at low temperature applying external magnetic field. Cucumber was grown in iron sufficient modified Hoagland nutrient solution. Moessbauer spectra of the frozen roots taken at 4.2 and 1.5 K, at 5 T external magnetic field support the identification of the main iron species (Fe{sup III}-carboxylates, hydrous ferric oxides, Fe{sup III}-sulfate-hydroxide) suggested according to its Moessbauer spectra taken between 35-200 K [1]. The magnetic ordering temperature of the hydrous ferric oxide and Fe{sup III}-sulfate-hydroxide was found to be in the range of 4.2-1.5 K, which suggests the incorporation of H{sub 3}O{sup +}, PO{sub 4}{sup 3-} and citrate into these minerals.

Synthesis and characterization of inorganic ion exchangers based on mixed oxide tin-titanium to be used in recovery of cadmium and nickel and photoluminescent studies

International Nuclear Information System (INIS)

Paganini, Paula Pinheiro

2007-01-01

This work presents the synthesis, characterization and adsorption studies of inorganic ion exchangers based on mixed tin-titanium oxide for recovery of cadmium and nickel metals from aqueous effluents, discarded in the environment mainly through Ni-Cd battery. The exchangers were synthesized by sol-gel modified method using a mixture of tin(IV) chloride and titanium(III) chloride and ammonium hydroxide, as precursors reagents. The materials obtained: SnO 2 /TiO 2 and SnO 2 /TiO 2 :Eu 3+ were characterized by infrared spectroscopy, thermal analysis, scattering electronic microscopy (SEM), X-ray powder diffraction (XRD) (powder method) and electronic spectroscopy (excitation and emission) for the europium doped exchanger. The same materials also were synthesized in polymeric matrix too and can be used in column, because the synthesized materials showed crystals size in nano metric scale. It was determined by the distribution ratios for metals taking as parameters the influence of pH, the concentration of metals (by adsorption isotherms) and the contact time (by adsorption kinetic). The inorganic ion exchanger presented high exchange capacity with adsorption percent above 90 por cent for the studied conditions, quickly kinetic, heterogeneous exchange surfaces, physic adsorption and spontaneous process of exchange. To the doped exchanger spectroscopy properties were studied and also it was calculated the intensity parameters and it was found a satisfactory quantum yield. (author)

Radium behaviour during ferric oxi-hydroxides crystallization

International Nuclear Information System (INIS)

Bassot, S.; Stammose, D.; Benitah, S.

2004-01-01

In uranium mill tailings, oxides and oxi-hydroxides are responsible of about 70% of the radium immobilization, half being associated to amorphous forms (mainly hydrous ferric oxides and hydrous manganese oxides). With time, crystallization of these amorphous forms can occur, inducing a redistribution of radium between solid and solution. If the amount of mobile radium increases, the impact of these tailings on the environment may become significant. The aim of this study is to determine the amount of radium released in solution during the crystallization process of hydrous ferric oxide (HFO). The transformation of Ra-HFO co-precipitate in crystallized forms (goethite, hematite, is studied by ageing at 40 deg C for different solution compositions. Both solids and solutions are sampled for different times and analysed. The solid evolution is followed by specific area measurements (about 250 m2/g for HFO and about 10-20 m 2 /g for crystallized form) and by determination of the amorphous fraction according to a selective extraction procedure. The solutions were analysed for 226 radium activity, iron concentration and pH. In order to discriminate the part of radium included in the solid and the part of radium fixed on the solid surface, radium sorption onto HFO and crystallized forms is studied as a function of pH. The modelling of the sorption curves with JCHESS 2.0 code allow to point out the mechanisms responsible of the 226-radium distribution between solid and solution during the crystallization process of HFO. (author)

Crystal chemistry and temperature behavior of the natural hydrous borate colemanite, a mineral commodity of boron

Science.gov (United States)

Lotti, Paolo; Gatta, G. Diego; Demitri, Nicola; Guastella, Giorgio; Rizzato, Silvia; Ortenzi, Marco Aldo; Magrini, Fabrizio; Comboni, Davide; Guastoni, Alessandro; Fernandez-Diaz, Maria Teresa

2018-05-01

Colemanite, CaB3O4(OH)3ṡH2O, is the most common hydrous Ca-borate, as well as a major mineral commodity of boron. In this study, we report a thorough chemical analysis and the low-temperature behavior of a natural sample of colemanite by means of a multi-methodological approach. From the chemical point of view, the investigated sample resulted to be relatively pure, its composition being very close to the ideal one, with only a minor substitution of Sr2+ for Ca2+. At about 270.5 K, a displacive phase transition from the centrosymmetric P21/ a to the acentric P21 space group occurs. On the basis of in situ single-crystal synchrotron X-ray (down to 104 K) and neutron diffraction (at 20 K) data, the hydrogen-bonding configuration of both the polymorphs and the structural modifications at the atomic scale at varying temperatures are described. The asymmetric distribution of ionic charges along the [010] axis, allowed by the loss of the inversion center, is likely responsible for the reported ferroelectric behavior of colemanite below the phase transition temperature.

Synthesis of Zn–Fe layered double hydroxides via an oxidation process and structural analysis of products

Energy Technology Data Exchange (ETDEWEB)

Morimoto, Kazuya, E-mail: kazuya.morimoto@aist.go.jp [Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 (Japan); Tamura, Kenji [Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Anraku, Sohtaro [Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Sato, Tsutomu [Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Suzuki, Masaya [Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 (Japan); Yamada, Hirohisa [Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

2015-08-15

The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn–Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species. - Graphical abstract: The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. - Highlights: • Iron valency affected the generation of Zn–Fe layered double hydroxides. • Zn–Fe layered double hydroxides were successfully synthesized using Fe(II). • Fe(II) species were likely to form trioctahedral hydroxide layers with Zn species.

Growth of Fe2O3/SnO2 nanobelt arrays on iron foil for efficient photocatalytic degradation of methylene blue

Science.gov (United States)

Lei, Rui; Ni, Hongwei; Chen, Rongsheng; Zhang, Bowei; Zhan, Weiting; Li, Yang

2017-04-01

Tin(IV) oxide has been intensively employed in optoelectronic devices due to its excellent electrical and optical properties. But the high recombination rates of the photogenerated electron-hole pairs of SnO2 nanomaterials often results in low photocatalytic efficiency. Herein, we proposed a facile route to prepare a novel Fe2O3/SnO2 heterojunction structure. The nanobelt arrays grown on iron foil naturally form a Schottky-type contact and provide a direct pathway for the photogenerated excitons. Hence, the Fe2O3/SnO2 nanobelt arrays exhibit much improved photocatalytic performance with the degradation rate constant on the Fe2O3/SnO2 film of approximately 12 times to that of α-Fe2O3 nanobelt arrays.

Electrochemical properties of mixed WC and Pt-black powders

Directory of Open Access Journals (Sweden)

MAJA D. OBRADOVIC

2008-12-01

Full Text Available The electrochemical characteristics of a mixture of Pt-black and WC powders and its catalytic activity for methanol and formic acid oxidation were investigated in acid solution. XRD and AFM measurements revealed that the WC powder employed for the investigation was a single-phase material consisting of crystallites/spherical particles of average size of about 50 nm, which were agglomerated into much larger particles. Cyclic voltammetry showed that the WC underwent electrochemical oxidation, producing tungstate species. In the case of the mixed Pt + WC powders, the tungstate species were deposited on the Pt as a thin film of hydrous tungsten oxide. Enhanced hydrogen intercalation in the hydrous tungsten oxide was observed and it was proposed to be promoted in mixed powders by the presence of hydrogen adatoms on bare Pt sites. The determination of Pt surface area in the Pt + WC layer by stripping of underpotentially deposited Cu revealed that the entire Pt surface was accessible for underpotential deposition of Cu. Investigation of the electrochemical oxidation of methanol and formic acid on Pt + WC and pure Pt layers did not indicate electrocatalytic promotion due to the presence of WC.

Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.

Science.gov (United States)

Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

2009-04-15

A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength.

New inorganic (an)ion exchangers with a higher affinity for arsenate and a competitive removal capacity towards fluoride, bromate, bromide, selenate, selenite, arsenite and borate

KAUST Repository

Chubar, Natalia

2011-12-01

Highly selective materials and effective technologies are needed to meet the increasingly stronger drinking water standards for targeted ionic species. Inorganic ion exchangers based on individual and mixed-metal hydrous oxides (or mixed adsorbents that contain inorganic ion exchangers in their composition) are adsorptive materials that are capable of lowering the concentrations of anionic contaminants, such as H 2AsO 4 -, H 3AsO 3, F -, Br -, BrO 3 -, HSeO 4 -, HSeO 3 - and H 3BO 3, to 10 μg/L or less. To achieve a higher selectivity towards arsenate, a new ion exchanger based on Mg-Al hydrous oxides was developed by a novel, cost-effective and environmentally friendly synthesis method via a non-traditional (alkoxide-free) sol-gel approach. The exceptional adsorptive capacity of the Mg-Al hydrous oxides towards H 2AsO 4 - (up to 200 mg[As]/gdw) is due to the high affinity of this sorbent towards arsenate (steep equilibrium isotherms) and its fast adsorption kinetics. Because of the mesoporous (as determined by N 2 adsorption and SEM) and layered (as determined by XRD and FTIR) structure of the ion-exchange material as well as the abundance of anion exchange sites (as determined by XPS and potentiometric titration) on its surface the material demonstrated very competitive (or very high) removal capacity towards other targeted anions, including fluoride, bromide, bromate, selenate, selenite, and borate. © 2011 IWA Publishing.

Treatment of dye wastewater with permanganate oxidation and in situ formed manganese dioxides adsorption: cation blue as model pollutant.

Science.gov (United States)

Liu, Ruiping; Liu, Huijuan; Zhao, Xu; Qu, Jiuhui; Zhang, Ran

2010-04-15

This study investigated the process of potassium permanganate (KMnO(4)) oxidation and in situ formed hydrous manganese dioxides (deltaMnO(2)) (i.e., KMnO(4) oxidation and deltaMnO(2) adsorption) for the treatment of dye wastewater. The effectiveness of decolorization, removing dissolved organic carbon (DOC), and increasing biodegradable oxygen demand (BOD) were compared among these processes of KMnO(4) oxidation, deltaMnO(2) adsorption, and KMnO(4) oxidation and deltaMnO(2) adsorption. DeltaMnO(2) adsorption contributed to the maximum DOC removal of 65.0%, but exhibited limited capabilities of decolorizing and increasing biodegradability. KMnO(4) oxidation alone at pH 0.5 showed satisfactory decrease of UV-vis absorption peaks, and the maximum BOD(5)/DOC value of 1.67 was achieved. Unfortunately, the DOC removal was as low as 27.4%. Additionally, the great amount of acid for pH adjustment and the much too low pH levels limited its application in practice. KMnO(4) oxidation and deltaMnO(2) adsorption at pH 2.0 was the best strategy prior to biological process, in balancing the objectives of decolorization, DOC removal, and BOD increase. The optimum ratio of KMnO(4) dosage to X-GRL concentration (R(KMnO(4)/X-GRL)) was determined to be 2.5, at which KMnO(4) oxidation and deltaMnO(2) adsorption contributed to the maximal DOC removal of 53.4%. Additionally, the optimum pH for X-GRL treatment was observed to be near 3.0. 2009 Elsevier B.V. All rights reserved.

Spat meta tial and als in w d temp water a Est poral v and se tuary ...

African Journals Online (AJOL)

sunny

reaches and the freshwater may flush heavy metals into the estuary from ..... food as well as from water (Shulkin et al., 2003; Silva et al., 2006). Various .... organic carbon, iron hydrous oxides and carbonates. ..... Conservation Area. Progress ...

Use of synthetic zeolites and other inorganic sorbents for the removal of radionuclides from aqueous wastes

International Nuclear Information System (INIS)

Samantha, S.K.; Singh, I.J.; Jain, S.; Sathi, S.; Venkatesan, K.; Ramaswamy, M.; Theyyunni, T.K.; Siddiqui, H.R.

1997-01-01

Several synthetic zeolites and inorganic sorbents were tested in the laboratory for the sorption of various radionuclides present in radioactive aqueous waste streams originating from nuclear installations. The sorption of the critical radionuclides like 137 Cs, 90 Sr and 60 Co from level waste solutions was studied using the synthetic zeolites 4A, 13X and AR1 of Indian origin. Granulated forms of ammonium molybdophosphate and CaSO 4 -BaSO 4 eutectoid were tested for the sorption of cesium and strontium respectively, from acidic solutions. The removal of radiostrontium from alkaline salt-loaded intermediate level reprocessing wastes was studied using hydrous ferric oxide-activated carbon composite sorbent, hydrous titania and hydrous manganese dioxide.. The results of these investigations are expected to be of value in formulating radioactive waste treatment schemes for achieving high decontamination and volume reduction factors. (author). 12 refs, 5 figs, 18 tabs

Melting of hydrous upper mantle and possible generation of andesitic magma: an approach from synthetic systems

Energy Technology Data Exchange (ETDEWEB)

Kushiro, I

1974-07-01

Phase equilibria in a portion of the system forsterite--plagioclase (An/sub 50/Ab/sub 50/ by weight)--silica--H/sub 2/O have been determined at 15 kbar pressure under H/sub 2/O-saturated conditions. The composition of the liquid pertinent to the piercing point forsterite + enstatite solid solution + amphibole + liquid + vapor is similar to that of calc-alkaline andesite. The electron microprobe analysis of the glass coexisting with the above three crystalline phases is very close to that of the piercing point determined by phase assemblage observations; however, the glass near (less than 8 ..mu..m) forsterite crystals is significantly depleted in the normative forsterite component. With the addition of 10 wt. percent KAlSi/sub 3/O/sub 8/, the composition of this piercing point becomes even closer to the compositions of calc-alkaline andesites. It is also shown that the liquid coexisting with forsterite and enstatite solid solution remains silica-rich (60 to 62 wt. percent) over a wide (approximately 100/sup 0/C) temperature range. The present experimental studies support the view that liquids similar in composition to calc-alkaline andesites can be generated by direct partial melting of hydrous upper mantle at least at or near 15 kbar.

(Liquid + liquid) equilibrium for systems composed of clove and allspice essential oil compounds and hydrous ethanol at T = 298.2 K

International Nuclear Information System (INIS)

Koshima, Cristina C.; Umeda, Thayla K.; Nakamoto, Karina T.; Venâncio, Larissa L.; Aracava, Keila K.; Rodrigues, Christianne E.C.

2016-01-01

Highlights: • A fraction enriched in oxyterpenes can be obtained via the deterpenation process. • Liquid extraction with hydrous ethanol can be applied to essential oil deterpenation. • Distribution coefficients of caryophyllene, methyl eugenol and eugenol were studied. • Eugenol has the highest distribution coefficient compared to the data in the literature. • Phase compositions were well described by the NRTL parameters. - Abstract: In the deterpenation process of essential oils, a fraction enriched in oxyterpenes is obtained. When compared to terpenic hydrocarbons, this fraction is more stable and soluble in water, maintaining the characteristic flavor and fragrance of the crude oil. Solvent extraction is an interestingly popular technique that is proposed for the fractionation of essential oils (once it can be performed under atmospheric pressure and ambient temperature) and contributes to the maintenance of the sensory quality of essential oils. The use of hydrous ethanol as a solvent for the (liquid + liquid) extraction process has shown advantages when the components of interest are completely soluble in ethanol, and their partition can be adjusted based on the level of hydration of the solvent. In addition, for some purposes, the fractions obtained from the separation process can be used without removing the solvent. Therefore, the primary goal of this study was to investigate the (liquid + liquid) equilibrium at T = (298.2 ± 0.1) K of model systems composed of (caryophyllene + eugenol + ethanol + water) (i.e., a clove essential oil model system) and (caryophyllene + methyl eugenol + eugenol + ethanol + water) (i.e., an allspice essential oil model system) to provide the information required for the proper design and optimization of the associated deterpenation processes. For both systems studied, it was noted that increased water content in the solvent decreases the extraction of the essential compounds and increases the selectivity of the

Supercapacitive performance of hydrous ruthenium oxide (RuO2 ...

Indian Academy of Sciences (India)

H2O) thin films by simple chemical bath deposition (CBD) method at low temperature on the stainless steel substrate. The prepared thin films are characterized for their structural and morphological properties by means of X-ray diffraction (XRD), ...

Supercapacitive performance of hydrous ruthenium oxide (RuO2 ...

Indian Academy of Sciences (India)

2016-08-26

SO4 electrolyte. RuO2.H2O film showed maximum specific capacitance of 192 F.g-1 at a scan rate of 20 mV.s-1. The charge–discharge studies of RuO2.H2O carried out at 300 A.cm-2 current density revealed the specific ...

Conversion of zircaloy to a massive chemically inert form

International Nuclear Information System (INIS)

Atkinson, A.; Kearsey, H.A.; Knibbs, R.H.; Mercer, A.C.; Nickerson, A.K.; Pearson, D.; Sambell, R.A.J.; Taylor, R.I.

1985-01-01

The report covers work carried out in the period July 1980 - December 1982 on the development and assessment of an aqueous route for the conversion of Zircaloy fuel element cladding to a stable oxide form and on alternative methods for incorporating the oxide into monolithic waste forms suitable for long-term storage and disposal. The work included two aspects, preliminary process development studies aimed at demonstrating the key steps in the process, and studies on the alternative immobilization techniques and the properties of the resulting waste forms. Experimental studies have shown that the ''hydrous zirconium oxide'' (with a residual fluoride content), following calcination at about 500 0 C, can be hot-pressed at 800-1000 0 C and 22.5 MPa to a high density ceramic waste form with good capacity for the incorporation of active species, such as U 4+ and Sr 2+ , and high leach resistance. Parallel studies have been carried out on the incorporation of the washed ''hydrous zirconium oxide'' in a range of cement matrices. A preliminary chemical engineering assessment of the overall process has been made and flowsheets for a plant to convert 250 kg Zircaloy/day have been prepared

Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water.

Science.gov (United States)

Wallis, Ilka; Prommer, Henning; Pichler, Thomas; Post, Vincent; Norton, Stuart B; Annable, Michael D; Simmons, Craig T

2011-08-15

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

A model of sulphur solubility for hydrous mafic melts: application to the determination of magmatic fluid compositions of Italian volcanoes

Directory of Open Access Journals (Sweden)

M. Pichavant

2005-06-01

Full Text Available We present an empirical model of sulphur solubility that allows us to calculate f S2 if P, T, fO2 and the melt composition, including H2O and S, are known. The model is calibrated against three main experimental data bases consisting in both dry and hydrous silicate melts. Its prime goal is to calculate the f S2 of hydrous basalts that currently lack experimental constraints of their sulphur solubility behaviour. Application of the model to Stromboli, Vesuvius, Vulcano and Etna eruptive products shows that the primitive magmas found at these volcanoes record f S2 in the range 0.1-1 bar. In contrast, at all volcanoes the magmatic evolution is marked by dramatic variations in f S2 that spreads over up to 9 orders of magnitude. The f S2 can either increase during differentiation or decrease during decompression to shallow reservoirs, and seems to be related to closed versus open conduit conditions, respectively. The calculated f S2 shows that the Italian magmas are undersaturated in a FeS melt, except during closed conduit conditions, in which case differentiation may eventually reach conditions of sulphide melt saturation. The knowledge of f S2, fO2 and fH2O allows us to calculate the fluid phase composition coexisting with magmas at depth in the C-O-H-S system. Calculated fluids show a wide range in composition, with CO2 mole fractions of up to 0.97. Except at shallow levels, the fluid phase is generally dominated by CO2 and H2O species, the mole fractions of SO2 and H2S rarely exceeding 0.05 each. The comparison between calculated fluid compositions and volcanic gases shows that such an approach should provide constraints on both the depth and mode of degassing, as well as on the amount of free fluid in magma reservoirs. Under the assumption of a single step separation of the gas phase in a closed-system condition, the application to Stromboli and Etna suggests that the main reservoirs feeding the eruptions and persistent

Target Transformation Constrained Sparse Unmixing (ttcsu) Algorithm for Retrieving Hydrous Minerals on Mars: Application to Southwest Melas Chasma

Science.gov (United States)

Lin, H.; Zhang, X.; Wu, X.; Tarnas, J. D.; Mustard, J. F.

2018-04-01

Quantitative analysis of hydrated minerals from hyperspectral remote sensing data is fundamental for understanding Martian geologic process. Because of the difficulties for selecting endmembers from hyperspectral images, a sparse unmixing algorithm has been proposed to be applied to CRISM data on Mars. However, it's challenge when the endmember library increases dramatically. Here, we proposed a new methodology termed Target Transformation Constrained Sparse Unmixing (TTCSU) to accurately detect hydrous minerals on Mars. A new version of target transformation technique proposed in our recent work was used to obtain the potential detections from CRISM data. Sparse unmixing constrained with these detections as prior information was applied to CRISM single-scattering albedo images, which were calculated using a Hapke radiative transfer model. This methodology increases success rate of the automatic endmember selection of sparse unmixing and could get more accurate abundances. CRISM images with well analyzed in Southwest Melas Chasma was used to validate our methodology in this study. The sulfates jarosite was detected from Southwest Melas Chasma, the distribution is consistent with previous work and the abundance is comparable. More validations will be done in our future work.

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2.

Science.gov (United States)

Konarev, Dmitri V; Troyanov, Sergey I; Shestakov, Alexander F; Yudanova, Evgeniya I; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-01-23

The reaction of tin(iv) phthalocyanine dichloride {Sn IV Cl 2 (Pc 2- )} with decamethylmetallocenes (Cp* 2 M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces Sn IV Cl 2 (Pc 2- ) to form the (Cp* 2 Co + ){Sn IV Cl 2 (Pc˙ 3- )}˙ - ·2C 6 H 4 Cl 2 (1) complex. The negative charge of {Sn IV Cl 2 (Pc˙ 3- )}˙ - is delocalized over the Pc macrocycle providing the alternation of the C-N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68μ B at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙ 3- macrocycles. These macrocycles form closely packed double stacks in 1 with effective π-π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of -80 K. Decamethylchromocene initially also reduces Sn IV Cl 2 (Pc 2- ) to form the [(Cp* 2 Cr + ){Sn VI Cl 2 (Pc˙ 3- )}˙ - complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp* 2 Cr by chloride anions originating from {Sn IV Cl 2 (Pc˙ 3- )}˙ - to form the complex {(Cp*CrCl 2 )(Sn IV (μ-Cl)(Pc 2- ))}·C 6 H 4 Cl 2 (2) in which the (Cp*CrCl 2 ) and {Sn IV (Pc 2- )} species are bonded through the μ-bridged Cl - anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp* 2 CrCl)(SnClPc)] complex.

Experimental investigation of changes in methane adsorption of bitumen-free Woodford Shale with thermal maturation induced by hydrous pyrolysis

Science.gov (United States)

Hu, Haiyan; Zhang, Tongwei; Wiggins-Camacho, Jaclyn D.; Ellis, Geoffrey S.; Lewan, Michael D.; Zhang, Xiayong

2014-01-01

This study quantifies the effects of organic-matter (OM) thermal maturity on methane (CH4) sorption, on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature Woodford Shale under five different time–temperature conditions. CH4-sorption isotherms at 35 °C, 50 °C, and 65 °C, and pressures up to 14 MPa on dry, solvent-extracted samples of the artificially matured Woodford Shale were measured. The results showed that CH4-sorption capacity, normalized to TOC, varied with thermal maturity, following the trend: maximum oil (367 °C) > oil cracking (400 °C) > maximum bitumen/early oil (333 °C) > early bitumen (300 °C) > immature stage (130 °C). The Langmuir constants for the samples at maximum-oil and oil-cracking stages are larger than the values for the bitumen-forming stages. The total pore volume, determined by N2 physisorption at 77 K, increases with increased maturation: mesopores, 2–50 nm in width, were created during the thermal conversion of organic-matter and a dramatic increase in porosity appeared when maximum-bitumen and maximum-oil generation stages were reached. A linear relationship between thermal maturity and Brunauer–Emmett–Teller (BET) surface area suggests that the observed increase in CH4-sorption capacity may be the result of mesopores produced during OM conversion. No obvious difference is observed in pore-size distribution and pore volume for samples with pores 2 physisorption at 273 K. The isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17.9 kJ mol−1 to 21.9 kJ mol−1 and from −85.4 J mol−1 K−1 to −101.8 J mol−1 K−1, respectively. These values are similar to the values of immature Woodford kerogen concentrate previously observed, but are larger than naturally matured organic-rich shales. High-temperature hydrous pyrolysis might have induced Lewis acid sites on both organic and mineral surfaces

Constraints on the Chemistry and Abundance of Hydrous Phases in Sub Continental Lithospheric Mantle: Implications for Mid-Lithospheric Discontinuities

Science.gov (United States)

Saha, S.; Dasgupta, R.; Fischer, K. M.; Mookherjee, M.

2017-12-01

The origins of a 2-10% reduction in seismic shear wave velocity (Vs) at depths of 60-160 km in sub continental lithospheric mantle (SCLM) regions, identified as the Mid Lithospheric Discontinuity (MLD) [e.g., 1] are highly debated [e.g., 2, 3]. One of the proposed explanations for MLDs is the presence of hydrous minerals such as amphibole and phlogopite at these depths [e.g., 2, 4, 5]. Although the stability and compositions of these phases in peridotite + H2O ± CO2 have been widely explored [e.g., 6], their composition and abundance as a function of permissible SCLM chemistry remain poorly understood. We have compiled phase equilibria experiments conducted over a range of pressure (0.5-8 GPa), temperature (680-1300 °C), major element peridotite compositions, and volatiles (H2O: 0.05-13.79 wt.% and CO2: 0.25-5.3 wt.%). The goal was to constrain how compositional parameters such as CaO and alkali/H2O affect the chemistry and abundance of amphibole and phlogopite. We observe that the abundance of amphibole increases with CaO content and decreasing alkali/H2O. The abundance of phlogopite varies directly with K2O content. Unlike phlogopite compositions that remain consistent, amphibole compositions show variability (pargastitic to K-richterite) depending on bulk CaO and Na2O. Mineral modes, obtained by mass balance on a melt/fluid free basis, were used to calculate aggregate shear wave velocity, Vs for the respective assemblages [e.g., 7] and compared with absolute values observed at MLD depths [e.g., 8]. Vs shows a strong inverse correlation with phlogopite and amphibole modes (particularly where phlogopite is absent). For the Mg# range of cratonic xenoliths, 5-10% phlogopite at MLD depths can match the observed Vs values, while CaO contents in cratonic xenoliths limit the amphibole abundance to 10%, which is lower than previous estimates based on heat flow calculations [e.g., 4]. The modes of hydrous and other phases and corresponding Vs values could be used to

A novel vanadium oxide deposit for the cathode of asymmetric lithium-ion supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Li, Jing-Mei; Hu, Chi-Chang [Department of Chemical Engineering, National Tsing Hua University, Hsin-Chu (China); Chang, Kuo-Hsin [Department of Chemical Engineering, National Chung Cheng University, Chia-Yi (China)

2010-12-15

Hydrous vanadium oxide (denoted as VO{sub x}.yH{sub 2}O) deposited at 0.4 V shows promising capacitive behavior in aqueous media containing concentrated Li ions. VO{sub x}.yH{sub 2}O annealed in air at 300 C for 1 h shows highly reversible Li-ion intercalation/de-intercalation behavior with specific capacitance reaching ca. 737 and 606 F g{sup -} {sup 1} at 25 and 500 mV s{sup -1} in 12 M LiCl between -0.2 and 0.8 V. In 14 M LiCl, retention of specific capacitance is about 95% when the scan rate is increased from 25 to 500 mV s{sup -} {sup 1}. This work is the first report showing the ultrahigh rate of Li-ion intercalation/de-intercalation in VO{sub x}.yH{sub 2}O. A so-called Li-ion supercapacitor of the asymmetric type consisting of a VO{sub x}.yH{sub 2}O cathode and a WO{sub 3}{sup .}zH{sub 2}O anode is proposed here. (author)

Phase chemistry and radionuclide retention from simulated tank sludges

International Nuclear Information System (INIS)

KRUMHANSL, JAMES L.; LIU, J.; ARTHUR, SARA E.; HUTCHERSON, SHEILA K.; QIAN, MORRIS; ANDERSON, HOWARD L.

2000-01-01

Decommissioning high level nuclear waste tanks will leave small amounts of residual sludge clinging to the walls and floor of the structures. The permissible amount of material left in the tanks depends on the radionuclide release characteristics of the sludge. At present, no systematic process exists for assessing how much of the remaining inventory will migrate, and which radioisotopes will remain relatively fixed. Working with actual sludges is both dangerous and prohibitively expensive. Consequently, methods were developed for preparing sludge simulants and doping them with nonradioactive surrogates for several radionuclides and RCRA metals of concern in actual sludges. The phase chemistry of these mixes was found to be a reasonable match for the main phases in actual sludges. Preliminary surrogate release characteristics for these sludges were assessed by lowering the ionic strength and pH of the sludges in the manner that would occur if normal groundwater gained access to a decommissioned tank. Most of the Se, Cs and Tc in the sludges will be released into the first pulse of groundwater passing through the sludge. A significant fraction of the other surrogates will be retained indefinitely by the sludges. This prolonged sequestration results from a combination coprecipitated and sorbed into or onto relatively insoluble phases such as apatite, hydrous oxides of Fe, Al, Bi and rare earth oxides and phosphates. The coprecipitated fraction cannot be released until the host phase dissolves or recrystallizes. The sorbed fraction can be released by ion exchange processes as the pore fluid chemistry changes. However, these releases can be predicted based on a knowledge of the fluid composition and the surface chemistry of the solids. In this regard, the behavior of the hydrous iron oxide component of most sludges will probably play a dominant role for many cationic radionuclides while the hydrous aluminum oxides may be more important in governing anion releases

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

Science.gov (United States)

Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

2016-06-01

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental investigation of hydrous pyrolysis of diesel fuel and the effect of pyrolysis products on performance of the candidate nuclear waste repository at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Jackson, K.J.; Carroll, S.A.

1994-01-01

It is thought that a significant amount of diesel fuel and other hydrocarbon-rich phases may remain inside the candidate nuclear waste repository at Yucca Mountain after construction and subsequent emplacement of radioactive waste. Although the proposed repository horizon is above the water table, the remnant hydrocarbon phases may react with hydrothermal solutions generated by high temperature conditions that will prevail for a period of time in the repository. The preliminary experimental results of this study show that diesel fuel hydrous pyrolysis is minimal at 200 degrees C and 70 bars. The composition of the diesel fuel remained constant throughout the experiment and the concentration of carboxylic acids in the aqueous phases was only slightly above the detection limit (1-2 ppm) of the analytical technique

Colloidal nature of radionuclides in seawater

International Nuclear Information System (INIS)

Feldman, I.

1976-01-01

There is considerable doubt that equilibrium calculations, i.e., employing solubility products and complex-ion stability constants, are valid for the submicro concentrations of radionuclides in seawater. The existence of radiocolloids should be expected in seawater. The great tendency of radiocolloids to adsorb onto finely-divided hydrous oxides makes their formation of significance in seawater, especially for artificial radionuclides. The subject of radiocolloid formation is reviewed in this chapter. It is shown that the 226 Ra/ 230 Th/U relationship found in seawater can be explained from the fact that the tendencies of these elements to form radiocolloids in seawater should decrease in order thorium > radium much greater than uranium. This explanation is much simpler than the prevailing oceanographic one. The theories for radiocolloid formation are discussed. The recent theory of Jones and Healy for the adsorption of hydrolyzable metal ions onto hydrous oxides is reviewed briefly, and its relevance to radiocolloid formation is pointed out

Structure of short-range-ordered iron(III)-precipitates formed by iron(II) oxidation in water containing phosphate, silicate, and calcium

Science.gov (United States)

Voegelin, A.; Frommer, J.; Vantelon, D.; Kaegi, R.; Hug, S. J.

2009-04-01

The oxidation of Fe(II) in water leads to the formation of Fe(III)-precipitates that strongly affect the fate of nutrients and contaminants in natural and engineered systems. Examples include the cycling of As in rice fields irrigated with As-rich groundwater or the treatment of drinking water for As removal. Knowledge of the types of Fe(III)-precipitates forming in such systems is essential for the quantitative modeling of nutrient and contaminant dynamics and for the optimization of water purification techniques on the basis of a mechanistic understanding of the relevant biogeochemical processes. In this study, we investigated the local coordination of Fe, P, and Ca in Fe(III)-precipitates formed by aeration of synthetic Fe(II)-containing groundwater with variable composition (pH 7, 2-30 mg/L Fe(II), 2-20 mg/L phosphate-P, 2-20 mg/L silicate-Si, 8 mM Na-bicarbonate or 2.5 mM Ca-&1.5 mM Mg-bicarbonate). After 4 hours of oxidation, Fe(III)-precipitates were collected on 0.2 µm nylon filters and dried. The precipitates were analyzed by Fe K-edge EXAFS (XAS beamline, ANKA, Germany) and by P and Ca K-edge XANES spectroscopy (LUCIA beamline, SLS, Switzerland). The Fe K-edge EXAFS spectra indicated that local Fe coordination in the precipitates systematically shifted with water composition. As long as water contained P, mainly short-range-ordered Fe(III)-phosphate formed (with molar P/Fe ~0.5). In the absence of P, Fe(III) precipitated as hydrous ferric oxide at high Si/Fe>0.5, as ferrihydrite at intermediate Si/Fe, and mainly as lepidocrocite at Si/Fe<0.2. Analysis of the EXAFS by shell-fitting indicated that Fe(III)-phosphates mainly contained mono- or oligomeric (edge- or corner-sharing) Fe and that the linkage between neighboring Fe(III)-octahedra changed from predominantly edge-sharing in Si-rich hydrous ferric oxide to edge- and corner-sharing in ferrihydrite. Electron microscopic data showed that changes in local precipitate structure were systematically

Role of binder in the synthesis of titania membrane

Indian Academy of Sciences (India)

Unknown

Abstract. The synthesis of titania membrane through sol–gel route involves hydrolysis of alkoxide, peptization of hydrous oxide of titanium to obtain a sol, adjustment of the sol viscosity by including a binder and filtration of the viscous sol through a microporous support, gelation and sintering to desired temperature.

Exploratory experiments to determine the effect of operational parameters on the efficiency of Subsurface Arsenic Removal (SAR) in rural Bangladesh

NARCIS (Netherlands)

Rhaman, M.; Bakker, M.; Borges Freitas, S.; Halem, D.; van Breukelen, B.M.; Ahmed, K.; Badruzzaman, A.B.

2015-01-01

The principle of subsurface arsenic (As) removal (SAR) is to extract anoxic groundwater, aerate it and re-inject it. Oxygen in the injected water reacts with iron in the resident groundwater to form hydrous ferric oxide (HFO). Dissolved As sorbs onto the HFO, which allows for the extraction of

Field Experiments and Reactive Transport Modeling of Subsurface Arsenic Removal in Bangladesh

NARCIS (Netherlands)

Rahman, M.M.

2017-01-01

The principle of Subsurface Arsenic (As) Removal (SAR) is to extract anoxic groundwater, aerate it and reinject it. Oxygen in the injected water reacts with iron in the resident groundwater to form hydrous ferric oxide (HFO). Dissolved As sorbs onto the HFO, which allows for the extraction of

Phase relations in the hydrous CMAS pyrolite in presence of KCl at 2 GPa

Science.gov (United States)

Safonov, O.

2012-04-01

In the upper mantle, chlorides are constituents of concentrated aqueous solutions (brines), as well as chloride-carbonate and carbonatite melts. Mineral assemblages coming from diverse depth levels show that mobile (K, Na)Cl-bearing fluids are able to provoke intensive metasomatism of the peridotitic mantle accompanied by melting. Scarce experimental studies on influence of brines on mineral equilibria in the peridotitic mantle (Stalder et al., 2008; Chu et al., 2011) indicate that influence of chlorides on water activity in a fluid equilibrated with forsterite enstatite at pressures above 2 GPa is very similar to their effect at lower "crustal" pressures (e.g. Aranovich, Newton, 1997): decrease of the H2O activity with an increase of the salt content results in an increase of the melting temperature of silicates. Nevertheless, these experiments were performed in the Al-free systems. Presence of Al would provoke an active interaction of alkali chlorides, namely KCl, with silicates with formation of new K-Al-bearing phases, such as phlogopite (in presence of H2O), which would influence on the melting of complex assemblages. In order to investigate an effect of KCl on phase relations in the Al2O3, CaO, Na2O-rich hydrous peridotite and on stability of garnet, pyroxenes, and amphiboles, in particular, experiments on interaction of the model CMAS pyrolite Fo57En17Prp14Di12 (+0.3 wt. % of Na2O) with the H2O-KCl fluid were performed at 2 GPa in the temperature interval 900-1200. Mixtures of synthetic forsterite, diopside, enstatite and pyrope in the above weight ratio were mixed with 14 wt. % of Mg(OH)2 corresponding to 4.4 wt. % of H2O in the system. 2.4, 3.7, 5 and 10 wt. % of KCl were added to silicate-H2O mixture. Experiments were performed using a piston-cylinder apparatus with ½-inch talc high-pressure cells calibrated via brucite = periclase + H2O and albite = jadeite + quartz equilibria curves. Temperature was controlled with accuracy ?1 with the W95Re5/W80Re20

The effects of hydrous ethanol gasoline on combustion and emission characteristics of a port injection gasoline engine

Directory of Open Access Journals (Sweden)

Xiaochen Wang

2015-09-01

Full Text Available Comparative experiments were conducted on a port injection gasoline engine fueled with hydrous ethanol gasoline (E10W, ethanol gasoline (E10 and pure gasoline (E0. The effects of the engine loads and the additions of ethanol and water on combustion and emission characteristics were analyzed deeply. According to the experimental results, compared with E0, E10W showed higher peak in-cylinder pressure at high load. Increases in peak heat release rates were observed for E10W fuel at all the operating conditions. The usage of E10W increased NOX emissions at a wide load range. However, at low load conditions, E10W reduced HC, CO and CO2 emissions significantly. E10W also produced slightly less HC and CO emissions, while CO2 emissions were not significantly affected at higher operating points. Compared with E10, E10W showed higher peak in-cylinder pressures and peak heat release rates at the tested operating conditions. In addition, decreases in NOX emissions were observed for E10W from 5 Nm to 100 Nm, while HC, CO and CO2 emissions were slightly higher at low and medium load conditions. From the results, it can be concluded that E10W fuel can be regarded as a potential alternative fuel for gasoline engine applications.

Synthesis and crystal structure of an oxovanadium(IV) complex with a pyrazolone ligand and its use as a heterogeneous catalyst for the oxidation of styrene under mild conditions.

Science.gov (United States)

Parihar, Sanjay; Pathan, Soyeb; Jadeja, R N; Patel, Anjali; Gupta, Vivek K

2012-01-16

1-Phenyl-3-methyl-4-touloyl-5-pyrazolone (ligand) was synthesized and used to prepare an oxovanadium(IV) complex. The complex was characterized by single-crystal X-ray analysis and various spectroscopic techniques. The single-crystal X-ray analysis of the complex shows that the ligands are coordinated in a syn configuration to each other and create a distorted octahedral environment around the metal ion. A heterogeneous catalyst comprising an oxovanadium(IV) complex and hydrous zirconia was synthesized, characterized by various physicochemical techniques, and successfully used for the solvent-free oxidation of styrene. The influence of the reaction parameters (percent loading, molar ratio of the substrate to H(2)O(2), amount of catalyst, and reaction time) was studied. The catalyst was reused three times without any significant loss in the catalytic activity.

thin films

Indian Academy of Sciences (India)

microscopy (SEM) studies, respectively. The Fourier transform ... Thin films; chemical synthesis; hydrous tin oxide; FTIR; electrical properties. 1. Introduction ... dehydrogenation of organic compounds (Hattori et al 1987). .... SEM images of (a) bare stainless steel and (b) SnO2:H2O thin film on stainless steel substrate at a ...

sharptooth catfish

African Journals Online (AJOL)

2010-02-28

Feb 28, 2010 ... metal toxicity (Muramoto, 1980; James et al., 1998). Effects of ...... non-nutritive molecules (Hopson and Wessels, 1990; Sorensen,. 1991; Kimball, 1983) ..... DURAL M, GÖKSU MZL and ÖZAK AA (2007) Investigation of heavy metal ... HEM JD (1977) Reactions of metal ions at surfaces of hydrous iron oxide.

Alternative solid forms for Savannah River Plant defense waste

International Nuclear Information System (INIS)

Stone, J.A.; Goforth, S.T.; Smith, P.K.

1980-01-01

Solid forms and processes were evaluated for immobilization of SRP high-level radioactive waste, which contains bulk chemicals such as hydrous iron and aluminium oxides. Borosilicate glass currently is the best overall choice. High-silica glass, tailored ceramics, and coated ceramics are potentially superior products, but require more difficult processes

Thermal behaviour of iron (II) oxalate dihydrate in the atmosphere of its conversion gases

Czech Academy of Sciences Publication Activity Database

Heřmánek, M.; Zbořil, R.; Mašláň, M.; Machala, L.; Schneeweiss, Oldřich

2006-01-01

Roč. 16, č. 13 (2006), s. 1273-1280 ISSN 0959-9428 R&D Projects: GA MŠk 1M0512 Institutional research plan: CEZ:AV0Z20410507 Keywords : hydrous ferrous oxalate * oxide nanoparticles * crystal-structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.287, year: 2006

The role of volatile-saturation and adiabatic ascent of moderately hydrous melts on the formation of orbicules and comb layers in shallow subvolcanic conduits (Fisher Lake, Sierra Nevada).

Science.gov (United States)

McCarthy, A. J.; Müntener, O.

2016-12-01

Orbicules and comb layers are enigmatic features found sparsely distributed along plutonic contacts in a wide range of igneous environments. We provide new insights into the mechanisms responsible for the formation of these features by studying the spatial distribution, mineralogy and geochemistry of comb layers and orbicules from the Northern Sierra Nevada, Fisher Lake (USA). Over a range of studied comb textured layering, we show that the large majority of comb layers are cumulates formed by the initiation of plagioclase growth as a comb textured mineral. Plagioclase fractionation is followed by pyroxenes + oxides fractionation. Continuous crystal fractionation and conductive cooling from the host rock leads to amphibole saturation and the formation of late stage comb textured amphibole, leading to the formation of plagioclase- and plagioclase-amphibole comb textures. The lack of amphibole comb textures on orbicule rims as opposed to their widespread occurrence in comb layers, suggests that the presence of a thermal gradient plays an important role in diversifying comb textures. We propose that comb layers and orbicules are unique features which are controlled by the volatile content of ascending melts and ascent mechanisms. Thermodynamic calculations indicate that near-adiabatic decompression of water-undersaturated melts (ca. 4wt% H2O) through the crust will lead to superheating and dissolution of pre-existing minerals. Upon saturation of volatiles at shallow depth, degassing-induced undercooling of the decompressing melt will trigger heterogeneous nucleation of plagioclase on host rocks and remobilized xenoliths. The rarity of orbicules and comb layers in volcanic and plutonic rocks worldwide suggests that adiabatic decompression of moderately hydrous melts leading to superheating is a rare phenomena, with most arc melts ascending and cooling in small reservoirs throughout the crust, prior to emplacement at shallow depth as crystal-bearing magmas.

Sorption behaviour of uranium and thorium on hydrons tin oxide from aqueous and mixed-solvent H2SO4 media

International Nuclear Information System (INIS)

Misak, N.Z.; Salema, H.N.; El-Naggar, J.M.

1983-01-01

At pH values > about 2 in 10 -3 -10 -2 M aqueous sulphate solutions, uranium seems to be sorbed by hydrous tin oxide mainly as cations, while thorium is sorced as cations and as the neutral complex. At pH values of about 1.1-1.4, both uranium and thorium seem to be mainly sorbed as the neutral complexes. while at lower pH values, sorption of anionic commplexes comes into play. The sorption of uranium generally increased progressively on addition of increasing amounts of methanol, ethanol or acetone. The sorption of thorium decreases a little at 0.01 N H 2 SO 4 and increases a little at 0.5 N H 2 SO 4 on adding the organic solvents. At 0.1 N H 2 SO 4 , the addition of 20percent of the organic solvents brings the sorption of thorium to almost negligible values, which seems to offer an attractive means for U/Th separation. (author)

Optimization of strontium adsorption from aqueous solution using (mn-Zr) oxide-pan composite spheres

International Nuclear Information System (INIS)

Inan, S.; Altas, Y.

2009-01-01

The processes based on adsorption and ion exchange have a great role for the pre-concentration and separation of toxic, long lived radionuclides from liquid waste. In Nuclear waste management, the removal of long lived, radiotoxic isotopes from radioactive waste such as strontium reduces the storage problems and facilitates the disposal of the waste. Depending on the waste type, a variety of adsorbents and/or ion exchangers are used. Due to the amorphous structure of hydrous oxides and their mixtures, they don't have reproducible properties. Besides, obtained powders are very fine particles and they can cause operational problems such as pressure drop and filtration. Therefore they are not suitable for column applications. These reasons have recently expedited the study on the preparation of organic-inorganic composite adsorbent beads for industrial applications. PAN, as a stable and porous support for fine particles, provides the utilization of ion exchangers in large scale column applications. The utilization of PAN as a support material with many inorganic ion exchangers was firstly achieved by Sebesta in the beginning of 1990's. Later on, PAN based composite ion exchangers were prepared and used for the removal of radionuclides and heavy metal ions from aqueous solution and waste waters. In this study, spherical (Mn-Zr)oxide-PAN composite were prepared for separation of strontium from aqueous solution in a wide pH range. Sr 2 + adsorption of composite adsorbent was optimized by using experimental design 'Central Composite Design' model.

Role of binder in the synthesis of titania membrane

Indian Academy of Sciences (India)

The synthesis of titania membrane through sol–gel route involves hydrolysis of alkoxide, peptization of hydrous oxide of titanium to obtain a sol, adjustment of the sol viscosity by including a binder and filtration of the viscous sol through a microporous support, gelation and sintering to desired temperature. The binder plays ...

Bulletin of Materials Science | Indian Academy of Sciences

Indian Academy of Sciences (India)

Preparation and characterization of DLC/SiO2/Al2O3 nanofiltration membrane .... Supercapacitive performance of hydrous ruthenium oxide (RuO2. .... transport studies of RAgSn2 compounds (R = Y, Tb, Dy, Ho and Er) with Cu3Au-type .... Structural characterization and complex impedance studies on fast ion conducting ...

Fabrication of polymer-supported nanosized hydrous manganese dioxide (HMO) for enhanced lead removal from waters

International Nuclear Information System (INIS)

Su, Qing; Pan, Bingcai; Pan, Bingjun; Zhang, Qingrui; Zhang, Weiming; Lv, Lu; Wang, Xiaoshu; Wu, Jun; Zhang, Quanxing

2009-01-01

In the current study, a new hybrid adsorbent HMO-001 was fabricated by impregnating nanosized hydrous manganese dioxide (HMO) onto a porous polystyrene cation exchanger resin (D-001) for enhanced lead removal from aqueous media. D-001 was selected as a support material mainly because of the potential Donnan membrane effect exerted by the immobilized negatively charged sulfonic acid groups bound to the polymeric matrix, which would result in preconcentration and permeation enhancement of lead ions prior to their effective sequestration by the impregnated HMO. HMO-001 was characterized by scanning electron micrograph (SEM), transmission electron micrograph (TEM), and X-ray diffraction (XRD). Lead adsorption onto HMO-001 was dependent upon solution pH due to the ion-exchange nature, and it can be represented by the Freundlich isotherm model and pseudo-first order kinetic model well. The maximum capacity of HMO-001 toward lead ion was about 395 mg/g. As compared to D-001, HMO-001 exhibited highly selective lead retention from waters in the presence of competing Ca 2+ , Mg 2+ , and Na + at much greater levels than the target toxic metal. Fixed-bed column adsorption of a simulated water indicated that lead retention on HMO-001 resulted in a conspicuous decrease of this toxic metal from 1 mg/L to below 0.01 mg/L (the drinking water standard recommended by WHO). The exhausted adsorbent particles are amenable to efficient regeneration by the binary NaAc-HAc solution for repeated use without any significant capacity loss. All the results validated the feasibility of HMO-001 for highly effective removal of lead from contaminated waters.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences; Volume 114; Issue 6. A new family of donor-acceptor systems comprising tin(IV) porphyrin and anthracene subunits: Synthesis, spectroscopy and energy transfer studies. A Ashok Kumar L Giribabu Bhaskar G Maiya. Volume 114 Issue 6 December 2002 pp 565-578 ...

AUTHOR INDEX

Indian Academy of Sciences (India)

Unknown

697. Kommana Praveen see Kumaraswamy K C. 367. Koraiem A I M see Shindy H A. 125. Krishnamurthy S Setharampattu see Raghuraman Kannan. 233. Kumar A Ashok. A new family of donor–acceptor systems comprising of tin(IV) porphyrin and anthracene subunits: Synthesis spectroscopy and energy transfer studies.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO2(AsO3OH)(AsO2(OH)2)]·H2O and anhydrous Rb[UO2(AsO3OH)(AsO2(OH)2)

International Nuclear Information System (INIS)

Yu, Na; Klepov, Vladislav V.; Villa, Eric M.; Bosbach, Dirk; Suleimanov, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.; Alekseev, Evgeny V.

2014-01-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )]·H 2 O (α-, β-RbUAs) and the anhydrous phase Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )] and α- and β- Rb[UO 2 (AsO 3 OH)(AsO 2 (OH) 2 )]·H 2 O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration

Organodioxygen complexes of some group 4B metal ions

International Nuclear Information System (INIS)

Tarafder, M.T.H.; Akhter Hossain; Gino Mariotto

2003-09-01

Organodioxygen complexes of some group 4B metal ions, viz., zirconium(IV), tin(IV) and lead(II) containing monodentate, bidentate and tridentate ligands were synthesized and characterized. The complexes have the compositions of [Zr(O)(O 2 )2C 5 H 5 N.H 2 O], [Zr(O)(O 2 - ) 2 .2OPPh 3 ], [Sn(O 2 )(C 9 H 6 NO) 2 ], [Sn(0 2 ) 2 .(CH 2 ) 2 (NH 2 ) 2 ], [Pb(O 2 - )(C 5 H 5 N) 2 NO 3 ], [Pb(O 2 )(C 8 H 6 NOH)], [Pb(O 2 - )(det)NO 3 ] and [PbO 2 - ) (C 5 H 4 NCOOH)NO 3 .H 2 O]. Because of apparent linearity of M- O 2 grouping, the V 1 (O-O) stretching modes were only Raman active, giving bands at 810- 841 cm 1 for the peroxo complexes (1, 3, ,4 and 6), while the bands in the superoxo complexes (2, 5, 7 and 8) appeared at 1020- 1100 cm -1 . The peroxo complex of Zr(IV) containing monodentate ligands were found to oxidize trans-stilbene to trans-stilbene oxide under stoichiometric conditions. The organoperoxo complexes of tin and lead were insensitive to oxidative processes. (author)

Diel cycles in dissolved barium, lead, iron, vanadium, and nitrite in a stream draining a former zinc smelter site near Hegeler, Illinois

Science.gov (United States)

Kay, R.T.; Groschen, G.E.; Cygan, G.; Dupre, David H.

2011-01-01

Diel variations in the concentrations of a number of constituents have the potential to substantially affect the appropriate sampling regimen in acidic streams. Samples taken once during the course of the day cannot adequately reflect diel variations in water quality and may result in an inaccurate understanding of biogeochemical processes, ecological conditions, and of the threat posed by the water to human health and the associated wildlife. Surface water and groundwater affected by acid drainage were sampled every 60 to 90. min over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, near Hegeler, Illinois. Diel variations related to water quality in the aquifer were not observed in groundwater. Diel variations were observed in the temperature, pH, and concentration of dissolved oxygen, nitrite, barium, iron, lead, vanadium, and possibly uranium in surface water. Temperature, dissolved oxygen, nitrite, barium, lead, and uranium generally attained maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally attained minimum values during the afternoon and maximum values during the night. Concentrations of dissolved oxygen were affected by the intensity of photosynthetic activity and respiration, which are dependent upon insolation. Nitrite, an intermediary in many nitrogen reactions, may have been formed by the oxidation of ammonium by dissolved oxygen and converted to other nitrogen species as part of the decomposition of organic matter. The timing of the pH cycles was distinctly different from the cycles found in Midwestern alkaline streams and likely was the result of the photoreduction of Fe3+ to Fe 2+ and variations in the intensity of precipitation of hydrous ferric oxide minerals. Diel cycles of iron and vanadium also were primarily the result of variations in the intensity of precipitation of hydrous ferric oxide minerals. The diel variation in the concentrations of lead, uranium

P R Deshmukh

Indian Academy of Sciences (India)

Home; Journals; Bulletin of Materials Science. P R Deshmukh. Articles written in Bulletin of Materials Science. Volume 34 Issue 6 October 2011 pp 1179-1183. Chemical synthesis and characterization of hydrous tin oxide (SnO2:H2O) thin films · S N Pusawale P R Deshmukh C D Lokhande · More Details Abstract Fulltext ...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

pp 565-578. A new family of donor-acceptor systems comprising tin(IV) porphyrin and anthracene subunits: Synthesis, spectroscopy and energy transfer studies · A Ashok Kumar L Giribabu Bhaskar G Maiya · More Details Abstract Fulltext PDF. A new family of covalently linked `Sn(IV) porphyrin-anthracene' diad (1), triad (2) ...

Synthesis and characterization of inorganic ion exchangers based on mixed oxide tin-titanium to be used in recovery of cadmium and nickel and photoluminescent studies; Sintese e caracterizacao de trocadores ionicos inorganicos a base de oxidos mistos estanho-titanio para utilizacao na recuperacao de cadmio e niquel e estudos fotoluminescentes

Energy Technology Data Exchange (ETDEWEB)

Paganini, Paula Pinheiro

2007-07-01

This work presents the synthesis, characterization and adsorption studies of inorganic ion exchangers based on mixed tin-titanium oxide for recovery of cadmium and nickel metals from aqueous effluents, discarded in the environment mainly through Ni-Cd battery. The exchangers were synthesized by sol-gel modified method using a mixture of tin(IV) chloride and titanium(III) chloride and ammonium hydroxide, as precursors reagents. The materials obtained: SnO{sub 2}/TiO{sub 2} and SnO{sub 2}/TiO{sub 2}:Eu{sup 3+} were characterized by infrared spectroscopy, thermal analysis, scattering electronic microscopy (SEM), X-ray powder diffraction (XRD) (powder method) and electronic spectroscopy (excitation and emission) for the europium doped exchanger. The same materials also were synthesized in polymeric matrix too and can be used in column, because the synthesized materials showed crystals size in nano metric scale. It was determined by the distribution ratios for metals taking as parameters the influence of pH, the concentration of metals (by adsorption isotherms) and the contact time (by adsorption kinetic). The inorganic ion exchanger presented high exchange capacity with adsorption percent above 90 por cent for the studied conditions, quickly kinetic, heterogeneous exchange surfaces, physic adsorption and spontaneous process of exchange. To the doped exchanger spectroscopy properties were studied and also it was calculated the intensity parameters and it was found a satisfactory quantum yield. (author)

Tin dioxide sol-gel derived films doped with platinum and antimony deposited on porous silicon

NARCIS (Netherlands)

Savaniu, C.; Arnautu, A.; Cobianu, C.; Craciun, G.; Flueraru, C.; Zaharescu, M.; Parlog, C.; Paszti, F.; van den Berg, Albert

1999-01-01

SnO2 sol-gel derived thin films doped simultaneously with Pt and Sb are obtained and reported for the first time. The Sn sources were tin(IV) ethoxide or tin(II) ethylhexanoate, while hexachloroplatinic acid (H2PtCl6) and antimony chloride (SbCl3) were used as platinum and antimony sources,

Adsorption of neptunium and plutonium on metal phosphites

International Nuclear Information System (INIS)

Silver, G.L.

1979-01-01

The removal of neptunium and plutonium from water by adsorption on titanium, zirconium, bismuth, thorium, and uranium phosphites was investigated. These phosphites hydrolyze in neutral or alkaline solution producing the hydrous metal oxides that are more effective adsorbents than the original phosphite compounds. Ageing the plutonium-238 polymer changes its adsorption characteristics on commercial bone char. 37 figures, 7 tables

Preliminary characterization and biological reduction of putative biogenic iron oxides (BIOS) from the Tonga-Kermadec Arc, southwest Pacific Ocean.

Science.gov (United States)

Langley, S; Igric, P; Takahashi, Y; Sakai, Y; Fortin, D; Hannington, M D; Schwarz-Schampera, U

2009-01-01

Sediment samples were obtained from areas of diffuse hydrothermal venting along the seabed in the Tonga sector of the Tonga-Kermadec Arc, southwest Pacific Ocean. Sediments from Volcano 1 and Volcano 19 were analyzed by X-ray diffraction (XRD) and found to be composed primarily of the iron oxyhydroxide mineral, two-line ferrihydrite. XRD also suggested the possible presence of minor amounts of more ordered iron (hydr)oxides (including six-line ferrihydrite, goethite/lepidocrocite and magnetite) in the biogenic iron oxides (BIOS) from Volcano 1; however, Mössbauer spectroscopy failed to detect any mineral phases more crystalline than two-line ferrihydrite. The minerals were precipitated on the surfaces of abundant filamentous microbial structures. Morphologically, some of these structures were similar in appearance to the known iron-oxidizing genus Mariprofundus spp., suggesting that the sediments are composed of biogenic iron oxides. At Volcano 19, an areally extensive, active vent field, the microbial cells appeared to be responsible for the formation of cohesive chimney-like structures of iron oxyhydroxide, 2-3 m in height, whereas at Volcano 1, an older vent field, no chimney-like structures were apparent. Iron reduction of the sediment material (i.e. BIOS) by Shewanella putrefaciens CN32 was measured, in vitro, as the ratio of [total Fe(II)]:[total Fe]. From this parameter, reduction rates were calculated for Volcano 1 BIOS (0.0521 day(-1)), Volcano 19 BIOS (0.0473 day(-1)), and hydrous ferric oxide, a synthetic two-line ferrihydrite (0.0224 day(-1)). Sediments from both BIOS sites were more easily reduced than synthetic ferrihydrite, which suggests that the decrease in effective surface area of the minerals within the sediments (due to the presence of the organic component) does not inhibit subsequent microbial reduction. These results indicate that natural, marine BIOS are easily reduced in the presence of dissimilatory iron-reducing bacteria, and that the

Thermodynamic data bases for multivalent elements: An example for ruthenium

International Nuclear Information System (INIS)

Rard, J.A.

1987-11-01

A careful consideration and understanding of fundamental chemistry, thermodynamics, and kinetics is absolutely essential when modeling predominance regions and solubility behavior of elements that exhibit a wide range of valence states. Examples of this are given using the ruthenium-water system at 298.15 K, for which a critically assessed thermochemical data base is available. Ruthenium exhibits the widest range of known aqueous solution valence states. Known solid anhydrous binary oxides of ruthenium are crystalline RuO 2 , RuO 4 , and possibly RuO 3 (thin film), and known hydroxides/hydrated oxides (all amorphous) are Ru(OH) 3 . H 2 O, RuO 2 . 2H 2 O, RuO 2 . H 2 O, and a poorly characterized Ru(V) hydrous oxide. Although the other oxides, hydroxides, and hydrous oxides are generally obtained as precipitates from aqueous solutions, they are thermodynamically unstable with regard to RuO 2 (cr) formation. Characterized aqueous species of ruthenium include RuO 4 (which slowly oxidizes water and which dissociates as a weak acid), RuO 4 - and RuO 4 2- (which probably contain lesser amounts of RuO 3 (OH) 2 - and RuO 3 (OH) 2 2- , respectively, and other species), Ru(OH) 2 2+ , Ru 4 (OH) 12 4+ , Ru(OH) 4 , Ru 3+ , Ru(OH) 2+ , Ru(OH) 2 + , Ru 2+ , and some hydroxytetramers with formal ruthenium valences of 3.75 ≥ Z ≥ 2.0. Potential pH diagrams of the predominance regions change significantly with concentration due to polymerization/depolymerization reactions. Failure to consider the known chemistry of ruthenium can yield large differences in predicted solubilities

Experimental and geochemical evidence for derivation of the El Capitan Granite, California, by partial melting of hydrous gabbroic lower crust

Science.gov (United States)

Ratajeski, K.; Sisson, T.W.; Glazner, A.F.

2005-01-01

Partial melting of mafic intrusions recently emplaced into the lower crust can produce voluminous silicic magmas with isotopic ratios similar to their mafic sources. Low-temperature (825 and 850??C) partial melts synthesized at 700 MPa in biotite-hornblende gabbros from the central Sierra Nevada batholith (Sisson et al. in Contrib Mineral Petrol 148:635-661, 2005) have major-element and modeled trace-element (REE, Rb, Ba, Sr, Th, U) compositions matching those of the Cretaceous El Capitan Granite, a prominent granite and silicic granodiorite pluton in the central part of the Sierra Nevada batholith (Yosemite, CA, USA) locally mingled with coeval, isotopically similar quartz diorite through gabbro intrusions (Ratajeski et al. in Geol Soc Am Bull 113:1486-1502, 2001). These results are evidence that the El Capitan Granite, and perhaps similar intrusions in the Sierra Nevada batholith with lithospheric-mantle-like isotopic values, were extracted from LILE-enriched, hydrous (hornblende-bearing) gabbroic rocks in the Sierran lower crust. Granitic partial melts derived by this process may also be silicic end members for mixing events leading to large-volume intermediate composition Sierran plutons such as the Cretaceous Lamarck Granodiorite. Voluminous gabbroic residues of partial melting may be lost to the mantle by their conversion to garnet-pyroxene assemblages during batholithic magmatic crustal thickening. ?? Springer-Verlag 2005.

The mechanism for degrading Orange II based on adsorption and reduction by ion-based nanoparticles synthesized by grape leaf extract

International Nuclear Information System (INIS)

Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

2015-01-01

Biomolecules taken from plant extracts have often been used in the single-step synthesis of iron-based nanoparticles (Fe NPs) due to their low cost, environmental safety and sustainable properties. However, the composition of Fe NPs and the degradation mechanism of organic contaminants by them are limited because these are linked to the reactivity of Fe NPs. In this study, Fe NPs synthesized by grape leaf extract served to remove Orange II. Batch experiments showed that more than 92% of Orange II was removed by Fe NPs at high temperature based on adsorption and reduction and confirmed by kinetic studies. To understand the role of Fe NPs in the removal process of azo dye, surface analysis via X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were employed, showing that the Fe NPs were composed of biomolecules, hydrous iron oxides and Fe 0 , thus providing evidence for the adsorption of Orange II onto hydrous iron oxides and its reduction by Fe 0 . Degraded products such as 2-naphthol were identified using LC–MS analysis. A degradation mechanism based on asymmetrical azo bond cleavage for the removal of Orange II was proposed

Development of a process for continuous extraction of uranium from seawater

International Nuclear Information System (INIS)

Yun, C.K.

1982-03-01

Hydrous titanium oxide, titanium phosphate, galena (PbS), polystyrene beads containing TBP were preliminarily tested, using artificial seawater. Galena indicated the capacity of 1.1mg U/g PbS and faster reaction rates, whereas, hydrous titanium oxide showed 0.6mg U/g Ti and slow rates. The adsorption performance of galena was not changed after repeated use and regeneration with dil. HCl solutions. The effective surface of galena beads was 0.4mm in depth. Elution of uranium form adsorbents was examined by both acid and alkali methods; the latter showed preferred condition. Secondary concentration of uranium by Amberlite IRA-400 was also studies. Eventually, two types of packed systems with galena (columns and panels) were installed in the seawater channel of a thermal power plant. The maximum adsorption of 150μg U/g PbS was obtained using the packed column. Based on the experimental data, the authors made a conceptual design for a test plant of the production capacity 12Kg U 3 O 8 /y. The construction would cost about $1 million and the operation cost is estimated at $115.20/lb U 3 O 8

The mechanism for degrading Orange II based on adsorption and reduction by ion-based nanoparticles synthesized by grape leaf extract

Energy Technology Data Exchange (ETDEWEB)

Luo, Fang; Yang, Die [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of Environments, University of South Australia, Mawson Lakes, SA 5095 (Australia); Chen, Zuliang, E-mail: zuliang.chen@unisa.edu.au [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of Environments, University of South Australia, Mawson Lakes, SA 5095 (Australia); Megharaj, Mallavarapu; Naidu, Ravendra [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of Environments, University of South Australia, Mawson Lakes, SA 5095 (Australia)

2015-10-15

Biomolecules taken from plant extracts have often been used in the single-step synthesis of iron-based nanoparticles (Fe NPs) due to their low cost, environmental safety and sustainable properties. However, the composition of Fe NPs and the degradation mechanism of organic contaminants by them are limited because these are linked to the reactivity of Fe NPs. In this study, Fe NPs synthesized by grape leaf extract served to remove Orange II. Batch experiments showed that more than 92% of Orange II was removed by Fe NPs at high temperature based on adsorption and reduction and confirmed by kinetic studies. To understand the role of Fe NPs in the removal process of azo dye, surface analysis via X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were employed, showing that the Fe NPs were composed of biomolecules, hydrous iron oxides and Fe{sup 0}, thus providing evidence for the adsorption of Orange II onto hydrous iron oxides and its reduction by Fe{sup 0}. Degraded products such as 2-naphthol were identified using LC–MS analysis. A degradation mechanism based on asymmetrical azo bond cleavage for the removal of Orange II was proposed.

Rare Earth Element Behavior During Incongruent Weathering and Varying Discharge Conditions in Silicate Dominated River Systems: The Australian Victorian Alps

Science.gov (United States)

Hagedorn, K. B.; Cartwright, I.

2008-12-01

The distribution of rare earth elements (REE) and trace elements was measured by ICP-MS on fresh, slightly weathered and weathered granite and surface water samples from a network of 11 pristine rivers draining the Australian Victorian Alps during (i) high and (ii) low discharge conditions. River water REE concentrations are largely derived from atmospheric precipitation (rain, snow), as indicated by similar Chondrite normalized REE patterns (higher LREE over HREE; negative Ce anomalies, positive Eu anomalies) and similar total REE concentrations during both dry and wet seasons. Calculations based on the covariance between REE and Cl concentrations and oxygen and hydrogen isotopes indicate precipitation input coupled with subsequent evaporation may account for 30% o 100% of dissolved REE in stream waters. The dissolved contribution to the granitic substratum to stream water comes mainly from the transformation of plagioclase to smectite, kaolinite and gibbsite and minor apatite dissolution. However, since most REE of the regional granite are present in accessory minerals (titanite, zircon, etc.) they do not significantly contribute to the river REE pool. REE concentrations drop sharply downstream as a result of dilution and chemical attenuation. A trend of downstream enrichment of the heavier REE is due to selective partitioning of the lighter REE (as both free REE or REECO3 complexes) to hydrous oxides of suspended Al which, in turn, is controlled by a downstream increase of pH to values > 6.1 (for free REE) and > 7.3 (for REECO3 complexes). Although most circumneutral waters were supersaturated with REE phosphate compounds, precipitation of LnPO4 is not believed to have been a dominant process because the predicted phosphate fractionation pattern is inconsistent with the observed trends. Negative saturation indices of hydrous ferric oxides also militate against surface complexation onto goethite. Instead, REE attenuation most likely resulted from adsorption onto

Manganese associated nanoparticles agglomerate of iron(III) oxide: synthesis, characterization and arsenic(III) sorption behavior with mechanism.

Science.gov (United States)

Gupta, Kaushik; Maity, Arjun; Ghosh, Uday Chand

2010-12-15

Three samples of manganese associated hydrous iron(III) oxide (MNHFO), prepared by incinerating metal hydroxide precipitate at T (± 5)=90, 300 and 600°C, showed increase of crystalline nature in XRD patterns with decreasing As(III) removal percentages. TEM images showed the increase of crystallinity from sample-1 (MNHFO-1) to sample-3 (MNHFO-3). Dimensions (nm) of particles estimated were 5.0, 7.0 and 97.5. Optimization of pH indicated that MNHFO-1 could remove aqueous As(III) efficiently at pH between 3.0 and 7.0. Kinetic and equilibrium data of reactions under the experimental conditions described the pseudo-second order and the Langmuir isotherm equations very well, respectively. The Langmuir capacity (q(m)) estimated was 691.04 mmol kg(-1). The values of enthalpy, Gibb's free energy and entropy changes (ΔH(0)=+23.23 kJ mol(-1), ΔG(0)=-3.43 to -7.20 kJ mol(-1) at T=283-323K, ΔS(0)=+0.094 kJ mol(-1)K(-1)) suggested that the reaction was endothermic, spontaneous and took place with increasing entropy. The As(III) sorbed by MNHFO-1 underwent surface oxidation to As(V), and evidences appeared from the XPS and FTIR investigations. MNHFO-1 packed column (internal diameter: 1.0 cm, height: 3.7 cm) filtered 11.5 dm(3) groundwater (105 μg As dm(-3)) with reducing arsenic concentration to ≤ 10 μg dm(-3). Copyright © 2010 Elsevier B.V. All rights reserved.

Reactive transport model of the formation of oxide-type Ni-laterite profiles (Punta Gorda, Moa Bay, Cuba)

Science.gov (United States)

Domènech, Cristina; Galí, Salvador; Villanova-de-Benavent, Cristina; Soler, Josep M.; Proenza, Joaquín A.

2017-10-01

Oxide-type Ni-laterite deposits are characterized by a dominant limonite zone with goethite as the economically most important Ni ore mineral and a thin zone of hydrous Mg silicate-rich saprolite beneath the magnesium discontinuity. Fe, less soluble, is mainly retained forming goethite, while Ni is redeposited at greater depth in a Fe(III) and Ni-rich serpentine (serpentine II) or in goethite, where it adsorbs or substitutes for Fe in the mineral structure. Here, a 1D reactive transport model, using CrunchFlow, of Punta Gorda oxide-type Ni-laterite deposit (Moa Bay, Cuba) formation is presented. The model reproduces the formation of the different laterite horizons in the profile from an initial, partially serpentinized peridotite, in 106 years, validating the conceptual model of the formation of this kind of deposits in which a narrow saprolite horizon rich in Ni-bearing serpentine is formed above peridotite parent rock and a thick limonite horizon is formed over saprolite. Results also confirm that sorption of Ni onto goethite can explain the weight percent of Ni found in the Moa goethite. Sensitivity analyses accounting for the effect of key parameters (composition, dissolution rate, carbonate concentration, quartz precipitation) on the model results are also presented. It is found that aqueous carbonate concentration and quartz precipitation significantly affects the laterization process rate, while the effect of the composition of secondary serpentine or of mineral dissolution rates is minor. The results of this reactive transport modeling have proven useful to validate the conceptual models derived from field observations.

The impact of the drought on the hydrous potentialities of the plain of Mejjate and SA Borders Western, (Morocco)

International Nuclear Information System (INIS)

Karima, Boukhari; Sadik, Er-Rouane; Abdeljalil, Gouzrou

2004-01-01

The field of study includes the plain of Mejjate and its Western termination, located at 70km in the Western South of Marrakech, on a surface of 2800 km 2 , delimited in North by the links of Jbilet, in the South by the High Western Atlas, in the East by wadi N'Fis and the West by the large basin of Essaouira-Meskala. The principal rural agglomerations are Imintanout, Chichaoua, Sebt Mzouda, Had Mejjate, Guemassa, Zaouiet Sidi Abdelmoumen Taouloukt and Bouabout. The principal socioeconomic activity is the breeding and the cereal farming in bour, the total surface irrigated in all the area is about 7500 ha. Precipitations have a continental mode of and type to semi-arid, characterized by an absence of the rains in the duration and summer months and rains brutal short to the remainder of the year. The annual average temperatures vary from 12 with 28 o C, with an annual average of 19.32 o C. The principal objective of this study consists in studying the impact of the dryness on the hydrous potentialities of the area of study. In this approach, one studied the variations in the course of the time of several components to know precipitations, the flows of the w adis a nd the sources and the piezometry of the Plio-quaternary tablecloth. Within the same framework and for better judging the relation, which exists between these arious components, one tried to carry out tests of linear correlation to examine whether there is a statistical bond between them.(Author)

Determination of radium and uranium isotopes in natural waters by sorption on hydrous manganese dioxide followed by alpha-spectrometry

International Nuclear Information System (INIS)

Bojanowski, R.; Radecki, Z.; Burns, K.

2005-01-01

Water samples, spiked with 133 Ba and 232 U radiotracers, are scavenged for radium and uranium isotopes using hydrous manganese dioxide which is produced in-situ, by reacting manganese (+2) and permanganate ions at pH 8-9. The precipitate is solubilized with ascorbic and acetic acids and the resulting solution filtered through a glass fibre filter GF/F to remove particulate matter. The radium is co-precipitated with barium ions by the addition of a saturated Na 2 SO 4 solution where a small amount of BaSO 4 suspension is introduced to initiate crystallization. The micro precipitate containing the radium is collected on a 0.1 membrane filter and the filtrate saved for follow-up uranium analysis. The 226 Ra on the filter is determined by alpha-spectrometry and its recovery is assessed by measuring the 133 Ba on the same filter using gamma-spectrometry. The filtrate containing uranium is passed through a Dowex AG 1 x 4 ion-exchange resin in the SO 4 2- form which retains uranium while other ions are eluted by dilute (0.25M) sulphuric acid. Uranium is eluted from the column by distilled water, electrodeposited on a silver disc and the uranium isotopes and their recovery are determined by alpha-spectrometry. The method was tested on a variety of natural and spiked water samples with known concentrations of 226 Ra and 238 U and was found to yield accurate results within ±10% RSD of the target values. (author)

Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

Science.gov (United States)

Filipek, L.H.; Chao, T.T.; Carpenter, R.H.

1981-01-01

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh ( Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Geochemistry of the furnace magnetite bed, Franklin, New Jersey, and the relationship between stratiform iron oxide ores and stratiform zinc oxide-silicate ores in the New Jersey highlands

Science.gov (United States)

Johnson, C.A.; Skinner, B.J.

2003-01-01

The New Jersey Highlands terrace, which is an exposure of the Middle Proterozoic Grenville orogenic belt located in northeastern United States, contains stratiform zinc oxide-silicate deposits at Franklin and Sterling Hill and numerous massive magnetite deposits. The origins of the zinc and magnetite deposits have rarely been considered together, but a genetic link is suggested by the occurrence of the Furnace magnetite bed and small magnetite lenses immediately beneath the Franklin zinc deposit. The Furnace bed was metamorphosed and deformed along with its enclosing rocks during the Grenvillian orogeny, obscuring the original mineralogy and obliterating the original rock fabrics. The present mineralogy is manganiferous magnetite plus calcite. Trace hydrous silicates, some coexisting with fluorite, have fluorine contents that are among the highest ever observed in natural assemblages. Furnace bed calcite has ??13C values of -5 ?? 1 per mil relative to Peedee belemnite (PDB) and ??18O values of 11 to 20 per mil relative to Vienna-standard mean ocean water (VSMOW). The isotopic compositions do not vary as expected for an original siderite layer that decarbonated during metamorphism, but they are consistent with nearly isochemical metamorphism of an iron oxide + calcite protolith that is chemically and minerlogically similar to iron-rich sediments found near the Red Sea brine pools and isotopically similar to Superior-type banded iron formations. Other magniferous magnite + calcite bodies occur at approximately the same stratigraphic position as far 50 km from the zinc deposits. A model is presented in which the iron and zinc deposits formed along the western edge of a Middle Proterozoic marine basin. Zinc was transported by sulfate-stable brines and was precipitated under sulfate-stable conditions as zincian carbonates and Fe-Mn-Zn oxides and silicates. Whether the zincian assemblages settled from the water column or formed by replacement reactions in shallowly

Study of possible economical ways of removing radium from drinking water

International Nuclear Information System (INIS)

Valentine, R.L.; Splinter, R.C.; Mulholland, T.S.; Baker, J.M.; Nogaj, T.M.

1988-01-01

This study was undertaken to determine variables that control the incidental removal of radium that has been observed to occur as a consequence of treatment to remove iron by oxidation--sand filtration. The study also evaluated the possibility of exploiting these factors to provide an inexpensive means of removing radium using existing or modified iron removal facilities. Studies were also conducted to evaluate radium sorption to hydrous manganese oxides and to evaluate the potential of radium sorption to filter sand as a novel removal technology. Results showed that radium sorption to iron and manganese oxides and filter sand appear to be controlled primarily by the presence of calcium and magnesium, which are believed to compete for sorption sites

Improved processes of molybdenum-99 production

International Nuclear Information System (INIS)

Dadachova, K.; La Riviere, K.; Anderon, P.

1997-01-01

Two improved processes of Molybdenum-99 production have been developed at ANSTO on laboratory scale. The first one allows to purify Mo of natural isotopic composition from tungsten impurities by using preferential adsorption of tungsten on hydrated tin(IV) oxide SnO 2 x nH 2 O before irradiation in the nuclear reactor. Mo-99 obtained via this route can be used for production of i nstant Tc-99m. As the starting material MoO 3 contains considerable amounts of tungsten impurity (W > 60 ppm), 5-7 days irradiation results in generation of W-188 in amounts sufficient to contaminate the final Tc-99m product with rhenium-188 (Re-188, 16.8 h half-life) - radioactive daughter of W-188. To overcome this problem, a method of MoO 3 purification from W, based on preferential adsorption of W by hydrated tin (IV) oxide has been developed. The contents of W in MoO 3 purified by this technique became 3 and retaining of Mo-99 on a large alumina column. Mo-99 is stripped off the column with 200 mL 1M NH 4 OH followed by loading this solution onto the AG 1x8 column. The next steps are different for each version of separation process

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

Science.gov (United States)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians

Science.gov (United States)

Kotarba, M.J.; Curtis, John B.; Lewan, M.D.

2009-01-01

This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 ??C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 ??C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% Rr, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. ??13C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the ??13C of the original kerogen, with 13C enriched kerogen generating more 13C enriched hydrocarbon gases than

Ps mantle transition zone imaging beneath the Colorado Rocky Mountains: Evidence for an upwelling hydrous mantle

Science.gov (United States)

Zhang, Zhu; Dueker, Kenneth G.; Huang, Hsin-Hua

2018-06-01

We analyze teleseismic P-to-S conversions for high-resolution imaging of the mantle transition zone beneath the Colorado Rocky Mountains using data from a dense PASSCAL seismic broadband deployment. A total of 6,021 P-to-S converted receiver functions are constructed using a multi-channel minimum-phase deconvolution method and migrated using the common converted point technique with the 3-D teleseismic P- and S-wave tomography models of Schmandt and Humphreys (2010). The image finds that the average depths of the 410-km discontinuity (the 410) and 660-km discontinuity (the 660) at 408 ± 1.9 km and 649 ± 1.6 km respectively. The peak-to-peak topography of both discontinuities is 33 km and 27 km respectively. Additionally, prominent negative polarity phases are imaged both above and below the 410. To quantify the mean properties of the low-velocity layers about 410 km, we utilize double gradient layer models parameterization to fit the mean receiver function waveform. This waveform fitting is accomplished as a grid-search using anelastic synthetic seismograms. The best-fitting model reveals that the olivine-wadsleyite phase transformation width is 21 km, which is significantly larger than anhydrous mineral physics prediction (4-10 km) (Smyth and Frost, 2002). The findings of a wide olivine-wadsleyite phase transformation and the negative polarity phases above and below the 410, suggest that the mantle, at least in the 350-450 km depth range, is significantly hydrated. Furthermore, a conspicuous negative polarity phase below the 660 is imaged in high velocity region, we speculate the low velocity layer is due to dehydration flux melting in an area of convective downwelling. Our interpretation of these results, in tandem with the tomographic image of a Farallon slab segment at 800 km beneath the region (Schmandt and Humphreys, 2010), is that hydrous and upwelling mantle contributes to the high-standing Colorado Rocky Mountains.

Linking interfacial chemistry of CO2 to surface structures of hydrated metal oxide nanoparticles: hematite.

Science.gov (United States)

Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

2013-05-14

A better understanding of interaction with dissolved CO2 is required to rationally design and model the (photo)catalytic and sorption processes on metal (hydr)oxide nanoparticles (NPs) in aqueous media. Using in situ FTIR spectroscopy, we address this problem for rhombohedral 38 nm hematite (α-Fe2O3) nanoparticles as a model. We not only resolve the structures of the adsorbed carbonate species, but also specify their adsorption sites and their location on the nanoparticle surface. The spectral relationships obtained present a basis for a new method of characterizing the microscopic structural and acid-base properties (related to individual adsorption sites) of hydrated metal (hydr)oxide NPs using atmospherically derived CO2 as a probe. Specifically, we distinguish two carbonate species suggesting two principally different adsorption mechanisms. One species, which is more weakly adsorbed, has an inner-sphere mononuclear monodentate structure which is formed by a conventional ligand-exchange mechanism. At natural levels of dissolved carbonate and pH from 3 to 11, this species is attached to the most acidic/reactive surface cations (surface states) associated with ferrihydrite-like surface defects. The second species, which is more strongly adsorbed, presents a mixed C and O coordination of bent CO2. This species uniquely recognizes the stoichiometric rhombohedral {104} facets in the NP texture. Like in gas phase, it is formed through the surface coordination of molecular CO2. We address how the adsorption sites hosting these two carbonate species are affected by the annealing and acid etching of the NPs. These results support the nanosize-induced phase transformation of hematite towards ferrihydrite under hydrous conditions, and additionally show that the process starts from the roughened areas of the facet intersections.

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})

Energy Technology Data Exchange (ETDEWEB)

Yu, Na; Klepov, Vladislav V. [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Villa, Eric M. [Department of Chemistry, Creighton University, 2500 California Plaza, Omaha NE 68178 (United States); Bosbach, Dirk [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Suleimanov, Evgeny V. [Department of Chemistry, Lobachevsky State University of Nizhny Novgorod, 603950 Nizhny Novgorod (Russian Federation); Depmeier, Wulf [Institut für Geowissenschaften, Universität zu Kiel, 24118 Kiel (Germany); Albrecht-Schmitt, Thomas E., E-mail: albrecht-schmitt@chem.fsu.edu [Department of Chemistry and Biochemistry, Florida State University, 102 Varsity Way, Tallahassee, FL 32306-4390 (United States); Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de [Forschungszentrum Jülich GmbH, Institute for Energy and Climate Research (IEK-6), 52428 Jülich (Germany); Institut für Kristallographie, RWTH Aachen University, 52066 Aachen (Germany)

2014-07-01

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.

Mechanism of formation of humus coatings on mineral surfaces 3. Composition of adsorbed organic acids from compost leachate on alumina by solid-state 13C NMR

Science.gov (United States)

Wershaw, R. L.; Llaguno, E.C.; Leenheer, J.A.

1996-01-01

The adsorption of compost leachate DOC on alumina is used as a model for elucidation of the mechanism of formation of natural organic coatings on hydrous metal oxide surfaces in soils and sediments. Compost leachate DOC is composed mainly of organic acid molecules. The solid-state 13C NMR spectra of these organic acids indicate that they are very similar in composition to aquatic humic substances. Changes in the solid-state 13C NMR spectra of compost leachate DOC fractions adsorbed on alumina indicate that the DOC molecules are most likely adsorbed on metal oxide surfaces through a combination of polar and hydrophobic interaction mechanisms. This combination of polar and hydrophobic mechanism leads to the formation of bilayer coatings of the leachate molecules on the oxide surfaces.

Antimony(V) Adsorption by Variable-Charge Minerals

Science.gov (United States)

2013-10-01

6‒] and inner-sphere [≡SOSb(OH)5‒] adsorption mechanisms. In general, however, the models generated for single ligand systems required reoptimization...HCO3 and CO3 ) effectively desorbed Sb(V) from hydrous metal (Al and Fe) oxides, clay minerals, and Sb(V)-contaminated sediments, relative to the...temperatures (20- 22°C). 7 A well- crystallized Georgia kaolinite (KGa-1b) from the Source Clays Repository of The Clay Minerals Society (West Lafayette

''In-situ'' spectro-electrochemical studies of radionuclide-contaminated surface films on metals

International Nuclear Information System (INIS)

Melendres, C.A.; Mini, S.; Mansour, A.N.

2000-01-01

The incorporation of heavy metal ions and radioactive contaminants into hydrous oxide films has been investigated in order to provide fundamental knowledge that could lead to the technological development of cost-effective processes and techniques for the decontamination of storage tanks, piping systems, surfaces, etc., in DOE nuclear facilities. The formation of oxide/hydroxide films was simulated by electrodeposition onto a graphite substrate from solutions of the appropriate metal salt. Synchrotron X-ray Absorption Spectroscopy (XAS), supplemented by Laser Raman Spectroscopy (LRS), was used to determine the structure and composition of the host oxide film, as well as the impurity ion. Results have been obtained for the incorporation of Ce, Sr, Cr, Fe, and U into hydrous nickel oxide films. Ce and Sr oxides/hydroxides are co-precipitated with the nickel oxides in separate phase domains. Cr and Fe, on the other hand, are able to substitute into Ni lattice sites or intercalate in the interlamellar positions of the brucite structure of Ni(OH) 2 . U was found to co-deposit as a U(VI) hydroxide. The mode of incorporation of metal ions depends both on the size and charge of the metal ion. The structure of iron oxide (hydroxide) films prepared by both anodic and cathodic deposition has also been extensively studied. The structure of Fe(OH) 2 was determined to be similar to that of α-Ni(OH) 2 . Anodic deposition from solutions containing Fe 2+ results in a film with a structure similar to γ-FeOOH. From the knowledge gained from the present studies, principles and methods for decontamination have become apparent. Contaminants sorbed on oxide surfaces or co-precipitated may be removed by acid wash and selective dissolution or complexation. Ions incorporated into lattice sites and interlamellar layers will require more drastic cleaning procedures. Electropolishing and the use of an electrochemical brush are among concepts that should be considered seriously for the latter

Oxic limestone drains for treatment of dilute, acidic mine drainage

Science.gov (United States)

Cravotta, Charles A.

1998-01-01

Limestone treatment systems can be effective for remediation of acidic mine drainage (AMD) that contains moderate concentrations of dissolved O2 , Fe3+ , or A13+ (1‐5 mg‐L‐1 ). Samples of water and limestone were collected periodically for 1 year at inflow, outflow, and intermediate points within underground, oxic limestone drains (OLDs) in Pennsylvania to evaluate the transport of dissolved metals and the effect of pH and Fe‐ and Al‐hydrolysis products on the rate of limestone dissolution. The influent was acidic and relatively dilute (pH 1 mg‐L‐1 ) but was near neutral (pH = 6.2‐7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)3 and AI(OH)3, were visible as loosely bound, orange‐yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)3 and AI(OH)3 particles were transported downflow. During the first 6 months of the experiment, Mn 2+ was transported conservatively through the OLDs; however, during the second 6 months, concentrations of Mn in effluent decreased by about 50% relative to influent. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of Mn as indicated by its enrichment relative to Fe in hydrous‐oxide particles and coatings on limestone. Despite thick (~1 mm) hydrous‐oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within the OLD where the limestone was not coated. The rate of limestone dissolution decreased with increased residence time, pH, and concentrations of Ca2+ and HCO3‐ and decreased PCO2. The following overall reaction shows alkalinity as an ultimate product of the iron hydrolysis reaction in an OLD:Fe2+ + 0.25 O2 +CaCO3 + 2.5 H2O --> Fe(OH)3 + 2 Ca2+ + 2 HCO3-where 2 moles of CaCO3 dissolve for each mole of Fe(OH)3 produced

Plutonium and americium in Lake Michigan sediments

International Nuclear Information System (INIS)

Edgington, D.N.; Alberts, J.J.; Wahlgren, M.A.; Karttunen, J.O.; Reeve, C.A.

1975-01-01

The vertical distributions of 239 , 240 Pu, 238 Pu, and 137 Cs have been measured in sediment cores taken from Lake Michigan. Sections from a limited number of cores have been analyzed for 241 Am. In addition, grab samples from ten locations in the southern basin of the lake have been analyzed for phase distribution of 239 , 240 Pu using a sequential extraction technique. The results indicate that the 239 , 240 Pu, 238 Pu, and 137 Cs from weapons testing, and the 241 Am formed in situ are concentrated in the sediments. A comparison of the total deposition of 239 , 240 Pu and 137 Cs indicates that 137 Cs may be valuable as a monitor for 239 , 240 Pu deposition in the sediments. Values of the 238 Pu/ 239 , 240 Pu ratio are in agreement with values reported in Lake Ontario sediments (and Lake Michigan plankton) and show little variation with depth. 241 Am data support the concept of in situ production with little preferential mobility after formation. Studies of sedimentary phase distributions show that 239 , 240 Pu is associated with hydrous oxide phases which are chemically stable under the prevailing conditions in lake sediments. Since Lake Michigan sediments remain aerobic, relatively little 239 , 240 Pu is available for chemical mobilization from the hydrous oxide or organic phases present in the sediments

Porous SnO2-CuO nanotubes for highly reversible lithium storage

Science.gov (United States)

Cheong, Jun Young; Kim, Chanhoon; Jung, Ji-Won; Yoon, Ki Ro; Kim, Il-Doo

2018-01-01

Facile synthesis of rationally designed structures is critical to realize a high performance electrode for lithium-ion batteries (LIBs). Among different candidates, tin(IV) oxide (SnO2) is one of the most actively researched electrode materials due to its high theoretical capacity (1493 mAh g-1), abundance, inexpensive costs, and environmental friendliness. However, severe capacity decay from the volume expansion and low conductivity of SnO2 have hampered its use as a feasible electrode for LIBs. Rationally designed SnO2-based nanostructures with conductive materials can be an ideal solution to resolve such limitations. In this work, we have successfully fabricated porous SnO2-CuO composite nanotubes (SnO2-CuO p-NTs) by electrospinning and subsequent calcination step. The porous nanotubular structure is expected to mitigate the volume expansion of SnO2, while the as-formed Cu from CuO upon lithiation allows faster electron transport by improving the low conductivity of SnO2. With a synergistic effect of both Sn and Cu-based oxides, SnO2-CuO p-NTs deliver stable cycling performance (91.3% of capacity retention, ∼538 mAh g-1) even after 350 cycles at a current density of 500 mA g-1, along with enhanced rate capabilities compared with SnO2.

The compression behavior of blödite at low and high temperature up to ~10GPa: Implications for the stability of hydrous sulfates on icy planetary bodies

Energy Technology Data Exchange (ETDEWEB)

Comodi, Paola; Stagno, Vincenzo; Zucchini, Azzurra; Fei, Yingwei; Prakapenka, Vitali

2017-03-01

Recent satellite inferences of hydrous sulfates as recurrent minerals on the surface of icy planetary bodies link with the potential mineral composition of their interior. Blödite, a mixed Mg-Na sulfate, is here taken as representative mineral of icy satellites surface to investigate its crystal structure and stability at conditions of the interior of icy bodies. To this aim we performed in situ synchrotron angle-dispersive X-ray powder diffraction experiments on natural blödite at pressures up to ~10.4 GPa and temperatures from ~118.8 K to ~490.0 K using diamond anvil cell technique to investigate the compression behavior and establish a low-to-high temperature equation of state that can be used as reference when modeling the interior of sulfate-rich icy satellites such as Ganymede. The experimentally determined volume expansivity, α, varies from 7.6 (7) 10^-5 K^-1 at 0.0001 GPa (from 118.8 to 413.15 K) to 2.6 (3) 10^-5 K^-1 at 10 GPa (from 313.0 to 453.0 K) with a δα/δ_P coefficient = -5.6(9)10^-6 GPa^-1 K^-1. The bulk modulus calculated from the least squares fitting of P-V data on the isotherm at 413 K using a second-order Birch - Murnaghan equation of state is 38(5) GPa, which gives the value of δK/δ_T equal to 0.01(5) GPa K^-1. The thermo-baric behavior of blödite appears strongly anisotropic with c lattice parameter being more deformed with respect to a and b. Thermogravimetric analyses performed at ambient pressure showed three endotherms at 413 K, 533 K and 973 K with weight losses of approximately 11%, 11% and 43% caused by partial dehydration, full dehydration and sulfate decomposition respectively. Interestingly, no clear evidence of dehydration was observed up to ~453 K and ~10.4 GPa, suggesting that pressure acts to stabilize the crystalline structure of blödite. The data collected allow to write the following equation of state, V(P, T) = V

New Insight into the Local Structure of Hydrous Ferric Arsenate Using Full-Potential Multiple Scattering Analysis, Density Functional Theory Calculations, and Vibrational Spectroscopy.

Science.gov (United States)

Wang, Shaofeng; Ma, Xu; Zhang, Guoqing; Jia, Yongfeng; Hatada, Keisuke

2016-11-15

Hydrous ferric arsenate (HFA) is an important arsenic-bearing precipitate in the mining-impacted environment and hydrometallurgical tailings. However, there is no agreement on its local atomic structure. The local structure of HFA was reprobed by employing a full-potential multiple scattering (FPMS) analysis, density functional theory (DFT) calculations, and vibrational spectroscopy. The FPMS simulations indicated that the coordination number of the As-Fe, Fe-As, or both in HFA was approximately two. The DFT calculations constructed a structure of HFA with the formula of Fe(HAsO 4 ) x (H 2 AsO 4 ) 1-x (OH) y ·zH 2 O. The presence of protonated arsenate in HFA was also evidenced by vibrational spectroscopy. The As and Fe K-edge X-ray absorption near-edge structure spectra of HFA were accurately reproduced by FPMS simulations using the chain structure, which was also a reasonable model for extended X-Ray absorption fine structure fitting. The FPMS refinements indicated that the interatomic Fe-Fe distance was approximately 5.2 Å, consistent with that obtained by Mikutta et al. (Environ. Sci. Technol. 2013, 47 (7), 3122-3131) using wavelet analysis. All of the results suggested that HFA was more likely to occur as a chain with AsO 4 tetrahedra and FeO 6 octahedra connecting alternately in an isolated bidentate-type fashion. This finding is of significance for understanding the fate of arsenic and the formation of ferric arsenate minerals in an acidic environment.

Evolution of sulfur speciation in bitumen through hydrous pyrolysis induced thermal maturation of Jordanian Ghareb Formation oil shale

Science.gov (United States)

Birdwell, Justin E.; Lewan, Michael; Bake, Kyle D.; Bolin, Trudy B.; Craddock, Paul R.; Forsythe, Julia C.; Pomerantz, Andrew E.

2018-01-01

Previous studies on the distribution of bulk sulfur species in bitumen before and after artificial thermal maturation using various pyrolysis methods have indicated that the quantities of reactive (sulfide, sulfoxide) and thermally stable (thiophene) sulfur moieties change following consistent trends under increasing thermal stress. These trends show that sulfur distributions change during maturation in ways that are similar to those of carbon, most clearly illustrated by the increase in aromatic sulfur (thiophenic) as a function of thermal maturity. In this study, we have examined the sulfur moiety distributions of retained bitumen from a set of pre- and post-pyrolysis rock samples in an organic sulfur-rich, calcareous oil shale from the Upper Cretaceous Ghareb Formation. Samples collected from outcrop in Jordan were subjected to hydrous pyrolysis (HP). Sulfur speciation in extracted bitumens was examined using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The most substantial changes in sulfur distribution occurred at temperatures up to the point of maximum bitumen generation (∼300 °C) as determined from comparison of the total organic carbon content for samples before and after extraction. Organic sulfide in bitumen decreased with increasing temperature at relatively low thermal stress (200–300 °C) and was not detected in extracts from rocks subjected to HP at temperatures above around 300 °C. Sulfoxide content increased between 200 and 280 °C, but decreased at higher temperatures. The concentration of thiophenic sulfur increased up to 300 °C, and remained essentially stable under increasing thermal stress (mg-S/g-bitumen basis). The ratio of stable-to-reactive+stable sulfur moieties ([thiophene/(sulfide+sulfoxide+thiophene)], T/SST) followed a sigmoidal trend with HP temperature, increasing slightly up to 240 °C, followed by a substantial increase between 240 and 320 °C, and approaching a constant value (∼0.95) at

Functionalization of niobium electrodes for the construction of impedimetric biosensors

International Nuclear Information System (INIS)

Helali, S.; Abdelghani, A.; Hafaiedh, I.; Martelet, C.; Prodromidis, M.I.; Albanis, T.; Jaffrezic-Renault, N.

2008-01-01

This paper describes the development of an impedimetric immunosensor, based on niobium/niobium oxide (Nb/NbOxHy) electrodes, for the detection of atrazine. Niobium oxide was anodically formed onto niobium electrodes at 25 V in 1 M H 2 SO 4 . Hydrous oxide layers were then silanized with APTES, and using glutaraldehyde as a cross linker, Fab fragment k47 antibody was covalently immobilized onto the surface of the electrodes. Electrochemical impedance spectroscopy (EIS) was used to characterize the building-up of the immunosensors as well as the binding of atrazine to its specific antibody. In presence of ferricyanide redox species and under a cathodic polarization voltage (- 1.2 V versus SCE), the relationship between the concentration of atrazine and the change of the electron transfer resistance value was studied

Study on radiosterilization of crude drug pill involving bezoar bovis

International Nuclear Information System (INIS)

Kimura, Syojiro; Sasaki, Masahiro; Kondo, Yuichi; Jo, Hisanobu; Kanbashi, Toshitaka.

1981-01-01

Radiolysis of bilirubin and cholic acids (cholic acid, desoxycholic acid and lithocholic acid) in hydrous pellet have been investigated with following parameters, which were hydrous content, radiation dose and the dose rate, to discuss the application of gamma -irradiation for sterilization of crude drug pill involving bezoar bovis. At 774 C/kg(3.0MR) irradiation for 5% and 10% hydrous contents pellets, the radiolysis percent of those components were less than 5%. However, the higher hydrous pellet, the radiolysis percents of those are more increase. At the same irradiated condition for 20% hydrous contents pellets, the radiolysis percents of those were 15--22%. The hydrous percent of commercial crude drug pill involving bezoar bovis are about 9%, so that the radiolysis of those components will be less than 5% on the sterilization. The radiolysis percent of bilirubin are constant to variation of radiation dose rate between 51.6--722.5C/kg.hr(0.2--2.8MR/hr). But, the values of cholic acids don't definite such as that of bilirubin, because of larger analitycal error. (author)

Separation of caesium-137 from fission products using phosphotungstic acid

International Nuclear Information System (INIS)

Murthy, T.S.; Balasubramaniam, K.R.; Ananthakrishnan, M.; Varma, R.N.

1977-01-01

Separation of caesium 137 from fission products using phosphotungstic acid is reported. Phosphotungstate caesium is precipitated as caesium from fission product waste solution in acid medium and subsequently purified. Separation of phosphate and tungstate ions has been done using a typical hydrous oxide like alumina. The exchange capacity of alumina for phosphate and tungstate ions, and the purity of the product are determined. Results are discussed. Based on the findings a procedure is recommended for caesium 137 separation. (A.K.)

Catalytic oxidation using nitrous oxide

Directory of Open Access Journals (Sweden)

Juan Carlos Beltran-Prieto

2017-01-01

Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

Progade PT path, prograde fluid flow, metasomatism and hydrous melting in the Osor high-grade HT-LP complex (Catalan Coastal Ranges-CCR, NE Iberia).

Science.gov (United States)

Reche, Joan; Martínez, Francisco; Leoz, Gisela

2015-04-01

Fast thermal pulses related to HT-LP metamorphism may imply dehydration reaction overstepping, higher than normal fluid production rates, quick local increases in Pfluid and common situations of Pfluid >> Plitostatic and surpassing locally the tensile stresses. This ambient would be favorable to transient hydrofracturing and fluid flow even if the ongoing HT-LP event develops on dominantly ductile crustal levels. In inner zones where temperatures are high enough, hydrous melting and melt migration would be favored as well. Such movement of fluids and melts would tend to be sustained if non-hydrostatic stresses are active during heating, and would be favored in high strain domains such high-T shear zones or along foliation planes. In such scenario, local metasomatic processes and mass-transfer phenomena are expected to occur along these high strain zones and so distributed along tectonic anisotropies. A variety of features found in high T Garnet - biotite-sillimanite±cordierite±plagioclase±K-feldspar±quartz metapelitic gneisses from the Osor Complex (Guilleries massif, CCR), testify from this kind of processes operating in the lower crustal section, at the amphibolite to granulite transition zone during a prograde Variscan HT-LP thermal pulse. Such features include: syn-D2 quartz veining, leucogranitoid (leucotonalite, trondhjemitic) lenses sub parallel to S2 dominant foliation, fibrolite-rich foliation planes and prograde sub-idiomorphic garnet developing preferentially near fluid migration channels (quartz veins) or near melt lenses.

Use of inorganic ion exchange materials for the treatment of liquid waste

International Nuclear Information System (INIS)

El-Naggar, I.M.; Zakaria, E.S.; El-Absy, M.A.; Abdel-Hamid, M.M.; Abo-Mesalam, M.M.; Shady, S.A.; Abdelwahab, M.A.; Aly, H.F.

1997-01-01

To examine the ion exchange behaviour of the double salts of polybasic acid with tetravalent metals type such as cerium(IV) and tin(IV) antimonates, different samples were prepared, heated at different temperatures and exposed to γ-irradiation. These samples were subject to X-ray, infra-red and thermal analysis. The exchange properties of the studied materials improved on increasing the Sb, Ce or Sn molar ratios and the drying temperature. The rate of the isotopic exchange was controlled by particle diffusion for the metal ions studied and was faster as the heating temperature was increased but slower for materials with a higher exchange capacity. The physical thermodynamic parameters have been evaluated which give some information regarding the mechanism of ion exchange on the surface of inorganic materials. The removal of radioactive isotopes of Na + , Cs + , Sr 2+ , Co 2+ and Eu 3+ was carried out by in-situ precipitation or by using preformed precipitate of tin(IV) and cerium(IV) antimonates. The products of in-situ precipitations act as ion exchange materials with high chemical and radioactive stabilities. The new materials have relatively high capacity compared with CeSb and SnSb. The irradiated cerium(IV) antimonate has been successfully used for the quantitative separation of cesium which suggests its use in the treatment of active liquid waste. (author). 24 refs, 7 figs, 17 tabs

The role of electrolyte anions (ClO4-, NO3-, and Cl-) in divalent metal (M2+) adsorption on oxide and hydroxide surfaces in salt solutions

International Nuclear Information System (INIS)

Criscenti, L.J.; Sverjensky, D.A.

1999-01-01

Adsorption of divalent metal ions (M 2+ ) onto oxide and hydroxide surfaces from solutions of strong electrolytes has typically been inferred to take place without the involvement of the electrolyte anion. Only in situations where M 2+ forms a strong enough aqueous complex with the electrolyte anion (for example, CdCl + or PbCl + ) has it been frequently suggested that the metal and the electrolyte anion adsorb simultaneously. A review of experimental data for the adsorption of Cd 2+ , Pb 2+ , Co 2+ , UO 2 2+ , Zn 2+ , Cu 2+ , Ba 2+ , Sr 2+ , and Ca 2+ onto quartz, silica, goethite, hydrous ferric oxide, corundum, γ-alumina, anatase, birnessite, and magnetite, from NaNO 3 , KNO 3 , NaCl, and NaClO 4 solutions over a wide range of ionic strengths (0.0001 M-1.0 M), reveals that transition and heavy metal adsorption behavior with ionic strength is a function of the type of electrolyte. In NaNO 3 solutions, metal adsorption exhibits little or no dependence on the ionic strength of the solution. However, in NaCl solutions, transition and heavy metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption decreases strongly with increasing ionic strength. In NaClO 4 solutions, metal adsorption exhibits little dependence on ionic strength but is often suggestive of an increase in metal adsorption with increasing ionic strength. Analysis of selected adsorption edges was carried out using the extended triple-layer model and aqueous speciation models that included metal-nitrate, metal-chloride, and metal-hydroxide complexes

Development and testing of spheroidal inorganic sorbents

International Nuclear Information System (INIS)

Collins, J.L.; Egan, B.Z.; Anderson, K.K.

1996-01-01

Objective was to develop sodium titanate (ST) microspheres, made by the HMTA (hexamethylenetetramine) internal gelation process, to remove radionuclides and heavy metals from waste streams at DOE sites. to determine the optimum amount of ST that can be embedded in hydrous Ti oxide (HTO) microspheres, batches of 9.2 to 23.3% ST in HTO were prepared. Crush strength of the air-dried microspheres was found to be highest. Sr was removed from simulated supernatant by all composite microspheres; 13.2% ST/HTO worked best

No effect of H2O degassing on the oxidation state of hydrous rhyolite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations in six obsidian samples from the Mexican and Cascade arcs

Science.gov (United States)

Waters, L.; Lange, R. A.

2011-12-01

The extent to which degassing affects the oxidation state of arc magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of magmas, and it has been proposed that degassing may induce either oxidation or reduction depending on the initial oxidation state. A commonly proposed oxidation reaction is related to H2O degassing: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt). Another mechanism by which H2O degassing can affect the iron redox state is if dissolved water affects the activity of ferrous and/or ferric iron in the melt. Although Moore et al. (1995) presented experiments showing no evidence of an affect of dissolved water on the activity of the ferric-ferrous ratio in silicate melts, other experimental results (e.g., Baker and Rutherford, 1996; Gaillard et al., 2001; 2003) indicate that there may be such an effect in rhyolite liquids. It has long been understood that rhyolites, owing to their low total iron concentrations, are more sensitive than other magma types to degassing-induced change in redox state. Therefore, a rigorous test of whether H2O degassing affects the redox state of arc magmas is best evaluated on rhyolites. In this study, a comparison is made between the pre-eruptive (pre-degassing) Fe2+ concentrations in six, phenocryst-poor (volatiles, as indicated by the low loss on ignition values (LOI ≤ 0.7 wt%). In order to test how much oxidation of ferrous iron occurred as a consequence of that degassing, we measured the ferrous iron concentration in the bulk samples by titration, using the Wilson (1960) method, which was successfully tested again three USGS and one Canadian Geological Survey standards. Our results indicate no detectable change within analytical error between pre- and post-eruptive FeO concentrations, with an average deviation of 0.09 wt% and a maximum deviation of 0.15 wt%. Our results show that H2O degassing has no effect on the redox state of

Ga2O for target, solvent extraction for radiochemical separation and SnO2 for the preparation of a 68Ge/68Ga generator

International Nuclear Information System (INIS)

Aardaneh, K.; Walt, T.N. van der

2006-01-01

The target for the production of 68 Ge consists of a disc of gallium suboxide, Ga 2 O, with a 19 mm diameter. The suboxide was primarily prepared by repeatedly mixing metallic Ga and Ga 2 O 3 at 700 deg C. The target (2.4 g) was quite stable under a long-time irradiation with a 34 MeV proton beam at a current of ∼80 μA. The dissolution of the target was performed using 12M sulphuric acid solution, assisted with the dropwise addition of 30% H 2 O 2 solution, and took less than 4 hours. A solvent extraction method, using a 9M H 2 SO 4 - 0.3M HCl/CCl 4 system, was employed for the radiochemical separation of 68 Ge from Ga and Zn radionuclides, while 0.05M HCl was used for the back extraction of 68 Ge from the organic phase. The 68 Ge obtained in the dilute HCl was directly loaded onto a column containing either a hydrous tin dioxide or a crystalline tin dioxide, obtained by calcinations of the hydrous oxide at 450, 700, and 900 deg C. The calcinated hydrous tin dioxide at 900 deg C showed the highest crystallinity and highest 68 Ga elution yield and was selected for use in the generator. The 68 Ga elution from the column generator packed with 2 g of tin dioxide, using 3 ml of 1M HCl, and yielded an average of 65%. The breakthrough of 68 Ge was 6.1 x 10 -4 %. (author)

Plutonium(IV) precipitates formed in alkaline media in the presence of various anions

Energy Technology Data Exchange (ETDEWEB)

Krot, N.N.; Shilov, V.P.; Yusov, A.B.; Tananaev, I.G.; Grigoriev, M.S.; Garnov, A.Yu.; Perminov, V.P.; Astafurova, L.N.

1998-09-01

The tendency of Pu(IV) to hydrolyze and form true solutions, colloid solutions, or insoluble precipitates has been known since the Manhattan Project. Since then, specific studies have been performed to examine in detail the equilibria of Pu(IV) hydrolytic reactions in various media. Great attention also has been paid to the preparation, structure, and properties of Pu(IV) polymers or colloids. These compounds found an important application in sol-gel technology for the preparation of nuclear fuel materials. A most important result of these works was the conclusion that Pu(IV) hydroxide, after some aging, consists of very small PuO{sub 2} crystallites and should therefore be considered to be Pu(IV) hydrous oxide. However, studies of the properties and behavior of solid Pu(IV) hydroxide in complex heterogeneous systems are rare. The primary goal of this investigation was to obtain data on the composition and properties of Pu(IV) hydrous oxide or other compounds formed in alkaline media under different conditions. Such information is important to understand Pu(IV) behavior and the forms of its existence in the Hanford Site alkaline tank waste sludge. This knowledge then may be applied in assessing plutonium criticality hazards in the storage, retrieval, and treatment of Hanford Site tank wastes as well as in understanding its contribution to the transuranic waste inventory (threshold at 100 nCi/g or about 5 {times} 10{sup {minus}6} M) of the separate solution and solid phases.

Plutonium(IV) precipitates formed in alkaline media in the presence of various anions

International Nuclear Information System (INIS)

Krot, N.N.; Shilov, V.P.; Yusov, A.B.; Tananaev, I.G.; Grigoriev, M.S.; Garnov, A.Yu.; Perminov, V.P.; Astafurova, L.N.

1998-09-01

The tendency of Pu(IV) to hydrolyze and form true solutions, colloid solutions, or insoluble precipitates has been known since the Manhattan Project. Since then, specific studies have been performed to examine in detail the equilibria of Pu(IV) hydrolytic reactions in various media. Great attention also has been paid to the preparation, structure, and properties of Pu(IV) polymers or colloids. These compounds found an important application in sol-gel technology for the preparation of nuclear fuel materials. A most important result of these works was the conclusion that Pu(IV) hydroxide, after some aging, consists of very small PuO 2 crystallites and should therefore be considered to be Pu(IV) hydrous oxide. However, studies of the properties and behavior of solid Pu(IV) hydroxide in complex heterogeneous systems are rare. The primary goal of this investigation was to obtain data on the composition and properties of Pu(IV) hydrous oxide or other compounds formed in alkaline media under different conditions. Such information is important to understand Pu(IV) behavior and the forms of its existence in the Hanford Site alkaline tank waste sludge. This knowledge then may be applied in assessing plutonium criticality hazards in the storage, retrieval, and treatment of Hanford Site tank wastes as well as in understanding its contribution to the transuranic waste inventory (threshold at 100 nCi/g or about 5 x 10 -6 M) of the separate solution and solid phases

Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

Science.gov (United States)

Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.

2009-01-01

Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.

Radiation-induced non-equilibrium redox chemistry of plutonium: implications for environmental migration

International Nuclear Information System (INIS)

Haschke, J.M.; Siekhaus, W.J.

2009-01-01

Static concentrations of plutonium oxidation states in solution and at surfaces in oxide-water systems are identified as non-equilibrium steady states. These kinetically controlled systems are described by redox cycles based on irreversible disproportionation of Pu(IV), Pu(V), and Pu(VI) in OH-bridged intermediate complexes and at OH-covered oxide surfaces. Steady state is fixed by continuous redox cycles driven by radioactivity-promoted electron-transfer and energetically favorable reactions of Pu(III) and Pu(VII) disproportionation products with H2O. A model based on the redox cycles accounts for the high steady-state (Pu) coexisting with Pu(IV) hydrous oxide at pH 0-15 and for predominance of Pu(V) and Pu(VI) in solution. The steady-state (Pu) depends on pH and the surface area of oxide in solution, but not on the initial Pu oxidation state. PuO 2+x formation is attributed to high Pu(V) concentrations existing at water-exposed oxide surfaces. Results infer that migration of Pu in an aqueous environment is controlled by kinetic factors unique to that site and that the predominant oxidation states in solution are Pu(V) and Pu(VI)

Advance in the study of removal of cesium from radioactive wastewater by inorganic ion exchangers

International Nuclear Information System (INIS)

Wang Songping; Wang Xiaowei; Du Zhihui

2014-01-01

The excellent performance in the removal of cesium from radioactive wastewater by inorganic ion exchangers has received extensive attention due to their characteristic physico-chemical features. The paper summarized research progress of removal of cesium by different inorganic ion exchangers such as silicoaluminate, salts of hetero polyacid, hexacyanoferrate, insoluble salts of acid with multivalent metals, insoluble hydrous oxides of multivalent metals and silicotitanate and reviewed several removal systems of cesium by inorganic ion exchangers which might offer China some reference in treatment and disposal of radioactive wastewater. (authors)

MnO2/CNT supported Pt and PtRu nanocatalysts for direct methanol fuel cells.

Science.gov (United States)

Zhou, Chunmei; Wang, Hongjuan; Peng, Feng; Liang, Jiahua; Yu, Hao; Yang, Jian

2009-07-07

Pt/MnO2/carbon nanotube (CNT) and PtRu/MnO2/CNT nanocomposites were synthesized by successively loading hydrous MnO2 and Pt (or PtRu alloy) nanoparticles on CNTs and were used as anodic catalysts for direct methanol fuel cells (DMFCs). The existence of MnO2 on the surface of CNTs effectively increases the proton conductivity of the catalyst, which then could remarkably improve the performance of the catalyst in methanol electro-oxidation. As a result, Pt/MnO2/CNTs show higher electrochemical active surface area and better methanol electro-oxidation activity, compared with Pt/CNTs. As PtRu alloy nanoparticles were deposited on the surface of MnO2/CNTs instead of Pt, the PtRu/MnO2/CNT catalyst shows not only excellent electro-oxidation activity to methanol with forward anodic peak current density of 901 A/gPt but also good CO oxidation ability with lower preadsorbed CO oxidation onset potential (0.33 V vs Ag/AgCl) and peak potential (0.49 V vs Ag/AgCl) at room temperature.

Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

Science.gov (United States)

Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

2018-04-01

The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

The Enzymatic Oxidation of Graphene Oxide

Science.gov (United States)

Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

2011-01-01

Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

Water-bearing, high-pressure Ca-silicates

Science.gov (United States)

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

2017-07-01

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

A new approach to evaluate factors controlling elemental sediment–seawater distribution coefficients (K{sub d}) in coastal regions, Japan

Energy Technology Data Exchange (ETDEWEB)

Takata, Hyoe, E-mail: takata@kaiseiken.or.jp [Marine Ecology Research Institute, Central Laboratory, Onjuku, Chiba (Japan); National Institute of Radiological Sciences, Chiba City, Chiba (Japan); Aono, Tatsuo; Tagami, Keiko; Uchida, Shigeo [National Institute of Radiological Sciences, Chiba City, Chiba (Japan)

2016-02-01

In numerical models to simulate the dispersion of anthropogenic radionuclides in the marine environment, the sediment–seawater distribution coefficient (K{sub d}) for various elements is an important parameter. In coastal regions, K{sub d} values are largely dependent on hydrographic conditions and physicochemical characteristics of sediment. Here we report K{sub d} values for 36 elements (Na, Mg, Al, K, Ca, V, Mn, Fe, Co, Ni, Cu, Se, Rb, Sr, Y, Mo, Cd, I, Cs, rare earth elements, Pb, {sup 232}Th and {sup 238}U) in seawater and sediment samples from 19 Japanese coastal regions, and we examine the factors controlling the variability of these K{sub d} values by investigating their relationships to hydrographic conditions and sediment characteristics. There was large variability in K{sub d} values for Al, Mn, Fe, Co, Ni, Cu, Se, Cd, I, Pb and Th. Variations of K{sub d} for Al, Mn, Fe, Co, Pb and Th appear to be controlled by hydrographic conditions. Although K{sub d} values for Ni, Cu, Se, Cd and I depend mainly on grain size, organic matter content, and the concentrations of hydrous oxides/oxides of Fe and Mn in sediments, heterogeneity in the surface characteristics of sediment particles appears to hamper evaluation of the relative importance of these factors. Thus, we report a new approach to evaluate the factors contributing to variability in K{sub d} for an element. By this approach, we concluded that the K{sub d} values for Cu, Se, Cd and I are controlled by grain size and organic matter in sediments, and the K{sub d} value for Ni is dependent on grain size and on hydrous oxides/oxides of Fe and Mn. - Highlights: • K{sub d}s for 36 elements were determined in 19 Japanese coastal regions. • K{sub d}s for several elements appeared to be controlled by multiple factors in sediments. • We evaluated these factors based on physico-chemical characteristics of sediments.

The competing oxide and sub-oxide formation in metal-oxide molecular beam epitaxy

International Nuclear Information System (INIS)

Vogt, Patrick; Bierwagen, Oliver

2015-01-01

The hetero-epitaxial growth of the n-type semiconducting oxides β-Ga 2 O 3 , In 2 O 3 , and SnO 2 on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga 2 O, In 2 O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO 2 , somewhat lower for In 2 O 3 , and the lowest for Ga 2 O 3 . Our findings can be generalized to further oxides that possess related sub-oxides

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

Science.gov (United States)

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

Studies of the chemistry of transuranium elements and technetium at the Institute of Physical Chemistry, Russian Academy of Sciences, supported by the US Department of Energy

International Nuclear Information System (INIS)

Peretrukhin, V.F.

1995-04-01

Studies at Hanford in the 1980s revealed the potential for actinides to form stable soluble complexes in alkaline media, simulating radioactive tank waste. Pu(IV) hydrous oxide and Pu(VI) solubility increased with hydroxide concentration, ionic strength, and aluminate/carbonate concentrations. Subsequent contacts between US and Russian researchers in 1993 led to a technical literature review of the chemistry of TRU and Tc in alkaline media; this review addresses oxidation states, solubility, speciation, redox reactions, electrochemistry, radiation chemistry, and separations in alkaline media. As an outgrowth, a program of fundamental and applied chemistry studies of TRU and Tc is being conducted at IPC/RAS with US DOE support: solubility, redox reagents, coprecipitation, and radiation chemistry. This overview provides information on the Hanford Site tank waste system, US DOE technological needs, and IPC/RAS developments

Formaldehyde as a carbon and electron shuttle between autotroph and heterotroph populations in acidic hydrothermal vents of Norris Geyser Basin, Yellowstone National Park

Energy Technology Data Exchange (ETDEWEB)

Moran, James J.; Whitmore, Laura M.; Isern, Nancy G.; Romine, Margaret F.; Riha, Krystin M.; Inskeep, William P.; Kreuzer, Helen W.

2016-03-19

The Norris Geyser Basin in Yellowstone National Park contains a large number of hydrothermal systems, which host microbial populations supported by primary productivity associated with a suite of chemolithotrophic metabolisms. We demonstrate that Metallosphaera yellowstonesis MK1, a facultative autotrophic archaeon isolated from a hyperthermal acidic hydrous ferric oxide (HFO) spring in Norris Geyser Basin, excretes formaldehyde during autotrophic growth. To determine the fate of formaldehyde in this low organic carbon environment, we incubated native microbial mat (containing M. yellowstonensis) from a HFO spring with 13C-formaldehyde. Isotopic analysis of incubation-derived CO2 and biomass showed that formaldehyde was both oxidized and assimilated by members of the community. Autotrophy, formaldehyde oxidation, and formaldehyde assimilation displayed different sensitivities to chemical inhibitors, suggesting that distinct sub-populations in the mat selectively perform these functions. Our results demonstrate that electrons originally resulting from iron oxidation can energetically fuel autotrophic carbon fixation and associated formaldehyde excretion, and that formaldehyde is both oxidized and assimilated by different organisms within the native microbial community. Thus, formaldehyde can effectively act as a carbon and electron shuttle connecting the autotrophic, iron oxidizing members with associated heterotrophic members in the HFO community.

Tin-antimony oxide oxidation catalysts

Energy Technology Data Exchange (ETDEWEB)

Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

1998-12-15

Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

Sputtered tin oxide and titanium oxide thin films as alternative transparent conductive oxides

Energy Technology Data Exchange (ETDEWEB)

Boltz, Janika

2011-12-12

Alternative transparent conductive oxides to tin doped indium oxide have been investigated. In this work, antimony doped tin oxide and niobium doped titanium oxide have been studied with the aim to prepare transparent and conductive films. Antimony doped tin oxide and niobium doped titanium oxide belong to different groups of oxides; tin oxide is a soft oxide, while titanium oxide is a hard oxide. Both oxides are isolating materials, in case the stoichiometry is SnO{sub 2} and TiO{sub 2}. In order to achieve transparent and conductive films free carriers have to be generated by oxygen vacancies, by metal ions at interstitial positions in the crystal lattice or by cation doping with Sb or Nb, respectively. Antimony doped tin oxide and niobium doped titanium oxide films have been prepared by reactive direct current magnetron sputtering (dc MS) from metallic targets. The process parameters and the doping concentration in the films have been varied. The films have been electrically, optically and structurally analysed in order to analyse the influence of the process parameters and the doping concentration on the film properties. Post-deposition treatments of the films have been performed in order to improve the film properties. For the deposition of transparent and conductive tin oxide, the dominant parameter during the deposition is the oxygen content in the sputtering gas. The Sb incorporation as doping atoms has a minor influence on the electrical, optical and structural properties. Within a narrow oxygen content in the sputtering gas highly transparent and conductive tin oxide films have been prepared. In this study, the lowest resistivity in the as deposited state is 2.9 m{omega} cm for undoped tin oxide without any postdeposition treatment. The minimum resistivity is related to a transition to crystalline films with the stoichiometry of SnO{sub 2}. At higher oxygen content the films turn out to have a higher resistivity due to an oxygen excess. After post

Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

Science.gov (United States)

Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

2017-06-01

The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

Studies on sorption of plutonium on inorganic exchangers from sodium carbonate medium

Energy Technology Data Exchange (ETDEWEB)

Pius, I C; Charyulu, M M; Sivaramakrishnan, C K [Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai (India); Venkataramani, B [Chemistry Division, Bhabha Atomic Research Centre, Mumbai (India)

1994-06-01

Sorption of Pu(IV) from sodium carbonate medium has been investigated by using different inorganic exchangers alumina, silica gel and hydrous titanium oxide. Distribution ratios of Pu(IV) for its sorption on these exchangers from sodium carbonate medium were found to be sufficiently high indicating the suitability of these exchangers for the removal of Pu(IV). The presence of uranium and dibutyl phosphate do not have any effect on distribution ratio. The 10% Pu(IV) breakthrough capacities for above exchangers have been determined with 5 ml bed at a flow rate of 30 ml/hour. (author). 4 refs., 2 tabs.

Actinide chemistry in the far field

International Nuclear Information System (INIS)

Livens, F.R.; Morris, K.; Parkman, R.; Moyes, L.

1996-01-01

The environmental chemistry of the actinides is complicated due both to the extensive redox and coordination chemistry of the elements and also to the complexity of the reactive phases encountered in natural environments. In the far field, interactions with reactive surfaces, coatings and colloidal particles will play a crucial role in controlling actinide mobility. By virtue of both their abundance and reactivity; clays and other layer aluminosilicate minerals, hydrous oxides and organic matter (humic substances) are all identified as having the potential to react with actinide ions and some possible modes of interaction are described, together with experimental evidence for their occurrence. (author)

Preventing colloidal fouling in reverse osmosis and nano filtration system. Application of electron beam surface analysis; Prevencion del ensuciamiento coloidal en sistemas de osmosis inversa y nanofiltracion. Aplicacion del analisis de superficies con haces de electrones.

Energy Technology Data Exchange (ETDEWEB)

Sanz Ataz, J.; Guerrero Gallego, L.; Taberna Camprubi, E.; Pena Garcia, N.M; Carulla Contreras, C.; Blavia Bergos, J.

2003-07-01

Particulate matter in natural waters and wastewaters can cause fouling in reverse osmosis and nano filtration membranes. Common foulants includes organic and inorganic colloids; hydrous aluminum and iron silicates, silt, iron and manganese oxides, calcium carbonate, microorganisms, polysaccharides, lipoproteins, biological debris, etc. Predicting fouling of dispersed materials on membrane surface and brine flow channels uses the silt density index (SDI) and modified fouling index (MFI). Scanning electron microscopy (SEM) coupled with energy X-ray microanalysis (EDX) of SDI filters contributes to obtain information about shape, size and chemical composition of foulants and cake layer. (Author) 6 refs.

A coordination chemistry approach for modeling trace element adsorption

International Nuclear Information System (INIS)

Bourg, A.C.M.

1986-01-01

The traditional distribution coefficient, Kd, is highly dependent on the water chemistry and the surface properties of the geological system being studied and is therefore quite inappropriate for use in predictive models. Adsorption, one of the many processes included in Kd values, is described here using a coordination chemistry approach. The concept of adsorption of cationic trace elements by solid hydrous oxides can be applied to natural solids. The adsorption process is thus understood in terms of a classical complexation leading to the formation of surface (heterogeneous) ligands. Applications of this concept to some freshwater, estuarine and marine environments are discussed. (author)

Optical properties and electronic transitions of zinc oxide, ferric oxide, cerium oxide, and samarium oxide in the ultraviolet and extreme ultraviolet

DEFF Research Database (Denmark)

Pauly, N; Yubero, F; Espinós, J P

2017-01-01

Optical properties and electronic transitions of four oxides, namely zinc oxide, ferric oxide, cerium oxide, and samarium oxide, are determined in the ultraviolet and extreme ultraviolet by reflection electron energy loss spectroscopy using primary electron energies in the range 0.3-2.0 ke...

Solid oxide fuel cells fueled with reducible oxides

Science.gov (United States)

Chuang, Steven S.; Fan, Liang Shih

2018-01-09

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing the solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.

Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs

Science.gov (United States)

Sekkal, W.; Zaoui, A.

2013-04-01

Under earth surface conditions, in ocean and natural water, calcium carbonate is ubiquitous, forming anhydrous and hydrous minerals. These hydrous phases are of considerable interest for their role as precursors to stable carbonate minerals. Atomistic simulation techniques have been employed here to perform a comprehensive and quantitative study of the structural and energetic stability of dry and hydrous surfaces of calcium carbonate polymorphs using two recently developed forcefields. Results show that the dry forms are prone to ductility; while hydrous phases are found to be brittle. The (001) surface of monohydrocalcite appears to be the most stable (0.99 J/m2) whereas for the ikaite phase, the (001) surface is the most stable. The corresponding value is 0.2 J/m2, i.e. even lower than the surface energy of the Beautiful computed morphology pictures are obtained with Xiao's model and are very similar to the observed SEM images.

Highly oxidising fluids generated during serpentinite breakdown in subduction zones.

Science.gov (United States)

Debret, B; Sverjensky, D A

2017-09-04

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

ANL-1(A) - Development of nondestructive evaluation methods for structural ceramics

International Nuclear Information System (INIS)

Ellingson, W.A.; Roberts, R.A.; Gopalsami, N.; Dieckman, S.; Hentea, T.; Vaitekunas, J.J.

1989-01-01

This section includes the following papers: Development of Nondestructive Evaluation Methods for Structural Ceramics; Effects of Flaws on the Fracture Behavior of Structural Ceramics; Design, Fabrication, and Interface Characterization of Ceramic Fiber-Ceramic Matrix Composites; Development of Advanced Fiber-Reinforced Ceramics; Modeling of Fibrous Preforms for CVD Infiltration; NDT of Advanced Ceramic Composite Materials; Joining of Silicon Carbide Reinforced Ceramics; Superconducting Film Fabrication Research; Short Fiber Reinforced Structural Ceramics; Structural Reliability and Damage Tolerance of Ceramic Composites for High-Temperature Applications; Fabrication of Ceramic Fiber-Ceramic Matrix Composites by Chemical Vapor Infiltration; Characterization of Fiber-CVD Matrix interfacial Bonds; Microwave Sintering of Superconducting Ceramics; Improved Ceramic Composites Through Controlled Fiber-Matrix Interactions; Evaluation of Candidate Materials for Solid Oxide Fuel Cells; Ceramic Catalyst Materials: Hydrous Metal Oxide Ion-Exchange Supports for Coal Liquefaction; and Investigation of Properties and Performance of Ceramic Composite Components

Magnetic resonance as a structural probe of a uranium (VI) sol-gel process

International Nuclear Information System (INIS)

King, C.M.; Thompson, M.C.; Buchanan, B.R.; King, R.B.; Garber, A.R.

1989-01-01

NMR investigations on the ORNL process for sol-gel synthesis of microspherical nuclear fuel (UO 2 ), has been useful in sorting out the chemical mechanism in the sol-gel steps. 13 C, 15 N, and 1 H NMR studies on the HMTA gelation agent (Hexamethylene tetramine, C 6 H l2 N 4 ) has revealed near quantitative stability of this adamantane-like compound in the sol-Gel process, contrary to its historical role as an ammonia source for gelation from the worldwide technical literature. 17 0 NMR of uranyl (UO 2 ++ ) hydrolysis fragments produced in colloidal sols has revealed the selective formation of a uranyl trimer, [(UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 3 ] + , induced by basic hydrolysis with the HMTA gelation agent. Spectroscopic results show that trimer condensation occurs during sol-gel processing leading to layered polyanionic hydrous uranium oxides in which HMTAH + is occluded as an ''intercalation'' cation. Subsequent sol-gel processing of microspheres by ammonia washing results in in-situ ion exchange and formation of a layered hydrous ammonium uranate with a proposed structural formula of (NH 4 ) 2 [(UO 2 ) 8 O 4 (OH) 10 ] · 8H 2 0. This compound is the precursor to sintered U0 2 ceramic fuel

Effects of Oxidation on Oxidation-Resistant Graphite

Energy Technology Data Exchange (ETDEWEB)

Windes, William [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Rebecca [Idaho National Lab. (INL), Idaho Falls, ID (United States); Carroll, Mark [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-05-01

The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidation rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.

Self-assembled manganese oxide structures through direct oxidation

KAUST Repository

Zhao, Chao; Wang, Qingxiao; Yang, Yang; Zhang, Bei; Zhang, Xixiang

2012-01-01

The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

Self-assembled manganese oxide structures through direct oxidation

KAUST Repository

Zhao, Chao

2012-12-01

The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

Directory of Open Access Journals (Sweden)

Jacques C. Védrine

2016-01-01

Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

Energy Technology Data Exchange (ETDEWEB)

Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O. [Auburn Univ., AL (United States). Dept. of Civil Engeneering; Roden, E.E. [Wisconsin Univ., Madison, WI (United States). Dept. of Geology and Geophysics

2007-07-01

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

International Nuclear Information System (INIS)

Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O.; Roden, E.E.

2007-01-01

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

Simulation of 3D mesoscale structure formation in concentrated aqueous solution of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19). Application of dynamic mean-field density functional theory

NARCIS (Netherlands)

van Vlimmeren, BAC; Maurits, NM; Zvelindovsky, AV; Sevink, GJA; Fraaije, JGEM

1999-01-01

We simulate the microphase separation dynamics of aqueous solutions of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19) by a dynamic variant of mean-field density functional theory for

Polyaniline: Aniline oxidation with strong and weak oxidants under various acidity

Energy Technology Data Exchange (ETDEWEB)

Bláha, Michal, E-mail: blaha@imc.cas.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokeš, Jan [Charles University, Faculty of Mathematics and Physics, 180 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)

2017-06-15

Aniline was oxidized with three strong inorganic oxidants (ammonium peroxydisulfate, cerium(IV) sulfate, potassium dichromate), two weak inorganic oxidants (iron(III) chloride, silver nitrate), and one organic oxidant (p-benzoquinone) in aqueous solutions of methanesulfonic acid (MSA) of various concentration. Whereas oxidation of aniline with ammonium peroxydisulfate yielded high-molecular-weight conducting polyaniline (PANI) in the whole acidity range, the oxidation with cerium(IV) sulfate led also to a single product close to PANI with considerably lower molecular weight and lower conductivity. Potassium dichromate gave PANI only at high concentration of MSA. The use of iron(III) chloride yielded composite mixtures of PANI and low-molecular-weight aniline oligomers. The oxidation of aniline with silver nitrate led to composites of silver and an organic part, which was constituted either by aniline oligomers or conducting polyaniline or both. p-Benzoquinone as oxidant produced mainly aniline oligomers with poor conductivity and 2,5-dianilino-p-benzoquinone-like structure detected in FTIR and Raman spectra when oxidation proceeded with weak oxidants. A general model of oxidation with strong and weak oxidants was formulated. - Highlights: • Comparison of aniline oxidation with oxidants of different redox potential. • UV–vis, FTIR and Raman spectroscopies combined with size-exclusion chromatography. • The contents of polymer and oligomers were analyzed and discussed. • General model of aniline oxidation with strong and weak oxidants was formulated.

Oxidative Decarboxylation of Levulinic Acid by Cupric Oxides

Directory of Open Access Journals (Sweden)

Lu Lin

2010-11-01

Full Text Available In this paper, cupric oxides was found to effectively oxidize levulinic acid (LA and lead to the decarboxylation of levulinic acid to 2-butanone. The effects of cupric oxide dosage, reaction time and initial pH value were investigated in batch experiments and a plausible mechanism was proposed. The results showed that LA decarboxylation over cupric oxides at around 300 °C under acidic conditions produced the highest yield of butanone (67.5%. In order to elucidate the catalytic activity of cupric oxides, XRD, AFM, XPS and H2-TPR techniques was applied to examine their molecular surfaces and their effects on the reaction process.

Oxide ceramics

International Nuclear Information System (INIS)

Ryshkewitch, E.; Richerson, D.W.

1985-01-01

The book explores single-phase ceramic oxide systems from the standpoint of physical chemistry and technology. This second edition also focuses on advances in technology since publication of the original edition. These include improvements in raw materials and forming and sintering techniques, and the major role that oxide ceramics have had in development of advanced products and processes. The text is divided into five major sections: general fundamentals of oxide ceramics, advances in aluminum oxide technology, advances in zirconia technology, and advances in beryllium oxide technology

ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

Energy Technology Data Exchange (ETDEWEB)

Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

1977-12-11

The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

Alumina composites for oxide/oxide fibrous monoliths

International Nuclear Information System (INIS)

Cruse, T. A.; Polzin, B. J.; Picciolo, J. J.; Singh, D.; Tsaliagos, R. N.; Goretta, K. C.

2000-01-01

Most work on ceramic fibrous monoliths (FMs) has focused on the Si 3 N 4 /BN system. In an effort to develop oxidation-resistant FMs, several oxide systems have recently been examined. Zirconia-toughened alumina and alumina/mullite appear to be good candidates for the cell phase of FMs. These composites offer higher strength and toughness than pure alumina and good high-temperature stability. By combining these oxides, possibly with a weaker high-temperature oxide as the cell-boundary phase, it should be possible to product a strong, resilient FM that exhibits graceful failure. Several material combinations have been examined. Results on FM fabrication and microstructural development are presented

Development and testing of inorganic sorbents made by the internal gelation process for radionuclide and heavy metal separations

International Nuclear Information System (INIS)

Egan, B.Z.; Collins, J.L.; Anderson, K.K.; Chase, C.W.

1995-01-01

The objectives of this task are to develop, prepare, and test microspheres and granular forms of inorganic ion exchangers to remove radionuclides and heavy metals from waste streams occurring at various sites. Several inorganic materials, such as hexacyanoferrates, titanates, phosphates, and oxides have high selectivities and efficiencies for separating and removing radionuclides such as uranium, technetium, cesium, and strontium, and metals such as cobalt, silver, zinc, and zirconium from aqueous waste streams. However, these sorbents frequently exist only as powders and consequently are not readily adaptable to continuous processing such as column chromatography. Making these inorganic ion exchangers as microspheres or granular forms improves the flow dynamics for column operations and expands their practical applications. Microspheres of several materials have been prepared at ORNL, and the effectiveness of zirconium monohydrogen phosphate and hydrous titanium oxide microspheres for removing radionuclides from hot cell waste solutions has been demonstrated

Progress report, Health Sciences Division, 1 April - 30 June, 1980

International Nuclear Information System (INIS)

1980-08-01

A prototype pocket-sized gamma radiation warning dosimeter is being tested. The sorption of arsenic on CRNL soils stripped of oxide coatings is being studied to give an indication of the role of hydrous oxides in oxides in arsenic migration. The migration of iodide through fractured rock is being studied. Improvements have been made in source preparation and measurement techniques in the collaborative experiments on accelerator measurement of low levels of carbon-14. Work in radiation biology is continuing on induction of genetic changes in yeast by radiation and other agents, on the free radicals responsible for these changes, on photoproducts formed in DNA by ultraviolet radiation, on methods to study DNA damage and repair in irradiated human cells, on radiation sensitivity of cells from humans with various diseases associated with susceptibility to cancer, and on induction of cancers in rats by radiation in combination with environmental chemicals. Studies on radon and thoron daugther dosimetry were initiated in conjunction with a Nuclear Energy Agency Working Group. A procedure for the separation of 35 S and 32 p in bioassay was developed. (LL)

Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

Science.gov (United States)

Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

2012-11-05

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

Different coordination modes for disulfoxides towards diorganotin(IV) dichlorides. X-ray crystal structures of 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) and adducts [{l_brace}Ph{sub 2}SnCl{sub 2}(meso-bpse){r_brace}{sub n}] and [{l_brace}n-Bu{sub 2}SnCl{sub 2}(pdtd){r_brace}{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Sousa, Gerimario F. de [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica], e-mail: gfreitas@unb.br; Ellena, Javier [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Malta, Valeria R.S. [Universidade Federal de Alagoas (UFAL), Maceio, AL (Brazil). Dept. de Quimica e Biotecnologia; Ardisson, Jose D. [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil). Lab. de Fisica Aplicada

2009-07-01

The reactions of meso-1,2-bis(phenylsulfinyl)ethane (meso-bpse) with Ph{sub 2}SnCl{sub 2}, 2-phenyl-1,3-dithiane trans-1-trans-3-dioxide (pdtd) with n-Bu{sub 2}SnCl{sub 2} and 1,2-cis-bis-(phenylsulfinyl) ethene (rac-,cis-cbpse) with Ph{sub 2}SnCl{sub 2}, in 1:1 molar ratio, yielded [{l_brace}Ph{sub 2}SnCl{sub 2}(meso-bpse){r_brace}{sub n}], [{l_brace}n-Bu{sub 2}SnCl{sub 2}(pdtd){r_brace}{sub 2}] and [{l_brace}Ph{sub 2}SnCl{sub 2}(rac,cis-cbpse){r_brace}x] (x = 2 or n), respectively. All adducts were studied by IR, Moessbauer and {sup 119}Sn NMR spectroscopic methods, elemental analysis and single crystal X-ray diffractometry. The X-ray crystal structure of [{l_brace}Ph{sub 2}SnCl{sub 2}(meso-bpse){r_brace}{sub n}] revealed the occurrence of infinite chains in which the tin(IV) atoms appear in a distorted octahedral geometry with Cl atoms in cis and Ph groups in trans positions. The X-ray crystal structure of [{l_brace}n-Bu{sub 2}SnCl{sub 2}(pdtd){r_brace}{sub 2}] revealed discrete centrosymmetric dimeric species in which the tin(IV) atoms possess a distorted octahedral geometry with bridging disulfoxides in cis and n-butyl moieties in trans positions. The spectroscopic data indicated that the adduct containing the rac,cis-cbpse ligand can be dimeric or polymeric. The X-ray structural analysis of the free rac-,cis-cbpse sulfoxide revealed that the crystals belong to the C2/c space group. (author)

Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

Science.gov (United States)

Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

2013-09-24

A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

Energy Technology Data Exchange (ETDEWEB)

Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

2016-09-06

Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

Oxidized Lipoprotein as a Major Vessel Cell Proliferator in Oxidized Human Serum.

Directory of Open Access Journals (Sweden)

Yoshiro Saito

Full Text Available Oxidative stress is correlated with the incidence of several diseases such as atherosclerosis and cancer, and oxidized biomolecules have been determined as biomarkers of oxidative stress; however, the detailed molecular relationship between generated oxidation products and the promotion of diseases has not been fully elucidated. In the present study, to clarify the role of serum oxidation products in vessel cell proliferation, which is related to the incidence of atherosclerosis and cancer, the major vessel cell proliferator in oxidized human serum was investigated. Oxidized human serum was prepared by free radical exposure, separated using gel chromatography, and then each fraction was added to several kinds of vessel cells including endothelial cells and smooth muscle cells. It was found that a high molecular weight fraction in oxidized human serum specifically induced vessel cell proliferation. Oxidized lipids were contained in this high molecular weight fraction, while cell proliferation activity was not observed in oxidized lipoprotein-deficient serum. Oxidized low-density lipoproteins induced vessel cell proliferation in a concentration-dependent manner. Taken together, these results indicate that oxidized lipoproteins containing lipid oxidation products function as a major vessel cell proliferator in oxidized human serum. These findings strongly indicate the relevance of determination of oxidized lipoproteins and lipid oxidation products in the diagnosis of vessel cell proliferation-related diseases such as atherosclerosis and cancer.

Anaerobic sulfide-oxidation in marine colorless sulfur-oxidizing bacteria

Digital Repository Service at National Institute of Oceanography (India)

LokaBharathi, P.A.; Nair, S.; Chandramohan, D.

Colorless sulfur-oxidizing bacteria are ubiquitous in Indian waters and have the ability to oxidize sulfide under anaerobic conditions. These bacteria can not only mediate the sulfur cycle oxidatively but also the nitrogen cycle reductively without...

Interactions between iron oxides and copper oxides under hydrothermal conditions

Energy Technology Data Exchange (ETDEWEB)

McGarvey, G B; Owen, D G

1995-08-01

Under hydrothermal conditions, magnetite and hematite have been shown to undergo interconversion reactions, the extent of which is controlled in part by the presence of copper oxides. In oxygenated water, the degree to which magnetite was oxidized to hematite was found to be dependent on the presence of CuO or Cu{sub 2}O. When these materials were absent, the oxidation of magnetite was limited by the dissolved oxygen in the aqueous system. Participation of the copper oxides in the oxidation process was confirmed by more complete conversion of magnetite was also influenced by the presence of the copper oxides. In addition to driving the reduction to completion, the presence of the copper oxides also exerted a strong influence over the morphology of the magnetite that formed. (author). 13 refs., 1 tab., 3 figs.

Radiation-induced cationic polymerization of limonene oxide, α-pinene oxide, and β-pinene oxide

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1984-01-01

After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weight. A cationic mechanism is evidenced by the strongly retarding effect of tri-n-propylamine on the polymerization rate. At 25 0 C, limonene oxide gives the highest polymerization rates, an average conversion of 36% per Mrad being obtained in comparison with values of 5.7 and 7.3% per Mrad for the α-pinene and β-pinene oxides, respectively. Similarly, the average anti DP/sub n/ decreases from 11.8 for the limonene oxide polymer to 5.6 and 4.0 for the α-pinene oxide and β-pinene oxide polymers, respectively. A high frequency of chain transfer to monomer is indicated in each case by the fact that the kinetic chain lengths are estimated to be on the order of a hundred times larger than the anti DP/sub n/ values. Structural characterization of the limonene oxide polymer by 1 H and 13 C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the α-pinene and β-pinene oxides show that in the polymerization of these monomers, the opening of the epoxide ring is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-dimethyl group in the main chain. The detection of isopropenyl end groups in the pinene oxide polymers is also consistent with this mode of propagation being followed by chain (proton) transfer to monomer

Synthesis and Characterization of Tin (IV Tungstate Nanoparticles – A Solid Acid Catalyst

Directory of Open Access Journals (Sweden)

Manoj Sadanandan

2012-12-01

Full Text Available Tin (IV tungstate, a tetravalent metal acid salt was synthesized in the nanoform by chemical coprecipitation method using EDTA as capping agent. The material was found to be stable in mineral acids, bases and organic solvents except  in HF and aquaregia. The material was characterized using EDS, TG/DTA, FTIR, XRD, SEM, HRTEM and BET surface area measurement. The molecular formula of the compound is 2SnO2 3WO3.5H2O determined from elemental analysis using TG/DTA. Surface morphology and particle size were obtained using SEM and HRTEM. The surface area was found to be 205-225m2/g. The Na+ exchange capacity found to be 3.8 meq/g, indicates the presence of surface hydroxyl group and hence the presence of Bronsted acid sites. The catalytic activity of the material was tested by using esterification and oxidation as model reactions. For the esterification of different alcohols, the percentage yield was found to be high for n-alcohol compared to isomeric alcohols. Oxidation of benzyl alcohol gives benzaldehyde and benzoic acid as the only products. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 12nd June 2012, Revised: 23rd July 2012, Accepted: 29th July 2012[How to Cite: S. Manoj, R. Beena, (2012. Synthesis and Characterization of tin(IV Tungstate Nanoparticles – A Solid Acid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (2: 105-111. doi:10.9767/bcrec.7.2.3622.105-111] [How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.2.3622.105-111 ] | View in 

Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

Science.gov (United States)

Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-07-28

Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Revisiting the iron pools in cucumber roots: identification and localization.

Science.gov (United States)

Kovács, Krisztina; Pechoušek, Jiří; Machala, Libor; Zbořil, Radek; Klencsár, Zoltán; Solti, Ádám; Tóth, Brigitta; Müller, Brigitta; Pham, Hong Diep; Kristóf, Zoltán; Fodor, Ferenc

2016-07-01

Fe deficiency responses in Strategy I causes a shift from the formation of partially removable hydrous ferric oxide on the root surface to the accumulation of Fe-citrate in the xylem. Iron may accumulate in various chemical forms during its uptake and assimilation in roots. The permanent and transient Fe microenvironments formed during these processes in cucumber which takes up Fe in a reduction based process (Strategy I) have been investigated. The identification of Fe microenvironments was carried out with (57)Fe Mössbauer spectroscopy and immunoblotting, whereas reductive washing and high-resolution microscopy was applied for the localization. In plants supplied with (57)Fe(III)-citrate, a transient presence of Fe-carboxylates in removable forms and the accumulation of partly removable, amorphous hydrous ferric oxide/hydroxyde have been identified in the apoplast and on the root surface, respectively. The latter may at least partly be the consequence of bacterial activity at the root surface. Ferritin accumulation did not occur at optimal Fe supply. Under Fe deficiency, highly soluble ferrous hexaaqua complex is transiently formed along with the accumulation of Fe-carboxylates, likely Fe-citrate. As (57)Fe-citrate is non-removable from the root samples of Fe deficient plants, the major site of accumulation is suggested to be the root xylem. Reductive washing results in another ferrous microenvironment remaining in the root apoplast, the Fe(II)-bipyridyl complex, which accounts for ~30 % of the total Fe content of the root samples treated for 10 min and rinsed with CaSO4 solution. When (57)Fe(III)-EDTA or (57)Fe(III)-EDDHA was applied as Fe-source higher soluble ferrous Fe accumulation was accompanied by a lower total Fe content, confirming that chelates are more efficient in maintaining soluble Fe in the medium while less stable natural complexes as Fe-citrate may perform better in Fe accumulation.

Geochemistry of REE in Acid Mine Drainage: Sorption onto Basaluminite and Schwertmannite.

Science.gov (United States)

Lozano Letellier, A.; Ayora, C.; Fernandez-Martinez, A.

2017-12-01

The geochemistry of Rare Earth Elements (REE) has been investigated in natural streams and in mine areas during the last decades. Most of these studies agree that REE are mobile in acidic waters and they transferred to a solid phase when pH increases. However, there is no agreement on the pH range, on which precipitates can retain REE and the mechanisms responsible for the retention. Thus, whereas some authors determined that hydrous ferric oxides (HFOs) scavenge REE from pH 3, other authors observed REE retention by hydrous aluminum oxides (HAOs) from pH 4 to 6.1. A field survey conducted in the Odiel River in the SW Spain showed that pH values higher than 5, REE, Cu, Al and Fe concentrations in the river were lower than expected from a theoretical mixture because they were trapped in the precipitates. For pH below 4, however, only schwertmannite (Fe8O8OH6SO4) and no basaluminite (Al4SO4OH10·5H2O) precipitated. Then, REE, Cu and Al behaved conservatively and Fe does not, indicating that REE are trapped in the Al but not in the Fe solid phase. These observations are perfectly consistent with the REE accumulation in the Al-rich precipitates in the AMD treatment systems. Taking into account these observations, sorption experiments with synthetic basaluminite and schwertmannite at different pH were performed in the laboratory. For Lanthanides and Yttrium, sorption edge took place at pH higher than 5, whereas Sc sorption started at pH 4. A surface complexation model is proposed to explain the retention mechanism onto these two precipitates. Both minerals, schwertmannite and basaluminite showed similar sorption behavior. However, as schwertmannite formation occurs at pH lower than 4, no REE elements are sorbed on it.

Selective carbon monoxide oxidation over Ag-based composite oxides

Energy Technology Data Exchange (ETDEWEB)

Guldur, C. [Gazi University, Ankara (Turkey). Chemical Engineering Department; Balikci, F. [Gazi University, Ankara (Turkey). Institute of Science and Technology, Environmental Science Department

2002-02-01

We report our results of the synthesis of 1 : 1 molar ratio of the silver cobalt and silver manganese composite oxide catalysts to remove carbon monoxide from hydrogen-rich fuels by the catalytic oxidation reaction. Catalysts were synthesized by the co-precipitation method. XRD, BET, TGA, catalytic activity and catalyst deactivation studies were used to identify active catalysts. Both CO oxidation and selective CO oxidation were carried out in a microreactor using a reaction gas mixture of 1 vol% CO in air and another gas mixture was prepared by mixing 1 vol% CO, 2 vol% O{sub 2}, 84 vol% H{sub 2}, the balance being He. 15 vol% CO{sub 2} was added to the reactant gas mixture in order to determine the effect of CO{sub 2}, reaction gases were passed through the humidifier to determine the effect of the water vapor on the oxidation reaction. It was demonstrated that metal oxide base was decomposed to the metallic phase and surface areas of the catalysts were decreased when the calcination temperature increased from 200{sup o}C to 500{sup o}C. Ag/Co composite oxide catalyst calcined at 200{sup o}C gave good activity at low temperatures and 90% of CO conversion at 180{sup o}C was obtained for the selective CO oxidation reaction. The addition of the impurities (CO{sub 2} or H{sub 2}O) decreased the activity of catalyst for selective CO oxidation in order to get highly rich hydrogen fuels. (author)

Oxidized limonene and oxidized linalool - concomitant contact allergy to common fragrance terpenes.

Science.gov (United States)

Bråred Christensson, Johanna; Karlberg, Ann-Therese; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Giménez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

2016-05-01

Limonene and linalool are common fragrance terpenes. Both oxidized R-limonene and oxidized linalool have recently been patch tested in an international setting, showing contact allergy in 5.2% and 6.9% of dermatitis patients, respectively. To investigate concomitant reactions between oxidized R-limonene and oxidized linalool in consecutive dermatitis patients. Oxidized R-limonene 3.0% (containing limonene hydroperoxides 0.33%) and oxidized linalool 6% (linalool hydroperoxides 1%) in petrolatum were tested in 2900 consecutive dermatitis patients in Australia, Denmark, Singapore, Spain, Sweden, and the United Kingdom. A total of 281 patients reacted to either oxidized R-limonene or oxidized linalool. Of these, 25% had concomitant reactions to both compounds, whereas 29% reacted only to oxidized R-limonene and 46% only to oxidized linalool. Of the 152 patients reacting to oxidized R-limonene, 46% reacted to oxidized linalool, whereas 35% of the 200 patients reacting to oxidized linalool also reacted to oxidized R-limonene. The majority of the patients (75%) reacted to only one of the oxidation mixtures, thus supporting the specificity of the reactions. The concomitant reactions to the two fragrance allergens suggest multiple sensitizations, which most likely reflect the exposure to the different fragrance materials in various types of consumer products. This is in accordance with what is generally seen for patch test reactions to fragrance materials. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

New insights into uranium (VI) sol-gel processing

International Nuclear Information System (INIS)

King, C.M.; Thompson, M.C.; Buchanan, B.R.; King, R.B.; Garber, A.R.

1990-01-01

Nuclear Magnetic Resonance (NMR) investigations on the Oak Ridge National Laboratory process for sol-gel synthesis of microspherical nuclear fuel (UO 2 ), has been extremely useful in sorting out the chemical mechanism in the sol-gel steps. 13 C, 15 N, and 1 H NMR studies on the HMTA gelation agent (Hexamethylene tetramine, C 6 H 12 N 4 ) has revealed near quantitative stability of this adamantane-like compound in the sol-gel process, contrary to its historical role as an ammonia source for gelation from the worldwide technical literature. 17 O NMR of uranyl (UO 2 ++ ) hydrolysis fragments produced in colloidal sols has revealed the selective formation of a uranyl trimer, [(UO 2 ) 3 (μ 3 -O)(μ 2 -OH) 3 ] + , induced by basic hydrolysis with the HMTA gelation agent. Spectroscopic results will be presented to illustrate that trimer condensation occurs during sol-gel processing leading to layered polyanionic hydrous uranium oxides in which HMTAH + is occluded as an ''intercalation'' cation. Subsequent sol-gel processing of microspheres by ammonia washing results in in-situ exchange and formation of a layered hydrous ammonium uranate with a proposed structural formula of (NH 4 ) 2 [(UO 2 ) 8 O 4 (OH) 10 ] · 8H 2 O. This compound is the precursor to sintered UO 2 ceramic fuel. 23 refs., 10 figs

Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

Energy Technology Data Exchange (ETDEWEB)

You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

2017-08-15

Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

OpenAIRE

Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

2012-01-01

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

Oxidation films morphology

International Nuclear Information System (INIS)

Paidassi, J.

1960-01-01

After studying the oxidation of several pure polyvalent metals (Fe, Cu, Mn, Ni, U) and of their oxides at high temperature and atmospheric pressure, the author suggests how to modify the usual representation of the oxide film (a piling of different oxide layers, homogeneous on a micrographic scale with a equi-axial crystallisation, free of mechanical tensions, with flat boundary surfaces) to have it nearer to reality. In this first part, the author exposes the study of the real micrographic structure of the oxidation film and gives examples of precipitation in the oxides during the cooling of the oxidised sample. (author) [fr

New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

Science.gov (United States)

Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

2018-05-01

The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

Science.gov (United States)

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Tungsten oxide nanowires grown on graphene oxide sheets as high-performance electrochromic material

International Nuclear Information System (INIS)

Chang, Xueting; Sun, Shibin; Dong, Lihua; Hu, Xiong; Yin, Yansheng

2014-01-01

Graphical abstract: Electrochromic mechanism of tungsten oxide nanowires-reduced graphene oxide composite. - Highlights: • A novel inorganic-nano-carbon hybrid composite was prepared. • The hybrid composite has sandwich-like structure. • The hybrid composite exhibited high-quality electrohcromic performance. - Abstract: In this work, we report the synthesis of a novel hybrid electrochromic composite through nucleation and growth of ultrathin tungsten oxide nanowires on graphene oxide sheets using a facile solvothermal route. The competition between the growth of tungsten oxide nanowires and the reduction of graphene oxide sheets leads to the formation of sandwich-structured tungsten oxide-reduced graphene oxide composite. Due to the strongly coupled effect between the ultrathin tungsten oxide nanowires and the reduced graphene oxide nanosheets, the novel electrochromic composite exhibited high-quality electrochromic performance with fast color-switching speed, good cyclic stability, and high coloration efficiency. The present tungsten oxide-reduced graphene oxide composite represents a new approach to prepare other inorganic-reduced graphene oxide hybrid materials for electrochemical applications

Experimental investigation and thermodynamic simulation of the uranium oxide-zirconium oxide-iron oxide system in air

Czech Academy of Sciences Publication Activity Database

Petrov, Y. B.; Udalov, Y. P.; Šubrt, Jan; Bakardjieva, Snejana; Sázavský, P.; Kiselová, M.; Selucký, P.; Bezdička, Petr; Joumeau, C.; Piluso, P.

2011-01-01

Roč. 37, č. 2 (2011), s. 212-229 ISSN 1087-6596 Institutional research plan: CEZ:AV0Z40320502 Keywords : uranium oxide * zirconium oxide * iron oxide * fusibility curve * oxygen partial pressure * crystallization * phase composition Subject RIV: CA - Inorganic Chemistry Impact factor: 0.492, year: 2011

It has been suggested that oxidative stress, especially oxidative ...

African Journals Online (AJOL)

nabipour

2012-02-14

Feb 14, 2012 ... 1Department of Clinical Biochemistry, Faculty of Medicine, Bushehr University of Medical Sciences, Bushehr, Iran. 2Department of Cardiology ... oxidative modification of low-density lipoproteins (LDL), may play a causative role in ... the oxidation of lipids in the cell membrane especially the oxidation of LDL.

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

Science.gov (United States)

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

Science.gov (United States)

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

Oxidation kinetics of (B6O) boron oxide

International Nuclear Information System (INIS)

Makarov, V.S.; Solov'ev, N.E.; Ugaj, Ya.A.

1987-01-01

Reactivity of B 6 O to oxygen is investigated. It is shown that the process of B 6 O oxidation in the air in the temperature range 760-1150 K results in the maximum transformation degree equal to 0.35. At the initial stages oxidation proceeds in kinetic regime, at final stages - in diffusion one, and high viscosity of B 2 O 3 probably affects the oxidation process

Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks

Science.gov (United States)

Jones, J. Graham; Warner, C. G.

1972-01-01

Graham Jones, J., and Warner, C. G. (1972).Brit. J. industr. Med.,29, 169-177. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks. Occupational and medical histories, smoking habits, respiratory symptoms, chest radiographs, and ventilatory capacities were studied in 14 steelworkers employed as deseamers of steel ingots for periods of up to 16 years. The men were exposed for approximately five hours of each working shift to fume concentrations ranging from 1·3 to 294·1 mg/m3 made up mainly of iron oxide with varying proportions of chromium oxide and nickel oxide. Four of the men, with 14 to 16 years' exposure, showed radiological evidence of pneumoconiosis classified as ILO categories 2 or 3. Of these, two had pulmonary function within the normal range and two had measurable loss of function, moderate in one case and mild in the other. Many observers would diagnose these cases as siderosis but the authors consider that this term should be reserved for cases exposed to pure iron compounds. The correct diagnosis is mixed-dust pneumoconiosis and the loss of pulmonary function is caused by the effects of the mixture of metallic oxides. It is probable that inhalation of pure iron oxide does not cause fibrotic pulmonary changes, whereas the inhalation of iron oxide plus certain other substances obviously does. Images PMID:5021996

The 2016 oxide electronic materials and oxide interfaces roadmap

DEFF Research Database (Denmark)

Lorenz, M.; Rao, M. S. Ramachandra; Venkatesan, T.

2016-01-01

of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap......, Pentcheva, and Gegenwart. Finally, Miletto Granozio presents the European action ‘towards oxide-based electronics’ which develops an oxide electronics roadmap with emphasis on future nonvolatile memories and the required technologies.In summary, we do hope that this oxide roadmap appears as an interesting...

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

Science.gov (United States)

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.

Improved Understanding of In Situ Chemical Oxidation Contaminant Oxidation Kinetics

Science.gov (United States)

2007-12-01

natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE perchloroethylene HSO5− peroxymonosulfate PNDA p...properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and stability in the subsurface, and develop a standardized natural...chlorinated ethenes For contaminant oxidation by activated S2O82−, it is more difficult to develop a general description of kobs vs. T because there are

Saline Playas on Qinghai-Tibet Plateau as Mars Analog for the Formation-Preservation of Hydrous Salts and Biosignatures

Science.gov (United States)

Wang, A.; Zheng, M.; Kong, F.; Sobron, P.; Mayer, D. P.

2010-12-01

Qinghai-Tibet (QT) Plateau has the highest average elevation on Earth (~ 4500 m, about 50-60% of atmospheric pressure at sea-level). The high elevation induces a tremendous diurnal (and seasonal) temperature swing caused by high level of solar irradiation during the day and low level of atmospheric insulation during the evening. In addition, the Himalaya mountain chain (average height >6100 m) in the south of the QT Plateau largely blocks the pathway of humid air from the Indian Ocean, and produces a Hyperarid region (Aridity Index, AI ~ 0.04), the Qaidam Basin (N32-35, E90-100) at the north edge of the QT Plateau. Climatically, the low P, T, large ΔT, high aridity, and high UV radiation all make the Qaidam basin to be one of the most similar places on Earth to Mars. Qaidam basin has the most ancient playas (up to Eocene) and the lakes with the highest salinity on QT Plateau. More importantly, Mg-sulfates appear in the evaporative salts within the most ancient playas (Da Langtang) at the northwest corner of Qaidam basin, which mark the final stage of the evaporation sequence of brines rich in K, Na, Ca, Mg, Fe, C, B, S, and Cl. The evaporation minerals in the saline playas of Qaidam basin, their alteration and preservation under hyperarid conditions can be an interesting analog for the study of Martian salts and salty regolith. We conducted a field investigation at Da Langtan playa in Qaidam basin, with combined remote sensing (ASTER on board of NASA’s Terra satellite, 1.656, 2.167, 2.209, 2.62, 2.336, 2.40 µm), in situ sensing of a portable NIR spectrometer (WIR, 1.25-2.5 µm continuous spectral range), and the laboratory analyses of collected samples from the field (ASD spectrometer, 0.4 -2.5 µm, and Laser Raman spectroscopy). The results indicate that the materials contributing the high albedo layers in playa deposits are carbonate-gypsum-bearing surface soils, salt-clay-bearing exhaumed Pleistocene deposits, dehydrated Na-sulfates, hydrous Mg

Characterization of tin oxide nanoparticles synthesized via oxidation from metal

International Nuclear Information System (INIS)

Abruzzi, R.C.; Dedavid, B.A.; Pires, M.J.R.; Streicher, M.

2014-01-01

The tin oxide (SnO_2) is a promising material with great potential for applications such as gas sensors and catalysts. This oxide nanostructures show higher activation efficiency due to its larger effective surface. This paper presents the synthesis and characterization of the tin oxide in different conditions, via oxidation of pure tin with nitric acid. Results obtained from the characterization of SnO_2 powder by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDX), Particle size by Dynamic Light Scattering (DLS) and Infrared Spectroscopy (FTIR) indicated that the conditions were suitable for the synthesis to obtain manometric tin oxide granules with crystalline structure of rutile. (author)

The oxidation; Okislenie

Energy Technology Data Exchange (ETDEWEB)

Nikitin, V I

1961-07-01

In this chapter of book author determine that alkylene tetra hydro-{gamma}-piron, oxidated by potassium permanganate in all cases of passed oxidation gave oxidation products, confirmatory their structure.

Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Kung, H.H.; Kundalkar, B.; Kung, M.C.; Cheng, W.H.

1980-02-21

Adsorption, temperature-programed desorption, and pulse reaction studies of cis-2-butene and butadiene on spinel zinc ferrite by previously described methods provided evidence that the selectivity for oxidative dehydrogenation of butenes increases when zinc is added to the iron oxide catalyst because selective oxidation and complete oxidation proceed on separate sites, as they do on pure iron; because the density of sites for selective oxidation is higher and the density of sites for complete combustion is lower than on pure iron oxide; and because the activity of the combustion sites is lower.

Direct Coal Oxidation in Modified Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Deleebeeck, Lisa; Gil, Vanesa; Ippolito, Davide

2017-01-01

Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon-carbonate s......Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon......-carbonate slurry or anode layer. The nature of the coal affects both open circuit voltage and power output. Highest OCV and power densities were observed for bituminous coal and by adding manganese oxide or praseodymium-doped ceria to the carbon/carbonate mixture. Comparing the carbon black fueled performance...... bituminous coal (73 mW/cm2)....

Mechanism of 1, 1-d2 propene oxidation over oxide catalysts

International Nuclear Information System (INIS)

Portefaix, J.L.; Figueras, F.; Forissier, M.

1980-01-01

CD 2 CHCH 3 was oxidized over bismuth molybdate, tin-antimony mixed oxides and supported molybdenum and vanadium oxide catalysts. The deuterium retention is high ( > 90%) in the recovered propene. Percentage retentions of deuterium in the acrolein agree with literature data when bismuth molybdate is used as catalyst. On Sb-Sn-O and supported Mo and V oxides, no isotope effect is noticed for the abstraction of the second hydrogen from the olefin. The slow step of the reaction may therefore be different for the oxidation of propene on Bi-Mo-O and Sb-Sn-O. The ethanal produced by oxidation of CD 2 CHCH 3 contains only minor amounts of deuterium, whatever the catalyst used. It is suggested that partial oxidation of propene to acrolein and C-C bond rupture are parallel reactions which involve different intermediates. Possible mechanisms adapted from organic chemistry are presented to explain these findings. 4 tables

Oxidation phase growth diagram of vanadium oxides film fabricated by rapid thermal annealing

Institute of Scientific and Technical Information of China (English)

Tamura KOZO; Zheng-cao LI; Yu-quan WANG; Jie NI; Yin HU; Zheng-jun ZHANG

2009-01-01

Thermal evaporation deposited vanadium oxide films were annealed in air by rapid thermal annealing (RTP). By adjusting the annealing temperature and time, a series of vanadium oxide films with various oxidation phases and surface morphologies were fabricated, and an oxidation phase growth diagram was established. It was observed that different oxidation phases appear at a limited and continuous annealing condition range, and the morphologic changes are related to the oxidation process.

Oxidation of urate by a therapeutic nitric oxide/air mixture

International Nuclear Information System (INIS)

Hicks, M.; Nguyen, L.; Day, R.; Rogers, P.

1996-01-01

Full text: Little is known about the potential toxicological consequences of therapeutic exposure of lung tissue to inhaled nitric oxide (NO). This route of administration is currently being successfully employed for the treatment of pulmonary hypertension and other lung pathologies including acute reperfusion injury in lung transplant patients. The toxicity of NO lies in its ability to act as an oxidant either in its own right or in concert with oxygen or with the superoxide free radical. One important interaction may be the reaction of these products with protective antioxidants in the lung epithelial lining fluid. One such antioxidant found in significant concentrations in both upper and lower airways is uric acid. In the present study, urate solutions (30μM) were exposed to a therapeutic concentration of NO gas, (35 ppm in air), for up to 90 minutes. Oxidative changes were followed spectrophotometrically and by HPLC. Significant loss of uric acid was observed with a concomitant formation of nitrite and allantoin, the stable oxidation product of NO and the major oxidation product of uric acid, respectively. No oxidation of urate was observed in the presence of air alone or when urate was incubated with nitrite. Uric acid oxidation could also be prevented by passing the NO / air stream through 10% KOH before the uric acid solution. This strategy removed trace amounts of higher oxides of nitrogen, (especially NO 2 ), from the NO / air stream. Thus, therapeutic inhalation of NO may deplete soluble antioxidants such as uric acid, especially during long-term chronic exposure unless care is taken to minimise formation of higher oxides of nitrogen

Effect of the Lithium Oxide Concentration on a Reduction of Lanthanide Oxides

International Nuclear Information System (INIS)

Choi, In-Kyu; Jeong, Myeong-Soo; Do, Jae-Bum; Seo, Chung-Seok

2007-01-01

The pyrochemical reduction process of spent oxide fuel is one of the options to handle spent PWR fuels in Korea. After spent oxide fuel is converted to a metallic form, fission products will be removed from the resultant uranium and higher actinide metals by an electrorefining process. The chemical behaviors of lanthanide oxides during the pyrochemical process has been extensively studied. It was also reported that about 30 to 50% of several lanthanide oxides were reduced to corresponding metals by an electrolytic reduction process having 1 wt% of a lithium oxide concentration. Korea Atomic Energy Research Institute (KAERI), however, has been used 3 wt% of lithium oxide to increase the applied current of the electrolytic reduction process. Though it was reported that U 3 O 8 was reduced to uranium metal having a high reduction yield at 3 wt% of the Li 2 O concentration, the effect of the lithium oxide concentration on the reduction of lanthanide oxides has not been clarified

Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

International Nuclear Information System (INIS)

Fossing, H.

1992-01-01

Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

Direct Coal Oxidation in Modified Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Deleebeeck, Lisa; Gil, Vanesa; Ippolito, Davide

2015-01-01

Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon-carbonate s......Hybrid direct carbon fuel cells employ a classical solid oxide fuel cell together with carbon dispersed in a carbonate melt on the anode side. In a European project, the utilization of various coals has been investigated with and without addition of an oxidation catalyst to the carbon......-carbonate slurry or anode layer. The nature of the coal affects both open circuit voltage and power output. Highest OCV and power densities were observed for bituminous coal and by adding manganese oxide or praseodymium-doped ceria to the carbon/carbonate mixture. Comparing the carbon black fueled performance...... bituminous coal (73 mW/cm2). © 2015 ECS - The Electrochemical Society...

Reduced sediment melting at 7.5-12 GPa: phase relations, geochemical signals and diamond nucleation

Science.gov (United States)

Brey, G. P.; Girnis, A. V.; Bulatov, V. K.; Höfer, H. E.; Gerdes, A.; Woodland, A. B.

2015-08-01

Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5-12 GPa and 800-1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325-394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at 10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich ( 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients ( D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in

Fate and Distribution of Heavy Metals in Wastewater Irrigated Calcareous Soils

Science.gov (United States)

Stietiya, Mohammed Hashem; Duqqah, Mohammad; Udeigwe, Theophilus; Zubi, Ruba; Ammari, Tarek

2014-01-01

Accumulation of heavy metals in Jordanian soils irrigated with treated wastewater threatens agricultural sustainability. This study was carried out to investigate the environmental fate of Zn, Ni, and Cd in calcareous soils irrigated with treated wastewater and to elucidate the impact of hydrous ferric oxide (HFO) amendment on metal redistribution among soil fractions. Results showed that sorption capacity for Zarqa River (ZR1) soil was higher than Wadi Dhuleil (WD1) soil for all metals. The order of sorption affinity for WD1 was in the decreasing order of Ni > Zn > Cd, consistent with electrostatic attraction and indication of weak association with soil constituents. Following metal addition, Zn and Ni were distributed among the carbonate and Fe/Mn oxide fractions, while Cd was distributed among the exchangeable and carbonate fractions in both soils. Amending soils with 3% HFO did not increase the concentration of metals associated with the Fe/Mn oxide fraction or impact metal redistribution. The study suggests that carbonates control the mobility and bioavailability of Zn, Ni, and Cd in these calcareous soils, even in presence of a strong adsorbent such as HFO. Thus, it can be inferred that in situ heavy metal remediation of these highly calcareous soils using iron oxide compounds could be ineffective. PMID:24723833

Fate and Distribution of Heavy Metals in Wastewater Irrigated Calcareous Soils

Directory of Open Access Journals (Sweden)

Mohammed Hashem Stietiya

2014-01-01

Full Text Available Accumulation of heavy metals in Jordanian soils irrigated with treated wastewater threatens agricultural sustainability. This study was carried out to investigate the environmental fate of Zn, Ni, and Cd in calcareous soils irrigated with treated wastewater and to elucidate the impact of hydrous ferric oxide (HFO amendment on metal redistribution among soil fractions. Results showed that sorption capacity for Zarqa River (ZR1 soil was higher than Wadi Dhuleil (WD1 soil for all metals. The order of sorption affinity for WD1 was in the decreasing order of Ni > Zn > Cd, consistent with electrostatic attraction and indication of weak association with soil constituents. Following metal addition, Zn and Ni were distributed among the carbonate and Fe/Mn oxide fractions, while Cd was distributed among the exchangeable and carbonate fractions in both soils. Amending soils with 3% HFO did not increase the concentration of metals associated with the Fe/Mn oxide fraction or impact metal redistribution. The study suggests that carbonates control the mobility and bioavailability of Zn, Ni, and Cd in these calcareous soils, even in presence of a strong adsorbent such as HFO. Thus, it can be inferred that in situ heavy metal remediation of these highly calcareous soils using iron oxide compounds could be ineffective.

Protein oxidation in aquatic foods

DEFF Research Database (Denmark)

Baron, Caroline P.

2014-01-01

The chapter discusses general considerations about protein oxidation and reviews the mechanisms involved in protein oxidation and consequences of protein oxidation on fish proteins. It presents two case studies, the first deals with protein and lipid oxidation in frozen rainbow trout......, and the second with oxidation in salted herring. The mechanisms responsible for initiation of protein oxidation are unclear, but it is generally accepted that free radical species initiating lipid oxidation can also initiate protein oxidation. The chapter focuses on interaction between protein and lipid...... oxidation. The protein carbonyl group measurement is the widely used method for estimating protein oxidation in foods and has been used in fish muscle. The chapter also talks about the impact of protein oxidation on protein functionality, fish muscle texture, and food nutritional value. Protein oxidation...

Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

Science.gov (United States)

2009-05-01

methyl tert butyl ether NAPL non-aqueous phase liquid NOD natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE...and persulfate; and Technical Objective 2, assess how soil properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and...to develop a general description of kobs vs. T because there are many reactions that can contribute to the concentration of the reactive intermediate

A new langbeinite-type phosphate: K2AlSn(PO43

Directory of Open Access Journals (Sweden)

Dan Zhao

2011-10-01

Full Text Available Single crystals of the title compound, dipotassium aluminium tin(IV tris[phosphate(V], K2AlSn(PO43, were synthesized by a high temperature reaction in a platinum crucible. In the structure, the AlIII and SnIV atoms occupy the same site on a threefold rotation axis with occupational disorder in a 1:1 ratio. In the three-dimensional structure, Al/SnO6 octahedra and PO4 tetrahedra are interconnected via their vertices, yielding a [Al/SnP3O12]n framework. The K atoms (site symmetry 3 reside in the large cavities delimited by the [Al/SnP3O12]n framework, and are surrounded by 12 O atoms.

Oxidation Resistant Graphite Studies

Energy Technology Data Exchange (ETDEWEB)

W. Windes; R. Smith

2014-07-01

The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

Oxidizer Scoping Studies

Energy Technology Data Exchange (ETDEWEB)

Chancellor, Christopher John [Los Alamos National Laboratory

2016-11-07

The purpose of this report is to present the results of the acceptable knowledge (AK) review of oxidizers present in active waste streams, provide a technical analysis of the oxidizers, and report the results of the scoping study testing. This report will determine the fastest burning oxidizer to be used in the development of a Test Plan for Preparation and Testing of Sorbents Mixed with Oxidizer found in Transuranic Waste (DWT-TP-001). The companion report, DWT-RPT-002, Sorbent Scoping Studies, contains similar information for sorbents identified during the AK review of TRU waste streams. The results of the oxidizer and sorbent scoping studies will be used to inform the QL1 test plan. The QL1 test results will support the development of a basis of knowledge document that will evaluate oxidizing chemicals and sorbents in TRU waste and provide guidance for treatment.

The properties of protective oxide scales containing cerium on alloy 800H in oxidizing and oxidizing/sulphidizing environments

NARCIS (Netherlands)

Haanappel, V.A.C.; Haanappel, V.A.C.; Fransen, T.; Geerdink, Bert; Gellings, P.J.; Stroosnijder, M.F.

1991-01-01

The corrosion protection of oxide scales formed by electrophoretic deposition in a cerium-containing sol on Alloy 800H, a 32Ni-20Cr steel, followed by firing in air at 1123 K was studied in oxidizing and mixed oxidizing/sulphidizing environments at elevated temperatures. In particular, the influence

Spectrographic determination of impurities in high-purity tantalum oxide and niobium oxide

International Nuclear Information System (INIS)

Anderson, S.T.G.; Russell, G.M.

1990-01-01

The development of spectrographic methods by direct current arc excitation and carrier distillation for the determination of impurities in tantalum and niobium oxides are described. Iron, silicon, aluminium, titanium, calcium, silver, tin, magnesium, and manganese can be determined in tantalum oxide and niobium oxide in concentrations ranging from 3 to 300 p.p.m. Niobium can be determined in tantalum oxide in concentrations ranging from 10 to 300 p.p.m. Tantalum cannot be determined in niobium oxide, and tungsten cannot be determined in either matrix as a result of the absence of sensitive lines in the spectra of these elements. Relative standard deviations of analyte element concentrations are in the region of 0,18 for tantalum oxide samples, and 0,13 for niobium oxide samples. A detailed laboratory method is included. 4 figs., 4 tabs., 3 refs

Efficient synthesis of graphene oxide and the mechanisms of oxidation and exfoliation

Science.gov (United States)

Yuan, Rui; Yuan, Jing; Wu, Yanping; Chen, Lei; Zhou, Huidi; Chen, Jianmin

2017-09-01

An efficient method for the preparation of graphene oxide (GO) was descried through inducing the ultrasonic in the rate-determining step of oxidation processes. Both the transformation procedures and the detailed molecular behavior of parent graphene (PG), partially oxidized graphene (PGO) and GO in H2SO4 and aqueous solution were investigated by molecular dynamic simulation (MD) combining with experiments. The results obtained from MD simulation show that the addition of KMnO4 truly marked the beginning of the reaction which carried out from the border of PG flakes to the centre. This oxidation procedure was the rate-determining step and mainly contained three steps: the boundary carbon atoms oxidized, the distance of the corresponding interlayer enlarged and the oxidizing agent diffused into the unoxidized region, the processes was repeated until oxidized completely. So, the introducing ultrasonic in this section can accelerate not only the exfoliation of layers but also the diffusion of oxidizer and finally raises the oxidation efficiency dramatically. To further clarify these simulation results, the GO was prepared by the method mentioned above. The analyses results for the X-ray diffraction (XRD), Raman spectra and X-ray photoelectron spectroscopy (XPS) of the resulting GO show that the ultrasonic method could perfectly shortens the oxidation time from 12 h to 3 h and forms the higher degree of oxidation products with more carboxylic acid groups on its edges. Thus, this study provides a better understanding of the transformation procedures of graphite and proposes an efficient way to produce GOs suitable for various chemical modifications.

Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors

International Nuclear Information System (INIS)

Sivakkumar, S.R.; Ko, Jang Myoun; Kim, Dong Young; Kim, B.C.; Wallace, G.G.

2007-01-01

A ternary composite of CNT/polypyrrole/hydrous MnO 2 is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO 2 and polypyrrole/hydrous MnO 2 are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO 2 and polypyrrole/hydrous MnO 2 binary composites estimated by CV technique in 1.0 M Na 2 SO 4 electrolyte are 281, 150 and 35 F g -1 at 20 mV s -1 and 209, 75 and 7 F g -1 at 200 mV s -1 , respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s -1 . The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g -1 at a current loading of 1.0 mA cm -2 during initial cycling, which decreased drastically to a value of 35 F g -1 at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials

Green oxidations: Titanium dioxide induced tandem oxidation coupling reactions

OpenAIRE

Jeena, Vineet; Robinson, Ross S

2009-01-01

Summary The application of titanium dioxide as an oxidant in tandem oxidation type processes is described. Under microwave irradiation, quinoxalines have been synthesized in good yields from the corresponding ?-hydroxyketones.

Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

Science.gov (United States)

Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.

1996-01-01

In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in

Photochemical reduction of uranyl nitrate

Energy Technology Data Exchange (ETDEWEB)

Duerksen, W.K.

1993-10-20

The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

Influence of rare earth oxides in the oxidation of chromia forming alloys

International Nuclear Information System (INIS)

Ramanathan, L.V.

1989-01-01

The influence of superficial application of rare earth oxides such as CeO sub(2), La sub(2)O sub(3), Nd sub(2)O sub(3), Sm sub(2)O sub(3), and Gd sub(2)O sub (3) to AISI 304 and 310 stainless steels, on their isothermal oxidation behavior at 900 sup(0) and 1000 sup(0)C, and cyclic oxidation behavior between 20 sup(0) and 1000 sup(0)C has been studied. The application of rare earth oxides (REO) has been found to increase the oxidation resistance at AISI 304. No significant improvements in oxidation resistance of AISI 310 were noted. The oxidation resistance of AISI 304 was highest in the presence of CeO sub(2) on its surface. The other REO in decreasing order of influence on oxidation resistance are La sub(2)O sub(3), Nd sub(2)O sub(3), Sm sub(2)O sub(3) and Gd sub(2)O sub(3). SEM investigations of the oxide scale morphology revealed that the improved resistance is probably due to the formation of a thin layer of fine grained compact Cr sub(2)O sub(3) and the higher adhesion of the scale to its increased plasticity. (author)

Non-oxidative and oxidative torrefaction characterization and SEM observations of fibrous and ligneous biomass

International Nuclear Information System (INIS)

Chen, Wei-Hsin; Lu, Ke-Miao; Lee, Wen-Jhy; Liu, Shih-Hsien; Lin, Ta-Chang

2014-01-01

Highlights: • Non-oxidative and oxidative torrefaction of biomass is studied. • Two fibrous biomasses and two ligneous biomasses are tested. • SEM observations of four biomasses are provided. • Fibrous biomass is more sensitive to O 2 concentration than ligneous biomass. • The performance of non-oxidative torrefaction is better than that of oxidative torrefaction. - Abstract: Oxidative torrefaction is a method to reduce the operating cost of upgrading biomass. To understand the potential of oxidative torrefaction and its impact on the internal structure of biomass, non-oxidative and oxidative torrefaction of two fibrous biomass materials (oil palm fiber and coconut fiber) and two ligneous ones (eucalyptus and Cryptomeria japonica) at 300 °C for 1 h are studied and compared with each other. Scanning electron microscope (SEM) observations are also performed to explore the impact of torrefaction atmosphere on the lignocellulosic structure of biomass. The results indicate that the fibrous biomass is more sensitive to O 2 concentration than the ligneous biomass. In oxidative torrefaction, an increase in O 2 concentration decreases the solid yield. The energy yield is linearly proportional to the solid yield, which is opposite to the behavior of non-oxidative torrefaction. The performance of non-oxidative torrefaction is better than that of oxidative torrefaction. As a whole, ligneous biomass can be torrefied in oxidative environments at lower O 2 concentrations, whereas fibrous biomass is more suitable for non-oxidative torrefaction

Synthesis of graphene oxide through different oxidation degrees for solar cells

Science.gov (United States)

Zhang, Xiaoshan; Wang, Huan; Huang, Tianjiao; Wen, Lingling; Zhou, Liya

2018-03-01

Graphene is known as an electro-chemical material and widely used in electro-chemical devices, especially in solar cell. Decreasing the thickness of the layer is a critical way to improve the electrochemical property of solar cells as far as possible. Among the various oxidation approaches, presented herein is a facile approach, which is easier, less cost and more effective, environmental benign with the greener processing and without any requirement for post purification, towards the synthesis of graphene oxide (GO) with different oxidation degrees by potassium ferrate (K2FeO4). A modified method using less amount of oxidizing agent is reported herein. It is the pretreatment of the synthesis of graphite, which maintains the thermal cycle of the system. This novel reports to compound GO with controlled oxidation degrees can not only increase the quantity of oxygen-containing functional groups on GO surface, increase space between graphene oxide layer and facilitate the dispersion of graphene in aqueous solution. Thus, the modified method shows prospect for large-scale production of graphene oxide and its novel application, in addition to its derivative and market potential for solar cells.

Anodic oxidation

CERN Document Server

Ross, Sidney D; Rudd, Eric J; Blomquist, Alfred T; Wasserman, Harry H

2013-01-01

Anodic Oxidation covers the application of the concept, principles, and methods of electrochemistry to organic reactions. This book is composed of two parts encompassing 12 chapters that consider the mechanism of anodic oxidation. Part I surveys the theory and methods of electrochemistry as applied to organic reactions. These parts also present the mathematical equations to describe the kinetics of electrode reactions using both polarographic and steady-state conditions. Part II examines the anodic oxidation of organic substrates by the functional group initially attacked. This part particular

Oxidative Stress in Neurodegeneration

Directory of Open Access Journals (Sweden)

Varsha Shukla

2011-01-01

Full Text Available It has been demonstrated that oxidative stress has a ubiquitous role in neurodegenerative diseases. Major source of oxidative stress due to reactive oxygen species (ROS is related to mitochondria as an endogenous source. Although there is ample evidence from tissues of patients with neurodegenerative disorders of morphological, biochemical, and molecular abnormalities in mitochondria, it is still not very clear whether the oxidative stress itself contributes to the onset of neurodegeneration or it is part of the neurodegenerative process as secondary manifestation. This paper begins with an overview of how oxidative stress occurs, discussing various oxidants and antioxidants, and role of oxidative stress in diseases in general. It highlights the role of oxidative stress in neurodegenerative diseases like Alzheimer's, Parkinson's, and Huntington's diseases and amyotrophic lateral sclerosis. The last part of the paper describes the role of oxidative stress causing deregulation of cyclin-dependent kinase 5 (Cdk5 hyperactivity associated with neurodegeneration.

Cerium oxide and platinum nanoparticles protect cells from oxidant-mediated apoptosis

International Nuclear Information System (INIS)

Clark, Andrea; Zhu Aiping; Sun Kai; Petty, Howard R.

2011-01-01

Catalytic nanoparticles represent a potential clinical approach to replace or correct aberrant enzymatic activities in patients. Several diseases, including many blinding eye diseases, are promoted by excessive oxidant stress due to reactive oxygen species (ROS). Cerium oxide and platinum nanoparticles represent two potentially therapeutic nanoparticles that de-toxify ROS. In the present study, we directly compare these two classes of catalytic nanoparticles. Cerium oxide and platinum nanoparticles were found to be 16 ± 2.4 and 1.9 ± 0.2 nm in diameter, respectively. Using surface plasmon-enhanced microscopy, we find that these nanoparticles associate with cells. Furthermore, cerium oxide and platinum nanoparticles demonstrated superoxide dismutase catalytic activity, but did not promote hemolytic or cytolytic pathways in living cells. Importantly, both cerium oxide and platinum nanoparticles reduce oxidant-mediated apoptosis in target cells as judged by the activation of caspase 3. The ability to diminish apoptosis may contribute to maintaining healthy tissues.

Interface and oxide traps in high-κ hafnium oxide films

International Nuclear Information System (INIS)

Wong, H.; Zhan, N.; Ng, K.L.; Poon, M.C.; Kok, C.W.

2004-01-01

The origins of the interface trap generation and the effects of thermal annealing on the interface and bulk trap distributions are studied in detail. We found that oxidation of the HfO 2 /Si interface, removal of deep trap centers, and crystallization of the as-deposited film will take place during the post-deposition annealing (PDA). These processes will result in the removal of interface traps and deep oxide traps and introduce a large amount of shallow oxide traps at the grain boundaries of the polycrystalline film. Thus, trade-off has to be made in considering the interface trap density and oxide trap density when conducting PDA. In addition, the high interface trap and oxide trap densities of the HfO 2 films suggest that we may have to use the SiO 2 /HfO 2 stack or hafnium silicate structure for better device performance

Oxidation mechanisms occurring in wines

OpenAIRE

Oliveira, Carla Maria; Ferreira, António César Silva; Freitas, Victor De; Silva, Artur M. S.

2011-01-01

The present review aims to show the state of the art on the oxidation mechanisms occurring in wines, as well as the methods to monitor, classify and diagnose wine oxidation. Wine oxidation can be divided in enzymatic oxidation and non-enzymatic oxidation. Enzymatic oxidation almost entirely occurs in grape must and is largely correlated with the content of hydroxycinnamates, such as caffeoyltartaric acid and paracoumaroyltartaric acid, and flavan-3-ols. Non-enzymatic oxidation, al...

Improved Anode for a Direct Methanol Fuel Cell

Science.gov (United States)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the

Oxidation of uraninite

International Nuclear Information System (INIS)

Janeczek, J.; Ewing, R.C.

1993-06-01

Samples of uraninite and pitchblende annealed at 1200 degrees C in H 2 , and untreated pitchblende were sequentially oxidized in air at 180-190 degrees C, 230 degrees C, and 300 degrees C. Uraninite and untreated pitchblende oxidized to the U 4 O 9 -type oxide, and their x-ray symmetry remained isometric up to 300 degrees C. Reduced pitchblende, after oxidation to UO 2+x and U 4 O 9 -type oxides, transformed into α-U 3 O 8 at 300 degrees C. Two major mechanisms control uraninite and untreated pitchblende stability during oxidation: 1. Th and/or lanthanide elements maintain charge balance and block oxygen interstitials near impurity cations; 2. the uraninite structure saturates with respect to excess and radiation-induced oxygen interstitials. Untreated pitchblende during oxidation behaved similarly to irradiated UO 2 in spent nuclear fuel; whereas, reduced pitchblende resembled non-irradiated UO 2 . An analysis of the data in the literature, as well as our own efforts (XRD, EMPA, SEM, AEM) to identify U 3 O 7 in samples form Cigar Lake, Canada, failed to provide conclusive evidence of the natural occurrence of tetragonal αU 3 O 7 . Most probably, reported occurrences of U 3 O 7 are mixtures of isometric uraninites of slightly different compositions, 45 refs

Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

Science.gov (United States)

Javanaud, Cedric; Michotey, Valerie; Guasco, Sophie; Garcia, Nicole; Anschutz, Pierre; Canton, Mathieu; Bonin, Patricia

2011-11-01

Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Thermally exfoliated graphite oxide

Science.gov (United States)

Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

2011-01-01

A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

Study of the behaviour of inorganic ion exchangers in the treatment of medium active effluents. Part IV

International Nuclear Information System (INIS)

Beaven, G.W.; Cross, J.E.; Hooper, E.W.

1988-01-01

This report summarises some of the results from an ongoing experimental programme of work for the Department of the Environment on the potential use of inorganic ion exchangers for the treatment of medium active waste streams. Six different absorbers have been examined for their effectiveness in removing Am, Cs, Co, Sb, Ru, Eu, Ag, Zr, Nb, Zn and Mn ions from solutions varying from 4 M HNO 3 to 1 M NaNO 3 at pH 10. The ion exchangers tested were polyantimonic acid, hydrous titanium oxide, manganese dioxide, potassium copper hexacyanoferrate II, titanium phosphate and zirconium phosphate. The experimental results show that by suitable choice of absorber and operating conditions, good decontamination from all the radionuclides examined can be achieved. (author)

Zero-valent iron for the removal of soluble uranium in simulated DOE site groundwater

International Nuclear Information System (INIS)

Bostick, W.D.; Jarabek, R.J.; Fiedor, J.N.

1997-01-01

Groundwater at the Bear Creek Valley Characterization Area, located at the Oak Ridge Y-12 Plant, is contaminated with regulated metals and volatile organic compounds (VOCs) due to former site activities and disposal practices. The contaminant of principle concern, from the perspective of protecting human health, is soluble uranium, which is present in some waters at concentrations up to a few parts-per-million. We present product speciation and relative reaction kinetics; for removal of soluble uranium under oxic and anoxic conditions with use of zero-valent iron. Under oxic conditions, U(VI) is rapidly and strongly sorbed to hydrous ferric oxide particulate (open-quotes rustclose quotes), whereas uranium is slowly and incompletely reduced to U(IV) under anoxic conditions

The synthesis, characterization and properties of zirconium-chelating polymers

International Nuclear Information System (INIS)

Van Reenen, A.J.

1985-12-01

A series of homo- and copolymers based on the monomers : 2-propenoic acid, 2-methyl-2-propenoic acid, 2-chloro-2-propenoic acid, methylene butanedioic acid, ethenyl acetate and ethylene sulphonic acid have been synthesized and characterized. These polyelectrolytes were used with hydrous zirconium oxide to form novel dynamic membranes on Millipore filter substrates. These desalinating membranes were studied in terms of the chemical structure of the polyelectrolytes with regard to the effect of pH on their formation and performance characteristics. The effect of the charge density on the membranes was related to the membranes' figure of merit. Membrane studies were undertaken at pressures of 6 MPa and flow rates of 3,65 litres per minute. 59 figs., 20 tabs., 94 refs

Osmotic consolidation of suspensions and gels

International Nuclear Information System (INIS)

Miller, K.T.; Zukoski, C.F.

1994-01-01

An osmotic method for the consolidation of suspensions of ceramic particles is demonstrated. Concentrated solutions of poly(ethylene oxide) are separated from a suspension of ceramic particles by a semipermeable membrane, creating a gradient in solvent chemical potential. Solvent passes from the suspension into the polymer solution, lowering its free energy and consolidating the suspension. Dispersions of stable 8-nm hydrous zirconia particles were consolidated to over 47% by volume. Suspensions of α-alumina in three states of aggregation (dispersed, weakly flocculated, and strongly flocculated) were consolidated to densities greater than or equal to those produced in conventional pressure filtration. Moreover, the as-consolidated alumina bodies were partially drained of fluid during the osmotic consolidation process, producing cohesive partially dried bodies with improved handling characteristics

Process for anodizing aluminum foil

International Nuclear Information System (INIS)

Ball, J.A.; Scott, J.W.

1984-01-01

In an integrated process for the anodization of aluminum foil for electrolytic capacitors including the formation of a hydrous oxide layer on the foil prior to anodization and stabilization of the foil in alkaline borax baths during anodization, the foil is electrochemically anodized in an aqueous solution of boric acid and 2 to 50 ppm phosphate having a pH of 4.0 to 6.0. The anodization is interrupted for stabilization by passing the foil through a bath containing the borax solution having a pH of 8.5 to 9.5 and a temperature above 80 0 C. and then reanodizing the foil. The process is useful in anodizing foil to a voltage of up to 760 V

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

Science.gov (United States)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Oxidant/antioxidant balance in animal nutrition and health: the role of protein oxidation

Directory of Open Access Journals (Sweden)

Pietro eCeli

2015-10-01

Full Text Available This review examines the role that oxidative stress, and protein oxidation in particular, plays in nutrition, metabolism and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functional modifications. Protein oxidation seems to be involved in pathological conditions such as respiratory diseases and parasitic infection; however some studies also suggest that protein oxidation plays a crucial role in the regulation of important physiological functions such as reproduction, nutrition, metabolism, lactation, gut health and neonatal physiology. As the characterization of the mechanisms by which oxidative stress may influence metabolism and health is attracting considerable scientific interest, the aim of this review is to present veterinary scientists and clinicians with various aspects of oxidative damage to proteins.

High temperature oxidation test of oxide dispersion strengthened (ODS) steel claddings

International Nuclear Information System (INIS)

Narita, Takeshi; Ukai, Shigeharu; Kaito, Takeji; Ohtsuka, Satoshi; Matsuda, Yasushi

2006-07-01

In a feasibility study of ODS steel cladding, its high temperature oxidation resistance was evaluated. Although addition of Cr is effective for preventing high temperature oxidation, excessively higher amount of Cr leads to embrittlement due to the Cr-rich α' precipitate formation. In the ODS steel developed by the Japan Atomic Energy Agency (JAEA), the Cr content is controlled in 9Cr-ODS martensite and 12Cr-ODS ferrite. In this study, high temperature oxidation test was conducted for ODS steels, and their results were compared with that of conventional austenitic stainless steel and ferritic-martensitic stainless steel. Following results were obtained in this study. (1) 9Cr-ODS martensitic and 12Cr-ODS ferritic steel have superior high temperature oxidation resistance compared to 11mass%Cr PNC-FMS and even 17mass% SUS430 and equivalent to austenitic PNC316. (2) The superior oxidation resistance of ODS steel was attributed to earlier formation of the protective alpha-Cr 2 O 3 layer at the matrix and inner oxide scale interface. The grain size of ODS steel is finer than that of PNC-FMS, so the superior oxidation resistance of ODS steel can be attributed to the enhanced Cr-supplying rate throughout the accelerated grain boundary diffusion. Finely dispersed Y 2 O 3 oxide particles in the ODS steel matrix may also stabilized the adherence between the protective alpha-Cr 2 O 3 layer and the matrix. (author)

"A New Class of Creep Resistant Oxide/Oxide Ceramic Matrix Composites"

Energy Technology Data Exchange (ETDEWEB)

Dr. Mohit Jain, Dr. Ganesh Skandan, Prof. Roger Cannon, Rutgers University

2007-03-30

Despite recent progress in the development of SiC-SiC ceramic matrix composites (CMCs), their application in industrial gas turbines for distributed energy (DE) systems has been limited. The poor oxidation resistance of the non-oxide ceramics warrants the use of envrionmental barrier coatings (EBCs), which in turn lead to issues pertaining to life expectancy of the coatings. On the other hand, oxide/oxide CMCs are potential replacements, but their use has been limited until now due to the poor creep resistance at high temperatures, particularly above 1200 oC: the lack of a creep resistant matrix has been a major limiting factor. Using yttrium aluminum garnet (YAG) as the matrix material system, we have advanced the state-of-the-art in oxide/oxide CMCs by introducing innovations in both the structure and composition of the matrix material, thereby leading to high temperature matrix creep properties not achieved until now. An array of YAG-based powders with a unique set of particle characteristics were produced in-house and sintered to full density and compressive creep data was obtained. Aided in part by the composition and the microstructure, the creep rates were found to be two orders of magnitude smaller than the most creep resistant oxide fiber available commercially. Even after accounting for porosity and a smaller matrix grain size in a practical CMC component, the YAG-based matrix material was found to creep slower than the most creep resistant oxide fiber available commercially.

An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

Science.gov (United States)

Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

2015-09-14

Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts.

Size of oxide vacancies in fluorite and perovskite structured oxides

DEFF Research Database (Denmark)

Chatzichristodoulou, Christodoulos; Norby, Poul; Hendriksen, Peter Vang

2015-01-01

An analysis of the effective radii of vacancies and the stoichiometric expansion coefficient is performed on metal oxides with fluorite and perovskite structures. Using the hard sphere model with Shannon ion radii we find that the effective radius of the oxide vacancy in fluorites increases...... with increasing ion radius of the host cation and that it is significantly smaller than the radius of the oxide ion in all cases, from 37% smaller for HfO2 to 13 % smaller for ThO2. The perovskite structured LaGaO3 doped with Sr or Mg or both is analyzed in some detail. The results show that the effective radius...... of an oxide vacancy in doped LaGaO3 is only about 6 % smaller than the oxide ion. In spite of this the stoichiometric expansion coefficient (a kind of chemical expansion coefficient) of the similar perovskite, LaCrO3, is significantly smaller than the stoichiometric expansion coefficient of the fluorite...

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

OpenAIRE

Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

2014-01-01

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

Oxidation of zirconium alloys in steam: influence of tetragonal zirconia on oxide growth mechanism

International Nuclear Information System (INIS)

Godlewski, J.

1990-07-01

The oxidation of zirconium alloys in presence of steam, presents after a 'parabolic' growth law, an acceleration of the oxidation velocity. This phenomenon limits the use of zirconium alloys as nuclear fuel cladding element. In order to determine the physico-chemical process leading to this kinetic transition, two approaches have been carried out: the first one has consisted to determine the composition of the oxide layer and its evolution with the oxidation time; and the second one to determine the oxygen diffusion coefficients in the oxide layers of pre- and post-transition as well as their evolution with the oxidation time. The composition of the oxide layers has been determined by two analyses techniques: the X-ray diffraction and the laser Raman spectroscopy. This last method has allowed to confirm the presence of tetragonal zirconium oxide in the oxide layers. Analyses carried out by laser Raman spectroscopy on oxides oblique cuttings have revealed that the tetragonal zirconium oxide is transformed in monoclinic phase during the kinetic transition. A quantitative approach has allowed to corroborate the results obtained by these two techniques. In order to determine the oxygen diffusion coefficients in the oxides layers, two diffusion treatments have been carried out: 1)under low pressure with D 2 18 O 2 ) under high pressure in an autoclave with H 2 18 O. The oxygen 18 concentration profiles have been obtained by two analyses techniques: the nuclear microprobe and the secondary ions emission spectroscopy. The obtained profiles show that the mass transport is made by the volume and particularly by the grain boundaries. The corresponding diffusion coefficients have been calculated with the WHIPPLE and LE CLAIRE solution. The presence of tetragonal zirconium oxide, its relation with the kinetic transition, and the evolution of the diffusion coefficients with the oxidation time, are discussed in terms of internal stresses in the oxide layer and of the oxide layer

Sputtered indium oxide films

International Nuclear Information System (INIS)

Gillery, F.H.

1986-01-01

A method is described for depositing on a substrate multiple layer films comprising at least one primary layer of a metal oxide and at least one primary layer of a metal other than the metal of the oxide layer. The improvement described here comprises improving the adhesion between the metal oxide and metal layers by depositing between the layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers. An article of manufacture is described comprising a nonmetallic substrate, and deposited thereon in any order: a. at least one coating layer of metal; b. at least one coating layer of an oxide of a metal other than the metal of the metal layer; and c. deposited between the metal and metal oxide layers an intermediate metal-containing layer having an affinity for both the metal and metal oxide layers

Studies on O/M ratio determination in uranium oxide, plutonium oxide and uranium-plutonium mixed oxide

International Nuclear Information System (INIS)

Sampath, S.; Chawla, K.L.

1975-01-01

Thermogravimetric studies were carried out in unsintered and sintered samples of uranium oxide, plutonium oxide and uranium-plutonium mixed oxide under different atmospheric conditions (air, argon and moist argon/hydrogen). Moisture loss was found to occur below 200 0 C for uranium dioxide samples, upto 700 0 C for sintered plutonium dioxide and negligible for sintered samples. The O/M ratios for non-stoichiometric uranium dioxide (sintered and unsintered), plutonium dioxide and mixed uranium and plutonium oxides (sintered) could be obtained with a precision of +- 0.002. Two reference states UOsub(2.000) and UOsub(2.656) were obtained for uranium dioxide and the reference state MOsub(2.000) was used for other cases. For unsintered plutonium dioxide samples, accurate O/M ratios could not be obtained of overlap of moisture loss with oxygen loss/gain. (author)

Actinide oxide photodiode and nuclear battery

Energy Technology Data Exchange (ETDEWEB)

Sykora, Milan; Usov, Igor

2017-12-05

Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxides are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.

Porous ceramics out of oxides

International Nuclear Information System (INIS)

Bakunov, V.S.; Balkevich, V.L.; Vlasov, A.S.; Guzman, I.Ya.; Lukin, E.S.; Poluboyarinov, D.N.; Poliskij, R.Ya.

1977-01-01

A review is made of manufacturing procedures and properties of oxide ceramics intended for high-temperature thermal insulation and thermal protection applications. Presented are structural characteristics of porous oxide refractories and their properties. Strength and thermal conductivity was shown to depend upon porosity. Described is a procedure for manufacturing porous ceramic materials from aluminium oxide, zirconium dioxide, magnesium oxide, beryllium oxide. The thermal resistance of porous ceramics from BeO is considerably greater than that of other high-refractoriness oxides. Listed are areas of application for porous materials based on oxides

Thermal oxidation of silicon with two oxidizing species

International Nuclear Information System (INIS)

Vild-Maior, A.A.; Filimon, S.

1979-01-01

A theoretical model for the thermal oxidation of silicon in wet oxygen is presented. It is shown that the presence of oxygen in the oxidation furnace has an important effect when the water temperature is not too high (less than about 65 deg C). The model is in good agreement with the experimental data. (author)

Staphylococcal response to oxidative stress

Directory of Open Access Journals (Sweden)

Rosmarie eGaupp

2012-03-01

Full Text Available Staphylococci are a versatile genus of bacteria that are capable of causing acute and chronic infections in diverse host species. The success of staphylococci as pathogens is due in part to their ability to mitigate endogenous and exogenous oxidative and nitrosative stress. Endogenous oxidative stress is a consequence of life in an aerobic environment; whereas, exogenous oxidative and nitrosative stress are often due to the bacteria’s interaction with host immune systems. To overcome the deleterious effects of oxidative and nitrosative stress, staphylococci have evolved protection, detoxification, and repair mechanisms that are controlled by a network of regulators. In this review, we summarize the cellular targets of oxidative stress, the mechanisms by which staphylococci sense oxidative stress and damage, oxidative stress protection and repair mechanisms, and regulation of the oxidative stress response. When possible, special attention is given to how the oxidative stress defense mechanisms help staphylococci control oxidative stress in the host.

SPH based modelling of oxide and oxide film formation in gravity die castings

International Nuclear Information System (INIS)

Ellingsen, K; M'Hamdi, M; Coudert, T

2015-01-01

Gravity die casting is an important casting process which has the capability of making complicated, high-integrity components for e.g. the automotive industry. Oxides and oxide films formed during filling affect the cast product quality. The Smoothed particle hydrodynamics (SPH) method is particularly suited to follow complex flows. The SPH method has been used to study filling of a gravity die including the formation and transport of oxides and oxide films for two different filling velocities. A low inlet velocity leads to a higher amount of oxides and oxide films in the casting. The study demonstrates the usefulness of the SPH method for an increased understanding of the effect of different filling procedures on the cast quality. (paper)

Review Of Plutonium Oxidation Literature

International Nuclear Information System (INIS)

Korinko, P.

2009-01-01

A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles ( 250 (micro)m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

Synthesis of Graphene Oxide by Oxidation of Graphite with Ferrate(VI) Compounds: Myth or Reality?

Science.gov (United States)

Sofer, Zdeněk; Luxa, Jan; Jankovský, Ondřej; Sedmidubský, David; Bystroň, Tomáš; Pumera, Martin

2016-09-19

It is well established that graphene oxide can be prepared by the oxidation of graphite using permanganate or chlorate in an acidic environment. Recently, however, the synthesis of graphene oxide using potassium ferrate(VI) ions has been reported. Herein, we critically replicate and evaluate this new ferrate(VI) oxidation method. In addition, we test the use of potassium ferrate(VI) for the synthesis of graphene oxide under various experimental routes. The synthesized materials are analyzed by a number of analytical methods in order to confirm or disprove the possibility of synthesizing graphene oxide by the ferrate(VI) oxidation route. Our results confirm the unsuitability of using ferrate(VI) for the oxidation of graphite on graphene oxide because of its high instability in an acidic environment and low oxidation power in neutral and alkaline environments. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation of Ethylene Carbonate on Li Metal Oxide Surfaces

DEFF Research Database (Denmark)

Østergaard, Thomas M.; Giordano, Livia; Castelli, Ivano Eligio

2018-01-01

Understanding the reactivity of the cathode surface is of key importance to the development of batteries. Here, density functional theory is applied to investigate the oxidative decomposition of the electrolyte component, ethylene carbonate (EC), on layered LixMO(2) oxide surfaces. We compare...

Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

Science.gov (United States)

Renaud, Gilles

Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having

Performance evaluation of CNT/polypyrrole/MnO{sub 2} composite electrodes for electrochemical capacitors

Energy Technology Data Exchange (ETDEWEB)

Sivakkumar, S.R. [Department of Applied Chemistry and Biotechnology, Hanbat National University, San 16-1, Dukmyung-Dong, Yusung-Gu, Daejeon 305-719 (Korea, Republic of); Ko, Jang Myoun [Department of Applied Chemistry and Biotechnology, Hanbat National University, San 16-1, Dukmyung-Dong, Yusung-Gu, Daejeon 305-719 (Korea, Republic of)]. E-mail: jmko@hanbat.ac.kr; Kim, Dong Young [Optoelectronic Materials Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650 (Korea, Republic of); Kim, B.C. [ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia); Wallace, G.G. [ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia)

2007-09-15

A ternary composite of CNT/polypyrrole/hydrous MnO{sub 2} is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO{sub 2} and polypyrrole/hydrous MnO{sub 2} are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO{sub 2} and polypyrrole/hydrous MnO{sub 2} binary composites estimated by CV technique in 1.0 M Na{sub 2}SO{sub 4} electrolyte are 281, 150 and 35 F g{sup -1} at 20 mV s{sup -1} and 209, 75 and 7 F g{sup -1} at 200 mV s{sup -1}, respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s{sup -1}. The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g{sup -1} at a current loading of 1.0 mA cm{sup -2} during initial cycling, which decreased drastically to a value of 35 F g{sup -1} at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials.

Oxidation of zirconium-aluminum alloys

International Nuclear Information System (INIS)

Cox, B.

1967-10-01

Examination of the processes occurring during the oxidation of Zr-1% A1, Zr-3% A1, and Zr-1.5% A1-0.5% Mo alloys has shown that in steam rapid oxidation occurs predominantly around the Zr 3 A1 particles, which at low temperatures appear to be relatively unattacked. The unoxidised particles become incorporated in the oxide, and become fully oxidised as the film thickens. This rapid localised oxidation is preceded by a short period of uniform film growth, during which the oxide film thickness does not exceed ∼200A-o. Thus the high oxidation rates can probably be ascribed to aluminum in solution in the zirconium matrix, although its precise mode of operation has not been determined. Once the solubility limit of aluminum is exceeded, the size, distribution and number of intermetallic particles affects the oxidation rate merely by altering the distribution of regions of metal giving high oxidation rates. The controlling process during the early stages of oxidation is electron transport and not ionic transport. Thus, the aluminum in the oxide film is presumably increasing the ionic conductivity more than the electronic. The oxidation rates in atmospheric pressure steam are very high and their irregular temperature dependence suggests that the oxidation rate will be pressure dependent. This was confirmed, in part, by a comparison with oxidation in moist air. It was found that the rate of development of white oxide around intermetallic particles was considerably reduced by the decrease in the partial pressure of H 2 O; the incubation period was not much different, however. (author)

Influences of iron, manganese, and dissolved organic carbon on the hypolimnetic cycling of amended mercury

Energy Technology Data Exchange (ETDEWEB)

Chadwick, Shawn P. [University of Wisconsin-Madison, Environmental Chemistry and Technology Program, 660 North Park Street, Madison, WI 53706-1481 (United States)]. E-mail: spchadwick@wisc.edu; Babiarz, Chris L. [University of Wisconsin-Madison, Environmental Chemistry and Technology Program, 660 North Park Street, Madison, WI 53706-1481 (United States); Hurley, James P. [University of Wisconsin-Madison, Environmental Chemistry and Technology Program, 660 North Park Street, Madison, WI 53706-1481 (United States); University of Wisconsin Aquatic Sciences Center, 1975 Willow Drive Madison, WI 53706-1177 (United States); Armstrong, David E. [University of Wisconsin-Madison, Environmental Chemistry and Technology Program, 660 North Park Street, Madison, WI 53706-1481 (United States)

2006-09-01

The biogeochemical cycling of iron, manganese, sulfide, and dissolved organic carbon were investigated to provide information on the transport and removal processes that control the bioavailability of isotopic mercury amended to a lake. Lake profiles showed a similar trend of hypolimnetic enrichment of Fe, Mn, DOC, sulfide, and the lake spike ({sup 202}Hg, purity 90.8%) and ambient of pools of total mercury (HgT) and methylmercury (MeHg). Hypolimnetic enrichment of Fe and Mn indicated that reductive mobilization occurred primarily at the sediment-water interface and that Fe and Mn oxides were abundant within the sediments prior to the onset of anoxia. A strong relationship (r {sup 2} = 0.986, n = 15, p < 0.001) between filterable Fe and Mn indicated that reduction of Fe and Mn hydrous oxides in the sediments is a common in-lake source of Fe(II) and Mn(II) to the hypolimnion and that a consistent Mn : Fe mass ratio of 0.05 exists in the lake. A strong linear relationship of both the filterable [Fe] (r {sup 2} = 0.966, n = 15, p < 0.001) and [Mn] (r {sup 2} = 0.964, n = 15, p < 0.001) to [DOC] indicated a close linkage of the cycles of Fe and Mn to DOC. Persistence of iron oxides in anoxic environments suggested that DOC was being co-precipitated with Fe oxide and released into solution by the reductive dissolution of the oxide. The relationship between ambient and lake spike HgT (r {sup 2} = 0.920, n = 27, p < 0.001) and MeHg (r {sup 2} = 0.967, n = 23, p < 0.001) indicated that similar biogeochemical processes control the temporal and spatial distribution in the water column. The larger fraction of MeHg in the lake spike compared to the ambient pool in the hypolimnion suggests that lake spike may be more available for methylation. A linear relationship of DOC to both filterable ambient HgT (r {sup 2} = 0.406, n = 27, p < 0.001) and lake spike HgT (r {sup 2} = 0.314, n = 15, p = 0.002) suggest a role of organic matter in Hg transport and cycling. However, a weak

Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

Science.gov (United States)

Tojo, Tomohiro; Shinohara, Masaki; Fujisawa, Kazunori; Muramatsu, Hiroyuki; Hayashi, Takuya; Ahm Kim, Yoong; Endo, Morinobu

2012-10-01

Through coating with graphene oxides, we have developed a chemical route to the bulk production of long, thin manganese oxide (MnO2) nanowires that have high electrical conductivity. The average diameter of these hybrid nanowires is about 25 nm, and their average length is about 800 nm. The high electrical conductivity of these nanowires (ca. 189.51+/-4.51 µS) is ascribed to the homogeneous coating with conductive graphene oxides as well as the presence of non-bonding manganese atoms. The growth mechanism of the nanowires is theoretically supported by the initiation of morphological conversion from graphene oxide to wrapped structures through the formation of covalent bonds between manganese and oxygen atoms at the graphene oxide edge.

Oxidative stress

Directory of Open Access Journals (Sweden)

Osredkar Joško

2012-05-01

Full Text Available The human organism is exposed to the influence of various forms of stress, either physical, psychological or chemical, which all have in common that they may adversely affect our body. A certain amount of stress is always present and somehow directs, promotes or inhibits the functioning of the human body. Unfortunately, we are now too many and too often exposed to excessive stress, which certainly has adverse consequences. This is especially true for a particular type of stress, called oxidative stress. All aerobic organisms are exposed to this type of stress because they produce energy by using oxygen. For this type of stress you could say that it is rather imperceptibly involved in our lives, as it becomes apparent only at the outbreak of certain diseases. Today we are well aware of the adverse impact of radicals, whose surplus is the main cause of oxidative stress. However, the key problem remains the detection of oxidative stress, which would allow us to undertake timely action and prevent outbreak of many diseases of our time. There are many factors that promote oxidative stress, among them are certainly a fast lifestyle and environmental pollution. The increase in oxidative stress can also trigger intense physical activity that is directly associated with an increased oxygen consumption and the resulting formation of free radicals. Considering generally positive attitude to physical activity, this fact may seem at first glance contradictory, but the finding has been confimed by several studies in active athletes. Training of a top athlete daily demands great physical effort, which is also reflected in the oxidative state of the organism. However, it should be noted that the top athletes in comparison with normal individuals have a different defense system, which can counteract the negative effects of oxidative stress. Quite the opposite is true for irregular or excessive physical activity to which the body is not adapted.

Nitric oxide: a physiologic messenger.

Science.gov (United States)

Lowenstein, C J; Dinerman, J L; Snyder, S H

1994-02-01

To review the physiologic role of nitric oxide, an unusual messenger molecule that mediates blood vessel relaxation, neurotransmission, and pathogen suppression. A MEDLINE search of articles published from 1987 to 1993 that addressed nitric oxide and the enzyme that synthesizes it, nitric oxide synthase. Animal and human studies were selected from 3044 articles to analyze the clinical importance of nitric oxide. Descriptions of the structure and function of nitric oxide synthase were selected to show how nitric oxide acts as a biological messenger molecule. Biochemical and physiologic studies were analyzed if the same results were found by three or more independent observers. Two major classes of nitric oxide synthase enzymes produce nitric oxide. The constitutive isoforms found in endothelial cells and neurons release small amounts of nitric oxide for brief periods to signal adjacent cells, whereas the inducible isoform found in macrophages releases large amounts of nitric oxide continuously to eliminate bacteria and parasites. By diffusing into adjacent cells and binding to enzymes that contain iron, nitric oxide plays many important physiologic roles. It regulates blood pressure, transmits signals between neurons, and suppresses pathogens. Excess amounts, however, can damage host cells, causing neurotoxicity during strokes and causing the hypotension associated with sepsis. Nitric oxide is a simple molecule with many physiologic roles in the cardiovascular, neurologic, and immune systems. Although the general principles of nitric oxide synthesis are known, further research is necessary to determine what role it plays in causing disease.

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

International Nuclear Information System (INIS)

Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

2010-01-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

Energy Technology Data Exchange (ETDEWEB)

Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

2010-07-01

V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide.

Science.gov (United States)

Zhong, Rui; Zhang, Zhao; Zhao, Hongguo; He, Xianru; Wang, Xin; Zhang, Rui

2018-05-30

Graphene oxide (GO), modified with anti-aging agent p -phenylenediamine (PPD), was added into nitrile rubber (NBR) in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR), Raman, and X-ray diffraction (XRD). Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA) show an increased storage modulus (G') and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn⁻Wall⁻Ozawa (FWO) equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO⁻PPD. In addition, mechanical properties (tensile strength and elongation at break) of both before and after aged NBR/GO⁻PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

Catalytic Oxidation of Cyanogen Chloride over a Monolithic Oxidation Catalyst

National Research Council Canada - National Science Library

Campbell, Jeffrey

1997-01-01

The catalytic oxidation of cyanogen chloride was evaluated over a monolithic oxidation catalyst at temperatures between 200 and 300 deg C in air employing feed concentrations between 100 and 10,000 ppm...

Reversible solid oxide fuel cells (R-SOFCs) with chemically stable proton-conducting oxides

KAUST Repository

Bi, Lei

2015-07-01

Proton-conducting oxides offer a promising way of lowering the working temperature of solid oxide cells to the intermediate temperate range (500 to 700. °C) due to their better ionic conductivity. In addition, the application of proton-conducting oxides in both solid oxide fuel cells (SOFCs) and sold oxide electrolysis cells (SOECs) provides unique advantages compared with the use of conventional oxygen-ion conducting conductors, including the formation of water at the air electrode site. Since the discovery of proton conduction in some oxides about 30. years ago, the development of proton-conducting oxides in SOFCs and SOECs (the reverse mode of SOFCs) has gained increased attention. This paper briefly summarizes the development in the recent years of R-SOFCs with proton-conducting electrolytes, focusing on discussing the importance of adopting chemically stable materials in both fuel cell and electrolysis modes. The development of electrode materials for proton-conducting R-SOFCs is also discussed. © 2015 Elsevier B.V.

Oxidant/Antioxidant Balance in Animal Nutrition and Health: The Role of Protein Oxidation.

Science.gov (United States)

Celi, Pietro; Gabai, Gianfranco

2015-01-01

This review examines the role that oxidative stress (OS), and protein oxidation in particular, plays in nutrition, metabolism, and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functional modifications. Protein oxidation seems to be involved in pathological conditions, such as respiratory diseases and parasitic infection; however, some studies also suggest that protein oxidation plays a crucial role in the regulation of important physiological functions, such as reproduction, nutrition, metabolism, lactation, gut health, and neonatal physiology. As the characterization of the mechanisms by which OS may influence metabolism and health is attracting considerable scientific interest, the aim of this review is to present veterinary scientists and clinicians with various aspects of oxidative damage to proteins.

Copper-mediated oxidative degradation of catecholamines and oxidative damage of protein

Energy Technology Data Exchange (ETDEWEB)

Goncalves, P.R.; Harria, M.I.N.; Felix, J.M.; Hoffmann, M.E. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Biologia

1997-12-31

Full text. Degradative oxidation of catecholamines has been a matter of large interest in recent years due to the evidences associating their autoxidation with the etiology of neurotoxic and cardiotoxic processes. In this work we present data on the degradative oxidation of catecholamines of physiological importance: isoproterenol (IP), epinephrine (EP), norepinephrine (NEP), deoxyepinephrine (DEP) and dopamine (DA). The degradative oxidation of the catecholamines was followed by measurement of spectral changes and oxygen consumption by neutral aqueous solutions. The data show that Cu{sup 2+} strongly accelerated the rate of catecholamine oxidation, following the decreasing order; EP>DEP>IP>NEP>DA. The production of superoxide anion radical during catecholamine oxidation was very slow, even in the presence of Cu{sup 2+}. The ability of IP to induce damages on bovine serum albumin (BSA) was determined by measuring the formation of carbonyl-groups in the protein, detected by reduction with tritiated Na BH{sub 4}. The incubation of BSA with IP (50-500{mu}M), in the presence of 100{mu}M Cu{sup 2+} leaded to an increased and dose dependent {sup 3} H-incorporation by the oxidized protein. The production of oxidative damage by IP/Cu{sup 2+} was accompanied by marked BSA fragmentation, detected by SDS-polyacrylamide gel dependent (25-400{mu}M IP) des appearance of the original BSA band and appearance of smaller fragments spread in the gel, when incubation has been done in the presence of 100{mu}M Cu{sup 2+}. These results suggest that copper-catalysed oxidative degradation of proteins induced by catecholamines might be critically involved in the toxic action of these molecules

Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

International Nuclear Information System (INIS)

Dzhordano, N.; Bart, D.; Madzhori, R.

1984-01-01

A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

PREFACE: Semiconducting oxides Semiconducting oxides

Science.gov (United States)

Catlow, Richard; Walsh, Aron

2011-08-01

Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

Mechanism and Thermochemistry of Coal Char Oxidation and Desorption of Surface Oxides

DEFF Research Database (Denmark)

Levi, Gianluca; Causà, Mauro; Lacovig, Paolo

2017-01-01

The present study investigates the coal char combustion by a combination of thermochemical and X-ray photoemission spectroscopy (XPS) analyses. Thermoanalytical methods (differential thermogravimetry, differential scanning calorimetry, and temperature-programmed desorption) are used to identify...... the key reactive steps that occur upon oxidation and heating of coal char (chemisorption, structural rearrangement and switchover of surface oxides, and desorption) and their energetics. XPS is used to reveal the chemical nature of the surface oxides that populate the char surface and to monitor...... functionalities prevail. The rearrangement of epoxy during preoxidation goes together with activation of the more stable and less reactive carbon sites. Results are in good agreement with semi-lumped kinetic models of carbon oxidation, which include (1) formation of "metastable" surface oxides, (2) complex...

Rare earth oxide doping in oxide cathodes

International Nuclear Information System (INIS)

Engelsen, Daniel den; Gaertner, Georg

2006-01-01

The effect on life performance and poisoning with O 2 by doping oxide cathodes with rare earth oxides and pseudo rare earth oxides, notably yttria, is qualitatively explained in terms of electrolysis of BaO during emission of electrons. Doped cathodes show less electrolysis and consume therefore less Ba during life: consequently, doped cathodes have a better life performance. However, the lower Ba-production makes doped cathodes more sensitive to oxygen poisoning. The experimentally found relation between conductivity and yttria concentration was the motive to propose a new model for the crystal imperfections in BaO. In this new imperfection model most Y 3+ -ions will combine with barium vacancies, therefore, the increase of the conductivity is modest and also the effect on the position of the Fermi level is modest. By assuming a combination of bulk and surface conductivity, the agreement between experiment and theory can be improved further

Effects of stress on the oxide layer thickness and post-oxidation creep strain of zircaloy-4

International Nuclear Information System (INIS)

Lim, Sang Ho; Yoon, Young Ku

1986-01-01

Effects of compressive stress generated in the oxide layer and its subsequent relief on oxidation rate and post-oxidation creep characteristics of zircaloy-4 were investigated by oxidation studies in steam with and without applied tensile stress and by creep testing at 700 deg C in high purity argon. The thickness of oxide layer increased with the magnitude of tensile stress applied during oxidation at 650 deg C in steam whereas similar phenomenon was not observed during oxidation at 800 deg C. Zircaloy-4 specimens oxidized at 600 deg C in steam without applied stress exhibited higher creep strain than that shown by unoxidized specimens when creep-tested in argon. Zircaloy-4 specimens oxidized at 600 deg C steam under the applied stress of 8.53MPa and oxidized at 800 deg C under the applied stress of 0 and 8.53MPa exhibited lower strain than that shown by unoxidized specimen. The above experimental results were accounted for on the basis of interactions among applied stress during oxidation, compressive stress generated in the oxide layer and elasticity of zircaloy-4 matrix. (Author)

Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

International Nuclear Information System (INIS)

Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

2001-01-01

The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

Characterization and uranium bioleaching performance of mixed iron- and sulfur-oxidizers versus iron-oxidizers

International Nuclear Information System (INIS)

Qian Li; Jing Sun; Dexin Ding; Qingliang Wang; Wenge Shi; Eming Hu; Xiaoyu Jiang; University of South China, Hengyang; Xingxing Wang

2017-01-01

In order to develop and apply mixed iron- and sulfur-oxidizers in uranium bioleaching, the characteristics of a mixed iron- and sulfur-oxidizing consortium (Consortium ISO) were comparatively investigated versus an iron-oxidizing consortium (Consortium IO). The results showed, the Consortium ISO exerted stronger oxidative ability and acid-producing ability than Consortium IO did. The synergy of sulfur-oxidizers and iron-oxidizers could change the structure and properties of the passivation substance, and work positively for eliminating the accumulation of passivation substance. In the bioleaching process, the uranium bioleaching experiments showed the recovery percentage of uranium reached 99.5% with Consortium ISO, 6.3% more than that of Consortium IO. (author)

Thin zirconium oxides

International Nuclear Information System (INIS)

Oviedo, Cristina

2000-01-01

Polycrystalline Zr and two pure Zr single-crystal samples, one oriented with the normal to the surface parallel to the c-axis of the hcp structure (Z1) and the other with the normal perpendicular to c (Z2), were oxidised at 10 -8 , 10 -7 and 10 -6 Torr and room temperature. Oxidation kinetics, composition and thicknesses of the oxide films formed in each case were analyzed using XPS (X-ray Photoelectron Spectroscopy) as the main technique. The oxidation kinetics followed logarithmic laws in all cases. The deconvolution of XPS Zr3d peaks indicated the formation of two Zr-O compounds before the formation of ZrO 2 . Varying the photoelectrons take-off angle, the compound distribution inside the oxide films could be established. Thus, it was confirmed that the most external oxide, in contact with the gas, was ZrO 2 . The thickness of the films grown at the different pressures was determined. In the polycrystalline samples, thicknesses between 15 and 19 ± 2Angstroem were obtained for pressures between 10 -8 and 10 -6 Torr, in close coincidence with the determined ones for Z2. The thicknesses measured in Z1 were smaller, reaching 13 ± 2Angstroem for the oxidations performed at 10 -6 Torr. (author)

Selection of a Commercial Anode Oxide Coating for Electro-oxidation of Cyanide

Directory of Open Access Journals (Sweden)

Lanza Marcos Roberto V.

2002-01-01

Full Text Available This paper presents a study of the performance of two commercial dimensionally stable anode (DSA® oxide coatings in the electrochemical process for cyanide oxidation. The coatings studied were 70TiO2/30RuO2 and 55Ta2O5/45IrO2, on Ti substrate. The efficiency of both materials in the electro-oxidation of free cyanide was compared using linear voltammetry and electrolysis at constant potential. The 70TiO2/30RuO2 electrode shows a better performance in the electro-oxidation of free cyanide.

Staged membrane oxidation reactor system

Science.gov (United States)

Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

2012-09-11

Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

Global DNA methylation and oxidative stress biomarkers in workers exposed to metal oxide nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Liou, Saou-Hsing; Wu, Wei-Te; Liao, Hui-Yi [National Institute of Environmental Health Sciences, National Health Research Institutes, Zhunan, Miaoli County, Taiwan (China); Chen, Chao-Yu; Tsai, Cheng-Yen; Jung, Wei-Ting [Department of Chemistry, Fu Jen Catholic University, New Taipei City, Taiwan (China); Lee, Hui-Ling, E-mail: huilinglee3573@gmail.com [Department of Chemistry, Fu Jen Catholic University, New Taipei City, Taiwan (China)

2017-06-05

Highlights: • Global methylation and oxidative DNA damage levels in nanomaterial handling workers were assessed. • 8-isoprostane in exhaled breath condensate of workers exposed to nanoparticles was higher. • 8-OHdG was negatively correlated with global methylation. • Exposure to metal oxide nanoparticles may lead to global methylation and DNA oxidative damage. - Abstract: This is the first study to assess global methylation, oxidative DNA damage, and lipid peroxidation in workers with occupational exposure to metal oxide nanomaterials (NMs). Urinary and white blood cell (WBC) 8-hydroxydeoxyguanosine (8-OHdG), and exhaled breath condensate (EBC) 8-isoprostane were measured as oxidative stress biomarkers. WBC global methylation was measured as an epigenetic alteration. Exposure to TiO{sub 2}, SiO{sub 2,} and indium tin oxide (ITO) resulted in significantly higher oxidative biomarkers such as urinary 8-OHdG and EBC 8-isoprostane. However, significantly higher WBC 8-OHdG and lower global methylation were only observed in ITO handling workers. Significant positive correlations were noted between WBC and urinary 8-OHdG (Spearman correlation r = 0.256, p = 0.003). Furthermore, a significant negative correlation was found between WBC 8-OHdG and global methylation (r = −0.272, p = 0.002). These results suggest that exposure to metal oxide NMs may lead to global methylation, DNA oxidative damage, and lipid peroxidation.

Oxide ultrathin films science and technology

CERN Document Server

Pacchioni, Gianfranco

2012-01-01

A wealth of information in one accessible book. Written by international experts from multidisciplinary fields, this in-depth exploration of oxide ultrathin films covers all aspects of these systems, starting with preparation and characterization, and going on to geometrical and electronic structure, as well as applications in current and future systems and devices. From the Contents: Synthesis and Preparation of Oxide Ultrathin Films Characterization Tools of Oxide Ultrathin Films Ordered Oxide Nanostructures on Metal Surfaces Unusual Properties of Oxides and Other Insulators in the Ultrathin Limit Silica and High-K Dielectrics Thin Films in Microelectronics Oxide Passive Films and Corrosion Protection Oxide Films as Catalytic Materials and as Models of Real Catalysts Oxide Films in Spintronics Oxide Ultrathin Films in Solid Oxide Fuel Cells Transparent Conducting and Chromogenic Oxide Films as Solar Energy Materials Oxide Ultrathin Films in Sensor Applications Ferroelectricity in Ultrathin Film Capacitors T...

METAL OXIDE NANOPARTICLES

Energy Technology Data Exchange (ETDEWEB)

FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

2007-10-01

This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide

Directory of Open Access Journals (Sweden)

Rui Zhong

2018-05-01

Full Text Available Graphene oxide (GO, modified with anti-aging agent p-phenylenediamine (PPD, was added into nitrile rubber (NBR in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR, Raman, and X-ray diffraction (XRD. Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA show an increased storage modulus (G’ and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG and differential scanning calorimetry (DSC. Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn–Wall–Ozawa (FWO equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO–PPD. In addition, mechanical properties (tensile strength and elongation at break of both before and after aged NBR/GO–PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

On the Design of Oxide Films, Nanomaterials, and Heterostructures for Solar Water Oxidation Photoanodes

Science.gov (United States)

Kronawitter, Coleman Xaver

Photoelectrochemistry and its associated technologies show unique potential to facilitate the large-scale production of solar fuels—those energy-rich chemicals obtained through conversion processes driven by solar energy, mimicking the photosynthetic process of green plants. The critical component of photoelectrochemical devices designed for this purpose is the semiconductor photoelectrode, which must be optically absorptive, chemically stable, and possess the required electronic band alignment with respect to the redox couple of the electrolyte to drive the relevant electrochemical reactions. After many decades of investigation, the primary technological obstacle remains the development of photoelectrode structures capable of efficient and stable conversion of light with visible frequencies, which is abundant in the solar spectrum. Metal oxides represent one of the few material classes that can be made photoactive and remain stable to perform the required functions. The unique range of functional properties of oxides, and especially the oxides of transition metals, relates to their associated diversity of cation oxidation states, cation electronic configurations, and crystal structures. In this dissertation, the use of metal oxide films, nanomaterials, and heterostructures in photoelectrodes enabling the solar-driven oxidation of water and generation of hydrogen fuel is examined. A range of transition- and post-transition-metal oxide material systems and nanoscale architectures is presented. The first chapters present results related to electrodes based on alpha-phase iron(III) oxide, a promising visible-light-active material widely investigated for this application. Studies of porous films fabricated by physical vapor deposition reveal the importance of structural quality, as determined by the deposition substrate temperature, on photoelectrochemical performance. Heterostructures with nanoscale feature dimensionality are explored and reviewed in a later chapter

The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

Science.gov (United States)

Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

2016-05-01

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mechanisms of electrochemical reduction and oxidation of nitric oxide

NARCIS (Netherlands)

Vooys, de A.C.A.; Beltramo, G.L.; Riet, van B.; Veen, van J.A.R.; Koper, M.T.M.

2004-01-01

A summary is given of recent work on the reactivity of nitric oxide on various metal electrodes. The significant differences between the reactivity of adsorbed NO and NO in solution are pointed out, both for the reduction and the oxidation reaction(s). Whereas adsorbed NO can be reduced only to