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Sample records for hydrous oxide inorganic

  1. Method for preparing hydrous zirconium oxide gels and spherules

    DOEpatents

    Collins, Jack L.

    2003-08-05

    Methods for preparing hydrous zirconium oxide spherules, hydrous zirconium oxide gels such as gel slabs, films, capillary and electrophoresis gels, zirconium monohydrogen phosphate spherules, hydrous zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite sorbent, zirconium monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite, hydrous zirconium oxide fiber materials, zirconium oxide fiber materials, hydrous zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite and spherules of barium zirconate. The hydrous zirconium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process are useful as inorganic ion exchangers, catalysts, getters and ceramics.

  2. Thin film hydrous metal oxide catalysts

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.

    1995-01-01

    Thin film (<100 nm) hydrous metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

  3. Preparation and properties of coated, uniform, inorganic colloidal particles: I. Aluminum (hydrous) oxide on hematite, chromia, and titania

    SciTech Connect

    Kratohvil, S.; Matijevic, E. )

    1987-10-01

    Spherical alumina (hydrous) oxide particles of narrow size distribution were prepared by first hydrolyzing aluminum sulfate solutions at elevated temperatures in the presence of urea. The system was quenched before any solids were formed. Dilution of the prepared solutions at room temperature led to sol formation. The same procedure produced surface coatings on admixed, preformed solid particles. Uniform hematite, chromium hydroxide, and titania were used as core materials. The thickness of the coatings could be varied by proper adjustment of the concentrations of particles, aluminum salt solutions, and reaction time.

  4. Improved diffusive gradients in thin films (DGT) measurement of total dissolved inorganic arsenic in waters and soils using a hydrous zirconium oxide binding layer.

    PubMed

    Sun, Qin; Chen, Jing; Zhang, Hao; Ding, Shiming; Li, Zhu; Williams, Paul N; Cheng, Hao; Han, Chao; Wu, Longhua; Zhang, Chaosheng

    2014-03-18

    A high-capacity diffusive gradients in thin films (DGT) technique has been developed for measurement of total dissolved inorganic arsenic (As) using a long shelf life binding gel layer containing hydrous zirconium oxide (Zr-oxide). Both As(III) and As(V) were rapidly accumulated in the Zr-oxide gel and could be quantitatively recovered by elution using 1.0 M NaOH for freshwater or a mixture of 1.0 M NaOH and 1.0 M H2O2 for seawater. DGT uptake of As(III) and As(V) increased linearly with deployment time and was independent of pH (2.0-9.1), ionic strength (0.01-750 mM), the coexistence of phosphate (0.25-10 mg P L(-1)), and the aging of the Zr-oxide gel up to 24 months after production. The capacities of the Zr-oxide DGT were 159 μg As(III) and 434 μg As(V) per device for freshwater and 94 μg As(III) and 152 μg As(V) per device for seawater. These values were 5-29 times and 3-19 times more than those reported for the commonly used ferrihydrite and Metsorb DGTs, respectively. Deployments of the Zr-oxide DGT in As-spiked synthetic seawater provided accurate measurements of total dissolved inorganic As over the 96 h deployment, whereas ferrihydrite and Metsorb DGTs only measured the concentrations accurately up to 24 and 48 h, respectively. Deployments in soils showed that the Zr-oxide DGT was a reliable and robust tool, even for soil samples heavily polluted with As. In contrast, As in these soils was underestimated by ferrihydrite and Metsorb DGTs due to insufficient effective capacities, which were likely suppressed by the competing effects of phosphate.

  5. Method for preparing hydrous iron oxide gels and spherules

    DOEpatents

    Collins, Jack L.; Lauf, Robert J.; Anderson, Kimberly K.

    2003-07-29

    The present invention is directed to methods for preparing hydrous iron oxide spherules, hydrous iron oxide gels such as gel slabs, films, capillary and electrophoresis gels, iron monohydrogen phosphate spherules, hydrous iron oxide spherules having suspendable particles homogeneously embedded within to form composite sorbents and catalysts, iron monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent, iron oxide spherules having suspendable particles homogeneously embedded within to form a composite of hydrous iron oxide fiber materials, iron oxide fiber materials, hydrous iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, dielectric spherules of barium, strontium, and lead ferrites and mixtures thereof, and composite catalytic spherules of barium or strontium ferrite embedded with oxides of Mg, Zn, Pb, Ce and mixtures thereof. These variations of hydrous iron oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters, dielectrics, and ceramics.

  6. Semivolatile organic (GC-MS) and inorganic analyses of groundwater samples during the hydrous pyrolysis/oxidation (HPO) field test in Visalia, CA, 1997

    SciTech Connect

    Chiarappa, M; Knauss, K G; Kumamoto, G; Leif, R N; Newmark, R L

    1998-02-05

    Hydrous pyrolysis/oxidation (HPO) is a novel, in situ, thermal-remediation technology that uses hot, oxygenated groundwater to completely oxidize a wide range of organic pollutants. A field demonstration of HPO was performed during the summer of 1997 at the Southern California Edison Pole Yard in Visalia, California, a site contaminated with creosote. The goal of the field experiment was to confirm the success of HPO under field remediation conditions. The groundwater was heated by steam injections, and oxygen was added by co-injection of compressed air. The progress of the HPO remediation process was evaluated by monitoring groundwater from multiple wells for dissolved oxygen, dissolved inorganic carbon, and dissolved organic contaminant levels. Analyses of groundwater chemistry allowed us to measure the concentrations of creosote components and to identify oxygenated intermediates produced by the HPO treatment. Dissolved organic carbon levels increased in response to steam injections because of the enhanced dissolution and mobilization of the creosote into the heated groundwater. Elevated concentrations of phenols and benzoic acid were measured in wells affected by the steam injections. Concentrations of other oxygenated compounds (i.e., fluorenone, anthrone, and 9,10-anthracenedione) increased in response to the steam injections. The production of these partially oxidized compounds is consistent with the aqueous-phase HPO reactions of creosote. Additional changes in the groundwater in response to steam injection were also consistent with the groundwater HPO chemistry. A drop in dissolved oxygen was observed in the aquifer targeted for the steam injections, and isotope shifts in the dissolved inorganic pool reflected the input of oxidized carbon derived from the creosote carbon.

  7. Adsorption of inorganic and organic ligands onto hydrous aluminum oxide: evaluation of surface charge and the impacts on particle and NOM removal during water treatment.

    PubMed

    Pommerenk, Peter; Schafran, Gary C

    2005-09-01

    The variable removal from solution of sulfate, orthophosphate, fluoride, five simple organic acids, and natural organic matterfromtwo sources by adsorption on aluminum hydroxide was examined to assess their potential influence on coagulation during drinking water treatment. Measurements of electrophoretic mobility were conducted with adsorption studies to provide means of evaluating the impact of the adsorption of these anions on the removal of particulate material during coagulation at water treatment facilities. The three inorganic ions exhibited widely different trends in terms of removal from solution and effect on the surface charge of the aluminum hydroxide. Phosphate was nearly completely removed from solution across a wide pH range and was observed to lower surface charge and shift the isoelectric point. Sulfate was removed to a lesser extent than phosphate, lowered the surface charge on the precipitate, but did not shiftthe isoelectric point. Fluoride was well-removed through adsorption but exhibited no influence on the charge of the hydrous aluminum oxide. The organic acids similarly displayed varying abilities to be removed through adsorption and different influences on surface charge. The results indicate the importance of the number and location of functional groups and their acid/ base properties. The ability to strongly influence surface charge illustrates the impact that adsorption of these anions can have on particle stability.

  8. Inorganic particulates in removal of heavy metal toxic ions--part X: rapid and efficient removal of Hg(II) ions from aqueous solutions by hydrous ferric and hydrous tungsten oxides.

    PubMed

    Mishra, Suddhodan P; Vijaya

    2006-04-15

    A radiotracer technique has been used to study the removal of Hg(II) ions from aqueous solutions by synthesized and well-characterized hydrous ferric oxide (HFO) and hydrous tungsten oxide (HTO). Adsorptive concentration (10(-4)-10(-8) mol dm(-3)), pH (ca 4.0-10.0) and temperatures (303-333 K) were examined for assessing optimal conditions for removal of these ions. The uptake of Hg(II) ions, fitted well with the Freundlich isotherm, increased with increasing temperature. No significant desorption took place in the present temperature range. The presence of other anions and cations affected the uptake of Hg(II) markedly. Irradiation of hydrous ferric oxide and tungsten oxide by using a 11.1 x 10(9)Bq (Ra-Be) neutron source having a neutron flux of 3.9 x 10(6)cm(-2)s(-1) with the associated gamma-dose rate of 1.72 Gy h(-1) did not influence the extent of adsorption of Hg(II) significantly.

  9. Ion exchange properties of novel hydrous metal oxide materials

    SciTech Connect

    Gardner, T.J.; McLaughlin, L.I.

    1996-12-31

    Hydrous metal oxide (HMO) materials are inorganic ion exchangers which have many desirable characteristics for catalyst support applications, including high cation exchange capacity, anion exchange capability, high surface area, ease of adjustment of acidity and basicity, bulk or thin film preparation, and similar chemistry for preparation of various transition metal oxides. Cation exchange capacity is engineered into these materials through the uniform incorporation of alkali cations via manipulation of alkoxide chemistry. Specific examples of the effects of Na stoichiometry and the addition of SiO{sub 2} to hydrous titanium oxide (HTO) on ion exchange behavior will be given. Acid titration and cationic metal precursor complex exchange will be used to characterize the ion exchange behavior of these novel materials.

  10. Inorganic particulates in removal of heavy metal toxic ions IX. Rapid and efficient removal of Hg(II) by hydrous manganese and tin oxides.

    PubMed

    Mishra, Shuddhodan P; Dubey, Som Shankar; Tiwari, Diwakar

    2004-11-01

    Batch studies have been carried out in the removal of Hg(II) from aqueous solutions by using well-synthesized and -characterized hydrous manganese oxide (HMO) and hydrous tin oxide (HTO) employing a radiotracer technique. Results obtained reveal that increased sorptive concentration (10(-8)-10(-2) mol dm(-3)), temperature (298-328 K), and pH (ca. 2.0-10.5) enhance the removal efficiency of these solids. First-order uptake of Hg(II) on HMO and HTO follows the Freundlich adsorption isotherm for entire concentration range. Positive values of DeltaH0 for the uptake process on both solids indicate endothermic uptake and desorption experiments point to irreversible uptake. Radiation stability of the adsorbents has also been assessed using a 300-mCi (Ra-Be) neutron source having an integral neutron flux of 3.85 x 10(6) N cm(-2) s(-1) and associated with a nominal gamma-dose of ca. 1.72 Gy/h.

  11. Method for preparing hydrous titanium oxide spherules and other gel forms thereof

    DOEpatents

    Collins, J.L.

    1998-10-13

    The present invention are methods for preparing hydrous titanium oxide spherules, hydrous titanium oxide gels such as gel slabs, films, capillary and electrophoresis gels, titanium monohydrogen phosphate spherules, hydrous titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite sorbent, titanium monohydrogen phosphate spherules having suspendible particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, titanium oxide spherules in the form of anatase, brookite or rutile, titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite, hydrous titanium oxide fiber materials, titanium oxide fiber materials, hydrous titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite, titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite and spherules of barium titanate. These variations of hydrous titanium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters and ceramics. 6 figs.

  12. Method for preparing hydrous titanium oxide spherules and other gel forms thereof

    DOEpatents

    Collins, Jack L.

    1998-01-01

    The present invention are methods for preparing hydrous titanium oxide spherules, hydrous titanium oxide gels such as gel slabs, films, capillary and electrophoresis gels, titanium monohydrogen phosphate spherules, hydrous titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite sorbent, titanium monohydrogen phosphate spherules having suspendible particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, titanium oxide spherules in the form of anatase, brookite or rutile, titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite, hydrous titanium oxide fiber materials, titanium oxide fiber materials, hydrous titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite, titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite and spherules of barium titanate. These variations of hydrous titanium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters and ceramics.

  13. Formulation and method for preparing gels comprising hydrous hafnium oxide

    DOEpatents

    Collins, Jack L; Hunt, Rodney D; Montgomery, Frederick C

    2013-08-06

    Formulations useful for preparing hydrous hafnium oxide gels contain a metal salt including hafnium, an acid, an organic base, and a complexing agent. Methods for preparing gels containing hydrous hafnium oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including hafnium, an acid, an organic base, and a complexing agent.

  14. Formulation and method for preparing gels comprising hydrous aluminum oxide

    DOEpatents

    Collins, Jack L.

    2014-06-17

    Formulations useful for preparing hydrous aluminum oxide gels contain a metal salt including aluminum, an organic base, and a complexing agent. Methods for preparing gels containing hydrous aluminum oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including aluminum, an organic base, and a complexing agent.

  15. Formulation and method for preparing gels comprising hydrous cerium oxide

    SciTech Connect

    Collins, Jack L; Chi, Anthony

    2013-05-07

    Formulations useful for preparing hydrous cerium oxide gels contain a metal salt including cerium, an organic base, and a complexing agent. Methods for preparing gels containing hydrous cerium oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including cerium, an organic base, and a complexing agent.

  16. [Mechanism study of fluoride adsorption by hydrous metal oxides].

    PubMed

    Guo, Hui-Chao; Li, Wen-Jun; Chang, Zhi-Dong; Wang, Huan-Ying; Zhou, Yue

    2011-08-01

    Hydrous oxides of cerium, aluminum, nickel and copper were prepared by alkaline precipitation method. Langmuir adsorption isotherm was studied and specific surface area was measured by BET method through N2 adsorption-desorption process. IR characterization of hydrous metal oxides before and after fluoride adsorption was also studied. Results show that different hydrous metal oxides have different specific surface areas and their pore size distributions also are not all the same. Adsorption capacity is not directly dependent on the specific surface area. Isotherm study indicates that the adsorption follows Langmuir model and shows the feature of monolayer adsorption. IR study before and after fluoride adsorption shows that different hydrous metal oxides have similar adsorption sites in the same IR region as well as adsorption sites in the different IR region. The comprehensive interaction of these adsorption sites with fluoride ions results in the different adsorption capacity of different hydrous metal oxides.

  17. Hydrous oxide ion-exchange compound catalysts

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.

    1990-01-01

    A catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchange with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

  18. Catalysis using hydrous metal oxide ion exchangers

    DOEpatents

    Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

    1983-07-21

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  19. Catalysis using hydrous metal oxide ion exchanges

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

    1985-01-01

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  20. Hydrous metal oxide catalysts for oxidation of hydrocarbons

    SciTech Connect

    Miller, J.E.; Dosch, R.G.; McLaughlin, L.I.

    1993-07-01

    This report describes work performed at Sandia under a CRADA with Shell Development of Houston, Texas aimed at developing hydrous metal oxide (HMO) catalysts for oxidation of hydrocarbons. Autoxidation as well as selective oxidation of 1-octene was studied in the presence of HMO catalysts based on known oxidation catalysts. The desired reactions were the conversion of olefin to epoxides, alcohols, and ketones, HMOs seem to inhibit autoxidation reactions, perhaps by reacting with peroxides or radicals. Attempts to use HMOs and metal loaded HMOs as epoxidation catalysts were unsuccessful, although their utility for this reaction was not entirely ruled out. Likewise, alcohol formation from olefins in the presence of HMO catalysts was not achieved. However, this work led to the discovery that acidified HMOs can lead to carbocation reactions of hydrocarbons such as cracking. An HMO catalyst containing Rh and Cu that promotes the reaction of {alpha}-olefins with oxygen to form methyl ketones was identified. Although the activity of the catalyst is relatively low and isomerization reactions of the olefin simultaneously occur, results indicate that these problems may be addressed by eliminating mass transfer limitations. Other suggestions for improving the catalyst are also made. 57 refs.

  1. Interaction of tetracycline with aluminum and iron hydrous oxides.

    PubMed

    Gu, Cheng; Karthikeyan, K G

    2005-04-15

    The effect of solution chemistry (pH, sorbate-to-sorbent ratio, ionic strength (/)) and reaction time on the sorption of tetracycline to the hydrous oxides of Al (HAO) and Fe (HFO) was examined. Sorption to HAO increased with increasing pH upto pH 7 (no such trend for HFO) above which it decreased at higher pH values for both the hydrous oxides. Experimental results indicate that ligand-promoted dissolution is occurring during tetracycline sorption to these hydrous oxides. Ligand-promoted dissolution was more significantfor HAO than HFO attributable to the difference in labile surface sites between these two sorbents. The ability of tetracycline to form strong complexes with Al and Fe will increase the solubility of these minerals. Sorption of tetracycline was quite rapid and equilibrium was achieved after 8 h. However, soluble metal (Me: Al or Fe) concentrations attained equilibrium only after 24 h. Ligand-promoted dissolution appears to be a two-step process; initially, 1:1 Me-tetracycline soluble complexes are formed and as the reaction progresses 2:1 complexes existed. Increasing / (from 0.01 to 0.5 M) decreased the sorption extent only at higher sorbate-to-sorbent ratios suggesting the dominance of inner-sphere type complexes at low equilibrium tetracycline concentrations. Spectroscopic evidence indicates that tricarbonylamide and carbonyl functional groups of tetracycline could be responsible for sorption to mineral surfaces. Our research findings will increase understanding of the environmental occurrence, fate, and transport characteristics of antibiotics, which are considered as emerging organic contaminants.

  2. Adsorption of phosphate from aqueous solution by hydrous zirconium oxide.

    PubMed

    Rodrigues, Liana Alvares; Maschio, Leandro José; Coppio, Luciana de Simone Cividanes; Thim, Gilmar Patrocínio; da Silva, Maria Lúcia Caetano Pinto

    2012-06-01

    Synthetic ZrO2 x nH2O was used for phosphate removal from aqueous solution. The optimum adsorbent dose obtained for phosphate adsorption on to hydrous zirconium oxide was 0.1 g. The kinetic process was described very well by a pseudo-second-order rate model. The phosphate adsorption tended to increase with the decrease in pH. The adsorption capacity increased from 61 to 66 mg g(-1) when the temperature was increased from 298 to 338 K. A phosphate desorption of approximately 74% was obtained using water at pH 12.

  3. Thermal cleanups using dynamic underground stripping and hydrous pyrolysis oxidation

    SciTech Connect

    Aines, R D; Knauss, K; Leif, R; Newmark, R L

    1999-05-01

    In the early 1990s, in collaboration with the School of Engineering at the University of California, Berkeley, Lawrence Livermore National Laboratory developed dynamic underground stripping (DUS), a method for treating subsurface contaminants with heat that is much faster and more effective than traditional treatment methods. more recently, Livermore scientists developed hydrous pyrolysis/oxidation (HPO), which introduces both heat and oxygen to the subsurface to convert contaminants in the ground to such benign products as carbon dioxide, chloride ion, and water. This process has effectively destroyed all contaminants it encountered in laboratory tests. With dynamic underground stripping, the contaminants are vaporized and vacuumed out of the ground, leaving them still to be destroyed elsewhere. Hydrous pyrolysis/oxidation technology takes the cleanup process one step further by eliminating the treatment, handling, and disposal requirements and destroying the contamination in the ground. When used in combination, HPO is especially useful in the final polishing of a site containing significant free-product contaminant, once the majority of the contaminant has been removed.

  4. Development of hydrous titanium oxide catalysts for upgrading coal liquids

    SciTech Connect

    Lott, S.; Dosch, R.

    1993-07-01

    Improved efficiency in direct coal liquefaction processes can be obtained by developing catalysts with better activity, selectivity, and life. In previous exploratory research at Sandia National Laboratories, catalysts prepared via hydrous metal oxide (HMO) ion exchangers have been shown to have potential for application to a number of reactions associated with the conversion of coal to liquid fuels. In the present effort, one member of this class of catalysts, hydrous titanium oxide (HTO), has been developed for use in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of coal liquids. The unsupported (or bulk) NiMo-HTO catalyst performed well for HDS/HDN of a coal derived liquid as compared to the benchmark Shell 324 catalyst. The CoMo-HTO, while performing better than the Shell 324 catalyst, did not perform quite as well as the NiMo-HTO. In a side-by-side comparison of supported NiMo-HTO catalysts with commercial counterparts, the supported NiMo-HTO catalysts outperformed the Shell 324 and Amocat 1C catalysts on a weight of Mo basis. On a catalyst weight basis, the NiMo-HTO coated catalyst on a Shell 324 blank under performed Shell 324, while the NiMo-HTO coated catalyst on an Amocat 1C support performed as well as the Amocat 1C catalyst.

  5. Synthesis and characterization of a mesoporous hydrous zirconium oxide used for arsenic removal from drinking water

    SciTech Connect

    Bortun, Anatoly; Bortun, Mila; Pardini, James; Khainakov, Sergei A.; Garcia, Jose R.

    2010-02-15

    Powder (20-50 {mu}m) mesoporous hydrous zirconium oxide was prepared from a zirconium salt granular precursor. The effect of some process parameters on product morphology, porous structure and adsorption performance has been studied. The use of hydrous zirconium oxide for selective arsenic removal from drinking water is discussed.

  6. Experimental Methodology for Determining Optimum Process Parameters for Production of Hydrous Metal Oxides by Internal Gelation

    SciTech Connect

    Collins, J.L.

    2005-10-28

    The objective of this report is to describe a simple but very useful experimental methodology that was used to determine optimum process parameters for preparing several hydrous metal-oxide gel spheres by the internal gelation process. The method is inexpensive and very effective in collection of key gel-forming data that are needed to prepare the hydrous metal-oxide microspheres of the best quality for a number of elements.

  7. Kinetics of oxytetracycline reaction with a hydrous manganese oxide.

    PubMed

    Rubert, Kennedy F; Pedersen, Joel A

    2006-12-01

    Tetracycline antibiotics comprise a class of broad spectrum antimicrobial agents finding application in human therapy, animal husbandry, aquaculture, and fruit crop production. To better understand the processes affecting these antibiotics in soils and sediments, the kinetics of oxytetracycline transformation by a hydrous manganese oxide (MnO2) were investigated as a function of reactant concentration, pH, and temperature. Oxytetracycline was rapidly degraded by MnO2. Initial reaction rates exhibited pronounced pH-dependence, increasing as pH decreased. Reaction of oxytetracycline with MnO2 was accompanied by generation of Mn(II) ions, suggesting oxidative transformation of the antibiotic. At pH 5.6, apparent reaction orders for oxytetracycline and MnO2 were 0.7 and 0.8. Reaction order with respect to H+ was 0.6 between pH 4 and 9. Initial reaction rates increased by a factor of approximately 2.4 for 10 degrees C temperature increases; the apparent activation energy (60 kJ x mol(-1)) was consistent with a surface-controlled reaction. Reactivity of tetracycline antibiotics toward MnO2 increased in the following order: rolitetracyline oxytetracycline < or =tetracycline approximately meclocycline < chlortetracycline. The initial rate of chlortetracycline degradation by MnO2 was substantially larger than that of the other tetracycline antibiotics investigated. MnO2 reactivity toward oxytetracycline decreased with time; a retarded rate equation was used to describe oxytetracycline reaction with MnO2 under declining rate conditions. This study indicates that natural manganese oxides in soils and sediments are likely to promote appreciable degradation of tetracycline antibiotics, and that reaction rates are strongly dependent on reaction time scale and solution conditions.

  8. Dietary bioavailability of Cu adsorbed to colloidal hydrous ferric oxide

    USGS Publications Warehouse

    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.

  9. Inorganic Halogen Oxidizers.

    DTIC Science & Technology

    1984-02-22

    this series of compounds is needed to verify this effect. The F NMR spectra of these salts were recorded in an- hydrous HF solutions at 29 °C. In...The yield of only 55% for CIF6BF4 can be attributed to the following factors: (i) hang-up of some mother liquor on »he filter cake; (ii) possibly...basis of NF4HF:. With most of ’me Ni4Ili2 * allies losi being due lo hang up of some mother liquor on the CsSbF6 filter cake during the metathc teal

  10. Preparation and characterization of cellulose/hydrous niobium oxide hybrid.

    PubMed

    Maschio, Leandro José; Pereira, Paulo Henrique Fernandes; Da Silva, Maria Lucia Caetano Pinto

    2012-07-01

    A composite of cellulose extracted from bagasse with Nb2O5·nH2O in three different proportions (16.67, 37.5 and 50.0 wt%) was prepared using the co-precipitation method. The materials were characterized by X-ray diffractometry (XRD), Fourier transform infra-red spectroscopy (FTIR), thermogravimetric analysis (TG/DTG), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). TG data obtained show that the presence of inorganic material influenced slightly the stability of the hybrid material. The precipitation of 16.67 wt.% of oxide was sufficient to inhibit the combustion peaks present in the DSC curve of cellulose. This work will help find new applications for these materials.

  11. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  12. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  13. Spectroscopic probes of the structure of hydrous uranium oxide precursors to UO sub 2 ceramic fuel

    SciTech Connect

    Thompson, M.C.; King, C.M. ); King, R.B. . Dept. of Chemistry)

    1989-01-01

    Fourier Transform infrared spectroscopy, x-ray powder diffraction and thermal analysis show that one example of ammonium diuranate'' observed as an intermediate in the U(VI) sol-gel process is a layered hydrous uranium oxide with a proposed structural formula of (NH){sub 4}{sub 2}((UO{sub 2}){sub 8}O{sub 4}(OH){sub 10}){center dot}8H{sub 2}O, an ammonium ion intercalate. Examples of polyamine intercalation compounds hydrous uranium oxide are also given.

  14. Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

    PubMed

    Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

    2014-11-18

    Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

  15. Formation of metallic and metal hydrous oxide dispersions

    NASA Technical Reports Server (NTRS)

    Matijevic, E.; Sapieszko, R. S.

    1979-01-01

    The formation, via hydrothermally induced precipitation from homogeneous solution, of a variety of well-defined dispersions of metallic and hydrous metal in the conditions under which the particles are produced (e.g., pH and composition of the growth medium, aging temperature, rate of heating, or degree of agitation) can be readily discerned by following changes in the mass, composition, and morphology of the final solid phase. The generation of colloidal dispersions in the absence of gravity convection or sedimentation effects may result in the appearance of morphological modifications not previously observed in terrestrially formed hydrosols.

  16. Inorganic Halogen Oxidizer Research.

    DTIC Science & Technology

    1982-04-21

    nitrogen from composition of NF 4CIO 4. The FOCIO 3, prepared in this a liquid nitrogen drs ice slush used to cool the reaction cylinder, the manner...as metastable solid, which underwent decotipositiot to the ic rresjstnding 11i0* salts and 02 in the temperature range 20 50 O( t he It (t* salts were...34, Vol. 4. Masson et Cie, Paris, 1975. Trans. 2. 72. 1298 (1976). C -9/c- IC APPENDIX D IReprinted from Inorganic Chemistry, 18, 2572 (1979).1 Copyright

  17. Pd oxides/hydrous oxides as highly efficient catalyst for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Yan, Liang; Yao, Shikui; Chang, Jinfa; Liu, Changpeng; Xing, Wei

    2014-03-01

    A novel Pd-based catalyst for formic acid electrooxidation (FAEO) was prepared by annealing commercial Pd/C catalyst under the O2 atmosphere at 100 °C, which exhibits excellent catalytic activity and stability for FAEO due to introduction of Pd oxides/hydrous oxides (POHOs). The catalytic activity of the as-prepared catalyst towards FAEO is 1.86 times of the commercial Pd/C catalyst in 0.5 M H2SO4 + 0.5 M HCOOH solution. Chronoamperometric curves show obvious improvement of the as-prepared catalyst electrocatalytic stability for FAEO. It is confirmed that POHOs can provide the required oxygen species for intermediate CO oxidation during the oxidation process of formic acid.

  18. Inorganic Halogen Oxidizer Research

    DTIC Science & Technology

    1975-02-26

    KEY WORDS (Continue on reverse aide il necesxary and identity by block number) Synthesis, Novel Oxidizers, Perchlorates, Fluorination , Halogen...C. J. Schack, R. D. Wilson, and E. C. Curtis, 5th European Fluorine Symposium, Avie.nore, Scotland (September 1974) 20. "New Energetic Halogen...elimination lasers. For NF-, no evidence for protonation was found at tempera- tures as low as -78 C. Furthermore, attempts to fluorinate NH. AsF

  19. Inorganic Halogen Oxidizer Research

    DTIC Science & Technology

    1981-04-21

    only one case known,2󈧮 where FCIO2 is fluorinated by the very strong oxidizer PtF6 according to: 2-FCIO2 + 2PtF -0 CIF 0 PtF 4. ClO2 PtF6 2 6 2 2 6...Formulas ClO2 CiO2 Reaction with F2 C110 Cl 0 Reaction with F 6 2 6 2 27 C27 Reaction with F2 CIFO) FCIO2 Formation C120 CI 0 Reaction with F 2 CIF 0 CIF

  20. Sol gel synthesis of hydrous ruthenium oxide nanonetworks from 1,2-epoxides

    NASA Astrophysics Data System (ADS)

    Walker, Jeremy; Bruce King, R.; Tannenbaum, Rina

    2007-08-01

    Hydrous ruthenium oxide (RuO 2· xH 2O) xerogels were synthesized through the addition of a 1,2-epoxide, propylene oxide, to commercial hydrated ruthenium chloride, "RuCl 3· xH 2O," in ethanol. After a blue-black monolithic gel formed in 4 h, the samples were allowed to age for 24 h and were dried in ambient conditions. The dried samples were then characterized by XPS, XRD, DTA and TGA. XPS showed the Ru(3 d5/2) peak at a binding energy of 281.7 eV, corresponding to that of hydrous ruthenium oxide. XRD data revealed the synthesized material as amorphous. Heating the sample in inert atmospheres caused the complete reduction of the oxide to the zero-valent state, whereas heating the sample in air resulted in both crystalline anhydrous RuO 2 and zero-valent ruthenium, depending on the method of heating. DTA traces showed an endotherm ending at 150 °C, corresponding to the loss of coordinated water, as well as two higher temperature crystallization exotherms when the sample was heated in both inert and oxygen-rich atmospheres. TGA runs also confirmed the complete reduction of the hydrous oxide when heated in nitrogen below 270 °C and the formation of anhydrous ruthenium oxide when heated in air, confirming the XRD results.

  1. Sol-gel synthesis of hydrous ruthenium oxide nanonetworks from 1,2-epoxides

    SciTech Connect

    Walker, Jeremy; Bruce King, R.; Tannenbaum, Rina

    2007-08-15

    Hydrous ruthenium oxide (RuO{sub 2}.xH{sub 2}O) xerogels were synthesized through the addition of a 1,2-epoxide, propylene oxide, to commercial hydrated ruthenium chloride, 'RuCl{sub 3}.xH{sub 2}O,' in ethanol. After a blue-black monolithic gel formed in 4 h, the samples were allowed to age for 24 h and were dried in ambient conditions. The dried samples were then characterized by XPS, XRD, DTA and TGA. XPS showed the Ru(3d{sub 5/2}) peak at a binding energy of 281.7 eV, corresponding to that of hydrous ruthenium oxide. XRD data revealed the synthesized material as amorphous. Heating the sample in inert atmospheres caused the complete reduction of the oxide to the zero-valent state, whereas heating the sample in air resulted in both crystalline anhydrous RuO{sub 2} and zero-valent ruthenium, depending on the method of heating. DTA traces showed an endotherm ending at 150 deg. C, corresponding to the loss of coordinated water, as well as two higher temperature crystallization exotherms when the sample was heated in both inert and oxygen-rich atmospheres. TGA runs also confirmed the complete reduction of the hydrous oxide when heated in nitrogen below 270 deg. C and the formation of anhydrous ruthenium oxide when heated in air, confirming the XRD results. - Graphical abstract: Heating of hydrous ruthenium oxide, RuO{sub 2}.xH{sub 2}O, under an inert atmosphere, results in its complete reduction to the zero-valent state, whereas heating it in air results in both crystalline anhydrous RuO{sub 2} and zero-valent ruthenium, depending on the method of heating.

  2. Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

    USGS Publications Warehouse

    Verplanck, P.L.; Nordstrom, D.K.; Taylor, H.E.; Kimball, B.A.

    2004-01-01

    Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

  3. Electrochemical capacitor performance of hydrous ruthenium oxide/mesoporous carbon composite electrodes

    NASA Astrophysics Data System (ADS)

    Jang, Jong H.; Han, Sangjin; Hyeon, Taeghwan; Oh, Seung M.

    Ruthenium/carbon composite materials are prepared by impregnating ruthenium(III) acetylacetonate into a mesoporous carbon (average pore diameter=12 mn, pore volume=3.6 cm 3 g -1) and then heat treatment at 320 °C for 2 h under an argon atmosphere. The metallic ruthenium nanoparticles are converted to pseudo-capacitive hydrous ruthenium oxide by electrochemical oxidation at 0.75 V (versus SCE) for 2 h in 2.0 M H 2SO 4. The specific capacitance of the composite electrodes, which is the sum of the double-layer capacitance of mesoporous carbon and the pseudo-capacitance of hydrous ruthenium oxide, reaches 243 F g -1 with heavy loading. As the loading is increased, however, the degree of ruthenium utilization for a pseudo-capacitor becomes poorer, presumably due to a limited conversion to the hydrous oxide form. The rate capability of composite electrodes also decreases with increase in ruthenium loading, due to an increase in both the equivalent series resistance (ESR) and the overall capacitance value. The ESR enlargement is caused mainly an increase in the electrolyte resistance within pores which, in turn, results from a pore narrowing with ruthenium loading Hindered ionic motion in narrowed pores can explain this feature. An increase in the RC time constant with ruthenium loading is further verified by ac impedance measurements.

  4. Effect of competitive ions on the arsenic removal by mesoporous hydrous zirconium oxide from drinking water

    SciTech Connect

    Bortun, Anatoly; Bortun, Mila; Pardini, James; Khainakov, Sergei A.

    2010-11-15

    Adsorption properties of 302-type commercially available hydrous zirconium oxide (302-HZO) towards arsenic and some competitive anions and cations have been studied under batch and column conditions. Due to amphoteric properties, anion exchange performance of hydrous zirconium oxide is pH dependent. Media exhibits high affinity towards arsenic in a broad pH range, with high adsorption capacity at pH < 8. It was shown that silicate and phosphate ions are arsenic's main competitors affecting media adsorption capacity. Presence of transition metal cations in <1 ppm does not affect 302-HZO capacity on arsenic, whereas alkaline-earth cations improve arsenic removal. The possibility for significant increase of 302-HZO adsorption capacity on arsenic at pH > 8 by using 'solid acidifier' technique is discussed. Results of 302-HZO field trials are presented.

  5. An exploratory program for using hydrous metal oxide ion exchangers as Fischer-Tropsch catalysts

    SciTech Connect

    Lynch, A.W.; Dosch, R.G.; Sault, A.G.

    1990-01-01

    The purpose of this program is to investigate the potential of hydrous metal oxide (HMO) ion exchangers, invented at Sandia National Laboratories, as Fischer-Tropsch (F-T) catalysts. Metals known to be active in F-T synthesis (e.g. Fe, Co) were ion exchanged on hydrous metal oxide supports. Although HMO catalysts based on Zr, Nb, and Ta have been investigated in direct coal liquefaction studies, this effect focused on formulations based on the hydrous titanium oxide (HTO) system. The program has the goals of developing a catalyst with (1) high activity, (2) selectively to fuel range or other useful products, and (3) better properties for use in slurry reactors. The program has three main tasks: (1) catalyst synthesis, to develop methods for preparing catalysts having desirable F-T properties, (2) characterization, to investigate catalysts proving to have desirable properties by a variety of analytical techniques to determine correlations between activity and material properties and (3) testing to determine activity and selectivity of catalysts. This paper discussed results of activity testing of Ruhrchemie catalyst and some catalyst formulations prepared using ion exchange on hydrous titanium oxide and precipitation. For example, at 250{degree}C the Ruhrchemie catalyst converts {approximately}50% of the syngas feed to reaction products. In comparison, iron catalysts prepared by ion exchange and precipitation had conversions ranging from 20 to 50% over a temperature range of 250 to 275{degree}C of the syngas feed. In addition, results are Auger surface analysis of Ruhrchemie catalyst are presented. 6 refs., 2 figs., 2 tabs.

  6. Reactions of metal ions at surfaces of hydrous iron oxide

    USGS Publications Warehouse

    Hem, J.D.

    1977-01-01

    Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

  7. Quartz and Hydrous Iron-oxide Impactites from the Bee Bluff Structure of South Texas

    NASA Astrophysics Data System (ADS)

    Graham, R. A.; Martin, M.; Morosin, B.

    2005-07-01

    Breccia impactite samples are found to have been strongly influenced by high pressure shock waves controlled by the thin veneer of sandstone, siltstone and a thin layer of iron-rich siltstone target rocks. Carrizo sandstone is converted to a hard grey breccia containing comminuted quartz bound with tightly adhering alpha goethite. Transformations in the hydrous iron-oxide binder and hydrous iron-rich siltstone in virtually all impactite samples dominate the scientific issues. Goethite is found in numerous samples including spherules loose on the site, `sky bombs,' in suevite in a Rosetta Stone containing five different impactite clasts, and in samples with hydrodynamic instabilities. Localized melting in quartz at particle interfaces is observed throughout. SEM and EDX analysis shows regions of fused quartz, some in the ballen structure characteristic of lechatleriete. Acicular goethite nanocrystals and submicron spheres are abundant. The high pressure-high temperature pulse of the impact produces an environment in which transformation to the iron-rich hydrous oxide to goethite, hematite and steam is to be expected.

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

    PubMed

    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.

  9. Removal of cerium ions from aqueous solution by hydrous ferric oxide--a radiotracer study.

    PubMed

    Dubey, Som Shankar; Rao, Battula Sreenivasa

    2011-02-28

    Radiotracer technique has been used to study the removal behavior of Ce (III) ions from aqueous solutions by synthesized and well characterized hydrous ferric oxide (HFO). Adsorptive concentration (10(-4)-10(-8) mol dm(-3)), pH (ca 4.0-10.0) and temperature (303-333 K) were examined for assessing optimal conditions for removal of these ions. The uptake of Ce (III) ions, which fitted well for Freundlich and D-R isotherms, increased with increase in the temperature and no significant desorption took place in the studied temperature range. The presence of some anions/cations affected the uptake of metal ion markedly. Irradiation of hydrous ferric oxide and tungsten oxide by using a 11.1×10(9) Bq (Ra-Be) neutron source having a neutron flux of 3.9×10(6) cm(-2) s(-1) with associated γ-dose rate of 1.72 Gy/h did not influence the extent of adsorption of Ce (III) significantly. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. Sorption of the antimicrobial ciprofloxacin to aluminum and iron hydrous oxides.

    PubMed

    Gu, Cheng; Karthikeyan, K G

    2005-12-01

    Solution chemistry (pH, ionic strength (I), and sorbate-to-sorbent ratio) effects on ciprofloxacin sorption to hydrous oxides of Al (HAO) and Fe (HFO) were investigated using macroscopic and spectroscopic analyses. Sorption to both HAO and HFO showed a strong pH-dependent behavior, following the fraction of zwitterionic species over the entire pH range studied. Increase in I from 0.01 to 0.5 M had an insignificant effect on the extent of ciprofloxacin sorption, and isotherms were well-described by the Langmuir model. HFO possessed a higher sorption capacity (0.066 mmol kg(-1)) than HAO (0.041 mmol kg(-1)). Ligand-promoted dissolution of hydrous oxides, more pronounced for HAO, was observed in the presence of ciprofloxacin, but at a fairly high initial concentration (0.5 mM). Attenuated total reflectance Fourier transform infrared spectroscopy analysis indicated that different types of ciprofloxacin surface complexes are formed with HAO and HFO; while a monodentate mononuclear complex (with -COO-) appears likely between ciprofloxacin and HAO, keto O and one O from COO- seem to be involved in the formation of a six-membered ring with Fe on the HFO surface. The study results are expected to increase our understanding of the environmental reactivity of fluoroquinolones, an important class of antimicrobial compounds.

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

    DOEpatents

    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.

  12. Spectroscopic probes of the structure of hydrous uranium oxide precursors to UO{sub 2} ceramic fuel

    SciTech Connect

    Thompson, M.C.; King, C.M.; King, R.B.

    1989-12-31

    Fourier Transform infrared spectroscopy, x-ray powder diffraction and thermal analysis show that one example of ``ammonium diuranate`` observed as an intermediate in the U(VI) sol-gel process is a layered hydrous uranium oxide with a proposed structural formula of (NH){sub 4}{sub 2}[(UO{sub 2}){sub 8}O{sub 4}(OH){sub 10}]{center_dot}8H{sub 2}O, an ammonium ion intercalate. Examples of polyamine intercalation compounds hydrous uranium oxide are also given.

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

    SciTech Connect

    Collins, Jack Lee; Hunt, Rodney Dale; Simmerman, S. G.

    2009-02-01

    A simple test-tube methodology was used to determine optimum process parameters for preparing hydrous hafnium oxide microspheres by the internal gelation process. Broth formulations of hafnyl chloride [HfOCl{sub 2}], hexamethylenetetramine, and urea were found that can be used to prepare hydrous hafnium oxide gel spheres in the temperature range of 70-90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations in order to equate the test-tube gelation times with actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broths.

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

    SciTech Connect

    Collins, Jack Lee; Pye, S. L.

    2009-02-01

    A simple test-tube methodology was used to determine optimum process parameters for preparing hydrous aluminum oxide microspheres by the internal gelation process. Broth formulations of aluminum, hexamethylenetetramine, and urea were found that can be used to prepare hydrous aluminum oxide gel spheres in the temperature range of 60-90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations in order to equate the test-tube gelation times with actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broths.

  15. Ianthinite: A rare hydrous uranium oxide mineral from Akkavaram, Andhra Pradesh, India

    NASA Astrophysics Data System (ADS)

    Singh, Yamuna; Viswanathan, R.; Parashar, K. K.; Srivastava, S. K.; Ramesh Babu, P. V.; Parihar, P. S.

    2014-02-01

    Ianthinite is the only known uranyl oxide hydrate mineral that contains both U6 + and U4 + . For the first time, we report ianthinite from India (at Akkavaram, Andhra Pradesh), which is hosted in basement granitoids. The mineral occurs in the form of tiny grains, encrustations and coatings in intimate association with uraninite and uranophane. X-ray diffraction (XRD) data reveals that d-spacings of the investigated ianthinite are in close agreement with the corresponding values given for ianthinite standard in International Centre for Diffraction Data (ICDD) card no. 12-272. The crystallographic parameters of the studied ianthinite are: ao = 11.3 (1) Å, bo = 7.19 (3) Å and co = 30.46 (8) Å, with a unit cell volume of 2474 (27) Å3. The association of investigated ianthinite with uraninite suggests that the former has formed due to oxidation of the latter. Since a major part of the uraninite was exposed to oxidizing meteoric water, much of it has been transformed into hydrous uranium oxide (ianthinite) and very little part remained unaltered as uranium oxide (uraninite). Absence of schoepite in the investigated ianthinite suggests that after its formation it (ianthinite) was not exposed to oxygen/oxidizing meteoric water. As the oxidation was partial and short lived, some amount of primary uraninite is also preserved.

  16. Influence of electron donor/acceptor concentrations on hydrous ferric oxide (HFO) bioreduction.

    PubMed

    Fredrickson, James K; Kota, Sreenivas; Kukkadapu, Ravi K; Liu, Chongxuan; Zachara, John M

    2003-04-01

    Dissimilatory metal-reducing bacteria (DMRB) facilitate the reduction of Fe and Mn oxides in anoxic soils and sediments and play an important role in the cycling of these metals and other elements such as carbon in aqueous environments. Previous studies investigating the reduction of Fe(III) oxides by DMRB focused on reactions under constant initial electron donor (lactate) and electron acceptor (Fe oxide) concentrations. Because the concentrations of these reactants can vary greatly in the environment and would be expected to influence the rate and extent of oxide reduction, the influence of variable electron acceptor and donor concentrations on hydrous ferric oxide (HFO) bioreduction was investigated. Batch experiments were conducted in pH 7 HCO3 buffered media using Shewanella putrefaciens strain CN32. In general, the rate of Fe(III) reduction decreased with increasing HFO:lactate ratios, resulting in a relatively greater proportion of crystalline Fe(III) oxides of relatively low availability for DMRB. HFO was transformed to a variety of crystalline minerals including goethite, lepidocrocite, and siderite but was almost completely dissolved at high lactate to HFO ratios. These results indicate that electron donor and acceptor concentrations can greatly impact the bioreduction of HFO and the suite of Fe minerals formed as a result of reduction. The respiration driven rate of Fe(II) formation from HFO is believed to be a primary factor governing the array of ferrous and ferric iron phases formed during reduction.

  17. Formation of Green Rust and Immobilization of Nickel in Response to Bacterial Reduction of Hydrous Ferric Oxide

    SciTech Connect

    Parmar, N.; Gorby, Yuri A.; Beveridge, Terrance J.; Ferris, F G.

    2001-04-01

    This investigation documents the formation of Green Rust (GR) and immobilization of Ni2+ in response to bacterial reduction of hydrous ferric oxide (HFO) reduction experiments provided evidence that the solid-phase partitioning of Ni2+ in GR extended from equilibrium solid-solution behavior.

  18. Nitrite reduction with hydrous ferric oxide and Fe(II): stoichiometry, rate, and mechanism.

    PubMed

    Tai, Yuan-Liang; Dempsey, Brian A

    2009-02-01

    Fe(II)/Fe(III) oxide is an important redox couple in environmental systems. Recent studies have revealed unique characteristics of Fe(II)/Fe(III) oxide and reactions with oxidizing or reducing agents. Nitrite was used as an oxidizing agent in this study in order to probe details of these reactions and hydrous ferric oxide (HFO) was used as the Fe(III) oxide phase. Abiotic nitrite reduction is a significant global producer of nitric oxide (a catalyst for production of tropospheric ozone) and nitrous oxide (a greenhouse gas and contributor to stratospheric ozone depletion). All experiments were conducted at pH 6.8 using a strictly anoxic environment with mass-balance measurements for Fe(II). Oxidation of Fe(II) was negligible in the absence of HFO. The reaction was fast in the presence of HFO and was described by d[Fe(II)]/dt=-k(overall)[Fe(II)(diss)][Fe(II)(solid-bound)][NO(2)(-)] (k(overall)=2.59x10(-7)microM(-2)min(-1)) for Fe(II)/Fe(III) molar ratios less than 0.30. The reaction was inhibited for higher Fe(II)/HFO ratios. The concentration of solid-bound Fe(II) was constant after an initial equilibration period and the reaction stopped when dissolved Fe(II) was depleted even though substantial solid-bound Fe(II) and nitrite remained. The results regarding rate-dependence and conservation of solid-bound Fe(II) and inhibition of reaction at high Fe(II)/Fe(III) ratios were similar to our earlier results for the Fe(II)/HFO/O(2) system [Park, B., Dempsey, B.A., 2005. Heterogeneous oxidation of Fe(II) on ferric oxide at neutral pH and a low partial pressure of O(2). Environmental Science and Technology 39(17), 6494-6500.].

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

    SciTech Connect

    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.

  20. A radium assay technique using hydrous titanium oxide adsorbent for the Sudbury Neutrino Observatory

    NASA Astrophysics Data System (ADS)

    Andersen, T. C.; Black, R. A.; Blevis, I.; Boger, J.; Bonvin, E.; Chen, M.; Cleveland, B. T.; Dai, X.; Dalnoki-Veress, F.; Doucas, G.; Farine, J.; Fergani, H.; Fowler, M. M.; Hahn, R. L.; Hallman, E. D.; Hargrove, C. K.; Heron, H.; Hooper, E.; Howard, K. H.; Jagam, P.; Jelley, N. A.; Knox, A. B.; Lee, H. W.; Levine, I.; Locke, W.; Majerus, S.; McFarlane, K.; McGregor, G.; Miller, G. G.; Moorhead, M.; Noble, A. J.; Omori, M.; Rowley, J. K.; Shatkay, M.; Shewchuk, C.; Simpson, J. J.; Sinclair, D.; Tanner, N. W.; Taplin, R. K.; Trent, P. T.; Wang, J.-X.; Wilhelmy, J. B.; Yeh, M.

    2003-04-01

    As photodisintegration of deuterons mimics the disintegration of deuterons by neutrinos, the accurate measurement of the radioactivity from thorium and uranium decay chains in the heavy water in the Sudbury Neutrino Observatory (SNO) is essential for the determination of the total solar neutrino flux. A radium assay technique of the required sensitivity is described that uses hydrous titanium oxide adsorbent on a filtration membrane together with a β-α delayed coincidence counting system. For a 200 tonne assay the detection limit for 232Th is a concentration of ˜3×10 -16 g Th/g water and for 238U of ˜3×10 -16 g U/g water. Results of assays of both the heavy and light water carried out during the first 2 years of data collection of SNO are presented.

  1. [Sorption-desorption of phosphate in wastewater by hydrous iron oxide].

    PubMed

    Xiang, Xue-Min; Liu, Ying; Zhou, Ji-Ti; Wang, Ren

    2008-11-01

    FeCl3 was used t o prepare hydrous iron oxide (HIO) as a n absorbent for phosphate (P) sorption and desorption study. The results showed that as pH decreased, the sorption capacity of HIO increased, and the sorption kinetics followed the second-order model, and the sorption isotherm could be fitted by the Langmuir equation. A 50 g/L NaOH solution was used for desorption of P from HIO, and the desorption rate could be reached over 98% . No relation was found between desorption rate and adsorption capacity. Based on above results, HIO was applied to adsorption of P from supernatant of sludge thickener, and after desorption, more than 90% of P was recovered. According to the results obtained, an effective system for P removal and recovery from municipal wastewater was suggested, which includes the following processes: adsorption, desorption, regeneration of HIO, and of recovery of P from P-rich desorption solution.

  2. Surface and textural heterogeneity of fresh hydrous ferric oxides in water and in the dry state

    SciTech Connect

    Bottero, J.Y.; Arnaud, M.; Villieras, F.; Michot, L.J.; Donato, P.; Francois, M. . Groupe de Recherche sur l'Eau et les Solides Divises)

    1993-08-01

    Fresh hydrous ferric oxides (HFO) are formed by precipitation of Fe[sup 3+] solution or ferric polycations initially formed at very acidic pH at different neutralization ratios n = 2 and 2.5 at pH 6.5 the precipitates are particles with a positive surface charge. The IEP and the surface charge measured in NaCl electrolyte vary with n. But in all cases IEP or ZPSE are lower than 8.3. The adsorption of sodium dodecane sulfonate molecules at 20 C allows us to compare the different samples formed by precipitation from n = 0, n = 2, and n = 2.5 solutions and named' n = 0, n = 2, and n = 2.5. Using the two-dimensional adsorption on heterogeneous surfaces theory of Case's group, it is possible to compare the different solids relatively to the affinity of surfactants for the surfaces.

  3. In situ destruction of contaminants via hydrous pyrolysis/oxidation. Visalia Field Test

    SciTech Connect

    Newmark, Robin L.; Aines, Roger D.; Knauss, Kevin; Leif, Roald; Chiarappa, Marina; Hudson, Bryant; Carrigan, Charles; Tompson, Andy; Richards, Jim; Eaker, Craig; Weidner, Randall; Sciarotta, Terry

    1998-12-01

    A field test of hydrous pyrolysis/oxidation (HPO) was conducted during the summer of 1997, during a commercial application of thermal remediation (Dynamic Underground Stripping (DUS)) at the Visalia Pole Yard (a super-fund site) in southern California. At Visalia, Southern California Edison Co. is applying the DUS thermal remediation method to clean up a large (4.3 acre) site contaminated with pole-treating compounds. This is a full-scale cleanup, during which initial extraction of contaminants is augmented by combined steam/air injection in order to enhance the destruction of residual contaminants by HPO. Laboratory results indicate that the contaminants at Visaha react at similar rates to TCE, which has been the focus of extensive laboratory work (Knauss et al., 1998a-c). Field experimental results from this application yield valuable information (1) confirming the destruction of contaminants in soil and groundwater by HPO, (2) validating the predictive models used to design HP0 steam injection systems, (3) demonstrating that accurate field measurements of the critical fluid parameters can be obtained using existing monitoring wells and (4) obtaining a reasonable prediction of the cost and effectiveness of HPO, working at a commercial scale and with commercial partners. The goal of our additional study and demonstration in conjunction with Edison has been to obtain early proof of hydrous pyrolysis/oxidation in the field, and validate our predictive models and monitoring strategies. This demonstration provides valuable economic and practicability data obtained on a commercial scale, with more detailed field validation than is commonly available on a commercially-conducted cleanup. The results of LLNL' s field experiments constrain the destruction rates throughout the site, and enable site management to make accurate estimates of total in situ destruction based on the recovered carbon. As of October, 1998, over 900,000 lb of contaminant have been removed from the

  4. Mass production of two-dimensional oxides by rapid heating of hydrous chlorides

    PubMed Central

    Zhao, Chunsong; Zhang, Haitian; Si, Wenjie; Wu, Hui

    2016-01-01

    Two-dimensional (2D) nanoscale oxides have attracted research interest owing to their electronic, magnetic optical and catalytic properties. If they could be manufactured on a large scale, 2D oxides would be attractive for applications ranging from electronics to energy conversion and storage. Herein, we report facile fabrication of oxide nanosheets by rapid thermal annealing of corresponding hydrous-chloride compounds. By heating CrCl3·6H2O, ZrOCl2·8H2O, AlCl3·6H2O and YCl3·6H2O crystals as precursors, we immediately collect large quantities of ultrathin Cr2O3, ZrO2, Al2O3 and Y2O3 nanosheets, respectively. The formation of layered nanosheets relies on exfoliation driven by rapid evaporation of water and/or other gas molecules generated under annealing. Our route allows simple, efficient and inexpensive production of 2D oxides. As a demonstration, we evaluate Cr2O3 nanosheets prepared by our method as anodes in lithium-ion batteries and find superior performance in comparison with their microcrystalline counterparts. PMID:27610589

  5. Mass production of two-dimensional oxides by rapid heating of hydrous chlorides

    NASA Astrophysics Data System (ADS)

    Zhao, Chunsong; Zhang, Haitian; Si, Wenjie; Wu, Hui

    2016-09-01

    Two-dimensional (2D) nanoscale oxides have attracted research interest owing to their electronic, magnetic optical and catalytic properties. If they could be manufactured on a large scale, 2D oxides would be attractive for applications ranging from electronics to energy conversion and storage. Herein, we report facile fabrication of oxide nanosheets by rapid thermal annealing of corresponding hydrous-chloride compounds. By heating CrCl3.6H2O, ZrOCl2.8H2O, AlCl3.6H2O and YCl3.6H2O crystals as precursors, we immediately collect large quantities of ultrathin Cr2O3, ZrO2, Al2O3 and Y2O3 nanosheets, respectively. The formation of layered nanosheets relies on exfoliation driven by rapid evaporation of water and/or other gas molecules generated under annealing. Our route allows simple, efficient and inexpensive production of 2D oxides. As a demonstration, we evaluate Cr2O3 nanosheets prepared by our method as anodes in lithium-ion batteries and find superior performance in comparison with their microcrystalline counterparts.

  6. Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

    USGS Publications Warehouse

    Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

    2004-01-01

    Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional

  7. Removal of fluoride by hydrous manganese oxide-coated alumina: performance and mechanism.

    PubMed

    Teng, Shao-Xiang; Wang, Shu-Guang; Gong, Wen-Xin; Liu, Xian-Wei; Gao, Bao-Yu

    2009-09-15

    A novel hydrous-manganese-oxide-coated alumina (HMOCA) material was prepared through a redox process. The adsorbent was characterized by SEM, BET surface area measurement, XRD, pH(PZC) measurement, FTIR spectroscopy, and XPS. The manganese oxides were amorphous and manganese existed mainly in the +IV oxidation state. Batch and column experiments were carried out to investigate the adsorption potential of the adsorbent. Fluoride adsorption onto HMOCA followed the pseudo-second-order equation well with a correlation coefficient greater than 0.99. Both external and intraparticle diffusion contributed to the rate of transfer and removal. The adsorption of fluoride was thought to take place mainly by ion-exchange. Optimum removal of fluoride occurred in a pH range of 4.0-6.0. The maximum adsorption capacity calculated from the Langmuir model was 7.09 mg/g. The presence of HCO(3)(-), SO(4)(2-) and PO(4)(3-) had negative effects on the adsorption of fluoride. The adsorbed fluoride can be released by alkali solution. Column studies were performed and 669 bed volumes were treated with the effluent fluoride under 1.0mg/L at an influent F(-) concentration of 5.0mg/L and flow rate of 2.39 m(3)/(m(2)h) (empty bed contact time=7.5 min).

  8. Rates of hydrous ferric oxide crystallization and the influence on coprecipitated arsenate.

    PubMed

    Ford, Robert G

    2002-06-01

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 degrees C. Comparison of extraction data and X-ray diffraction results confirmed that hematite and goethite were the primary transformation products. HFO transformation was significantly retarded at or above an arsenate solid loading of 29 455 mg As/kg HFO. However, HFO transformation proceeded at a significant rate for arsenate solid loadings of 4208 and 8416 mg As/kg HFO. At a solid loading of 8416 mg As/kg HFO, XRD results suggested arsenate primarily partitioned to hematite. Comparison of HFO transformation rates observed in this research to rates obtained from the literature at pH 6 and temperatures ranging from 24 to 70 degrees C suggests that arsenate stabilization could be realized in oxic environments with a significantfraction of iron (hydr)oxides. While this process has not been documented in natural systems, the predicted half-life for transformation of an arsenic-bearing HFO is approximately 300 days at 25 degrees C at solid loading < 8415 mg As/kg HFO. The projected time frame for arsenate stabilization indicates this process should be considered during development of conceptual and analytical models describing arsenic fate and transport in oxic systems containing reactive iron (hydr)oxides. The likelihood of this process would depend on the chemical dynamics of the soil or sediment system relative to iron (hydr)oxide precipitation-dissolution reactions and the potential retarding/competing influence of ions such as silicate and organic matter.

  9. Stable iron isotope fractionation between aqueous Fe(II) and hydrous ferric oxide.

    PubMed

    Wu, Lingling; Beard, Brian L; Roden, Eric E; Johnson, Clark M

    2011-03-01

    Despite the ubiquity of poorly crystalline ferric hydrous oxides (HFO, or ferrihydrite) in natural environments, stable Fe isotopic fractionation between HFO and other Fe phases remains unclear. In particular, it has been difficult to determine equilibrium Fe isotope fractionation between aqueous Fe(II) and HFO due to fast transformation of the latter to more stable minerals. Here we used HFO stabilized by the presence of dissolved silica (2.14 mM), or a Si-HFO coprecipitate, to determine an equilibrium Fe(II)-HFO fractionation factor using a three-isotope method. Iron isotope exchange between Fe(II) and HFO was rapid and near complete with the Si-HFO coprecipitate, and rapid but incomplete for HFO in the presence of dissolved silica, the latter case likely reflecting blockage of oxide surface sites by sorbed silica. Equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factors of -3.17 ± 0.08 (2σ)‰ and -2.58 ± 0.14 (2σ)‰ were obtained for HFO plus silica and the Si-HFO coprecipitate, respectively. Structural similarity between ferrihydrite and hematite, as suggested by spectroscopic studies, combined with the minor isotopic effect of dissolved silica, imply that the true equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factor in the absence of silica may be ∼-3.2‰. These results provide a critical interpretive context for inferring the stable isotope effects of Fe redox cycling in nature.

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

    SciTech Connect

    Collins, Jack Lee; Chi, Anthony

    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.

  11. Biotransformation of Ni-substituted hydrous ferric oxide by an Fe(III)-reducing bacterium.

    PubMed

    Fredrickson, J K; Zachara, J M; Kukkadapu, R K; Gorby, Y A; Smith, S C; Brown, C F

    2001-02-15

    The reductive biotransformation of a Ni(2+)-substituted (5 mol %) hydrous ferric oxide (NiHFO) by Shewanella putrefaciens, strain CN32, was investigated under anoxic conditions at circumneutral pH. Our objectives were to define the influence of Ni2+ substitution on the bioreducibility of the HFO and the biomineralization products formed and to identify biogeochemical factors controlling the phase distribution of Ni2+ during bioreduction. Incubations with CN32 and NiHFO were sampled after 14 and 32 d, and both aqueous chemistry and solid phases were characterized. By comparison of these results with a previous study (Fredrickson, J. K.; Zachara, J. M.; Kennedy, D. W.; Dong, H.; Onstott, T. C.; Hinman, N. W.; Li, S. W. Geochim. Cosmochim. Acta 1998, 62, 3239-3257), it was concluded that coprecipitated/sorbed Ni2+ inhibited the bioreduction of HFO through an undefined chemical mechanism. Mössbauer spectroscopy allowed analysis of the residual HFO phase and the identity and approximate mass percent of biogenic mineral phases. The presence of AQDS, a soluble electron shuttle that obviates need for cell--oxide contact, was found to counteract the inhibiting effect of Ni2+. Nickel was generally mobilized during bioreduction in a trend that correlated with final pH, except in cases where PO4(3-) was present and vivianite precipitation occurred. CN32 promoted the formation of Ni(2+)-substituted magnetite (Fe2IIIFe(1-x)IINixIIO4) in media with AQDS but without PO4(3-). The formation of this biogenic coprecipitate, however, had little discernible impact on final aqueous Ni2+ concentrations. These results demonstrate that coprecipitated Ni can inhibit dissimilatory microbial reduction of amorphous iron oxide, but the presence of humic acids may facilitate the immobilization of Ni within the crystal structure of biogenic magnetite.

  12. Arsenate sorption by hydrous ferric oxide incorporated onto granular activated carbon with phenol formaldehyde resins coating.

    PubMed

    Zhuang, J M; Hobenshield, E; Walsh, T

    2008-04-01

    A simple and effective method was developed using phenol formaldehyde (PF) resins to immobilize hydrous ferric oxide (HFO) onto granular activated carbon (GAC). The resulting sorbent possesses advantages for both the ferric oxide and the GAC, such as a great As-affinity of ferric oxide, large surface area of GAC, and enhanced physical strength. The studies showed that within one hour this sorbent was able to remove 85% of As(V) from water containing an initial As(V) concentration of 1.74 mg l(-1). The As(V) adsorption onto the sorbent was found to follow a pseudo-second order kinetics model. The adsorption isotherms were interpreted in terms of the Langmuir and Freundlich models. The equilibrium data fitted very well to both models. Column tests showed that this sorbent was able to achieve residual concentrations of As(V) in a range of 0.1-2.0 microg l(-1) while continuously treating about 180 bed volume (BV, 130 ml-BV) of arsenate water with an initial As(V) concentration of 1886 microg l(-1) at a filtration rate of 13.5 ml min(-1), i.e., an empty bed contact time (EBCT) of 9.6 min and a gram sorbent contact time (GSCT) of 0.15 min. After passing 635 BV of arsenate water, the exhausted sorbent was then tested by the Toxicity Characteristic Leaching Procedure (TCLP, US EPA Method 1311) test, and classified as non-hazardous for disposal. Hence, this HFO-PF-coated GAC has the capability to remove As(V) from industrial wastewater containing As(V) levels of about 2 mg l(-1).

  13. Removal of arsenite and arsenate using hydrous ferric oxide incorporated into naturally occurring porous diatomite.

    PubMed

    Jang, Min; Min, Soo-Hong; Kim, Tak-Hyun; Park, Jae Kwang

    2006-03-01

    In this study, a simplified and effective method was tried to immobilize iron oxide onto a naturally occurring porous diatomite. Experimental resultsfor several physicochemical properties and arsenic edges revealed that iron oxide incorporated into diatomite was amorphous hydrous ferric oxide (HFO). Sorption trends of Fe (25%)-diatomite for both arsenite and arsenate were similar to those of HFO, reported by Dixit and Hering (Environ. Sci. Technol. 2003, 37, 4182-4189). The pH at which arsenite and arsenate are equally sorbed was 7.5, which corresponds to the value reported for HFO. Judging from the number of moles of iron incorporated into diatomite, the arsenic sorption capacities of Fe (25%)-diatomite were comparable to or higher than those of the reference HFO. Furthermore, the surface complexation modeling showed that the constants of [triple bond]SHAsO4- or [triple bond]SAsO4(2-) species for Fe (25%)-diatomite were larger than those reference values for HFO or goethite. Larger differences in constants of arsenate surface species might be attributed to aluminum hydroxyl ([triple bond]Al-OH) groups that can work better for arsenate removal. The pH-controlled differential column batch reactor (DCBR) and small-scale column tests demonstrated that Fe (25%)-diatomite had high sorption speeds and high sorption capacities compared to those of a conventional sorbent (AAFS-50) that is known to be the first preference for arsenic removal performance in Bangladesh. These results could be explained by the fact that Fe (25%)-diatomite contained well-dispersed HFO having a great affinity for arsenic species and well-developed macropores as shown by scanning electron microscopy (SEM) and pore size distribution (PSD) analyses.

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

    SciTech Connect

    Wang, Wei; Guo, S.; Lee, I.; Ahmed, K.; Zhong, J.; Favors, Z.; Zaera, F.; Ozkan, M.; Ozkan, C. S

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    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.

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

    PubMed

    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.

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

    PubMed

    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.

  18. Enhanced removal of As (V) from aqueous solution using modified hydrous ferric oxide nanoparticles

    PubMed Central

    Huo, Lijuan; Zeng, Xibai; Su, Shiming; Bai, Lingyu; Wang, Yanan

    2017-01-01

    Hydrous ferric oxide (HFO) is most effective with high treatment capacity on arsenate [As(V)] sorption although its transformation and aggregation nature need further improvement. Here, HFO nanoparticles with carboxymethyl cellulose (CMC) or starch as modifier was synthesized for the purpose of stability improvement and As(V) removal from water. Comparatively, CMC might be the optimum stabilizer for HFO nanoparticles because of more effective physical and chemical stability. The large-pore structure, high surface specific area, and the non-aggregated nature of CMC-HFO lead to increased adsorption sites, and thus high adsorption capacities of As(V) without pre-treatment (355 mg·g−1), which is much greater than those reported in previous studies. Second-order equation and dual-mode isotherm model could be successfully used to interpret the sorption kinetics and isotherms of As(V), respectively. FTIR, XPS and XRD analyses suggested that precipitation and surface complexation were primary mechanisms for As(V) removal by CMC modified HFO nanoparticles. A surface complexation model (SCM) was used to simulate As adsorption over pH 2.5–10.4. The predominant adsorbed arsenate species were modeled as bidentate binuclear surface complexes at low pH and as monodentate complexes at high pH. The immobilized arsenic remained stable when aging for 270 d at room temperature. PMID:28098196

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

    PubMed Central

    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

  20. Enhanced removal of As (V) from aqueous solution using modified hydrous ferric oxide nanoparticles.

    PubMed

    Huo, Lijuan; Zeng, Xibai; Su, Shiming; Bai, Lingyu; Wang, Yanan

    2017-01-18

    Hydrous ferric oxide (HFO) is most effective with high treatment capacity on arsenate [As(V)] sorption although its transformation and aggregation nature need further improvement. Here, HFO nanoparticles with carboxymethyl cellulose (CMC) or starch as modifier was synthesized for the purpose of stability improvement and As(V) removal from water. Comparatively, CMC might be the optimum stabilizer for HFO nanoparticles because of more effective physical and chemical stability. The large-pore structure, high surface specific area, and the non-aggregated nature of CMC-HFO lead to increased adsorption sites, and thus high adsorption capacities of As(V) without pre-treatment (355 mg·g(-1)), which is much greater than those reported in previous studies. Second-order equation and dual-mode isotherm model could be successfully used to interpret the sorption kinetics and isotherms of As(V), respectively. FTIR, XPS and XRD analyses suggested that precipitation and surface complexation were primary mechanisms for As(V) removal by CMC modified HFO nanoparticles. A surface complexation model (SCM) was used to simulate As adsorption over pH 2.5-10.4. The predominant adsorbed arsenate species were modeled as bidentate binuclear surface complexes at low pH and as monodentate complexes at high pH. The immobilized arsenic remained stable when aging for 270 d at room temperature.

  1. Superconducting magnetic separation of phosphate using freshly formed hydrous ferric oxide sols.

    PubMed

    Li, Yiran; Li, Zhiyong; Xu, Fengyu; Zhang, Weimin

    2017-02-01

    Paramagnetic materials, such as ferric hydroxides, which are cost-effective and highly-efficient, have been little studied in relation to the magnetic separation process. In this study, freshly formed hydrous ferric oxide (HFO) sols were used to remove aqueous phosphate, followed by superconducting magnetic separation. The magnetization of HFO was determined to be 5.7 emu/g in 5.0 T. The particle size distributions ranged from 1 to 80 μm. Ferrihydrite was the primary mineral phase according to XRD analysis. Dissolved P (DP) was first adsorbed on HFO, and second, the P-containing HFO were separated by high gradient superconducting magnetic separation (HGSMS) to remove the Total P (TP). To obtain a P concentration of <0.05 mg/l in the effluent, 0.3, 1.0 and 1.3 g/l HFO were added to 2.5, 5 and 10 mg/l P solutions. The capacity of the HGSMS canister for capturing P-adsorbed HFO depends on the magnetic intensity and flow rate. In the 5.0 T HGSMS at a 1.0 cm/s flow rate, there were 75 column volumes in a single HGSMS cycle. The P concentration increased by 37.5 times after regeneration. Approximately 170 mg/l TP was measured in the backwash water.

  2. Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles.

    PubMed

    Pan, Bingcai; Xu, Jingsheng; Wu, Bing; Li, Zhigang; Liu, Xitong

    2013-08-20

    Here we fabricated a novel nanocomposite HZO-201, an encapsulated nanosized hydrous zirconium oxide (HZO) within a commercial porous polystyrene anion exchanger D201, for highly efficient defluoridation of water. HZO-201 exhibited much higher preference than activated alumina and D201 toward fluoride removal when competing anions (chloride, sulfate, nitrate, and bicarbonate) coexisted at relatively high levels. Fixed column adsorption indicated that the effective treatable volume of water with HZO-201 was about 7-14 times as much as with D201 irrespective of whether synthetic solution or groundwater was the feeding solution. In addition, HZO-201 could treat >3000 BV of the acidic effluent (around 3.5 mg F(-)/L) per run at pH 3.5, compared to only ∼4 BV with D201. The exhausted HZO-201 could be regenerated by NaOH solution for repeated use without any significant capacity loss. Such attractive performance of HZO-201 resulted from its specific hybrid structure, that is, the host anion exchanger D201 favors the preconcentration of fluoride ions inside the polymer based on the Donnan principle, and the encapsulated nanosized HZO exhibits preferable sequestration of fluoride through specific interaction, as further demonstrated by XPS spectra. The influence of solution pH, competitive anions, and contact time was also examined. The results suggested that HZO-201 has a great potential in efficient defluoridation of groundwater and acidic mine drainage.

  3. Enhanced removal of As (V) from aqueous solution using modified hydrous ferric oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Huo, Lijuan; Zeng, Xibai; Su, Shiming; Bai, Lingyu; Wang, Yanan

    2017-01-01

    Hydrous ferric oxide (HFO) is most effective with high treatment capacity on arsenate [As(V)] sorption although its transformation and aggregation nature need further improvement. Here, HFO nanoparticles with carboxymethyl cellulose (CMC) or starch as modifier was synthesized for the purpose of stability improvement and As(V) removal from water. Comparatively, CMC might be the optimum stabilizer for HFO nanoparticles because of more effective physical and chemical stability. The large-pore structure, high surface specific area, and the non-aggregated nature of CMC-HFO lead to increased adsorption sites, and thus high adsorption capacities of As(V) without pre-treatment (355 mg·g-1), which is much greater than those reported in previous studies. Second-order equation and dual-mode isotherm model could be successfully used to interpret the sorption kinetics and isotherms of As(V), respectively. FTIR, XPS and XRD analyses suggested that precipitation and surface complexation were primary mechanisms for As(V) removal by CMC modified HFO nanoparticles. A surface complexation model (SCM) was used to simulate As adsorption over pH 2.5-10.4. The predominant adsorbed arsenate species were modeled as bidentate binuclear surface complexes at low pH and as monodentate complexes at high pH. The immobilized arsenic remained stable when aging for 270 d at room temperature.

  4. Quartz and Hydrous Iron Oxides from the Bee Bluff Structure of South Texas

    NASA Astrophysics Data System (ADS)

    Graham, R. A.; Martin, M.; Thadhani, N. N.; Morosin, B.

    2006-07-01

    There is substantial information showing that the Bee Bluff structure is an impact site and that a residual crater can be identified. The thin hard cap of Carrizo Sandstone, Indio fm calcareous silt and a thin layer of iron-rich siltstone leads to impact processes in which the high pressure release wave proceeds promptly upward leading to a trapping of metamorphic products at the impact interface, a `bottom-up' pressure release. Release of water from goethite binder in the sandstone and from the iron-rich siltstone results in supersaturated steam in mixtures with iron and quartz compounds. Samples with quartz and hydrous iron oxide features are examined with optical microscopy, SEM, EDX and XRD. A quartz grain is found with a well defined PDF set. There is widespread amorphous quartz including lechatleriete. Nanocrystals of α-goethite in the acicular form are common. A condensation sphere from the `Uvalde Crater Rosetta Stone' shows a complex mixture of hematite, goethite, and alpha quartz with a trace of trydimite. Numerous samples are yet to be analyzed. The crater appears to have features that can serve as an Earth analog to Mars craters. A companion paper in the present proceedings summarizes prior work, adds new site detail, reports impact-loading analysis, and describes overall features of impactite samples from the site.

  5. Preferable uptake of phosphate by hydrous zirconium oxide nanoparticles embedded in quaternary-ammonium Chinese reed.

    PubMed

    Shang, Yanan; Xu, Xing; Qi, Shuto; Zhao, Yanxia; Ren, Zhongfei; Gao, Baoyu

    2017-02-12

    Phosphate capture from aqueous was conducted using hydrous zirconium oxide (HZO) embedded in quaternary-ammonium Chinese reed (CR-N(+)-HZO), and the characteristics of adsorbent was determined. HZO was dispersed as nanoparticles or nano-clusters on the external or inside the networking pores of CR-N(+)-HZO. The surface of CR-N(+)-HZO was heterogeneous with multiple adsorption sites, HZO nanocomposite and N(+)(CH2CH3)3Cl(-), which both contributed to the adsorption process. The phosphate uptake by CR-N(+)-HZO was optimal at pH 3.0 and phosphate uptake by HZO nanocomposite was greatly inhibited at alkaline pH. Kinetics studies suggested that both the intra-particle mass-transfer and external resistances were likely to be the rate controlling steps. The Qmax (maximum adsorption capacity) of phosphate uptake by CR-N(+)-HZO and CR-N(+) (30°C) calculated based on Langmuir model was about 59.2mg(P)/g(CR-N(+)-HZO) and 30.4mg(P)/g(CR-N(+)). A high usage efficiency of Zr in CR-N(+)-HZO was observed with calculated molar ratio of P/Zr to be 3.07.

  6. EXAFS Analyses of Innersphere Surface Complexations of Arsenate and Silicate on Natural Hydrous Ferric Oxides

    NASA Astrophysics Data System (ADS)

    Tommaseo, C. E.; Kersten, M.

    2002-12-01

    X-ray absorption spectroscopy (EXAFS) was used to determine the near range order of three elements (Fe, As, Si) on the surface of hydrous ferric oxide (HFO) from thermal water scales. Fe K-edge EXAFS analyses of the 2nd shell show a better fit including Si as backscattering neighbor. Validation of the Si-Fe bond was obtained by Si K-edge EXAFS spectra, where the light absorber element is surrounded favourably by much heavier second-shell elements. Least-squares fitting of the second-shell Fourier-filtered EXAFS spectrum in the k-range of 5-11 Å-1 yields in a Si-Fe distance of 3.10-3.13Å, and a Si-Si distance of 3.00Å. Both these interatomic distances and the coordination number N = 2 obtained for the Si-Fe shell are consistent with the formation of a corner-bridging bidentate binuclear (2C) surface complex on the HFO surface. The Si-Si bonds and existance of a vibrational band at 964 cm-1 in the infrared spectrum indicate polymerisation of the silicate on the HFO surface (Tommaseo and Kersten). As K-edge XANES analyses showed the As present in form of arsenate scavenged by the HFO phase. As and Si K-edge EXAFS analyses revealed both elements to compete for 2C surface complexation sites. A mean As-Fe distance of 3.03Å indicate an approx. equal distribution of arsenate between 2C (3.24Å) and another 1E (bidentate mononuclear surface complexation) sites (2.84Å). The average Fe-(O,OH) bond length of 2.09Å is compatible with a high proportion of distorted surficial FeIII(O,OH)6 octahedra in the colloidal HFO precipitates of the scale deposits. The slight distortion of the FeIII(O,OH)6 octahedra is consistent with the apparent strong binding of the 1E arsenate surface complexes (Manceau, 1995). The adverse effect of silicate would therefore be overpredicted without surface complexation models constructed to account for both surface functional groups. The Si K-edge EXAFS data provide also a basis for explaining at the molecular level the poisoning of HFO particle

  7. Sulfur in Hydrous, Oxidized Basaltic Magmas: Phase Equilibria and Melt Solubilities

    NASA Astrophysics Data System (ADS)

    Pichavant, M.; Scaillet, B.; di Carlo, I.; Rotolo, S.; Metrich, N.

    2006-05-01

    Basaltic magmas from subduction zone settings are typically S-rich and may be the ultimate source of sulfur in vapor phases emitted during eruptions of more silicic systems. To understand processes of sulfur recycling in subduction zones, the behaviour of S in hydrous, oxidized, mafic arc magmas must be known. Although experimental data on S-bearing basaltic melts are available for dry conditions, and under both reduced and oxidized fO2, no study has yet examined the effect of S in hydrous mafic melts. In this work, 3 starting compositions were investigated, a basaltic andesite, a K basalt and a picritic basalt. For each composition, experimental data for S-added (1 wt % elemental sulfur) and S-free charges were obtained under similar P-T- H2O-fO2. All experiments were performed at 4 kbar and at either 950 ° C (basaltic andesite), 1100 ° C (K basalt) or 1150 ° C (picritic basalt). These were carried out in an internally heated vessel pressurized with Ar-H2 mixtures and fitted with a drop-quench device, and lasted for between 15 and 99 h. Either Au (950 ° C) or AuPd alloys (1100 and 1150 ° C) were used as containers. These latter perform satisfactorily under strongly oxidizing conditions, i.e., for fO2 above NNO+1 at 1100 and 1150 ° C. Below NNO+1, Pd- Au-S-Fe phases appear in the charges, suggesting extensive interaction between S and the capsule material. Experimental redox conditions, determined from Ni-Pd-O sensors, ranged between NNO+1.3 to +4.1 (basaltic andesite), +0.6 to +2.0 (K basalt), and +0.3 to +3.6 (picritic basalt). H2O concentrations in melt ranged from 8.2 wt % (basaltic andesite), decreasing to 2.2-3.9 wt % (K basalt) and 2.5-5.0 wt % (picritic basalt). All 3 compositions studied crystallize anhydrite and Fe-Ni-S-O sulphide as saturating S-bearing phases, anhydrite at high fO2 and sulphide at lower fO2, although melt composition also influences their stability. Anhydrite is present at a fO2 as low as NNO+1.5 in the K basalt. In the picritic

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed Central

    Lund, Tracy J; Koretsky, Carla M; Landry, Christopher J; Schaller, Melinda S; Das, Soumya

    2008-01-01

    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. PMID:18783619

  10. Environmentally abundant anions influence the nucleation, growth, Ostwald ripening, and aggregation of hydrous Fe(III) oxides.

    PubMed

    Hu, Yandi; Lee, Byeongdu; Bell, Christopher; Jun, Young-Shin

    2012-05-22

    The simultaneous homogeneous and heterogeneous precipitation of hydrous Fe(III) oxides was investigated in the presence of environmentally ubiquitous anions (nitrate, chloride, and sulfate). Experiments were conducted with 10(-4) M Fe(III) at acidic pH (pH = 3.7 ± 0.2), which often occurs at acid mine drainage sites or geologic CO(2) storage aquifers near injection wells. Quartz was used as a model substrate for heterogeneous precipitation. Small angle X-ray scattering (SAXS) and grazing incidence SAXS (GISAXS), atomic force microscopy (AFM), and dynamic light scattering (DLS) measurements were conducted. In situ SAXS/GISAXS quantified the size, total particle volume, number, and surface area evolutions of the primary nanoparticles formed in the nitrate and chloride systems. In both systems, the heterogeneously precipitated particles were smaller than the homogeneously precipitated particles. Compared with chloride, the volume of heterogeneously precipitated hydrous Fe(III) oxides on the quartz surface was 10 times more in the nitrate system. After initial fast heterogeneous nucleation in both nitrate and chloride systems, nucleation, growth, and aggregation occurred in the nitrate system, whereas Ostwald ripening was the dominant heterogeneous precipitation process in the chloride system. In the sulfate system, fast growth of the heterogeneously precipitated particles and fast aggregation of the homogeneously precipitated particles led to the formation of particles larger than the detection limit of GISAXS/SAXS. Thus, the sizes of the particles precipitated on quartz surface and in solution were analyzed with AFM and DLS, respectively. This study provides unique qualitative and quantitative information about the location (on quartz surfaces vs in solutions), size, volume, and number evolutions of the newly formed hydrous iron oxide particles in the presence of quartz substrate and ubiquitous anions, which can help in understanding the fate and transport of

  11. 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

    NASA Technical Reports Server (NTRS)

    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.

  12. The Fouling of Zirconium(IV) Hydrous Oxide-Polyacrylate Dynamically Formed Membranes during the Nanofiltration of Lactic Acid Solutions.

    PubMed

    Polom, Ewa

    2013-12-10

    The results of investigations of flux decline during nanofiltration (NF) of lactic acid solutions using dynamically formed zirconium(IV) hydrous oxide/polyacrylate membranes (Zr(IV)/PAA) under conditions resulting in low and high lactic acid rejection are reported. The experimental permeate flux versus time curves were analyzed in the frame of resistance in a series model with the aim of developing the characteristic of resistances. Analysis of experimental data and results of calculations showed that the reduction of fouling effects in the investigated system could be achieved due to appropriate hydrodynamic process conditions and regular rinsing with deionized water.

  13. Comparison of nickel molybdenum hydrous metal oxides with commercial catalysts for HDS/HDN of coal liquids

    SciTech Connect

    Lott, S.E.; Gardner, T.J.; McLaughlin, L.I.; Oelfke, J.B.

    1994-06-01

    Improved efficiency in direct coal liquefaction processes can be obtained by developing catalysts with better activity, selectivity, and life. In previous exploratory research at Sandia National Laboratories, catalysts prepared via hydrous metal oxide (HMO) ion exchangers have been shown to have potential for application to a number of reactions associated with the conversion of coal to liquid fuels. In the present effort, one member of this class of catalysts, hydrous titanium oxide (HTO), has been used to develop catalysts for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of coal liquids. For HYD of pyrone, unsupported NiMoHTO catalysts performed better than commercial benchmark catalysts on either a catalyst weight or active metals basis. In a side-by-side comparison of supported NiMoHTO catalysts with commercial counterparts, the supported NiMoHTO catalysts outperformed the Shell 324 and Amocat 1C catalysts for HYD of pyrene. For HDS/HDN of coal liquids, the supported and bulk forms of the NiMoHTO catalysts equaled the performance of the commercial catalysts at 500, 1000, and 1500 psig while containing less active metals. Possible reasons for the high activity of the NiMoHTO catalysts are a high dispersion of the active MoS{sub 2} phase and a high acidity of the bulk NiMoHTO.

  14. The ecological effect of acid conditions and precipitation of hydrous metal oxides in a Rocky Mountain stream

    USGS Publications Warehouse

    McKnight, Diane M.; Feder, G.L.

    1984-01-01

    Periphyton and benthic invertebrates assemblages were studied at the confluence of two Rocky Mountain streams, Deer Creek and the Snake River near Montezuma, Colorado. Upstream from the confluence the Snake River is acidic and enriched in dissolved trace metals, while Deer Creek is a typical Rocky Mountain stream. In the Snake River, downstream from the confluence, the pH increases and hydrous metal oxides precipitate and cover the streambed. The algal and benthic invertebrate communities in the upstream reaches of the Snake River and in Deer Creek were very different. A liverwort, Scapania undulata var. undulata, was abundant in the Snake River, and although periphyton were very sparse, there were as many benthic invertebrates as in Deer Creek. Downstream from the confleunce, the precipitation of hydrous metal oxides greatly decreased the abundance of periphyton and benthic invertebrates. This study shows that in streams metal precipitates covering the streambed may have a more deleterious effect on stream communities than high metal-ion activities. ?? 1984 Dr. W. Junk Publishers.

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

    NASA Astrophysics Data System (ADS)

    Cho, Dong-Wan; Jeon, Byong-Hun; Jeong, Yoojin; Nam, In-Hyun; Choi, Ui-Kyu; Kumar, Rahul; Song, Hocheol

    2016-05-01

    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 m2 g-1) with irregular cracks caused by HZO inclusion and amine functional groups. The rate of Pb2+ adsorption by HZOCB was relatively rapid. Most of Pb2+ (89%) was adsorbed within 2.5 h. A binary sorbate system was noticeably favorable for F- adsorption as compared to single sorbate system. Adsorption of F- and Pb2+ followed pseudo-second order kinetics. The maximum sorption capacities obtained from Langmuir isotherm model were 22.1 and 222.2 mg g-1, respectively. The study demonstrates that the developed composite could be a potential adsorbent for the simultaneous remediation of F- and Pb2+ contamination in water.

  16. Preparation and characterization of composite electrodes of coconut-shell-based activated carbon and hydrous ruthenium oxide for supercapacitors

    NASA Astrophysics Data System (ADS)

    Dandekar, Mukta S.; Arabale, Girish; Vijayamohanan, K.

    The relationship between the structure-specific capacitance (F g -1) of a composite electrode consisting of activated coconut-shell carbon and hydrous ruthenium oxide (RuO x(OH) y) has been evaluated by impregnating various amounts of RuO x(OH) y into activated carbon that is specially prepared with optimum pore-size distribution. The composite electrode shows an enhanced specific capacitance of 250 F g -1 in 1 M H 2SO 4 with 9 wt.% ruthenium incorporated. Chemical and structural characterization of the composites reveals a homogeneous distribution of amorphous RuO x(OH) y throughout the porous network of the activated carbon. Electrochemical characterization indicates an almost linear dependence of capacitance on the amount of ruthenium owing to its pseudocapacitive nature.

  17. Arsenite adsorption on cryogels embedded with iron-aluminium double hydrous oxides: possible polishing step for smelting wastewater?

    PubMed

    Kumar, Prashanth Suresh; Onnby, Linda; Kirsebom, Harald

    2013-04-15

    Arsenic is among the most toxic elements and it commonly exists in water as arsenite (As(III)) and arsenate (As(V)) ions. As(III) removal often requires a pre-oxidation or pH adjustment step and it is a challenge to adsorb As(III) at circumneutral pH. In this study, iron-aluminium double hydrous oxides were synthesized and incorporated into cryogels. The resulting composite cryogels were evaluated for As(III) adsorption. Initial experiments indicated that the adsorbent showed similar adsorption kinetics for both As(V) and As(III) ions. The adsorption of As(III) best fit the Langmuir isotherm and the maximum adsorption capacity was 24.6 mg/g. Kinetic modeling indicated that the mechanism of adsorption was chemisorption, making the adsorbent-adsorbate interactions independent of charge and hence allowing the adsorbent to function equally efficient across pH 4-11. A Swedish smelting wastewater was used to evaluate the adsorption performance in continuous mode. The studies showed that the adsorbent was successful in reducing the arsenic concentrations below the European Union emission limit (0.15 mg/l) in a smelting wastewater collected after two precipitation processes. The arsenic removal was obtained without requiring a pH adjustment or a pre-oxidation step, making it a potential choice as an adsorbent for As(III) removal from industrial wastewaters. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Hydrous manganese oxide doped gel probe sampler for measuring in situ reductive dissolution rates. 1. Laboratory development.

    PubMed

    Farnsworth, Claire E; Hering, Janet G

    2010-01-01

    Reductive dissolution of redox-sensitive minerals such as manganese (Mn) oxides in natural sediments is an important mechanism for trace element mobilization into groundwater. A gel probe sampler has been constructed to study in situ reductive dissolution of Mn oxides. The gel consists of a polyacrylamide polymer matrix doped with hydrous Mn oxide (HMO). Gel slabs are mounted into a probe, which is designed to be inserted into the sediments. The amount of Mn released from the gel by reductive dissolution is determined by comparing the amount of Mn initially embedded into the gel with the amount remaining in the gel after exposure to conditions in the sediments or, in laboratory studies, to reducing agents. In this laboratory study, the performance of the gel probes was examined using the model reductant ascorbate and the Mn-reducing bacteria Shewanella oneidensis strain MR-1. In addition, a 1-D model was used to relate the reaction rates observed for HMO embedded in gels to those for HMO in suspension. One limitation of the HMO-doped gels for assessing microbial reduction rates is that the gels prevent direct contact between the microbes and the HMO and hence preclude enzymatic reduction at the cell surface. Nonetheless, the HMO-doped gel probes offer the possibility to establish a lower bound for Mn-reduction capacity in sediments.

  19. Hydrous manganese oxide doped gel probe sampler for measuring in situ reductive dissolution rates. 2. Field deployment.

    PubMed

    Farnsworth, Claire E; Griffis, Sarah D; Wildman, Richard A; Hering, Janet G

    2010-01-01

    In situ rates of reductive dissolution in submerged shoreline sediments at Lake Tegel (Berlin, Germany) were measured with a novel hydrous manganese (Mn) oxide-doped gel probe sampler in concert with equilibrium gel probe and sequential extraction measurements. Rates were low in the top 8 cm, then showed a peak from 8 to 14 cm, with a maximum at 12 cm depth. This rate corresponded with a peak in dissolved porewater iron (Fe) at 11 cm depth. Below 14 cm, the reductive dissolution rate reached an intermediate steady value. Lower rates at depth corresponded with increases in operationally defined fractions of carbonate-bound and organic- and sulfide-bound Mn and Fe as detected by sequential extraction. Observed rates of reductive dissolution, which reflect a capacity for Mn reduction rather than actual rates under ambient conditions, appear to correlate with porewater chemistry and sequential extraction fractions as expected in early sediment diagenesis, and are consistent with previous measurements of in situ reductive dissolution rates. Significant downward advection in this bank filtration setting depletes the Mn and Fe oxides in the sediments and enhances the transport of dissolved Fe and Mn into the infiltrating water.

  20. Characterisation of a new adsorbent (beta cyclodextrin modified hybrid hydrous iron-zirconium oxide) to remove fluoride from aqueous solution

    NASA Astrophysics Data System (ADS)

    Saha, Indranil

    2017-04-01

    Prolonged use of fluoride contaminated water (>1.5mg L -1) causes serious problems to public health and ultimately leads to skeletal fluorosis. There is an urgent need to develop more efficient fluoride scavenging materials for designing water filters. A simple and efficient adsorbent (CHIZO, beta-Cyclodextrin (b-CD) amended hydrous iron-zirconium hybrid oxide), has been developed, characterised and tested. The results indicate the efficacy of CHIZO on fluoride removal from an aqueous solution. The agglomerated micro structured composite material has several new features such as very poor crystallinity confirmed from TEM images. BET experiment reveals a surface area of 0.2070 m2 g- 1 and pore volume of 0.0476 cm3 g -1. The findings also indicate the highly pH dependent fluoride adsorption by CHIZO which decreases with an increase in pH, and pseudo-second order kinetics control the reaction.Isotherm study indicates Langmuir isotherm was the best fit model to describe the adsorption equilibrium. Significantly higher monolayer adsorption capacity of fluoride (31.35 mg g -1) than the host hydrous Fe-Zr oxide (8.21 mg g -1) at pH 7.0 and 303 K was observed. Thermodynamic parameter indicates spontaneous nature of CHIZO which is due to the exothermic nature of the reaction. Apart from this phosphate and sulphate have some impact (interference) on fluoride adsorption. b-CD forms inclusion complexes by taking up fluoride ions from water into its central cavity. Several factors are involved regarding high efficacy of the system such as the release of enthalpy-rich water molecules from its cavity, electrostatic interactions, hydrogen bonding and release of conformational strain. However, the regeneration is difficult because of probable entrapping of fluoride inside the cavity of b-CD with hydrogen bonding. It has been found that only 0.9 g of CHIZO is able to reduce the fluoride level to below 1.0 mg L -1 in one-litre of fluoride spiked (5.0 mg L- 1) natural water sample

  1. [The effects of organic matter and hydrous metal oxides on the anaerobic degradation of gamma-666, p,p'-DDT in Liaohe River sediments].

    PubMed

    Zhao, Xu; Quan, Xie; Zhao, Huimin; Chen, Shuo; Chen, Jingwen; Zhao, Yazhi

    2002-05-01

    Effects of organic matter and active Fe, Al, Mn oxides on the anaerobic degradation of gamma-666, p,p'-DDT were investigated by means of removing organic matter and hydrous metal oxides in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of gamma-666, p,p'-DDT followed pseudo-first-order kinetics in different sediments; but, the extents and rates of degradation were different, even the other conditions remained same. Anaerobic degradation rates of gamma-666, p,p'-DDT were 0.020 d-1, 0.009 d-1 respectively for the sediments without additional carbon resources. However, with additional carbon resources, the anaerobic degradation rates of gamma-666, p,p'-DDT were 0.071 d-1 and 0.054 d-1 in the original sediments respectively. After removing organic matter, the rates were decreased to 0.047 d-1, 0.037 d-1. In the sediments removed organic matter and hydrous metal oxides, the rates were increased to 0.067 d-1, 0.059 d-1. This results indicated that organic matter in the sediments accelerated the anaerobic degradation of gamma-666, p,p'-DDT; the hydrous metal oxides inhibited the anaerobic degradation of gamma-666 and p,p'-DDT.

  2. A model-based evaluation of sorptive reactivities of hydrous ferric oxide and hematite for U(VI).

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2007-06-15

    The sorption of uranyl onto hydrous ferric oxide (HFO) or hematite was measured by discontinuously titrating the suspensions with uranyl at pH 5.9, 6.8, and 7.8 under Pco2 = 10(-35)atm (sorption isotherms). Batch reactors were used with equilibration times up to 48 days. Sorption of 1 microM uranyl onto HFO was also measured versus pH (sorption edge). A diffuse double layer surface complexation model was calibrated by invoking three sorption species that were consistent with spectroscopic evidence for predominance of bidentate complexes at neutral pH and uranyl-carbonato complexes: > SOH:UO2OH(+1), (> SO)2: UO2CO3(-2), and (> SO)2:(UO2)3(OH)5(-1). The model was consistent with previously published isotherm and edge data. The model successfully predicted sorption data onto hematite, only adjusting for different measured specific surface area. Success in application of the model to hematite indicates that the hydrated surface of hematite has similar sorptive reactivity as HFO.

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

    PubMed

    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.

  4. Predicting divalent metal sorption to hydrous Al, Fe, and Mn oxides.

    PubMed

    Trivedi, P; Axe, L

    2001-05-01

    Intraparticle diffusion in microporous amorphous oxides of aluminum, iron, and manganese affects contaminant mobility and bioavailability in soils and sediments. This sorption is a lengthy process, as such, predictive methods to assess thermodynamic and transport parameters would be useful. Based on enthalpies observed in recent work, adsorption of Zn, Cd, and Sr to amorphous oxides is a physical type of reaction where the metal ions retain their waters of hydration. Consequently the adsorbate-surface interactions are a function of electrostatic forces of attraction. Accordingly, knowing the hydrated radius and the hydration number of a metal cation, a correlation is used to predict enthalpy and hence affinity. Using the resulting enthalpy and the Polanyi relation, the activation energy was evaluated for Ni and Ca. This Polanyi relationship reveals that for a given metal the activation energies with respect to these oxides are comparable. Additionally, metals of the same periodic group appear to form similar sorption complexes with a particular oxide and therefore have an equivalent Polanyi constant, alpha. Assuming a sinusoidal function describes the surface potential along the oxide surface, the surface diffusivity was predicted from the site activation theory. In this work, the predicted sorption parameters proved to be equivalent to experimental ones given the associated errors.

  5. Directed deposition of inorganic oxide networks on patterned polymer templates

    NASA Astrophysics Data System (ADS)

    Ford, Thomas James Robert

    Inspired by nature, we have successfully directed the deposition of inorganic oxide materials on polymer templates via a combination of top-down and bottom-up fabrication methods. We have functionally mimicked the hierarchical silica exoskeletons of diatoms, where specialized proteins chaperone the condensation of silicic acid into nanoscale silica networks confined by microscopic vesicle walls. We replaced the proteins with functionally analogous polyamines and vesicles with lithographically defined polymer templates. We grafted the polyamines either to the surface or throughout the template by changing the template chemistry and altering our grafting strategy. Exposure to an inorganic oxide precursor solution led to electrostatic aggregation at the polyamine chains, catalyzing hydrolysis and condensation to form long-range inorganic oxide nanoparticle networks. Grafted to epoxy surfaces, swelling effects and the hyperbranched brush morphology lead to the formation of nanofruit features that generated thin, conformal inorganic coatings. When the polyamines were grafted throughout hydrogel templates, we obtained composite networks that yielded faithful inorganic replicas of the original patterns. By varying the polyamine chain length and combustion parameters, we controlled the nanoparticle size, morphology, and crystalline phase. The polyamine morphology affected the resulting inorganic network in both fabrication schemes and we could control the depostion over multiple length scales. Because our methods were compatible with a variety of lithographic methods, we were able to generate inorganic replicas of 1D, 2D, and 3D polymer structures. These may be used for a wide range of applications, including sensing, catalysis, photonic, phononic, photovoltaic, and others that require well-defined inorganic structures.

  6. The Formation, Structure, and Ageing of As-Rich Hydrous Ferric Oxide at the Abandoned Sb Deposit Pezinok (Slovakia)

    SciTech Connect

    Majzlan,J.; Lalinska, B.; Chovan, M.; Jurkovic, L.; Milovska, S.; Gottlicher, J.

    2007-01-01

    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 {approx}380,000 m{sup 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{sub 2}; arsenopyrite, FeAsS; berthierite, FeSb{sub 2}S{sub 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 {mu}-XANES experiments indicate that As in the weathering rims is fully oxidized (As{sup 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{sub 2}O{sub 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{sup 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

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

    NASA Astrophysics Data System (ADS)

    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

  8. Kinetic Modeling of Phosphate Adsorption by Preformed and In situ formed Hydrous Ferric Oxides at Circumneutral pH

    PubMed Central

    Mao, Yanpeng; Yue, Qinyan

    2016-01-01

    Kinetics of phosphate removal by Fe(III) was investigated by both preformed and in situ formed hydrous ferric oxides (HFO) at pH 6.0–8.0. A pseudo-second-order empirical model was found to adequately describe phosphate removal in the two cases. The Elovich and intra-particle diffusion models, however, were only capable of describing phosphate adsorption to preformed HFO (PF-HFO). By using surface complexation kinetic models (SCKMs) to describe phosphate adsorption to PF-HFO, the adsorption rate constant (0.0386–0.205 mM−1 min−1 for SCKM-1 and 0.0680–0.274 mM−1 min−1 for SCKM-2) decreased with increasing pH while the protonation reaction rate constant in SCKM-2 (0.0776–0.0947 mM−1 min−1) increased over the pH range 6.0–8.0. Using the rate constants obtained from the process of phosphate adsorption to PF-HFO, the amount of active surface sites on the in situ formed HFO were calculated as 0.955 ± 0.170, 1.46 ± 0.39 and 2.98 ± 0.78 mM for pH = 6.0, 7.0 and 8, respectively. Generally, as the SCKMs incorporate phosphate complexation on HFO surface sites and protons competiting for the surface sites, they could provide a good description of the rate and extent of phosphate removal by both preformed and in-situ formed HFO over a wide range of conditions. PMID:27739456

  9. Rapid and efficient removal of fluoride ions from aqueous solution using a polypyrrole coated hydrous tin oxide nanocomposite.

    PubMed

    Parashar, Kamya; Ballav, Niladri; Debnath, Sushanta; Pillay, Kriveshini; Maity, Arjun

    2016-08-15

    Polypyrrole/hydrous tin oxide nanocomposites (PPy/HSnO NC 1, 2, 3, 4 and 5) were synthesized through encapsulating HSnO by the PPy via an in situ polymerization for fluoride removal. The optimized adsorbent i.e. PPy/HSnO NC 3 was characterized using FE-SEM, HR-TEM, ATR-FTIR, XRD, BET, TGA and zeta sizer. Microscopic images revealed the encapsulation of HSnO by precipitating PPy during polymerization. The FTIR and XRD studies confirmed the presence of both constituents. The BET surface area and pHpzc of the adsorbent were estimated to be 65.758m(2)/g and 7.6, respectively. The fluoride adsorption followed pseudo-second-order model and was commendably rapid. The monolayer adsorption capacity was found to be 26.16-28.99mg/g at pH 6.5±0.1. The thermodynamic parameters indicated the sorption of F(-) was spontaneous, endothermic and that physisorption occurred. The calculated activation energy (Ea∼20.05kJ/mol) provided further evidence of a physisorption mechanism. Moreover, the adsorbent performed very well over a considerably wide pH range of 3.5-8.5 and in the presence of other co-existing ions. The regeneration of the F(-) laden PPy/HSnO NC 3 showed a high desorption efficiency of 95.81% up to 3 cycles. Ground water tested results also demonstrate the potential utility of the PPy/HSnO NC as an effective adsorbent. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. No Evidence of Degassing-Induced Oxidation of Hydrous Andesites and Dacites: An Analytical Study

    NASA Astrophysics Data System (ADS)

    Crabtree, S. M.; Lange, R. A.

    2009-12-01

    There has been a long-standing discussion in the literature on the question of whether erupted lavas record the same (or similar) oxidation state as that of their source regions. For a melt that forms by equilibrium partial melting, it is required to have the same oxygen fugacity as that of its source. After it leaves its source region, however, the oxygen fugacity of the liquid can vary due to the effects of crystallization and/or degassing, with implications for the direction of its differentiation path and the potential to develop an ore deposit. In this study, we focus on the effects of degassing on the redox state of dacite and andesite magmas. Any effect of crystallization is eliminated by only considering samples that are remarkably crystal-poor (2-5% total crystals; 45-88% of which is plagioclase). The 12 andesite and dacite samples used for this study were all erupted from small, monogenetic, short-lived vents (Quaternary) in the western Mexican volcanic arc; they are all glassy and black, with no evidence of post-eruptive alteration. Total iron concentrations (FeOT) range from 3.1 to 6.5 wt%. All 12 samples are saturated with equilibrium pairs of titanomagnetite and ilmenite, which permits temperature and oxygen fugacity to be calculated (Ghiorso and Evans, 2008). Temperatures range from 760 (±18) to 1085 (±16) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.9 to + 0.7. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1988), which relates melt composition, oxygen fugacity and temperature to melt ferric-ferrous ratios. With temperature known, the plagioclase-liquid hygrometer of Lange et al. (2009) was applied and maximum melt water concentrations range from 8.3 to 2.8 wt%. Therefore, both the oxidation state and water concentration in the pre-eruptive magmas are known at the time of phenocryst growth. After eruption, the

  11. Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction

    NASA Astrophysics Data System (ADS)

    Johnson, Clark M.; Roden, Eric E.; Welch, Susan A.; Beard, Brian L.

    2005-02-01

    Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced 56Fe/ 54Fe ratios for Fe(II) aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II) aq-magnetite fractionation is -1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II) aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO 3) and ca. +0.9‰ for Ca-substituted siderite (Ca 0.15Fe 0.85CO 3) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have 56Fe/ 54Fe ratios that are up to 1‰ lower than Fe(II) aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II) aq. The relative order of δ 56Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II) aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ 56Fe >0‰, the calculated δ 56Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast

  12. Similarity of the Surface Reactivity of Hydrous Ferric Oxide and Hematite: Sorption and Redox of U(VI) and Fe(II)

    SciTech Connect

    Je-Hun Jang; Dempsey, Brian A.; Burgos, William D.; Yeh, George; Roden, Eric

    2004-03-17

    Hydrous Ferric Oxide (HFO) vs. Hematite--Thermodynamically distinctive bulk phases, but the surfaces could be similar due to hydration of the interface. Hypothesis--The surface of HFO is energetically similar to the surface of hematite. Objective--Compare the reactions of HFO and hematite with U(VI) and Fe(II). Experimental--The reactions of interests were (1) preparation of sub-micron hematite, (2) sorption of U(VI), and (3) redox of U(VI) and Fe(II) with HFO or hematite.

  13. Oxidation Chemistry of Inorganic Benzene Complexes.

    PubMed

    Fleischmann, Martin; Dielmann, Fabian; Balázs, Gábor; Scheer, Manfred

    2016-10-17

    The oxidation of the 28 VE cyclo-E6 triple-decker complexes [(Cp(R) Mo)2 (μ,η(6) :η(6) -E6 )] (E=P, Cp(R) =Cp(2 a), Cp*(2 b), Cp(Bn) (2 c)=C5 (CH2 Ph)5 ; E=As, Cp(R) =Cp*(3)) by Cu(+) or Ag(+) leads to cationic 27 VE complexes that retain their general triple-decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single-crystal X-ray diffraction. The cyclo-E6 middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ-system of the cyclo-E6 ligands in 2 a-3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Crystallization of oxidized, moderately hydrous arc basalt at mid- to lower-crustal pressures: Implications for andesite genesis

    USGS Publications Warehouse

    Blatter, Dawnika L.; Sisson, Thomas W.; Hankins, W. Ben

    2013-01-01

    This study focuses on the production of convergent margin calc-alkaline andesites by crystallization–differentiation of basaltic magmas in the lower to middle crust. Previous experimental studies show that dry, reduced, subalkaline basalts differentiate to tholeiitic (high Fe/Mg) daughter liquids, but the influences of H2O and oxidation on differentiation are less well established. Accordingly, we performed crystallization experiments at controlled oxidized fO2 (Re–ReO2 ≈ ΔNi–NiO + 2) on a relatively magnesian basalt (8.7 wt% MgO) typical of mafic magmas erupted in the Cascades near Mount Rainier, Washington. The basalt was synthesized with 2 wt% H2O and run at 900, 700, and 400 MPa and 1,200 to 950 °C. A broadly clinopyroxenitic crystallization interval dominates near the liquidus at 900 and 700 MPa, consisting of augite + olivine + orthopyroxene + Cr-spinel (in decreasing abundance). With decreasing temperature, plagioclase crystallizes, Fe–Ti-oxide replaces spinel, olivine dissolves, and finally amphibole appears, producing gabbroic and then amphibole gabbroic crystallization stages. Enhanced plagioclase stability at lower pressure narrows the clinopyroxenitic interval and brings the gabbroic interval toward the liquidus. Liquids at 900 MPa track along Miyashiro’s (Am J Sci 274(4):321–355, 1974) tholeiitic versus calc-alkaline boundary, whereas those at 700 and 400 MPa become calc-alkaline at silica contents ≥56 wt%. This difference is chiefly due to higher temperature appearance of magnetite (versus spinel) at lower pressures. Although the evolved liquids are similar in many respects to common calc-alkaline andesites, the 900 and 700 MPa liquids differ in having low CaO concentrations due to early and abundant crystallization of augite, with the result that those liquids become peraluminous (ASI: molar Al/(Na + K + 2Ca) > 1) at ≥61 wt% SiO2, similar to liquids reported in other studies of the high-pressure crystallization of hydrous basalts

  15. Crystallization of oxidized, moderately hydrous arc basalt at mid- to lower-crustal pressures: implications for andesite genesis

    NASA Astrophysics Data System (ADS)

    Blatter, Dawnika L.; Sisson, Thomas W.; Hankins, W. Ben

    2013-09-01

    This study focuses on the production of convergent margin calc-alkaline andesites by crystallization-differentiation of basaltic magmas in the lower to middle crust. Previous experimental studies show that dry, reduced, subalkaline basalts differentiate to tholeiitic (high Fe/Mg) daughter liquids, but the influences of H2O and oxidation on differentiation are less well established. Accordingly, we performed crystallization experiments at controlled oxidized fO2 (Re-ReO2 ≈ ΔNi-NiO + 2) on a relatively magnesian basalt (8.7 wt% MgO) typical of mafic magmas erupted in the Cascades near Mount Rainier, Washington. The basalt was synthesized with 2 wt% H2O and run at 900, 700, and 400 MPa and 1,200 to 950 °C. A broadly clinopyroxenitic crystallization interval dominates near the liquidus at 900 and 700 MPa, consisting of augite + olivine + orthopyroxene + Cr-spinel (in decreasing abundance). With decreasing temperature, plagioclase crystallizes, Fe-Ti-oxide replaces spinel, olivine dissolves, and finally amphibole appears, producing gabbroic and then amphibole gabbroic crystallization stages. Enhanced plagioclase stability at lower pressure narrows the clinopyroxenitic interval and brings the gabbroic interval toward the liquidus. Liquids at 900 MPa track along Miyashiro's (Am J Sci 274(4):321-355, 1974) tholeiitic versus calc-alkaline boundary, whereas those at 700 and 400 MPa become calc-alkaline at silica contents ≥56 wt%. This difference is chiefly due to higher temperature appearance of magnetite (versus spinel) at lower pressures. Although the evolved liquids are similar in many respects to common calc-alkaline andesites, the 900 and 700 MPa liquids differ in having low CaO concentrations due to early and abundant crystallization of augite, with the result that those liquids become peraluminous (ASI: molar Al/(Na + K + 2Ca) > 1) at ≥61 wt% SiO2, similar to liquids reported in other studies of the high-pressure crystallization of hydrous basalts (M

  16. Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

    NASA Astrophysics Data System (ADS)

    Rancourt, Denis G.; Thibault, Pierre-Jean; Mavrocordatos, Denis; Lamarche, Gilles

    2005-02-01

    We have used room temperature and cryogenic 57Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells ( Bacillus subtilis or Bacillus licheniformis, ˜10 8 cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10 -2, 10 -3, or 10 -4 mol/L) under open oxic conditions and at different pH (6-9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall ( Bacillus subtilis) surface complexed Fe, where Fe(III) (10 -3.5-10 -4.5 mol/L) was added to a fixed concentration of cells (˜10 8 cells/mL) under open oxic conditions and at various pH (2.5-4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe 2+ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe 2+ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary

  17. Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part II--mechanism.

    PubMed

    Newcombe, R L; Strawn, D G; Grant, T M; Childers, S E; Möller, G

    2008-03-01

    The removal mechanism of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE) was examined. A 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a 3-month tertiary effluent average of 0.011 mg/L phosphorus. In addition to aqueous geochemical modeling, experiments with surface charge, scanning electron microscopy, adsorptive capacity, thermal desorption, and most probable number of iron(III)-reducing bacteria were performed on samples from the system, to determine the major phosphorus-removal pathways. Results suggest that, in addition to filtration of particulate phosphorus, the low tertiary effluent total phosphorus result was achieved by adsorption.

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

    NASA Technical Reports Server (NTRS)

    Carroll, Michael R.; Rutherford, Malcolm J.

    1988-01-01

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

  19. The influence of hydrous Mn–Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands

    USGS Publications Warehouse

    Shope, Christopher L.; Xie, Ying; Gammons, Christopher H.

    2006-01-01

    Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn2+ and Mn2+ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.

  20. Inorganic sulfur oxidizing system in green sulfur bacteria.

    PubMed

    Sakurai, Hidehiro; Ogawa, Takuro; Shiga, Michiko; Inoue, Kazuhito

    2010-06-01

    Green sulfur bacteria use various reduced sulfur compounds such as sulfide, elemental sulfur, and thiosulfate as electron donors for photoautotrophic growth. This article briefly summarizes what is known about the inorganic sulfur oxidizing systems of these bacteria with emphasis on the biochemical aspects. Enzymes that oxidize sulfide in green sulfur bacteria are membrane-bound sulfide-quinone oxidoreductase, periplasmic (sometimes membrane-bound) flavocytochrome c sulfide dehydrogenase, and monomeric flavocytochrome c (SoxF). Some green sulfur bacteria oxidize thiosulfate by the multienzyme system called either the TOMES (thiosulfate oxidizing multi-enzyme system) or Sox (sulfur oxidizing system) composed of the three periplasmic proteins: SoxB, SoxYZ, and SoxAXK with a soluble small molecule cytochrome c as the electron acceptor. The oxidation of sulfide and thiosulfate by these enzymes in vitro is assumed to yield two electrons and result in the transfer of a sulfur atom to persulfides, which are subsequently transformed to elemental sulfur. The elemental sulfur is temporarily stored in the form of globules attached to the extracellular surface of the outer membranes. The oxidation pathway of elemental sulfur to sulfate is currently unclear, although the participation of several proteins including those of the dissimilatory sulfite reductase system etc. is suggested from comparative genomic analyses.

  1. Assessment of the Morphological, Biochemical, and Kinetic Properties for Candida rugosa Lipase Immobilized on Hydrous Niobium Oxide to Be Used in the Biodiesel Synthesis

    PubMed Central

    Miranda, Michele; Urioste, Daniele; Andrade Souza, Livia T.; Mendes, Adriano A.; de Castro, Heizir F.

    2011-01-01

    Lipase from Candida rugosa (CRL) was immobilized by covalent attachment on hydrous niobium oxide. The matrix could effectively be attached to the enzyme with high retention of activity and prevent its leakage. Following immobilization, CRL exhibited improved storage stability and performed better at higher incubation temperatures. In addition, the enzyme retained most of its catalytic efficiency after successive operational cycles. The immobilized derivative was also fully characterized with respect to its morphological properties: particle size, surface specific area, and pore size distribution. Structural integrity and conformational changes, such as surface cavities in the support, set by the lipase procedure, were observed by Scanning Electron Microscopy. Additionally, a comparative study between free and immobilized lipases was provided in terms of pH, temperature, and thermal stability. CRL derivative was evaluated for the synthesis of biodiesel employing babassu oil and short chain alcohols. The process was feasible only for oil and butanol reaction system. PMID:21876790

  2. Reduction of U(VI) by Fe(II) in the presence of hydrous ferric oxide and hematite: effects of solid transformation, surface coverage, and humic acid.

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2008-04-01

    Fe(II) was added to U(VI)-spiked suspensions of hydrous ferric oxide (HFO) or hematite to compare the redox behaviors of uranium in the presence of two different Fe(III) (oxyhydr)oxides. Experiments were conducted with low or high initial sorption density of U(VI) and in the presence or absence of humic acid (HA). About 80% of U(VI) was reduced within 3 days for low sorbed U(VI) conditions, with either hematite or HFO. The {Fe(3+)} in the low U(VI) experiments at 3 days, based on measured Fe(II) and U(VI) and the assumed presence of amorphous UO(2(s)), was consistent with control by HFO for either initial Fe(III) (oxyhydr)oxide. After about 1 day, partial re-oxidation to U(VI) was observed in the low sorbed U(VI) experiments in the absence of HA, without equivalent increase of dissolved U(VI). No reduction of U(VI) was observed in the high sorbed U(VI) experiments; it was hypothesized that the reduction required sorption proximity of U(VI) and Fe(II). Addition of 5mg/L HA slowed the reduction with HFO and had less effect with hematite. Mössbauer spectroscopy (MBS) of (57)Fe(II)-enriched samples identified the formation of goethite, hematite, and non-stoichiometric magnetite from HFO, and the formation of HFO, hydrated hematite, and non-stoichiometric magnetite from hematite.

  3. Sorption of dissolved organic carbon by hydrous aluminum and iron oxides occurring at the confluence of deer creek with the Snake River, Summit County, Colorado

    USGS Publications Warehouse

    McKnight, Diane M.; Bencala, K.E.; Zellweger, G.W.; Aiken, G.R.; Feder, G.L.; Thorn, K.A.

    1992-01-01

    Organic solute sorption by hydrous iron and aluminum oxides was studied in an acidic, metal-enriched stream (the Snake River) at its confluence with a pristine stream (Deer Creek). From 1979 to 1986, typically 40% of the dissolved organic carbon (DOC) was removed from solution by sorption onto aluminum and iron oxides, which precipitate as the two streamwaters mix. Upstream DOC concentrations, which increase during snowmelt, were identified as the most significant variables in a multiple regression for determining the DOC concentration below the confluence, and the extent of Al and Fe precipitation was much less significant. On hourly timescales, removal of Al and Fe varied erratically but DOC removal was steady, indicating that "sorbable" organic solutes are sorbed either by precipitating oxides or by oxides on the streambed. Characterization of two reactive DOC fractions (fulvic and hydrophilic acids) showed that sorption results in chemical fractionation. Molecules with greater contents of aromatic moieties, carboxylic acid groups, and amino acid residues were preferentially sorbed, which is consistent with the ligand exchange-surface complexation model.

  4. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    SciTech Connect

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  5. Trace Metal Contamination in Sediments from U.K. Estuaries: An Empirical Evaluation of the Role of Hydrous Iron and Manganese Oxides

    NASA Astrophysics Data System (ADS)

    Turner, A.

    2000-03-01

    Concentrations of reducible trace metals (available to hydroxylamine hydrochloride-acetic acid; HA) have been determined in sediments from contrasting estuaries around the United Kingdom; specifically, estuaries receiving contemporary anthropogenic inputs from catchments which are urbanized and industrialized to varying degrees (Clyde, Dee, Forth, Loughor, Mersey and Poole Harbour), and estuaries receiving inputs from mineralized catchments where working of sulphidic ore deposits was important in the past (Fal, Hayle, Helford and Tavy). Mean estuarine ratios of Fe:Mn ranged from less than 10 (Dee, Mersey, Loughor) to about 100 (Fal, Poole Harbour); inter-estuarine variations in the mass contributions of Fe and Mn were attributed to differences in geological and hydrological catchment characteristics, while intra-estuarine variations were attributed to local differences in hydraulic sorting of sediment and redox conditions. The relative contributions of hydrous Fe and Mn oxides to the accumulation of trace metals (Cr, Cu, Pb, Zn) was evaluated by applying different regression analyses to each estuarine dataset. Overall, the most significant correlations were with Fe, and in estuaries draining mineralized catchments where well-defined contaminant metal sources exist; poor correlations in other cases were related to the dissolution of additional metal-bearing phases, including carbonates, by the digest (Dee, Loughor), or the inability of low energy environments (Clyde, Poole Harbour) to buffer the impacts of local sources of contaminant metals. Mean estuarine concentrations of Pb and Zn ranged from about 25 μg g -1(Poole Harbour) to 200 μg g -1(Hayle), and 80 μg g -1(Forth) to 1500 μg g -1(Hayle), respectively. Pooled Pb and Zn data were defined by a single regression equation which was not controlled by the availability or abundance of oxidic material, suggesting common environmental and anthropogenic sources and similar sorptive and post-depositional behaviours

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

    USGS Publications Warehouse

    Parker, S.R.; Gammons, C.H.; Jones, C.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.

  7. Oxidative coupling of methane using inorganic membrane reactor

    SciTech Connect

    Ma, Y.H.; Moser, W.R.; Dixon, A.G.

    1995-12-31

    The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

  8. Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part I--performance.

    PubMed

    Newcombe, R L; Rule, R A; Hart, B K; Möller, G

    2008-03-01

    This work examines the performance of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE). A 3-month, 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a tertiary effluent average of 0.011 mg/L phosphorus. Iron doses to the plant were low, at 5 mg/L. Inline recycling of HFO solution rejects to the plant influent resulted in a maximum 90.3%, dose-dependent reduction of phosphorus in the secondary effluent at 4.5 ML/d (1.2 mgd). Other results included reduction of total suspended solids and turbidity. A mass balance analysis was performed. We conclude that HFO-RF-RECYCLE may allow very low levels of phosphorus discharge from municipal wastewater treatment plants with a ferric-iron-based tertiary filtration process and residual recycling.

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

    USGS Publications Warehouse

    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.

  10. Protein-mediated adhesion of the dissimilatory Fe(III)-reducing bacterium Shewanella alga BrY to hydrous ferric oxide

    SciTech Connect

    Caccavo, F. Jr.

    1999-11-01

    The rate and extent of bacterial Fe(III) mineral reduction are governed by molecular-scale interactions between the bacterial cell surface and the mineral surface. These interactions are poorly understood. This study examined the role of surface proteins in the adhesion of Shewanella alga BrY to hydrous ferric oxide (HFO). Enzymatic degradation of cell surface polysaccharides had no effect on cell adhesion to HFO. The proteolytic enzymes Streptomyces griseus protease and chymotrypsin inhibited the adhesion of S. alga BrY cells to HFO through catalytic degradation of surface proteins. Trypsin inhibited S. alga BrY adhesion solely through surface-coating effects. Protease and chymotrypsin also mediated desorption of adhered S. alga BrY cells from HFO while trypsin did not mediate cell desorption. Protease removed a single peptide band that represented a protein with an apparent molecular mass of 50 kDa. Chymotrypsin removed two peptide bands that represented proteins with apparent molecular masses of 60 and 31 kDa. These proteins represent putative HGO adhesion molecules. A. alga BrY adhesion was inhibited by up to 46% when cells were cultured at sub-MICs of chloramphenicol, suggesting that protein synthesis is necessary for adhesion. Proteins extracted from the surface of S. alga BrY cells inhibited adhesion to HFO by up to 41%. A number of these proteins bound specifically to HFO, suggesting that a complex system of surface proteins mediates S. alga BrY adhesion to HFO.

  11. Protein-Mediated Adhesion of the Dissimilatory Fe(III)-Reducing Bacterium Shewanella alga BrY to Hydrous Ferric Oxide

    PubMed Central

    Caccavo, Frank

    1999-01-01

    The rate and extent of bacterial Fe(III) mineral reduction are governed by molecular-scale interactions between the bacterial cell surface and the mineral surface. These interactions are poorly understood. This study examined the role of surface proteins in the adhesion of Shewanella alga BrY to hydrous ferric oxide (HFO). Enzymatic degradation of cell surface polysaccharides had no effect on cell adhesion to HFO. The proteolytic enzymes Streptomyces griseus protease and chymotrypsin inhibited the adhesion of S. alga BrY cells to HFO through catalytic degradation of surface proteins. Trypsin inhibited S. alga BrY adhesion solely through surface-coating effects. Protease and chymotrypsin also mediated desorption of adhered S. alga BrY cells from HFO while trypsin did not mediate cell desorption. Protease removed a single peptide band that represented a protein with an apparent molecular mass of 50 kDa. Chymotrypsin removed two peptide bands that represented proteins with apparent molecular masses of 60 and 31 kDa. These proteins represent putative HFO adhesion molecules. S. alga BrY adhesion was inhibited by up to 46% when cells were cultured at sub-MICs of chloramphenicol, suggesting that protein synthesis is necessary for adhesion. Proteins extracted from the surface of S. alga BrY cells inhibited adhesion to HFO by up to 41%. A number of these proteins bound specifically to HFO, suggesting that a complex system of surface proteins mediates S. alga BrY adhesion to HFO. PMID:10543817

  12. Dietary Uptake of Cu Sorbed to Hydrous Iron Oxide is Linked to Cellular Toxicity and Feeding Inhibition in a Benthic Grazer.

    PubMed

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

    2016-02-02

    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 10(4) 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.

  13. High sensitivity measurement of 224Ra and 226Ra in water with an improved hydrous titanium oxide technique at the Sudbury Neutrino Observatory

    NASA Astrophysics Data System (ADS)

    Aharmim, B.; Cleveland, B. T.; Dai, X.; Doucas, G.; Farine, J.; Fergani, H.; Ford, R.; Hahn, R. L.; Hallman, E. D.; Jelley, N. A.; Lange, R.; Majerus, S.; Mifflin, C.; Noble, A. J.; O'Keeffe, H. M.; Rodriguez-Jimenez, R.; Sinclair, D.; Yeh, M.

    2009-06-01

    The existing hydrous titanium oxide (HTiO) technique for the measurement of 224Ra and 226Ra in the water at the Sudbury Neutrino Observatory (SNO) has been changed to make it faster and less sensitive to trace impurities in the HTiO eluate. Using HTiO-loaded filters followed by cation exchange adsorption and HTiO co-precipitation, Ra isotopes from 200 to 450 tonnes of heavy water can be extracted and concentrated into a single sample of a few millilitres with a total chemical efficiency of 50%. Combined with beta-alpha coincidence counting, this method is capable of measuring 1.5×10-3 μBq/kg of 224Ra and 3.3×10-3 μBq/kg of 226Ra from the 232Th and 238U decay chains, respectively, for a 275 tonne D2O assay, which are equivalent to 4×10-16 g Th/g and 3×10-16 g U/g in heavy water.

  14. Absorption of inorganic halides produced from Freon 12 by calcium carbonate containing iron(III) oxide

    SciTech Connect

    Imamura, Seiichiro; Matsuba, Yoichi; Yamada, Etsu; Takai, Kenji; Utani, Kazunori

    1997-09-01

    Inorganic halides produced by the catalytic decomposition of Freon 12 were fixed by calcium carbonate, which is the main component of limestone. Iron(III) oxide, which is present as a contaminant in limestone, promoted the absorption of the halides by calcium carbonate at low temperatures. The supposed action of iron(III) oxide was to first react with inorganic halides, forming iron halides, and, then, transfer them to calcium carbonate to replace carbonate ion in a catalytic way. Thus, calcium carbonate containing iron oxides (limestone) can be used as an effective absorbent for the inorganic halogens produced during the decomposition of Freons.

  15. Simultaneous removal of As(V) and Cr(VI) from water by macroporous anion exchanger supported nanoscale hydrous ferric oxide composite.

    PubMed

    Hua, Ming; Yang, Bowen; Shan, Chao; Zhang, Weiming; He, Shiya; Lv, Lu; Pan, Bingcai

    2017-03-01

    As(V) and Cr(VI) are both highly toxic anionic pollutants and commonly co-exist in some industrial effluents and contaminated waters. In this study, simultaneous removal of them was efficiently achieved by employing a composite adsorbent (HFO-201) fabricated by immobilizing nanoscale hydrous ferric oxide (HFO) within a macroporous anion exchanger D201. The HFO-201 composite possesses two types of adsorption sites, i.e. the quaternary ammonium groups fixed on the D201 matrix and the embedded HFO nanoparticles. In the binary solution, the adsorption kinetic processes of both As(V) and Cr(VI) by HFO-201 were well fitted with the pseudo-first order kinetic model. Furthermore, HFO-201 exhibited a significantly higher adsorption capacity toward As(V) than D201 and an identical adsorption capacity toward Cr(VI) to D201. During the removal process, As(V) was captured by both the electrostatic attraction from the fixed quaternary ammonium groups and the formation of inner-sphere complex with the embedded HFO nanoparticles. Whereas, Cr(VI) was primarily adsorbed by the fixed ammonium groups. Fixed-bed treatment of As(V)/Cr(VI) binary synthetic water by HFO-201 resulted in elimination of As (from 1.0 to below 0.01 mg/L) and Cr (from 5.0 to below 0.05 mg/L), with the treatment capacity of 1700 bed volume (BV). Moreover, the exhausted HFO-201 was amenable to efficient in situ regeneration with a binary NaOH-NaCl solution for repeated use without any significant capacity loss.

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

    PubMed

    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.

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

    USGS Publications Warehouse

    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.

  18. Combined Hydrous Ferric Oxide and Quaternary Ammonium Surfactant Tailoring of Granular Activated Carbon for Concurrent Arsenate and Perchlorate Removal

    SciTech Connect

    Jang, M.; Cannon, F; Parette, R; Yoon, S; Chen, W

    2009-01-01

    Activated carbon was tailored with both iron and quaternary ammonium surfactants so as to concurrently remove both arsenate and perchlorate from groundwater. The iron (hydr)oxide preferentially removed the arsenate oxyanion but not perchlorate; while the quaternary ammonium preferentially removed the perchlorate oxyanion, but not the arsenate. The co-sorption of two anionic oxyanions via distinct mechanisms has yielded intriguing phenomena. Rapid small-scale column tests (RSSCTs) with these dually prepared media employed synthetic waters that were concurrently spiked with arsenate and perchlorate; and these trial results showed that the quaternary ammonium surfactants enhanced arsenate removal bed life by 25-50% when compared to activated carbon media that had been preloaded merely with iron (hydr)oxide; and the surfactant also enhanced the diffusion rate of arsenate per the Donnan effect. The authors also employed natural groundwater from Rutland, MA which contained 60 microg/L As and traces of silica, and sulfate; and the authors spiked this with 40 microg/L perchlorate. When processing this water, activated carbon that had been tailored with iron and cationic surfactant could treat 12,500 bed volumes before 10 microg/L arsenic breakthrough, and 4500 bed volumes before 6 microg/L perchlorate breakthrough. Although the quaternary ammonium surfactants exhibited only a slight capacity for removing arsenate, these surfactants did facilitate a more favorably positively charged avenue for the arsenate to diffuse through the media to the iron sorption site (i.e. via the Donnan effect).

  19. The influence of hydrous ferric oxide, earthworms, and a hypertolerant plant on arsenic and iron bioavailability, fate, and transport in soils.

    PubMed

    Maki, Benjamin C; Hodges, Kathryn R; Ford, Scott C; Sofield, Ruth M

    2016-10-24

    Historic applications of lead arsenate pesticides and smelting activities have resulted in elevated concentrations of arsenic in Washington State soils. For example, old orchard topsoils in Washington have concentrations reaching upwards of 350 mg As/kg soil with an estimated 187,590 acres of arsenic contamination from pesticide application alone. Iron oxides have been indicated as a key factor in modulating the fate and transport of arsenic in the soil environment. We employed a factorial design to investigate the role of a specific iron oxide, hydrous ferric oxide (HFO), and terrestrial organisms on the mobility, bioavailability, and fate of arsenic and iron in locally collected soils. Earthworms in soils amended with both arsenic and HFO had 47.2 % lower arsenic tissue concentrations compared to those in soils only amended with arsenic. Similarly, arsenic leachate concentrations and plant tissue concentrations were lower when HFO was present, although this was with a reduced magnitude and was not consistently significant. A lack of significance of HFO in three of the linear models for leachate and plant bioavailability, however, indicates that the role of HFO in arsenic mobility, bioavailability, and fate is more complicated than can be explained by the simple addition or not of HFO. For example, our analyses showed that earthworms decreased pH and increased bioavailability for both arsenic and iron as demonstrated by increases in leachate and plant tissue concentrations. The mechanisms for this could include a biotransformation of earthworm-ingested arsenic combined with an earthworm-induced change in pH. We also found that arsenic amendments increased the mobility and bioavailability of iron, evidenced by increased iron concentrations in earthworms, plants, and leachate. A mechanistic explanation for this change in bioavailability is not readily apparent but does support a need for more work on bioavailability when mixtures are present. From these results

  20. 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

    SciTech Connect

    Koretsky, Carla

    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

  1. Probing the interactions between lignin and inorganic oxides using atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Wang, Jingyu; Qian, Yong; Deng, Yonghong; Liu, Di; Li, Hao; Qiu, Xueqing

    2016-12-01

    Understanding the interactions between lignin and inorganic oxides has both fundamental and practical importance in industrial and energy fields. In this work, the specific interactions between alkali lignin (AL) and three inorganic oxide substrates in aqueous environment are quantitatively measured using atomic force microscopy (AFM). The results show that the average adhesion force between AL and metal oxide such as Al2O3 or MgO is nearly two times bigger than that between AL and nonmetal oxide such as SiO2 due to the electrostatic difference and cation-π interaction. When 83% hydroxyl groups of AL is blocked by acetylation, the adhesion forces between AL and Al2O3, MgO and SiO2 decrease 43, 35 and 75% respectively, which indicate hydrogen bonds play an important role between AL and inorganic oxides, especially in AL-silica system.

  2. Sb(III) and Sb(V) Sorption onto Al-Rich Phases: Hydrous Al Oxide and the Clay Minerals Kaolinite KGa-1b and Oxidized and Reduced Nontronite NAu-1

    SciTech Connect

    Ilgen, Anastasia G.; Trainor, Thomas P.

    2012-11-13

    We have studied the immobilization of Sb(III) and Sb(V) by Al-rich phases - hydrous Al oxide (HAO), kaolinite (KGa-1b), and oxidized and reduced nontronite (NAu-1) - using batch experiments to determine the uptake capacity and the kinetics of adsorption and Extended X-ray Absorption Fine Structure (EXAFS) Spectroscopy to characterize the molecular environment of adsorbed Sb. Both Sb(III) and Sb(V) are adsorbed in an inner-sphere mode on the surfaces of the studied substrates. The observed adsorption geometry is mostly bidentate corner-sharing, with some monodentate complexes. The kinetics of adsorption is relatively slow (on the order of days), and equilibrium adsorption isotherms are best fit using the Freundlich model. The oxidation state of the structural Fe within nontronite affects the adsorption capacity: if the clay is reduced, the adsorption capacity of Sb(III) is slightly decreased, while Sb(V) uptake is increased significantly. This may be a result of the presence of dissolved Fe(II) in the reduced nontronite suspensions or associated with the structural rearrangements in nontronite due to reduction. These research findings indicate that Sb can be effectively immobilized by Al-rich phases. The increase in Sb(V) uptake in response to reducing structural Fe in clay can be important in natural settings since Fe-rich clays commonly go through oxidation-reduction cycles in response to changing redox conditions.

  3. Stimulation of thaumarchaeal ammonia oxidation by ammonia derived from organic nitrogen but not added inorganic nitrogen.

    PubMed

    Levičnik-Höfferle, Spela; Nicol, Graeme W; Ausec, Luka; Mandić-Mulec, Ines; Prosser, James I

    2012-04-01

    Ammonia oxidation, the first step in nitrification, is performed by autotrophic bacteria and thaumarchaea, whose relative contributions vary in different soils. Distinctive environmental niches for the two groups have not been identified, but evidence from previous studies suggests that activity of thaumarchaea, unlike that of bacterial ammonia oxidizers, is unaffected by addition of inorganic N fertilizer and that they preferentially utilize ammonia generated from the mineralization of organic N. This hypothesis was tested by determining the influence of both inorganic and organic N sources on nitrification rate and ammonia oxidizer growth and community structure in microcosms containing acidic, forest soil in which ammonia oxidation was dominated by thaumarchaea. Nitrification rate was unaffected by the incubation of soil with inorganic ammonium but was significantly stimulated by the addition of organic N. Oxidation of ammonia generated from native soil organic matter or added organic N, but not added inorganic N, was accompanied by increases in abundance of the thaumarchaeal amoA gene, a functional gene for ammonia oxidation, but changes in community structure were not observed. Bacterial amoA genes could not be detected. Ammonia oxidation was completely inhibited by 0.01% acetylene in all treatments, indicating ammonia monooxygenase-dependent activity. The findings have implications for current models of soil nitrification and for nitrification control strategies to minimize fertilizer loss and nitrous oxide production. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  4. Cu-ZSM-5: A biomimetic inorganic model for methane oxidation.

    PubMed

    Vanelderen, Pieter; Hadt, Ryan G; Smeets, Pieter J; Solomon, Edward I; Schoonheydt, Robert A; Sels, Bert F

    2011-12-01

    The present work highlights recent advances in elucidating the methane oxidation mechanism of inorganic Cu-ZSM-5 biomimic and in identifying the reactive intermediates that are involved. Such molecular understanding is important in view of upgrading abundantly available methane, but also to comprehend the working mechanism of genuine Cu-containing oxidation enzymes.

  5. Liquid Crystalline Behavior and Related Properties of Colloidal Systems of Inorganic Oxide Nanosheets

    PubMed Central

    Nakato, Teruyuki; Miyamoto, Nobuyoshi

    2009-01-01

    Inorganic layered crystals exemplified by clay minerals can be exfoliated in solvents to form colloidal dispersions of extremely thin inorganic layers that are called nanosheets. The obtained “nanosheet colloids” form lyotropic liquid crystals because of the highly anisotropic shape of the nanosheets. This system is a rare example of liquid crystals consisting of inorganic crystalline mesogens. Nanosheet colloids of photocatalytically active semiconducting oxides can exhibit unusual photoresponses that are not observed for organic liquid crystals. This review summarizes experimental work on the phase behavior of the nanosheet colloids as well as photochemical reactions observed in the clay and semiconducting nanosheets system.

  6. Inorganic metal oxide/organic polymer nanocomposites and method thereof

    DOEpatents

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-03-30

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal inorganic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophillic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the composite material, providing superb mixing of the component phases in the energetic nanocomposite.

  7. Oxidation control of fluxes for mixed-valent inorganic oxide materials synthesis

    NASA Astrophysics Data System (ADS)

    Schrier, Marc David

    This dissertation is concerned with controlling the flux synthesis and ensuing physical properties of mixed-valence metal oxides. Molten alkali metal nitrates and hydroxides have been explored to determine and exploit their variable redox chemistries for the synthesis of mixed-valent oxide materials. Cationic and anionic additives have been utilized in these molten salts to control the relative concentrations of the redox-active species present to effectively tune and cap the electrochemical potential of the flux. Atoms like bismuth, copper, and manganese are capable of providing different numbers of electrons for bonding. With appropriate doping near the metal-insulator transition, many of these mixed-valent inorganic metal oxides exhibit extraordinary electronic and magnetic properties. Traditionally, these materials have been prepared by classical high temperature solid state routes where microscopic homogeneity is hard to attain. In these routes, the starting composition dictates the doping level, and in turn, the formal oxidation state achieved. Molten flux syntheses developed in this work have provided the potential for preparing single-phase, homogeneous, and crystalline materials. The redox-active fluxes provide a medium for enhanced doping and mixed-valency control in which the electrochemical potential adjusts the formal oxidation state, and the doping takes place to maintain charge neutrality. The two superconductor systems investigated are: (1) the potassium-doped barium bismuth oxides, and (2) the alkali metal- and alkaline earth metal-doped lanthanum copper oxides. Controlled oxidative doping has been achieved in both systems by two different approaches. The superconducting properties of these materials have been assessed, and the materials have been characterized by powder X-ray diffraction and e-beam microprobe elemental analyses. In the course of these studies, several other materials have been identified. Analysis of these materials, and the

  8. Elevated trimethylarsine oxide (TMAO) and inorganic arsenic in northern hemisphere summer monsoonal wet deposition.

    PubMed

    Savage, Laurie; Carey, Manus Patrick; Hossain, Mahmud; Islam, M Rafiqul; de Silva, P Mangala C S; Williams, Paul Nicholas; Meharg, Andrew A

    2017-10-04

    Arsenic speciation, their inputs, for wet deposition are not well understood. Here we demonstrate that trimethylarsine oxide (TMAO) and inorganic arsenic are the dominant species in summer, Indian subcontinent, Bangladesh, monsoonal, wet deposition, with inorganic arsenic dominating, accounting for ~80% of total arsenic in this medium. Lower concentrations of both species were found in the winter, Indian subcontinent, Sri Lankan, monsoonal, wet deposition. The only other species present was dimethylarsinic acid (DMAA), but this was usually below limits of detection (LoD). We hypothesise that TMAO and inorganic arsenic in monsoonal wet deposition is predominantly of marine origin. For TMAO, the potential source is the atmospheric oxidation of marine derived trimethyl arsine (TMA). For inorganic arsenic, our evidence suggests entrainment of water column inorganic arsenic into atmospheric particulates. These conclusions are based on weather trajectory analysis, and to the strong correlations with known wet deposition marine derived elements: boron, iodine and selenium. The finding that TMAO and inorganic arsenic are widely present, and elevated, in monsoonal wet deposition identifies major knowledge gaps that need to be addressed regarding understanding arsenic's global cycle.

  9. From iron oxide nanoparticles towards advanced iron-based inorganic materials designed for biomedical applications.

    PubMed

    Figuerola, Albert; Di Corato, Riccardo; Manna, Liberato; Pellegrino, Teresa

    2010-08-01

    In the last decade the progress achieved on the synthesis of inorganic nanostructures has been accompanied by the parallel exploitation of these systems in various fields, among them are biology and medicine. We provide here an overview of the iron-based inorganic nanostructured materials that have been developed and tested in these fields. We will highlight the major concepts on the preparation, physical properties and applications of such nanostructures, starting from the most investigated iron oxide nanoparticles. We will describe then the new generation of inorganic hybrid nanostructures, which are structures that integrate in each nano-object multiple inorganic nanocrystals of different materials. In our discussion we will focus on those works that have provided a sound proof of concept on the potential of the various systems as diagnostic and therapeutic agents. Copyright 2010 Elsevier Ltd. All rights reserved.

  10. Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Lee, Jooyoung; Sher Shah, Selim Arif; Yoo, Pil J.; Lim, Byungkwon

    2017-04-01

    This letter describes an aqueous-phase synthetic route to hydrous ruthenium oxide (RuO2) nanoparticles and their conversion into crystalline ones via a thermal annealing process. Electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were employed to characterize hydrous and crystalline RuO2 nanoparticles. The hydrous RuO2 nanoparticles exhibited higher activity for hydrogen evolution reaction than commercial Pt catalyst, while the crystalline RuO2 nanoparticles showed better performance for oxygen evolution reaction than IrO2 catalyst. With these hydrous and crystalline RuO2 catalysts, we were able to achieve highly efficient overall electrochemical water splitting.

  11. IR studies of EDTA alkaline salts interaction with the surface of inorganic oxides

    NASA Astrophysics Data System (ADS)

    Ryczkowski, J.

    2005-10-01

    The adsorption of alkaline salts of ethylenediaminetetraacetic acid (EDTA) on inorganic supports characterized by the different value of the isoelectric point of the surface (IEPS) has been investigated by transmission and photoacoustic (PA) FT-IR. The IR spectra in the 1800-1200 cm -1 region of the supported complexones are different from those of the unsupported compounds. The results obtained imply that the observed changes in the properties of adsorbed complexones are mainly due to interaction of the carboxyl groups of chelate molecule with inorganic oxide hydroxyl groups. The models of those interactions have been proposed. The IEPS value has a noticeable influence on the nature of the interactions observed. Based on the experimental data the ability of inorganic oxide interaction with the chelate molecule can be presented as follows: V 2O 5 < SiO 2 < TiO 2 < MgO < Al 2O 3 < ZrO 2-La < ZrO 2.

  12. Megafans as Hydrous Environments

    NASA Technical Reports Server (NTRS)

    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

  13. Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

    DOEpatents

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-11-16

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

  14. Thermal stability of ladderane lipids as determined by hydrous pyrolysis

    USGS Publications Warehouse

    Jaeschke, A.; Lewan, M.D.; Hopmans, E.C.; Schouten, S.; Sinninghe, Damste J.S.

    2008-01-01

    Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 ??C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 ??C. At temperatures >140 ??C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 ??C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C31 hopane 22S/(22S + 22R) ratio 0.5). ?? 2008 Elsevier Ltd.

  15. Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

    DOE PAGES

    Lichterman, Michael F.; Sun, Ke; Hu, Shu; ...

    2015-10-25

    Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation are unstable,more » either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.« less

  16. Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

    SciTech Connect

    Lichterman, Michael F.; Sun, Ke; Hu, Shu; Zhou, Xinghao; McDowell, Matthew T.; Shaner, Matthew R.; Richter, Matthias H.; Crumlin, Ethan J.; Carim, Azhar I.; Saadi, Fadl H.; Brunschwig, Bruce S.; Lewis, Nathan S.

    2015-10-25

    Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation are unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.

  17. Electrochemical properties of inorganic nanoporous oxide coated electrodes

    NASA Astrophysics Data System (ADS)

    Leonard, Kevin C.

    The ability to produce clean water and produce and store clean energy is essential to society. Hence, technologies that facilitate clean energy and clean water are of great importance. This study focused on utilizing nanoporous insulating oxide materials to alter the chemistry at the electrode/electrolyte interface to improve the performance of a number of clean energy and clean water technologies. Here we have shown that applying a thin-film of SiO2 nanoparticles to an electrochemical capacitor electrode can increase the energy storage capacity by up to 50% at high power ratings. We have developed a geometric model to describe the coating of the porous electrode to explain the increased performance at high power ratings. We have also shown that the coated electrochemical capacitor exhibits a higher capacitance when normalized to BET surface area, suggesting that the coated surface is behaving fundamentally differently than the uncoated surface. We attribute the increase in capacitance to the inherent surface potential of the oxide coating and have shown that if we alter the surface potential of the oxide, we can in turn alter the electrochemical capacitance. In addition, we have determined that when used in capacitive deionization systems, these coatings can increase ion removal and accelerate regeneration, allowing for higher efficiency and less waste water. We have demonstrated that a nanoporous oxide coating can increase the gas production rate and lower the overpotential of the hydrogen evolution reaction via water electrolysis on both stainless steel and carbon electrodes. In addition, this work presents data on utilizing nanoporous oxide coatings on Li-Ion battery cathodes to improve high temperature capacity fade. We also introduce a novel thin-film battery/electrochemical capacitor hybrid device, which can improve the performance of simple thin-film batteries.

  18. Interactions of inorganic oxide nanoparticles with sewage biosolids.

    PubMed

    Rottman, Jeff; Shadman, Farhang; Sierra-Alvarez, Reyes

    2012-01-01

    The use of nanoparticles (NPs) in manufacturing continues to increase despite the growing concern over their potential environmental and health effects. Understanding the interaction of NPs and sewage sludge is crucial for determining the ultimate fate of NPs released to municipal wastewater treatment plants (WWTPs) as those interactions will determine whether the bulk of the material is retained in the sludge or released in the effluent stream. Analyzing the affinity of aluminum oxide, cerium oxide, and silicon oxide NPs, which are commonly used in semiconductor manufacturing processes, for biosolids used in municipal WWTPs provides a basis for estimating their removal efficiency. Batch studies were performed and the NPs were shown to partition onto the cellular surface. At the maximum equilibrium values tested (75-92 mg nanoparticles/L), the concentration of Al(2)O(3), CeO(2) and SiO(2) associated with the sludge was 137, 238, and 28 mg/g-sludge VSS, respectively. These results suggest that electrostatic interactions play a major role in determining NP association with biosolids.

  19. Comparative compressibility of hydrous wadsleyite

    NASA Astrophysics Data System (ADS)

    Chang, Y.; Jacobsen, S. D.; Thomas, S.; Bina, C. R.; Smyth, J. R.; Frost, D. J.; Hauri, E. H.; Meng, Y.; Dera, P. K.

    2010-12-01

    Determining the effects of hydration on the density and elastic properties of wadsleyite, β-Mg2SiO4, is critical to constraining Earth’s global geochemical water cycle. Whereas previous studies of the bulk modulus (KT) have studied either hydrous Mg-wadsleyite, or anhydrous Fe-bearing wadsleyite, the combined effects of hydration and iron are under investigation. Also, whereas KT from compressibility studies is relatively well constrained by equation of state fitting to P-V data, the pressure derivative of the bulk modulus (K’) is usually not well constrained either because of poor data resolution, uncertainty in pressure calibrations, or narrow pressure ranges of previous single-crystal studies. Here we report the comparative compressibility of dry versus hydrous wadsleyite with Fo90 composition containing 1.9(2) wt% H2O, nearly the maximum water storage capacity of this phase. The composition was characterized by EMPA and nanoSIMS. The experiments were carried out using high-pressure, single-crystal diffraction up to 30 GPa at HPCAT, Advanced Photon Source. By loading three crystals each of hydrous and anhydrous wadsleyite together in the same diamond-anvil cell, we achieve good hkl coverage and eliminate the pressure scale as a variable in comparing the relative value of K’ between the dry and hydrous samples. We used MgO as an internal diffraction standard, in addition to recording ruby fluorescence pressures. By using neon as a pressure medium and about 1 GPa pressure steps up to 30 GPa, we obtain high-quality diffraction data for constraining the effect of hydration on the density and K’ of hydrous wadsleyite. Due to hydration, the initial volume of hydrous Fo90 wadsleyite is larger than anhydrous Fo90 wadsleyite, however the higher compressibility of hydrous wadsleyite leads to a volume crossover at 6 GPa. Hydration to 2 wt% H2O reduces the bulk modulus of Fo90 wadsleyite from 170(2) to 157(2) GPa, or about 7.6% reduction. In contrast to previous

  20. All-inorganic inverse perovskite solar cells using zinc oxide nanocolloids on spin coated perovskite layer.

    PubMed

    Shibayama, Naoyuki; Kanda, Hiroyuki; Yusa, Shin-Ichi; Fukumoto, Shota; Baranwal, Ajay K; Segawa, Hiroshi; Miyasaka, Tsutomu; Ito, Seigo

    2017-01-01

    We confirmed the influence of ZnO nanoparticle size and residual water on performance of all inorganic perovskite solar cells. By decreasing the size of the ZnO nanoparticles, the short-circuit current density (Jsc) and open circuit photovoltage (Voc) values are increased and the conversion efficiency is improved. Although the Voc value is not affected by the influence of residual water in the solution for preparing the ZnO layer, the Jsc value drops greatly. As a result, it was found that it is important to use the oxide nanoparticles with a small particle diameter and to reduce the water content in the oxide forming material in order to manufacture a highly efficient all inorganic perovskite solar cells.

  1. All-inorganic inverse perovskite solar cells using zinc oxide nanocolloids on spin coated perovskite layer

    NASA Astrophysics Data System (ADS)

    Shibayama, Naoyuki; Kanda, Hiroyuki; Yusa, Shin-ichi; Fukumoto, Shota; Baranwal, Ajay K.; Segawa, Hiroshi; Miyasaka, Tsutomu; Ito, Seigo

    2017-07-01

    We confirmed the influence of ZnO nanoparticle size and residual water on performance of all inorganic perovskite solar cells. By decreasing the size of the ZnO nanoparticles, the short-circuit current density ( Jsc) and open circuit photovoltage ( Voc) values are increased and the conversion efficiency is improved. Although the Voc value is not affected by the influence of residual water in the solution for preparing the ZnO layer, the Jsc value drops greatly. As a result, it was found that it is important to use the oxide nanoparticles with a small particle diameter and to reduce the water content in the oxide forming material in order to manufacture a highly efficient all inorganic perovskite solar cells.

  2. Relationship between hydrous and ordinary pyrolysis

    SciTech Connect

    Burnham, A.K.

    1993-06-01

    Pyrolysis results are reviewed briefly with the intent of drawing comparisons between open, high pressure, and hydrous pyrolysis. Empirically, the degree of pyrolysis severity to form volatile products in open pyrolysis is similar to that required to form an expelled oil phase in hydrous pyrolysis. The yields of hydrocarbons from open pyrolysis are close to those from hydrous pyrolysis, but hydrous pyrolysis tends to assist the separation of hydrocarbons from polar materials. Pressure has a small but measurable affect on the generation kinetics.

  3. The crystal chemistry of inorganic metal borohydrides and their relation to metal oxides.

    PubMed

    Černý, Radovan; Schouwink, Pascal

    2015-12-01

    The crystal structures of inorganic homoleptic metal borohydrides are analysed with respect to their structural prototypes found amongst metal oxides in the inorganic databases such as Pearson's Crystal Data [Villars & Cenzual (2015). Pearson's Crystal Data. Crystal Structure Database for Inorganic Compounds, Release 2014/2015, ASM International, Materials Park, Ohio, USA]. The coordination polyhedra around the cations and the borohydride anion are determined, and constitute the basis of the structural systematics underlying metal borohydride chemistry in various frameworks and variants of ionic packing, including complex anions and the packing of neutral molecules in the crystal. Underlying nets are determined by topology analysis using the program TOPOS [Blatov (2006). IUCr CompComm. Newsl. 7, 4-38]. It is found that the Pauling rules for ionic crystals apply to all non-molecular borohydride crystal structures, and that the latter can often be derived by simple deformation of the close-packed anionic lattices c.c.p. and h.c.p., by partially removing anions and filling tetrahedral or octahedral sites. The deviation from an ideal close packing is facilitated in metal borohydrides with respect to the oxide due to geometrical and electronic considerations of the BH4(-) anion (tetrahedral shape, polarizability). This review on crystal chemistry of borohydrides and their similarity to oxides is a contribution which should serve materials engineers as a roadmap to design new materials, synthetic chemists in their search for promising compounds to be prepared, and materials scientists in understanding the properties of novel materials.

  4. CRYSTAL CHEMISTRY OF HYDROUS MINERALS

    SciTech Connect

    Y. ZHAO; ET AL

    2001-02-01

    Hydrogen has long been appreciated for its role in geological processes of the Earth's crust. However, its role in Earth's deep interior has been neglected in most geophysical thinking. Yet it is now believed that most of our planet's hydrogen may be locked up in high pressure phases of hydrous silicate minerals within the Earth's mantle. This rocky interior (approximately 7/8 of Earth's volume) is conjectured to contain 1-2 orders of magnitude more water than the more obvious oceans (the ''hydrosphere'') and atmosphere. This project is aimed at using the capability of neutron scattering from hydrogen to study the crystal chemistry and stability of hydrogen-bearing minerals at high pressures and temperatures. At the most basic level this is a study of the atomic position and hydrogen bond itself. We have conducted experimental runs on hydrous minerals under high pressure and high temperature conditions. The crystallographic structure of hydrous minerals at extreme conditions and its structural stability, and hydrogen bond at high P-T conditions are the fundamental questions to be addressed. The behavior of the hydrous minerals in the deep interior of the Earth has been discussed.

  5. Investigation of oxidation and migration processes of inorganic compounds in ink-corroded manuscripts

    NASA Astrophysics Data System (ADS)

    Kanngießer, Birgit; Hahn, Oliver; Wilke, Max; Nekat, Bettina; Malzer, Wolfgang; Erko, Alexei

    2004-10-01

    We studied the oxidation and migration processes of inorganic compounds in iron gall inks with a combination of micro X-ray fluorescence analysis (micro-XRF) and micro X-ray absorption near edge structure spectroscopy (micro-XANES). With elemental mapping by micro-XRF, the correlation of the minor elements in the ink to the major element Fe was investigated. Along concentration profiles of Fe, micro-XANES measurements were carried out in order to determine the oxidation state and the local environment. With the help of model inks, we could show that Cu is a further important element in the paper degradation process due to iron gall ink corrosion.

  6. Nanoscale growth and patterning of inorganic oxides using DNA nanostructure templates.

    PubMed

    Surwade, Sumedh P; Zhou, Feng; Wei, Bryan; Sun, Wei; Powell, Anna; O'Donnell, Christina; Yin, Peng; Liu, Haitao

    2013-05-08

    We describe a method to form custom-shaped inorganic oxide nanostructures by using DNA nanostructure templates. We show that a DNA nanostructure can modulate the rate of chemical vapor deposition of SiO2 and TiO2 with nanometer-scale spatial resolution. The resulting oxide nanostructure inherits its shape from the DNA template. This method generates both positive-tone and negative-tone patterns on a wide range of substrates and is compatible with conventional silicon nanofabrication processes. Our result opens the door to the use of DNA nanostructures as general-purpose templates for high-resolution nanofabrication.

  7. Thermochemistry of dense hydrous magnesium silicates

    NASA Technical Reports Server (NTRS)

    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.

  8. Thermochemistry of dense hydrous magnesium silicates

    NASA Technical Reports Server (NTRS)

    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.

  9. Oxidative properties and chemical stability of fluoronanotubes in matrixes of binary inorganic compounds.

    PubMed

    Peng, Haiqing; Gu, Zhenning; Liu, Yu; Chiang, Ivana W; Smalley, Richard E; Hauge, Robert H; Khabashesku, Valery N; Margrave, John L

    2003-01-01

    The chemical stability of fluoronanotubes in selected solid inorganic matrixes has been studied by initially mixing and mechanically grinding the components and subsequently heating them at temperatures ranging from 35 to 600 degrees C. The inorganic compounds selected for matrixes included halides (KBr, KI, Lil, LiBr, LiCl, NaCl, Znl2), oxides (Li2O, Fe2O3, PbO, MnO), lithium peroxide (Li2O2), potassium superoxide (KO2), sulfides (Li2S and ZnS), zinc selenide (ZnSe), lithium nitride (Li3N), and aluminum phosphide (AIP). Solid products, resulting from the proceeding chemical reactions, were analyzed by X-ray diffraction, Raman spectroscopy, and SEM/EDX elemental analysis. Gaseous and volatile products were identified with the help of the TGA/MS technique. Experimental data presented in this paper provide clear evidence that fluoronanotubes are not chemically inert toward the solid matrixes studied and exhibit significant oxidative properties in the redox reactions occurring under various temperatures, depending on the nature of the inorganic compound.

  10. Coating of uniform inorganic particles with polymers, I

    SciTech Connect

    Oyama, H.T.; Sprycha, R.; Xie, Yuming; Partch, R.E.; Matijevic, E. . Center for Advanced Materials Processing)

    1993-10-15

    Uniform spherical silica particles have been first coated with aluminum hydrous oxide and then with poly(divinylbenzene). To produce the outer shell, the inorganic cores were pretreated with a vinyl coupling agent, then divinylbenzene, and an initiator in hot mineral spirits. The thickness of the alumina or polymer layers could be controlled by adjusting the experimental parameters. The same procedure was used to coat irregularly shaped commercial alumina particles. The charge of the so prepared particles was determined by potentiometric titrations, which showed that the polymer coating was permeable to the reactants. Thus, the titration curves were determined by the properties of the cores.

  11. Sorption of uranium(VI) onto hydrous ferric oxide-modified zeolite: Assessment of the effect of pH, contact time, temperature, selected cations and anions on sorbent interactions.

    PubMed

    Nekhunguni, Pfano Mathews; Tavengwa, Nikita Tawanda; Tutu, Hlanganani

    2017-09-19

    Zeolites are commonly used as adsorbents for metal removal in most applications e.g. in wastewater. However, the ubiquity of iron in such systems may, in the long-term, distort the true interactions and mechanisms of contaminant removal as a result of modification of the zeolite surface. In this study, this potential phenomenon was assessed for the removal of uranium(VI) from aqueous solution by hydrous ferric oxide-modified zeolite (HFOMZ). This was prepared by precipitating iron hydroxide (the common precipitate of iron in aqueous systems) onto zeolite. The prepared HFOMZ was characterised by the scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR). Batch adsorption experiments were performed to assess the effect of: pH, initial uranium(VI) concentration, adsorbent dosage, contact time, temperature, presence of cations (Pb(2+), Cr(3+), Cu(2+), Mn(2+) and Co(2+)) and anions ( [Formula: see text] , [Formula: see text] and [Formula: see text] ) on the adsorption of uranium(VI). Kinetic studies under these conditions indicated that the pseudo second-order kinetic model (R(2) > 0.99) best described the adsorption behaviour, implying that this could be proceeding through a chemisorption process. The experimental data was best described by the Freundlich isotherm model (R(2) > 0.93), an implication that the adsorption surface was heterogeneous. The thermodynamic parameters calculated from the experimental data suggested that the adsorption of U(VI) onto HFOMZ was spontaneous and exothermic in nature. The adsorption of U(VI) onto HFOMZ was dominated by complexation with strong ionizable hydroxyl sites on the hydrous ferric oxide surfaces and the edge sites of the zeolite. At pH values from 2 to 6, increased adsorption was observed and this decreased at higher pH values (above 6). This corresponded with the changes in speciation as determined by the PHREEQC modelling code. The presence of the cations (Pb(2+), Cr(3+), Cu(2+), Mn(2

  12. Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

    PubMed

    Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

    2015-11-03

    Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

  13. Synthesis and Characterization of a Layered Manganese Oxide: Materials Chemistry for the Inorganic or Instrumental Methods Lab

    ERIC Educational Resources Information Center

    Ching, Stanton; Neupane, Ram P.; Gray, Timothy P.

    2006-01-01

    A three-week laboratory project involving synthesis and characterization of a layered manganese oxide provides an excellent vehicle for teaching important concepts of inorganic chemistry and instrumental methods related to non-molecular systems. Na-birnessite is an easily prepared manganese oxide with a 7 A interlayer spacing and Na[superscript +]…

  14. Synthesis and Characterization of a Layered Manganese Oxide: Materials Chemistry for the Inorganic or Instrumental Methods Lab

    ERIC Educational Resources Information Center

    Ching, Stanton; Neupane, Ram P.; Gray, Timothy P.

    2006-01-01

    A three-week laboratory project involving synthesis and characterization of a layered manganese oxide provides an excellent vehicle for teaching important concepts of inorganic chemistry and instrumental methods related to non-molecular systems. Na-birnessite is an easily prepared manganese oxide with a 7 A interlayer spacing and Na[superscript +]…

  15. Ammonia-oxidizing archaea respond positively to inorganic nitrogen addition in desert soils.

    PubMed

    Marusenko, Yevgeniy; Garcia-Pichel, Ferran; Hall, Sharon J

    2015-02-01

    In soils, nitrogen (N) addition typically enhances ammonia oxidation (AO) rates and increases the population density of ammonia-oxidizing bacteria (AOB), but not that of ammonia-oxidizing archaea (AOA). We asked if long-term inorganic N addition also has similar consequences in arid land soils, an understudied yet spatially ubiquitous ecosystem type. Using Sonoran Desert top soils from between and under shrubs within a long-term N-enrichment experiment, we determined community concentration-response kinetics of AO and measured the total and relative abundance of AOA and AOB based on amoA gene abundance. As expected, N addition increased maximum AO rates and the abundance of bacterial amoA genes compared to the controls. Surprisingly, N addition also increased the abundance of archaeal amoA genes. We did not detect any major effects of N addition on ammonia-oxidizing community composition. The ammonia-oxidizing communities in these desert soils were dominated by AOA as expected (78% of amoA gene copies were related to Nitrososphaera), but contained unusually high contributions of Nitrosomonas (18%) and unusually low numbers of Nitrosospira (2%). This study highlights unique traits of ammonia oxidizers in arid lands, which should be considered globally in predictions of AO responses to changes in N availability. © FEMS 2014. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  16. Fully inorganic oxide-in-oxide ultraviolet nanocrystal light emitting devices.

    PubMed

    Brovelli, Sergio; Chiodini, Norberto; Lorenzi, Roberto; Lauria, Alessandro; Romagnoli, Marco; Paleari, Alberto

    2012-02-21

    The development of integrated photonics and lab-on-a-chip platforms for environmental and biomedical diagnostics demands ultraviolet electroluminescent materials with high mechanical, chemical and environmental stability and almost complete compatibility with existing silicon technology. Here we report the realization of fully inorganic ultraviolet light-emitting diodes emitting at 390 nm with a maximum external quantum efficiency of ~0.3%, based on SnO(2) nanoparticles embedded in SiO(2) thin films obtained from a solution-processed method. The fabrication involves a single deposition step onto a silicon wafer followed by a thermal treatment in a controlled atmosphere. The fully inorganic architecture ensures superior mechanical robustness and optimal chemical stability in organic solvents and aqueous solutions. The versatility of the fabrication process broadens the possibility of optimizing this strategy and extending it to other nanostructured systems for designed applications, such as active components of wearable health monitors or biomedical devices.

  17. Study of Organic and Inorganic Binders on Strength of Iron Oxide Pellets

    NASA Astrophysics Data System (ADS)

    Srivastava, Urvashi; Kawatra, S. Komar; Eisele, Timothy C.

    2013-08-01

    Bentonite is a predominant binder used in iron ore pelletization. However, the presence of a high content of silica and alumina in bentonite is considered undesirable for ironmaking operations. The objective of this study was to identify the alternatives of bentonite for iron ore pelletization. To achieve this goal, different types of organic and inorganic binders were utilized to produce iron oxide pellets. The quality of these iron oxide pellets was compared with pellets made using bentonite. All pellets were tested for physical strength at different stages of pelletization to determine their ability to survive during shipping and handling. The results show that organic binders such as lactose monohydrate, hemicellulose, and sodium lignosulfonate can provide sufficient strength to indurated pellets.

  18. Water oxidation surface mechanisms replicated by a totally inorganic tetraruthenium–oxo molecular complex

    PubMed Central

    Piccinin, Simone; Sartorel, Andrea; Aquilanti, Giuliana; Goldoni, Andrea; Bonchio, Marcella; Fabris, Stefano

    2013-01-01

    Solar-to-fuel energy conversion relies on the invention of efficient catalysts enabling water oxidation through low-energy pathways. Our aerobic life is based on this strategy, mastered by the natural Photosystem II enzyme, using a tetranuclear Mn–oxo complex as oxygen evolving center. Within artificial devices, water can be oxidized efficiently on tailored metal-oxide surfaces such as RuO2. The quest for catalyst optimization in vitro is plagued by the elusive description of the active sites on bulk oxides. Although molecular mimics of the natural catalyst have been proposed, they generally suffer from oxidative degradation under multiturnover regime. Here we investigate a nano-sized Ru4–polyoxometalate standing as an efficient artificial catalyst featuring a totally inorganic molecular structure with enhanced stability. Experimental and computational evidence reported herein indicates that this is a unique molecular species mimicking oxygenic RuO2 surfaces. Ru4–polyoxometalate bridges the gap between homogeneous and heterogeneous water oxidation catalysis, leading to a breakthrough system. Density functional theory calculations show that the catalytic efficiency stems from the optimal distribution of the free energy cost to form reaction intermediates, in analogy with metal-oxide catalysts, thus providing a unifying picture for the two realms of water oxidation catalysis. These correlations among the mechanism of reaction, thermodynamic efficiency, and local structure of the active sites provide the key guidelines for the rational design of superior molecular catalysts and composite materials designed with a bottom–up approach and atomic control. PMID:23479603

  19. Hybrid flow system for automatic dynamic fractionation and speciation of inorganic arsenic in environmental solids.

    PubMed

    Zhang, Yanlin; Miró, Manuel; Kolev, Spas D

    2015-03-03

    An integrated flow analysis system and protocol are proposed for the first time for automatic dynamic flow-through fractionation of inorganic arsenic (arsenite and arsenate) in environmental solids in combination with its real-time speciation. Four extractants (i.e., (1) 0.05 M ammonium sulfate, (2) 0.05 M ammonium dihydrogen phosphate, (3) 0.2 M ammonium oxalate, and (4) a mixture of 0.2 M ammonium oxalate and 0.1 M ascorbic acid at 96 °C) are applied sequentially to the sample to measure bioaccessible inorganic arsenic associated with (1) nonspecifically sorbed phases, (2) specifically sorbed phases, (3) amorphous plus poorly crystalline hydrous oxides of iron and aluminum, and (4) well-crystallized hydrous oxides of Fe and Al, respectively. The kinetic extraction profiles of arsenite and total inorganic arsenic are obtained for each extractant by automatic collection of a given number of its aliquots (subfractions) exposed to the solid sample. Arsenite and total inorganic arsenic in each subfraction are converted to arsine sequentially by hydride generation at pH 4.50 and in 1.14 M hydrochloric acid, respectively. Arsine is absorbed into a potassium permanganate solution, the discoloration of which is related to the concentration of the corresponding arsenic species. The proposed method is successfully validated by analyzing a soil reference material (NIST 2710a) and a sediment sample.

  20. Dietary inorganic nitrate reverses features of metabolic syndrome in endothelial nitric oxide synthase-deficient mice.

    PubMed

    Carlström, Mattias; Larsen, Filip J; Nyström, Thomas; Hezel, Michael; Borniquel, Sara; Weitzberg, Eddie; Lundberg, Jon O

    2010-10-12

    The metabolic syndrome is a clustering of risk factors of metabolic origin that increase the risk for cardiovascular disease and type 2 diabetes. A proposed central event in metabolic syndrome is a decrease in the amount of bioavailable nitric oxide (NO) from endothelial NO synthase (eNOS). Recently, an alternative pathway for NO formation in mammals was described where inorganic nitrate, a supposedly inert NO oxidation product and unwanted dietary constituent, is serially reduced to nitrite and then NO and other bioactive nitrogen oxides. Here we show that several features of metabolic syndrome that develop in eNOS-deficient mice can be reversed by dietary supplementation with sodium nitrate, in amounts similar to those derived from eNOS under normal conditions. In humans, this dose corresponds to a rich intake of vegetables, the dominant dietary nitrate source. Nitrate administration increased tissue and plasma levels of bioactive nitrogen oxides. Moreover, chronic nitrate treatment reduced visceral fat accumulation and circulating levels of triglycerides and reversed the prediabetic phenotype in these animals. In rats, chronic nitrate treatment reduced blood pressure and this effect was also present during NOS inhibition. Our results show that dietary nitrate fuels a nitrate-nitrite-NO pathway that can partly compensate for disturbances in endogenous NO generation from eNOS. These findings may have implications for novel nutrition-based preventive and therapeutic strategies against cardiovascular disease and type 2 diabetes.

  1. Dietary inorganic nitrate reverses features of metabolic syndrome in endothelial nitric oxide synthase-deficient mice

    PubMed Central

    Carlström, Mattias; Larsen, Filip J.; Nyström, Thomas; Hezel, Michael; Borniquel, Sara; Weitzberg, Eddie; Lundberg, Jon O.

    2010-01-01

    The metabolic syndrome is a clustering of risk factors of metabolic origin that increase the risk for cardiovascular disease and type 2 diabetes. A proposed central event in metabolic syndrome is a decrease in the amount of bioavailable nitric oxide (NO) from endothelial NO synthase (eNOS). Recently, an alternative pathway for NO formation in mammals was described where inorganic nitrate, a supposedly inert NO oxidation product and unwanted dietary constituent, is serially reduced to nitrite and then NO and other bioactive nitrogen oxides. Here we show that several features of metabolic syndrome that develop in eNOS-deficient mice can be reversed by dietary supplementation with sodium nitrate, in amounts similar to those derived from eNOS under normal conditions. In humans, this dose corresponds to a rich intake of vegetables, the dominant dietary nitrate source. Nitrate administration increased tissue and plasma levels of bioactive nitrogen oxides. Moreover, chronic nitrate treatment reduced visceral fat accumulation and circulating levels of triglycerides and reversed the prediabetic phenotype in these animals. In rats, chronic nitrate treatment reduced blood pressure and this effect was also present during NOS inhibition. Our results show that dietary nitrate fuels a nitrate–nitrite–NO pathway that can partly compensate for disturbances in endogenous NO generation from eNOS. These findings may have implications for novel nutrition-based preventive and therapeutic strategies against cardiovascular disease and type 2 diabetes. PMID:20876122

  2. Effects of inorganics on the degradation of micropollutants with vacuum UV (VUV) advanced oxidation.

    PubMed

    Duca, Clara; Imoberdorf, Gustavo; Mohseni, Madjid

    2017-02-21

    This research focused on the effects of inorganic water constituents on the efficiency of vacuum UV (VUV) for the degradation of micropollutants in surface water supplies. Atrazine was used as a model miropollutant, and bicarbonate, sulphate, and nitrate were used as the most common inorganic constituents in the water matrix. First, the absorbance of radiation at 254 and 185 nm was measured in the presence of different ions. At 254 nm, only nitrate showed a measurable absorption coefficient of [Formula: see text] = 3.51 M[Formula: see text] cm[Formula: see text], and all other ions showed a molar absorption coefficient below the detection limit. However, at 185 nm, all the ions showed high absorption coefficients, with nitrate giving the highest absorption coefficient of [Formula: see text] = 5568 M[Formula: see text] cm[Formula: see text]. Second, the hydroxyl radical (HO[Formula: see text]) scavenging effects of the same inorganic ions were evaluated; nitrate and bicarbonate showed a negative effect during the UV/H2O2 and VUV advanced oxidation processes. Sulfate was photolyzed with 185 nm UV to form HO[Formula: see text], and for this reason, it assisted the degradation of the target micropollutant, as demonstrated by increases in the degradation rate constant. An additional component of this work involved developing a method for measuring the quantum yield of atrazine at 185 nm. This made it possible to distinguish the contribution of OH radical attach from that of direct photolysis towards the degradation of atrazine.

  3. A systematic investigation of the preparation and properties of composite carbon molecular sieves containing inorganic oxides

    NASA Technical Reports Server (NTRS)

    Foley, Henry C.

    1990-01-01

    The objective of this research is to define the methodology for the preparation and characterization of new carbon-based molecular sieves with composite structures. Carbon molecular sieves have found increasing application in the field of separation and purification of gases. These materials are relatively easy to prepare and their surfaces can be modified to some extent. It is expected that by combining inorganic oxides with the carbonaceous structure one can begin to design composite materials with a wider range of possible chemical and physical properties. In this way, the IOM-CMS materials may confer distinct advantages over pure carbon molecular sieves, not just for separation, but also for catalysis. The most recent results in the design and characterization of these IOM-CMS materials are reviewed and summarized. Directions for further research are also presented.

  4. Response of anaerobic ammonium oxidation to inorganic nitrogen fluctuations in temperate estuarine sediments

    NASA Astrophysics Data System (ADS)

    Teixeira, Catarina; Magalhães, Catarina; Joye, Samantha B.; Bordalo, Adriano A.

    2016-07-01

    The discovery of anaerobic ammonium oxidation (anammox) highlighted the importance of alternative metabolic pathways to inorganic nitrogen removal in natural environments, particularly in those subjected to increased nitrate inputs, such as estuaries. Laboratory enrichment experiments were used to test the effect of increasing loads of nitrate (NO3-), nitrite (NO2-), and ammonium (NH4+) on the anammox process. Three Atlantic temperate estuaries (NW Portugal) were investigated along a salinity gradient, and anammox activity was measured under different NO3-, NO2-, and NH4+ treatments, using the isotope pairing technique. Obtained results showed that NO3- stimulated denitrification but not anammox, whereas NO2- additions had a positive effect on anammox activity, confirming its role as a key environmental control. On the other hand, increasing NH4+ concentrations seemed to inhibit anammox for low salinity sites. Our findings suggested an important role of the natural availability of nitrogen compounds in regulating anammox and the magnitude of anammox versus denitrification in estuarine environments.

  5. A systematic investigation of the preparation and properties of composite carbon molecular sieves containing inorganic oxides

    NASA Technical Reports Server (NTRS)

    Foley, Henry C.

    1990-01-01

    The objective of this research is to define the methodology for the preparation and characterization of new carbon-based molecular sieves with composite structures. Carbon molecular sieves have found increasing application in the field of separation and purification of gases. These materials are relatively easy to prepare and their surfaces can be modified to some extent. It is expected that by combining inorganic oxides with the carbonaceous structure one can begin to design composite materials with a wider range of possible chemical and physical properties. In this way, the IOM-CMS materials may confer distinct advantages over pure carbon molecular sieves, not just for separation, but also for catalysis. The most recent results in the design and characterization of these IOM-CMS materials are reviewed and summarized. Directions for further research are also presented.

  6. An inorganic geochemical argument for coupled anaerobic oxidation of methane and iron reduction in marine sediments.

    PubMed

    Riedinger, N; Formolo, M J; Lyons, T W; Henkel, S; Beck, A; Kasten, S

    2014-03-01

    Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

  7. Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites with excellent decolorization performance

    SciTech Connect

    Zhou, Junli; Yu, Lin; Sun, Ming; Ye, Fei; Lan, Bang; Diao, Guiqiang; He, Jun

    2013-02-15

    Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled in the presence of CTAB, and subsequently pillared with Keggin ions. The obtained CTAB-Al-MO with the basal spacing of 1.59 nm could be stable at 300 Degree-Sign C for 2 h and also possesses high total pore volumes (0.41 cm Superscript-Three g{sup -1}) and high specific BET surface area (161 m{sup 2} g{sup -1}), which is nine times larger than that of the pristine (19 m{sup 2} g{sup -1}). Possible formation process for the highly thermal stable CTAB-Al-MO is proposed here. The decolorization experiments of methyl orange showed that the obtained CTAB-Al-MO exhibit excellent performance in wastewater treatment and the decolorization rate could reach 95% within 5 min. - Graphical Abstract: Well-ordered organic-inorganic hybrid LMO nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled by CTAB, and subsequently pillared with Keggin ions. Highlights: Black-Right-Pointing-Pointer A two-step synthesis method was used to prepare the CTAB-Al-MO. Black-Right-Pointing-Pointer The CTAB-Al-MO has the large basal spacing and high specific BET surface area. Black-Right-Pointing-Pointer The thermal stability of the well-ordered CTAB-Al-MO could obviously improve. Black-Right-Pointing-Pointer The CTAB-Al-MO exhibits excellent oxidation and absorption ability to remove organic pollutants.

  8. Compilation, evaluation, and prediction of triple-layer model constants for ions on Fe(III) and Mn(IV) hydrous oxides

    SciTech Connect

    Smith, R.W.; Jenne, E.A.

    1988-11-01

    This report includes recommendations for further work. A brief discussion of the formulation of the Triple Layer Model (TLM) of the oxide/water interfaces is given in Section 3. Table of literature values for TLM constants are given in Section 4.0. In addition, the sources of uncertainties in the TLM constants are discussed. Equations useful for the prediction of TLM parameters are presented in Section 6.0. Summaries of experimental conditions used by the various investigators referenced in this report are given in Appendix A. 43 refs., 4 figs., 12 tabs. (JL)

  9. Application of inorganic oxidants to the spectrophotometric determination of ribavirin in bulk and capsules.

    PubMed

    Darwish, Ibrahim A; Khedr, Alaa S; Askal, Hassan F; Mohamed, Ramadan M

    2006-01-01

    Eight spectrophotometric methods for determination of ribavirin have been developed and validated. These methods were based on the oxidation of the drug by different inorganic oxidants: ceric ammonium sulfate, potassium permanganate, ammonium molybdate, ammonium metavanidate, chromium trioxide, potassium dichromate, potassium iodate, and potassium periodate. The oxidation reactions were performed in perchloric acid medium for ceric ammonium sulfate and in sulfuric acid medium for the other reagents. With ceric ammonium sulfate and potassium permanganate, the concentration of ribavirin in its samples was determined by measuring the decrease in the absorption intensity of the colored reagents at 315 and 525 nm, respectively. With the other reagents, the concentration of ribavirin was determined by measuring the intensity of the developed colored reaction products at the wavelengths of maximum absorbance: 675, 780, 595, 595, 475, and 475 nm for reactions with ammonium molybdate, ammonium metavanidate, chromium trioxide, potassium dichromate, potassium iodate, and potassium periodate, respectively. Different variables affecting the reaction conditions were carefully studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9984-0.9998) were found between the absorbance readings and the concentrations of ribavirin in the range of 4-1400 microg/mL. The molar absorptivities were correlated with the oxidation potential of the oxidants used. The precision of the methods were satisfactory; the values of relative standard deviation did not exceed 1.64%. The proposed methods were successfully applied to the analysis of ribavirin in pure drug material and capsules with good accuracy and precision; the recovery values were 99.2-101.2 +/- 0.48-1.30%. The results obtained using the proposed spectrophotometric methods were comparable with those obtained with the official method stated in the United States Pharmacopeia.

  10. A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

    NASA Astrophysics Data System (ADS)

    Hossaini, Ryan; Chipperfield, Martyn P.; Saiz-Lopez, Alfonso; Fernandez, Rafael; Monks, Sarah; Feng, Wuhu; Brauer, Peter; Glasow, Roland

    2016-12-01

    Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by 2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea-salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub-ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1-5 × 104 atoms cm-3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to 4320 Gg Cl/yr, sustaining a background surface [Cl] of <0.1 to 0.5 × 103 atoms cm-3 over large areas. Globally, we estimate a tropospheric methane sink of 12-13 Tg CH4/yr due the CH4 + Cl reaction ( 2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for 10 to >20% of total boundary layer CH4 oxidation in some locations.

  11. High-pressure behavior of hydrous phases

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Tsuchiya, J.; Hermann, A.; Speziale, S.

    2016-12-01

    One of the most distinguishing features of the Earth is its surface water, which is a crucial component in making it a habitable planet. How this water is partitioned among the various reservoirs within the Earth's interior is of considerable interest to the Solid Earth Sciences community. In convergent plate margins such as subduction zone, the hydrous phases in the subducting slabs deliver water into the Earth's interior. Upon reaching greater depths, depending on the limits of their thermodynamic stability, the hydrous phases dehydrate, releasing water. A fraction of water is released back into the hydrosphere through arc volcanism. Recent estimates show that the worldwide flux of water from subducting slabs amounts to about one ocean mass over the age of the Earth. The water in the Earth's interior is stored in several distinct forms: as aqueous fluids; hydrous silicate melts; nominally anhydrous phases; grain boundaries, and various hydrous phases. Among these multiple hosts, hydrous phases are particularly important because they influence solid earth processes in the crust and mantle. The thermodynamic stability of hydrous phases dictates how efficiently they transport and store water in the Earth's interior. Their presence severely affects the onset of melting. Hydrous phases that are likely to be stable at higher pressures are often not recorded in natural samples. It is possible that these hydrous phases are not sampled by melts that arise from depths that are shallower than where high-pressure hydrous phases may occur. It is also possible that these hydrous phases do not survive exhumation. In addition, many hydrous phases might have limited thermal stability. High-pressure experiments and first-principles simulations based on density functional theory (DFT) have been crucial in enhancing our understanding of hydrous phases that are likely to be present in the Earth's mantle and subduction zones. In this study, we present DFT results and compare them with

  12. Formation and reactivity of inorganic and organic chloramines and bromamines during oxidative water treatment.

    PubMed

    Heeb, Michèle B; Kristiana, Ina; Trogolo, Daniela; Arey, J Samuel; von Gunten, Urs

    2017-03-01

    The formation and further reactions of halamines during oxidative water treatment can be relevant for water quality. In this study, we investigated the formation and reactivity of several inorganic and organic halamines (monochloramine, N-chloromethylamine, N-chlorodimethylamine, monobromamine, dibromamine, N-bromomethylamine, N,N-dibromomethylamine, and N-bromodimethylamine) by kinetic experiments, transformation product analysis, and quantum chemical computations. Kinetic model simulations were conducted to evaluate the relevance of halamines for various water treatment scenarios. Halamines were quickly formed from the reaction of chlorine and bromine with ammonia or organic amines. Species-specific second-order rate constants for the reaction of chlorine and bromine with ammonia, methyl- and dimethylamine were in the order of 10(6)-10(8) M(-1)s(-1). The formed halamines were found to be reactive towards phenolic compounds, forming halogenated phenols via electrophilic aromatic substitution (phenol and resorcinol) or quinones via electron transfer (catechol and hydroquinone). At near neutral pH, apparent second-order rate constants for these reactions were in the order of 10(-4)-10(-1) M(-1)s(-1) for chloramines and 10(1)-10(2) M(-1)s(-1) for bromamines. Quantum chemical computations were used to determine previously unknown aqueous pKa values, gas phase bond dissociation energies (BDE) and partial atomic charges of the halamines, allowing a better understanding of their reactivities. Kinetic model simulations, based on the results of this study, showed that during chlorination inorganic and organic chloramines are the main halamines formed. However, their further reactions with organic matter are outcompeted kinetically by chlorine. During ozonation, mainly inorganic bromamines are formed, since ozone quickly oxidizes organic amines. The further reactions of bromamine are typically outcompeted by ozone and thus generally of minor importance. The use of

  13. Fabrication of a new hydrous Zr(IV) oxide-based nanocomposite for enhanced Pb(II) and Cd(II) removal from waters.

    PubMed

    Hua, Ming; Jiang, Yingnan; Wu, Bian; Pan, Bingcai; Zhao, Xin; Zhang, Quanxing

    2013-11-27

    To overcome the technical bottleneck of fine hydrated Zr(IV) oxide particles in environmental remediation, we irreversibly impregnated nanosized hydrated Zr(IV) oxide inside a commercial cation exchange resin D-001 and obtained a new nanocomposite NZP. NZP exhibited efficient removal of lead and cadmium ions in a pH range of 2-6, where no Zr(IV) leaching was detected from NZP. As compared to D-001, NZP showed more preferable adsorption toward both toxic metals from the background Ca(II) solution at greater levels. The synthetic Pb(II) or Cd(II) solution containing other ubiquitous metal ions was employed as the feeding influent for column adsorption, and the results indicated that the treatable volume of NZP is around 3-4 times that of D-001 before reaching the breakthrough point set according to the effluent discharge standard of China. With respect to Pb(II) removal from an acidic mining effluent, the treatable volume of NZP was 13 times higher than that of D-001. The exhausted NZP could be effectively regenerated by HNO3-Ca(NO3)2 binary solution for repeated use without any significant capacity loss. The superior performance of NZP was attributed to the Donnan membrane effect exerted by the host D-001 as well as the impregnated HZO nanoparticles of specific interaction toward toxic metals, as confirmed by the comparative isothermal adsorption and X-ray photoelectron spectroscopic study.

  14. Sol-gel-processed inorganic oxides: organic polymer composites for second-order nonlinear optical applications

    NASA Astrophysics Data System (ADS)

    Zieba, Jaroslaw W.; Zhang, Yue; Prasad, Paras N.; Casstevens, Martin K.; Burzynski, Ryszard

    1992-12-01

    A new class of promising composite materials consisting of sol-gel processed inorganic oxides and organic polymers has been developed over the last several years. These materials have been shown to be homogeneous, mechanically stable and have excellent optical properties. Second-order nonlinear optical properties are dependent upon the active chromophore being aligned within the structure. We report here the studies on the second-order nonlinear optical properties of a new oxide:polymer composite. A second-order chromophore, (N,N- diethylamino-((Beta) )-nitrostyrene or DEANST) has been doped into a sol-gel/polymer composite comprised of polyvinylpyrrolidone (PVP) and silica. The removal of solvent from a simple sol-gel preparation causes a tremendous shrinkage of the pores of the matrix. In addition, this particular polymer is capable of being crosslinked at elevated temperatures. These two effects were used to retain the alignment of the chromophores within this unique host material. The second-harmonic generation technique was used as a function of time to ascertain the utility of this approach and to determine the precise roles of processing conditions and components necessary to bring about this effect. The results of this work indicate that this composite can preserve the alignment of DEANST to satisfactory levels, making it an excellent candidate for device applications.

  15. The patterning of sub-500 nm inorganic oxide and semiconducting polymeric structures

    NASA Astrophysics Data System (ADS)

    Hampton, Meredith J.; Williams, Stuart S.; Zhou, Zhilian; Nunes, Janine; Ko, Doo-Hyun; Templeton, Joseph L.; DeSimone, Joseph M.; Samulski, Edward T.

    2008-08-01

    The Pattern Replication In Non-wetting Templates (PRINT) technique has been extended to patterning of isolated features as well as embossed films of sub-500 nm "hard" inorganic oxides and nanocrystalline semiconductors and "soft" semiconducting polymers including TiO2, SnO2, ZnO, ITO, BaTiO3, CdSe, poly(3-hexylthiophene) (P3HT), Poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), and other polythiophene derivatives. The low surface energy, chemically resistant, air permeable elastomeric perflouropolyether (PFPE) based molds allow for numerous materials to be patterned on a variety of substrates including glass, transparent conductive oxides, and thin films of conducting polymer for a wide range of electronic and optical applications. Additionally, PRINT has been employed to pattern features with aspect ratios greater than 1, deposit a second layer of features on top of an initial layer without pattern destruction, and replicate sub-100 nm sized features for photovoltaics applications. Materials and patterns generated in this work were characterized using a variety of techniques including: Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and X-ray Diffraction (XRD).

  16. RNA transcript sequencing reveals inorganic sulfur compound oxidation pathways in the acidophile Acidithiobacillus ferrivorans.

    PubMed

    Christel, Stephan; Fridlund, Jimmy; Buetti-Dinh, Antoine; Buck, Moritz; Watkin, Elizabeth L; Dopson, Mark

    2016-04-01

    Acidithiobacillus ferrivorans is an acidophile implicated in low-temperature biomining for the recovery of metals from sulfide minerals. Acidithiobacillus ferrivorans obtains its energy from the oxidation of inorganic sulfur compounds, and genes encoding several alternative pathways have been identified. Next-generation sequencing of At. ferrivorans RNA transcripts identified the genes coding for metabolic and electron transport proteins for energy conservation from tetrathionate as electron donor. RNA transcripts suggested that tetrathionate was hydrolyzed by the tetH1 gene product to form thiosulfate, elemental sulfur and sulfate. Despite two of the genes being truncated, RNA transcripts for the SoxXYZAB complex had higher levels than for thiosulfate quinone oxidoreductase (doxDAgenes). However, a lack of heme-binding sites in soxX suggested that DoxDA was responsible for thiosulfate metabolism. Higher RNA transcript counts also suggested that elemental sulfur was metabolized by heterodisulfide reductase (hdrgenes) rather than sulfur oxygenase reductase (sor). The sulfite produced as a product of heterodisulfide reductase was suggested to be oxidized by a pathway involving the sat gene product or abiotically react with elemental sulfur to form thiosulfate. Finally, several electron transport complexes were involved in energy conservation. This study has elucidated the previously unknown At. ferrivorans tetrathionate metabolic pathway that is important in biomining.

  17. "Black-colored olivines" in peridotites: dehydrogenation from hydrous olivines

    NASA Astrophysics Data System (ADS)

    Arai, Shoji; Hoshikawa, Chihiro; Miura, Makoto

    2015-04-01

    Fresh olivines that are black to the naked eye are found in some dunites. Peridotites are easily converted to be black in color, when serpentinized, due to production of secondary fine magnetite particles. The dunites that contain fresh but black-colored olivines are usually coarse-grained. These coarse olivine grains are sometimes very heterogeneous in color; the blackish part grades to whitish parts in single grains. The black color is due to homegeneous distribution of minute (< 10 microns) black particles in olivine. They are rod-like or plate-like in shape in thin section, sometimes being aligned under crystallographic control of the host olivine. Olivines are clear and free of these inclusions around primary chromian spinel inclusions or chromian spinel lamellae (Arai, 1978). Raman spectroscopy indicates the minute black particles are magnetite always associated with diopside. It is interesting to note that olivine in mantle peridotites accompanied by the black-colored dunites is totally free of the black inclusions, giving the ordinary colors (pale yellow to whitish) of Mg-rich olivine. It is not likely that the magnetite inclusions formed through secondary oxidation of olivine by invasion of oxygen, which is possible along cracks or grain boundaries. They most probably formed due to dehydrogenation from primary OH-bearing olivines upon cooling. Hydrogen was quickly diffused out from the olivines to leave magnetite and excess silica. The excess silica was possibly combined with a monticellite component to form diopside. The OH-bearing (hydrous) olivines can be precipitated from hydrous magmas, and the hydrous nature of the magma can promote an increase in grain size due to faster diffusion of elements. The minute inclusions of magnetite + diopside is thus an indicator of primary hydrous character of host olivine.

  18. An SOA model for toluene oxidation in the presence of inorganic aerosols.

    PubMed

    Cao, Gang; Jang, Myoseon

    2010-01-15

    A predictive model for secondary organic aerosol (SOA) formation including both partitioning and heterogeneous reactions is explored for the SOA produced from the oxidation of toluene in the presence of inorganic seed aerosols. The predictive SOA model comprises the explicit gas-phase chemistry of toluene, gas-particle partitioning, and heterogeneous chemistry. The resulting products from the explicit gas phase chemistry are lumped into several classes of chemical species based on their vapor pressure and reactivity for heterogeneous reactions. Both the gas-particle partitioning coefficient and the heterogeneous reaction rate constant of each lumped gas-phase product are theoretically determined using group contribution and molecular structure-reactivity. In the SOA model, the predictive SOA mass is decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). OM(P) is estimated from the SOA partitioning model developed by Schell et al. (J. Geophys. Res. 2001, 106, 28275-28293 ) that has been used in a regional air quality model (CMAQ 4.7). OM(H) is predicted from the heterogeneous SOA model developed by Jang et al. (Environ. Sci. Technol. 2006, 40, 3013-3022 ). The SOA model is evaluated using a number of the experimental SOA data that are generated in a 2 m(3) indoor Teflon film chamber under various experimental conditions (e.g., humidity, inorganic seed compositions, NO(x) concentrations). The SOA model reasonably predicts not only the gas-phase chemistry, such as the ozone formation, the conversion of NO to NO(2), and the toluene decay, but also the SOA production. The model predicted that the OM(H) fraction of the total toluene SOA mass increases as NO(x) concentrations decrease: 0.73-0.83 at low NO(x) levels and 0.17-0.47 at middle and high NO(x) levels for SOA experiments with high initial toluene concentrations. Our study also finds a significant increase in the OM(H) mass fraction in the SOA generated with low initial toluene

  19. Poly(ethylene oxide)-bonded stationary phase for separation of inorganic anions in capillary ion chromatography.

    PubMed

    Linda, Roza; Lim, Lee Wah; Takeuchi, Toyohide

    2013-06-14

    A tosylated-poly(ethylene oxide) (PEO) reagent was reacted with primary amino groups of an aminopropylsilica packing material (TSKgel NH2-60) in acetonitrile to form PEO-bonded stationary phase. The reaction was a single and simple step reaction. The prepared stationary phase was able to separate inorganic anions. The retention behavior of six common inorganic anions on the prepared stationary phase was examined under various eluent conditions in order to clarify its separation/retention mechanism. The elution order of the tested anions was iodate, bromate, bromide, nitrate, iodide, and thiocyanate, which was similar as observed in common ion chromatography. The retention of inorganic anions could be manipulated by ion exchange interaction which is expected that the eluent cation is coordinated among the PEO chains and it works as the anion-exchange site. Cations and anions of the eluent therefore affected the retention of sample anions. We demonstrated that the retention of the analyte anions decreased with increasing eluent concentration. The repeatability of retention time for the six anions was satisfactory on this column with relative standard deviation values from 1.1 to 4.3% when 10mM sodium chloride was used as the eluent. Compared with the unmodified TSKgel NH2-60, the prepared stationary phase retained inorganic anions more strongly and the selectivity was also improved. The present stationary phase was applied for the determination of inorganic anions contained in various water samples.

  20. High rate performance of flexible pseudocapacitors fabricated using ionic-liquid-based proton conducting polymer electrolyte with poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonate) and its hydrous ruthenium oxide composite electrodes.

    PubMed

    Sellam; Hashmi, S A

    2013-05-01

    We report the studies on all-solid-state flexible pseudocapacitors based on poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) (PEDOT-PSS) and PEDOT-PSS/hydrous ruthenium oxide composite electrodes separated by nonaqueous proton conducting polymer electrolyte. Structural, thermal and electrochemical properties including high ionic conductivity (6.2 × 10(-2) S cm(-1) at 20 °C) of the polymer electrolyte, comprising ionic liquid 1-ethyl 3-methyl imidazolium hydrogen sulfate (EMIHSO4) immobilized in the blend of poly (vinyl alcohol) (PVA) and poly (vinyl pyrrolidone) (PVP), demonstrate its excellent suitability in supercapacitor fabrication. A substantial improvement in the specific capacitance (hence the specific energy) has been obtained when the PEDOT-PSS electrodes in the symmetrical pseudocapacitor are replaced by the composite electrodes PEDOT-PSS/RuO2·xH2O. High rate capability of the capacitor cell (with PEDOT-PSS electrodes) has been observed, as evidenced from the high knee frequency (∼966 Hz), low response time (∼70 ms) and high pulse power (∼10.2 kW kg(-1)), observed by impedance analysis. Almost rectangular (capacitive) cyclic voltammetric patterns for high scan rates (up to 15 V s(-1)) confirm the high rate performance of the pseudocapacitor. The PEDOT-PSS/RuO2·xH2O composite electrodes show the lower rate capability (knee frequency ∼312 Hz, response time ∼1 s, pulse power ∼3.2 kW kg(-1) and capacitive CV response up to 500 mV s(-1)) because of slow exchange of charges at the interfaces via RuO2·xH2O. However, the pseudocapacitor with composite electrodes shows higher rate performance relative to many reported RuO2·xH2O systems. About 15% improvement is noticed in the capacitance value when the capacitor with composite electrodes is initially charged and discharged up to ∼200 cycles. Thereafter, the cell shows almost constant value of specific capacitance (∼70 F g(-1)) for 1000 cycles.

  1. Electrical resistivity of assembled transparent inorganic oxide nanoparticle thin layers: influence of silica, insulating impurities, and surfactant layer thickness.

    PubMed

    Bubenhofer, Stephanie B; Schumacher, Christoph M; Koehler, Fabian M; Luechinger, Norman A; Sotiriou, Georgios A; Grass, Robert N; Stark, Wendelin J

    2012-05-01

    The electrical properties of transparent, conductive layers prepared from nanoparticle dispersions of doped oxides are highly sensitive to impurities. Production of cost-effective thin conducting films for consumer electronics often employs wet processing such as spin and/or dip coating of surfactant-stabilized nanoparticle dispersions. This inherently results in entrainment of organic and inorganic impurities into the conducting layer leading to largely varying electrical conductivity. Therefore, this study provides a systematic investigation on the effect of insulating surfactants, small organic molecules and silica in terms of pressure dependent electrical resistivity as a result of different core/shell structures (layer thickness). Application of high temperature flame synthesis gives access to antimony-doped tin oxide (ATO) nanoparticles with high purity. This well-defined starting material was then subjected to representative film preparation processes using organic additives. In addition ATO nanoparticles were prepared with a homogeneous inorganic silica layer (silica layer thickness from 0.7 to 2 nm). Testing both organic and inorganic shell materials for the electronic transport through the nanoparticle composite allowed a systematic study on the influence of surface adsorbates (e.g., organic, insulating materials on the conducting nanoparticle's surface) in comparison to well-known insulators such as silica. Insulating impurities or shells revealed a dominant influence of a tunneling effect on the overall layer resistance. Mechanical relaxation phenomena were found for 2 nm insulating shells for both large polymer surfactants and (inorganic) SiO(2) shells.

  2. Inorganic membrane reactors: A distributed feed approach for partial oxidation reactions

    SciTech Connect

    Tonkovich, A.L.Y.; Zilka, J.L.; Jimenez, D.M.

    1995-12-01

    Inorganic membrane reactors have been investigated for the oxidative dehydrogenation of ethane to ethylene. The production of ethylene competes with complete ethane combustion when the oxygen feed nears stoichiometric levels with ethane. High selectivity is achieved when the feed is oxygen-lean, but this results in a low ethane conversion per pass. A membrane reactor (MBR) has been experimentally demonstrated to improve ethylene yields per pass. A tube and shell reactor configuration is used and compared to a traditional tubular reactor (PFR). The oxygen feed is distributed along the length of the reactor through a porous alumina membrane. The distributed feed increases local ethane to oxygen feed ratios within the reactor, while introducing a low overall feed ratio into the MBR. Thus high ethylene selectivities can be obtained along with high ethane conversions. The MBR outperforms the PFR at low overall feed ratios. The performance of the two reactors merge as the feed ratio nears the stoichiometric point of two, and in some cases the PFR outperforms the MBR at higher feed ratios.

  3. Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

    PubMed

    Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

    2017-05-24

    Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

  4. Methylarsonous acid causes oxidative DNA damage in cells independent of the ability to biomethylate inorganic arsenic.

    PubMed

    Tokar, Erik J; Kojima, Chikara; Waalkes, Michael P

    2014-02-01

    Inorganic arsenic (iAs) and its toxic methylated metabolite, methylarsonous acid (MMA(III)), both have carcinogenic potential. Prior study shows iAs-induced malignant transformation in both arsenic methylation-proficient (liver) and methylation-deficient (prostate) cells, but only methylation-proficient cells show oxidative DNA damage (ODD) during this transformation. To further define whether arsenic methylation is necessary for transformation or ODD induction, here we chronically exposed these same liver or prostate cell lines to MMA(III) (0.25-1.0 μM) and tested for acquired malignant phenotype. Various metrics of oncogenic transformation were periodically assessed along with ODD during chronic MMA(III) exposure. Methylation-deficient and methylation-proficient cells both acquired a cancer phenotype with MMA(III) exposure at about 20 weeks, based on increased matrix metalloproteinase secretion, colony formation, and invasion. In contrast, prior work showed iAs-induced transformation took longer in biomethylation-deficient cells (~30 weeks) than in biomethylation-proficient cells (~18 weeks). In the present study, MMA(III) caused similar peak ODD levels at similar concentrations and at similar exposure times (18-22 weeks) in both cell types. At the approximate peak of ODD production, both cell types showed similar alterations in arsenic and oxidative stress adaptation factors (i.e., ABCC1, ABCC2, GST-π, SOD-1). Thus, MMA(III) causes oncogenic transformation associated with ODD in methylation-deficient cells, indicating that further methylation is not required to induce ODD. Together, these results show that MMA(III) and iAs cause an acquired malignant phenotype in methylation-deficient cells, yet iAs does not induce ODD. This indicates iAs likely has both genotoxic and non-genotoxic mechanisms dictated by the target cell's ability to methylate arsenic.

  5. Oxidative stress induced by inorganic nanoparticles in bacteria and aquatic microalgae--state of the art and knowledge gaps.

    PubMed

    von Moos, Nadia; Slaveykova, Vera I

    2014-09-01

    Nanotechnology has revolutionised many areas of modern life, technology and research, which is reflected in the steadily increasing global demand for and consumption of engineered nanomaterials and the inevitable increase of their release into the environment by human activity. The overall long-term impact of engineered nanomaterials on ecosystems is still unknown. Various inorganic nanoparticles have been found to exhibit bactericidal properties and cause growth inhibition in model aquatic microalgae, but the mechanisms of toxicity are not yet fully understood. The causal link between particle properties and biological effects or reactive oxygen species generation is not well established and represents the most eminent quest of nanoecotoxicological investigation. In this review, the current mechanistic understanding of the toxicity of inorganic metal and metal oxide engineered nanomaterials towards bacterial and aquatic microalgal model organisms based on the paradigm of oxidative stress is presented along with a detailed compilation of available literature on the major toxicity factors and research methods.

  6. Sulfide and sulfate saturation in hydrous silicate melts

    NASA Technical Reports Server (NTRS)

    Carroll, M. R.; Rutherford, M. J.

    1985-01-01

    A series of hydrothermal experiments was performed over a wide range of pressures, temperatures, oxygen fugacities, and melt FeO content, in order to examine the effects of physical changes on sulfur solubility in fractionated hydrous silicate melts. On the basis of the experimental results, it is concluded that upper crustal oxidation-reduction reactions and crystal fractionation processes may exert considerable influence on the amount of sulfur contained in magmas erupted at the surface. The application of the experimental results to investigations of volatile transport and volcanic degassing processes on the earth, Venus, and Mars is discussed

  7. Hydrous pyrolysis of pole treating chemicals: (a) initital measurement of hydrous pyrolysis rates for napthalene and pentachlorophenol; (b) solubility of flourene at temperatures up to 150{degrees}C

    SciTech Connect

    Leif, R. N., LLNL

    1997-11-15

    The temperature dependencies of the hydrous pyrolysis/oxidation (HPO) aqueous phase oxidation reactions of naphthalene and pentachlorophenol have been determined for phosphate buffered systems using Dickson-type reaction vessels. The HPO experimental temperatures ranged from 114{degrees}C to 148{degrees}C for naphthalene and 114{degrees}C to 137{degrees}C for pentachlorophenol. The loss of the organic species was used to determine activation energies of 95.8 kJ/mole for naphthalene oxidation and 84.8 kJ/mole for pentachlorophenol oxidation. Aqueous concentrations of target compounds and reaction intermediates were determined by gas chromatography and compound identification was verified by gas chromatography - mass spectrometry. During the experiments the pollutants were completely mineralized, as indicated by a stoichiometric production of inorganic carbon in the case of naphthalene and inorganic carbon and chloride in the case of pentachlorophenol. HPO of pentachlorophenol produced 2,3,5,6- tetrachlorophenol as an intermediate, whereas no intermediates amenable by GC were observed during the HPO of naphthalene. Measurements of the aqueous solubility of florin in an unbuffered solution have been made covering the temperature range from 20{degrees}C to 150{degrees}C. There is very good agreement between this data set and data previously published covering the lower temperature range (20{degrees}C to 75{degrees}C). Extension of the solubility measurements to higher temperatures covers the in situ temperatures achievable during field application of HPO and demonstrated a nearly exponential rise in aqueous solubility as a function of temperature, with a 10 fold increase in aqueous florin solubility going from 75{degrees}C to 125{degrees}C and a 20 fold increase in going from 75{degrees}C to 150{degrees}C.

  8. Inorganic arsenic causes cell apoptosis in mouse cerebrum through an oxidative stress-regulated signaling pathway.

    PubMed

    Yen, Cheng Chien; Ho, Tsung Jung; Wu, Chin Ching; Chang, Chun Fang; Su, Chin Chuan; Chen, Ya Wen; Jinn, Tzyy Rong; Lu, Tien Hui; Cheng, Po Wen; Su, Yi Chang; Liu, Shing Hwa; Huang, Chun Fa

    2011-06-01

    Arsenic pollution is a major public health problem worldwide. Inorganic arsenic (iAs) is usually more harmful than organic ones. iAs pollution increases the risk of human diseases such as peripheral vascular disease and cancer. However, the toxicological effects of iAs in the brain are mostly unclear. Here, we investigated the toxic effects and possible mechanisms of iAs in the cerebrum of mice after exposure to iAs (0.5 and 5 ppm (mg/l) As(2)O(3), via the drinking water), which was the possible human exposed dose via the ingestion in iAs-contaminated areas, for 6 consecutive weeks. iAs dose-dependently caused an increase of LPO production in the plasma and cerebral cortex. iAs also decreased the reduced glutathione levels and the expressions of NQO1 and GPx mRNA in the cerebral cortex. These impairments in the cerebral cortex caused by iAs exposure were significantly correlated with the accumulation of As. Moreover, iAs induced the production of apoptotic cells and activation of caspase-3, up-regulation of Bax and Bak, and down-regulation of Mcl-1 in the cerebral cortex. Exposure to iAs also triggered the expression of ER stress-related genes, including GRP78, GRP94, and CHOP. Meanwhile, an increase of p38 activation and dephosphorylation of ERK1/2 were shown in the cerebral cortex as a result of iAs-exposed mice. These iAs-induced damages and apoptosis-related signals could be significantly reversed by NAC. Taken together, these results suggest that iAs-induced oxidative stress causes cellular apoptosis in the cerebrum, signaling of p38 and ERK1/2, and ER stress may be involved in iAs-induced cerebral toxicity.

  9. ARSENIC (+3 OXIDATION STATE) METHYLTRANSFERASE AND THE INORGANIC ARSENIC METHYLATION PHENOTYPE

    EPA Science Inventory

    Inorganic arsenic is enzymatically methylated; hence, its ingestion results in exposure to the parent compound and various methylated arsenicals. Both experimental and epidemiological evidence suggest that some of the adverse health effects associated with chronic exposure to in...

  10. ARSENIC (+3 OXIDATION STATE) METHYLTRANSFERASE AND THE INORGANIC ARSENIC METHYLATION PHENOTYPE

    EPA Science Inventory

    Inorganic arsenic is enzymatically methylated; hence, its ingestion results in exposure to the parent compound and various methylated arsenicals. Both experimental and epidemiological evidence suggest that some of the adverse health effects associated with chronic exposure to in...

  11. Fabrication of a new type of organic-inorganic hybrid superlattice films combined with titanium oxide and polydiacetylene

    PubMed Central

    2012-01-01

    We fabricated a new organic-inorganic hybrid superlattice film using molecular layer deposition [MLD] combined with atomic layer deposition [ALD]. In the molecular layer deposition process, polydiacetylene [PDA] layers were grown by repeated sequential adsorption of titanium tetrachloride and 2,4-hexadiyne-1,6-diol with ultraviolet polymerization under a substrate temperature of 100°C. Titanium oxide [TiO2] inorganic layers were deposited at the same temperatures with alternating surface-saturating reactions of titanium tetrachloride and water. Ellipsometry analysis showed a self-limiting surface reaction process and linear growth of the nanohybrid films. The transmission electron microscopy analysis of the titanium oxide cross-linked polydiacetylene [TiOPDA]-TiO2 thin films confirmed the MLD growth rate and showed that the films are amorphous superlattices. Composition and polymerization of the films were confirmed by infrared spectroscopy. The TiOPDA-TiO2 nanohybrid superlattice films exhibited good thermal and mechanical stabilities. PACS: 81.07.Pr, organic-inorganic hybrid nanostructures; 82.35.-x, polymerization; 81.15.-z, film deposition; 81.15.Gh, chemical vapor deposition (including plasma enhanced CVD, MOCVD, ALD, etc.). PMID:22221520

  12. Fabrication of a new type of organic-inorganic hybrid superlattice films combined with titanium oxide and polydiacetylene.

    PubMed

    Yoon, Kwan-Hyuck; Han, Kyu-Seok; Sung, Myung-Mo

    2012-01-05

    We fabricated a new organic-inorganic hybrid superlattice film using molecular layer deposition [MLD] combined with atomic layer deposition [ALD]. In the molecular layer deposition process, polydiacetylene [PDA] layers were grown by repeated sequential adsorption of titanium tetrachloride and 2,4-hexadiyne-1,6-diol with ultraviolet polymerization under a substrate temperature of 100°C. Titanium oxide [TiO2] inorganic layers were deposited at the same temperatures with alternating surface-saturating reactions of titanium tetrachloride and water. Ellipsometry analysis showed a self-limiting surface reaction process and linear growth of the nanohybrid films. The transmission electron microscopy analysis of the titanium oxide cross-linked polydiacetylene [TiOPDA]-TiO2 thin films confirmed the MLD growth rate and showed that the films are amorphous superlattices. Composition and polymerization of the films were confirmed by infrared spectroscopy. The TiOPDA-TiO2 nanohybrid superlattice films exhibited good thermal and mechanical stabilities.PACS: 81.07.Pr, organic-inorganic hybrid nanostructures; 82.35.-x, polymerization; 81.15.-z, film deposition; 81.15.Gh, chemical vapor deposition (including plasma enhanced CVD, MOCVD, ALD, etc.).

  13. Nb-Ta, Nb-Mo and Nb-V oxides prepared from hybrid organic-inorganic precursors

    SciTech Connect

    Deligne, N.; Bayot, D.; Degand, M.; Devillers, M.

    2007-07-15

    New hybrid organic-inorganic materials based on group 5 elements and a well-defined polymeric matrix have been prepared and used as precursors for Nb-Ta and Nb-Mo mixed oxides. In this non-conventional but easily accessible route to multimetallic oxides, a copolymer of N,N-diallyl-N-hexylamine and maleic acid was synthesised and used as matrix to stabilise inorganic species generated in solution from (NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}.4H{sub 2}O, NH{sub 4}VO{sub 3} (gu){sub 3}[Nb(O{sub 2}){sub 4}] and (gu){sub 3}[Ta(O{sub 2}){sub 4}]. Solid-state studies indicate that the homogeneity of the blends can be kept up to about 0.5 mol Nb{sup V} and Ta{sup V} and 0.25 mol V{sup V} per mol of repeat units of the copolymer. The calcination conditions of these homogeneous hybrid precursors were optimised to produce Nb-Mo, Nb-Ta and Nb-V oxides. While the thermal treatment of the Nb-V hybrid blends led only to a mixture of different phases, the characterisation of the final phases by X-ray diffraction (XRD) proved the formation of pure Nb{sub 2}Mo{sub 3}O{sub 14} and showed that Nb-Ta oxides could be synthesised as single phases corresponding to a continuous series of solid solutions. - Graphical abstract: An alternative route based on hybrid organic-inorganic materials was implemented to synthesise Nb-Ta, Nb-Mo and Nb-V oxides. The hybrid materials were prepared by incorporation of inorganic salts based on Nb{sup V}, Ta{sup V}, V{sup V} and Mo{sup VI} in an organic polymer bearing cationic as well as anionic moieties. A thermal treatment of these hybrid blends has allowed the formation of multimetallic oxides.

  14. Evaluation of New Inorganic Sorbents for Strontium and Actinide Removal from High-Level Nuclear Waste Solutions

    SciTech Connect

    Hobbs, D.T.; Nyman, M.; Medvedev, D.G.; Tripathi, A.; Clearfield, A.

    2004-03-28

    Monosodium titanate (MST), a hydrous metal oxide sorbent, is the baseline material for the removal of 90Sr and alpha-emitting radionuclides (principally 238Pu, 239Pu, 240Pu and 237Np) from alkaline waste solutions generated during the processing of irradiated nuclear materials at the Savannah River Site. This material exhibits excellent performance characteristics for strontium removal. Plutonium removal is also good, but problematic at the estimated bonding concentration. We are currently developing new inorganic materials for improved sorption characteristics. These materials include sodium nonatitanates, pharmacosiderites and heteropolyniobates. We will present results evaluating the performance of these materials with simulated and actual high level nuclear waste solutions.

  15. Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper).

    PubMed

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

    2017-04-01

    In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300°C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300°C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents.

  16. Quantification of water in hydrous ringwoodite

    SciTech Connect

    Thomas, Sylvia -Monique; Jacobsen, Steven D.; Bina, Craig R.; Reichart, Patrick; Moser, Marcus; Hauri, Erik H.; Koch-Muller, Monika; Smyth, Joseph R.; Dollinger, Gunther

    2015-01-28

    Here, ringwoodite, γ-(Mg,Fe)2SiO4, 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 the crystal contains 1.43 ± 0.27 wt% H2O, thus confirming near-maximum amounts of H2O for this sample from the transition zone.

  17. Quantification of water in hydrous ringwoodite

    DOE PAGES

    Thomas, Sylvia -Monique; Jacobsen, Steven D.; Bina, Craig R.; ...

    2015-01-28

    Here, ringwoodite, γ-(Mg,Fe)2SiO4, 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 absolutemore » 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 the crystal contains 1.43 ± 0.27 wt% H2O, thus confirming near-maximum amounts of H2O for this sample from the transition zone.« less

  18. Integrated Spectroscopic Studies of Hydrous Sulfate Minerals

    NASA Technical Reports Server (NTRS)

    Dyar, M. D.; Lane, M. D.; Bishop, J. L.; OConnor, V.; Cloutis, E.; Hiroi, T.

    2005-01-01

    Sulfate minerals have been identified in Martian meteorites and on Mars using a suite of instruments aboard the MER rovers. These results have confirmed previous groundbased observations and orbital measurements that suggested their presence. The orbiting OMEGA instrument on Mars Express is also finding evidence for sulfate. In order to better interpret remote-sensing data, we present here the results of a coordinated visible/near infrared (VNIR) reflectance, Moussbauer (MB), and thermal emittance study of wellcharacterized hydrous sulfate minerals.

  19. Fundamental Mvssbauer Parameters of Hydrous Iron Sulfates

    NASA Technical Reports Server (NTRS)

    Rothstein, Y.; Dyar, M. D.; Schaefer, M. W.; Lane, M. D.; Bishop, J. L.

    2005-01-01

    Hydrous iron sulfates, which form as alteration products of sulfides, are rare on Earth. On Mars, the low temperature and pH found in the martian permafrost create ideal conditions for the formation of this group of minerals [1], which includes such phases as coquimbite (Fe2(SO4) 9H2O) and amarantite (FeSO4(OH) 3H2O). Viking, Mars Pathfinder, MER and OMEGA data [e.g., [2

  20. Temperature-induced transformation of electrochemically formed hydrous RuO2 layers over Ru(0001) model electrodes

    NASA Astrophysics Data System (ADS)

    Krause, Philipp P. T.; Camuka, Hava; Leichtweiss, Thomas; Over, Herbert

    2016-07-01

    Hydrous RuO2 reveals excellent performance both as a supercapacitor and as a heterogeneous oxidation catalyst. Molecular understanding of these processes needs, however, a model system with preferably low structural and morphological complexity. This goal is partly accomplished here by using single crystalline Ru(0001) as a template on which hydrous RuO2 is electrochemically formed. The hydrous RuO2 layers on Ru(0001) and their temperature induced transformation under ultra high vacuum (UHV) conditions are comprehensively characterized by scanning electron microscopy and X-ray photoemission spectroscopy. The hydrous RuO2 layer grows with an intricate morphology governed by the presence of step bunching regions of the Ru(0001) surface. Upon annealing to 200 °C in UHV the hydrous RuO2 layer transforms mostly into flat metallic Ru islands and occasionally into (100) and (111) oriented RuO2 particles aligned along the high symmetry direction of Ru(0001).Hydrous RuO2 reveals excellent performance both as a supercapacitor and as a heterogeneous oxidation catalyst. Molecular understanding of these processes needs, however, a model system with preferably low structural and morphological complexity. This goal is partly accomplished here by using single crystalline Ru(0001) as a template on which hydrous RuO2 is electrochemically formed. The hydrous RuO2 layers on Ru(0001) and their temperature induced transformation under ultra high vacuum (UHV) conditions are comprehensively characterized by scanning electron microscopy and X-ray photoemission spectroscopy. The hydrous RuO2 layer grows with an intricate morphology governed by the presence of step bunching regions of the Ru(0001) surface. Upon annealing to 200 °C in UHV the hydrous RuO2 layer transforms mostly into flat metallic Ru islands and occasionally into (100) and (111) oriented RuO2 particles aligned along the high symmetry direction of Ru(0001). Electronic supplementary information (ESI) available. See DOI: 10

  1. Inorganic nitrate promotes the browning of white adipose tissue through the nitrate-nitrite-nitric oxide pathway.

    PubMed

    Roberts, Lee D; Ashmore, Tom; Kotwica, Aleksandra O; Murfitt, Steven A; Fernandez, Bernadette O; Feelisch, Martin; Murray, Andrew J; Griffin, Julian L

    2015-02-01

    Inorganic nitrate was once considered an oxidation end product of nitric oxide metabolism with little biological activity. However, recent studies have demonstrated that dietary nitrate can modulate mitochondrial function in man and is effective in reversing features of the metabolic syndrome in mice. Using a combined histological, metabolomics, and transcriptional and protein analysis approach, we mechanistically defined that nitrate not only increases the expression of thermogenic genes in brown adipose tissue but also induces the expression of brown adipocyte-specific genes and proteins in white adipose tissue, substantially increasing oxygen consumption and fatty acid β-oxidation in adipocytes. Nitrate induces these phenotypic changes through a mechanism distinct from known physiological small molecule activators of browning, the recently identified nitrate-nitrite-nitric oxide pathway. The nitrate-induced browning effect was enhanced in hypoxia, a serious comorbidity affecting white adipose tissue in obese individuals, and corrected impaired brown adipocyte-specific gene expression in white adipose tissue in a murine model of obesity. Because resulting beige/brite cells exhibit antiobesity and antidiabetic effects, nitrate may be an effective means of inducing the browning response in adipose tissue to treat the metabolic syndrome.

  2. Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides

    NASA Astrophysics Data System (ADS)

    Rafiee, Ezzat; Shahebrahimi, Shabnam

    2017-07-01

    Organic-inorganic hybrid nano porous materials based on poly(ionic liquid)-polyoxometalate (PIL-POM) were reported. These hybrid materials were synthesized by the reaction of 4-vinyl pyridine with 1,3-propanesultone, followed by the polymerization and also sulfonate-functionalized cross-linked poly(4-vinylpyridine) and combining these polymers with H5PMo10V2O40 (PMo10V2). Activity of prepared PIL-PMo10V2 hybrids were investigated as catalysts for oxidation of sulfides with H2O2 as oxidant. For understanding catalytic activities of the PIL-PMo10V2 hybrids in oxidation of sulfides, effect of catalyst composition, substrate, and reaction conditions were studied. The results show that the PIL-PMo10V2 hybrids are active as selective heterogeneous catalysts for oxidation of sulfides and can be recovered and reused. The catalyst was characterized by FT-IR, TGA-DSC, XRD, SEM/EDX, BET, CV and zeta potential measurement. Also, average molecular weight of prepared catalysts were measured.

  3. Inorganic Nitrate Promotes the Browning of White Adipose Tissue through the Nitrate-Nitrite-Nitric Oxide Pathway

    PubMed Central

    Roberts, Lee D; Ashmore, Tom; Kotwica, Aleksandra O; Murfitt, Steven A; Fernandez, Bernadette O; Feelisch, Martin; Griffin, Julian L

    2015-01-01

    Inorganic nitrate was once considered an oxidation end-product of nitric oxide metabolism with little biological activity. However, recent studies have demonstrated that dietary nitrate can modulate mitochondrial function in man and is effective in reversing features of the metabolic syndrome in mice. Using a combined histological, metabolomics, and transcriptional and protein analysis approach we mechanistically define that nitrate not only increases the expression of thermogenic genes in brown-adipose tissue but also induces the expression of brown adipocyte-specific genes and proteins in white adipose tissue, substantially increasing oxygen consumption and fatty acid β-oxidation in adipocytes. Nitrate induces these phenotypic changes through a mechanism distinct from known physiological small molecule activators of browning, the recently identified nitrate-nitrite-nitric oxide pathway. The nitrate-induced browning effect was enhanced in hypoxia, a serious co-morbidity affecting white adipose tissue in obese individuals, and corrected impaired brown adipocyte-specific gene expression in white adipose tissue in a murine model of obesity. Since resulting beige/brite cells exhibit anti-obesity and anti-diabetic effects, nitrate may be an effective means of inducing the browning response in adipose tissue to treat the metabolic syndrome. PMID:25249574

  4. Stress proteins and oxidative damage in a renal derived cell line exposed to inorganic mercury and lead.

    PubMed

    Stacchiotti, Alessandra; Morandini, Fausta; Bettoni, Francesca; Schena, Ilaria; Lavazza, Antonio; Grigolato, Pier Giovanni; Apostoli, Pietro; Rezzani, Rita; Aleo, Maria Francesca

    2009-10-29

    A close link between stress protein up-regulation and oxidative damage may provide a novel therapeutic tool to counteract nephrotoxicity induced by toxic metals in the human population, mainly in children, of industrialized countries. Here we analysed the time course of the expression of several heat shock proteins, glucose-regulated proteins and metallothioneins in a rat proximal tubular cell line (NRK-52E) exposed to subcytotoxic doses of inorganic mercury and lead. Concomitantly, we used morphological and biochemical methods to evaluate metal-induced cytotoxicity and oxidative damage. In particular, as biochemical indicators of oxidative stress we detected reactive oxygen species (ROS) and nitrogen species (RNS), total glutathione (GSH) and glutathione-S-transferase (GST) activity. Our results clearly demonstrated that mercury increases ROS and RNS levels and the expressions of Hsp25 and inducible Hsp72. These findings are corroborated by evident mitochondrial damage, apoptosis or necrosis. By contrast, lead is unable to up-regulate Hsp72 but enhances Grp78 and activates nuclear Hsp25 translocation. Furthermore, lead causes endoplasmic reticulum (ER) stress, vacuolation and nucleolar segregation. Lastly, both metals stimulate the over-expression of MTs, but with a different time course. In conclusion, in NRK-52E cell line the stress response is an early and metal-induced event that correlates well with the direct oxidative damage induced by mercury. Indeed, different chaperones are involved in the specific nephrotoxic mechanism of these environmental pollutants and work together for cell survival.

  5. The metabolism of inorganic arsenic oxides, gallium arsenide, and arsine: a toxicochemical review.

    PubMed

    Carter, Dean E; Aposhian, H Vasken; Gandolfi, A Jay

    2003-12-15

    The aim of this review is to compare the metabolism, chemistry, and biological effects to determine if either of the industrial arsenicals (arsine and gallium arsenide) act like the environmental arsenic oxides (arsenite and arsenate). The metabolism of the arsenic oxides has been extensively investigated in the past 4 years and the differences between the arsenic metabolites in the oxidation states +III versus +V and with one or two methyl groups added have shown increased importance. The arsenic oxide metabolism has been compared with arsine (oxidation state -III) and arsenide (oxidation state between 0 to -III). The different metabolites appear to have different strengths of reaction for binding arsenic (III) to thiol groups, their oxidation-reduction reactions and their forming an arsenic-carbon bond. It is unclear if the differences in parameters such as the presence or absence of methyl metabolites, the rates of AsV reduction compared to the rates of AsIII oxidation, or the competition of phosphate and arsenate for cellular uptake are large enough to change biological effects. The arsine rate of decomposition, products of metabolism, target organ of toxic action, and protein binding appeared to support an oxidized arsenic metabolite. This arsine metabolite was very different from anything made by the arsenic oxides. The gallium arsenide had a lower solubility than any other arsenic compound and it had a disproportionate intensity of lung damage to suggest that the GaAs had a site of contact interaction and that oxidation reactions were important in its toxicity. The urinary metabolites after GaAs exposure were the same as excreted by arsenic oxides but the chemical compounds responsible for the toxic effects of GaAs are different from the arsenic oxides. The review concludes that there is insufficient evidence to equate the different arsenic compounds. There are several differences in the toxicity of the arsenic compounds that will require substantial

  6. Organic-inorganic random copolymers from methacrylate-terminated poly(ethylene oxide) with 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane: synthesis via RAFT polymerization and self-assembly behavior.

    PubMed

    Wei, Kun; Li, Lei; Zheng, Sixun; Wang, Ge; Liang, Qi

    2014-01-14

    In this contribution, we report the synthesis of organic-inorganic random polymers from methacrylate-terminated poly(ethylene oxide) (MAPEO) (Mn = 950) and 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MAPOSS) macromers via reversible addition-fragmentation chain transfer (RAFT) polymerization with 4-cyano-4-(thiobenzoylthio) valeric acid (CTBTVA) as the chain transfer agent. The organic-inorganic random copolymers were characterized by means of (1)H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results of GPC indicate that the polymerizations were carried out in a controlled fashion. Transmission electron microscopy (TEM) showed that the organic-inorganic random copolymers in bulk were microphase-separated and the POSS microdomains were formed via POSS-POSS interactions. In aqueous solutions the organic-inorganic random copolymers were capable of self-assembling into spherical nanoobjects as evidenced by transmission electron microscopy (TEM) and dynamic laser scattering (DLS). The self-assembly behavior of the organic-inorganic random copolymers was also found to occur in the mixtures with the precursors of epoxy. The nanostructures were further fixed via subsequent curing reaction and thus the organic-inorganic nanocomposites were obtained. The formation of nanophases in epoxy thermosets was confirmed by transmission electron microscopy (TEM) and dynamic mechanical thermal analysis (DMTA). The organic-inorganic nanocomposites displayed the enhanced surface hydrophobicity as evidenced by surface contact angle measurements.

  7. Oxide-based inorganic/organic and nanoporous spherical particles: synthesis and functional properties

    PubMed Central

    Shiba, Kota; Tagaya, Motohiro; Tilley, Richard D; Hanagata, Nobutaka

    2013-01-01

    This paper reviews the recent progress in the preparation of oxide-based and heteroatom-doped particles. Surfactant-templated oxide particles, e.g. silica and titania, are possible candidates for various potential applications such as adsorbents, photocatalysts, and optoelectronic and biological materials. We highlight nanoporous oxides of one element, such as silicon or titanium, and those containing multiple elements, which exhibit properties that are not achieved with individual components. Although the multicomponent nanoporous oxides possess a number of attractive functions, the origin of their properties is hard to determine due to compositional/structural complexity. Particles with a well-defined size and shape are keys for a quantitative and detailed discussion on the unique complex properties of the particles. From this viewpoint, we review the synthesis techniques of the oxide particles, which are functionalized with organic molecules or doped with heteroatoms, the physicochemical properties of the particles and the possibilities for their photofunctional applications as complex systems. PMID:27877569

  8. Oxide-based inorganic/organic and nanoporous spherical particles: synthesis and functional properties

    NASA Astrophysics Data System (ADS)

    Shiba, Kota; Tagaya, Motohiro; Tilley, Richard D.; Hanagata, Nobutaka

    2013-04-01

    This paper reviews the recent progress in the preparation of oxide-based and heteroatom-doped particles. Surfactant-templated oxide particles, e.g. silica and titania, are possible candidates for various potential applications such as adsorbents, photocatalysts, and optoelectronic and biological materials. We highlight nanoporous oxides of one element, such as silicon or titanium, and those containing multiple elements, which exhibit properties that are not achieved with individual components. Although the multicomponent nanoporous oxides possess a number of attractive functions, the origin of their properties is hard to determine due to compositional/structural complexity. Particles with a well-defined size and shape are keys for a quantitative and detailed discussion on the unique complex properties of the particles. From this viewpoint, we review the synthesis techniques of the oxide particles, which are functionalized with organic molecules or doped with heteroatoms, the physicochemical properties of the particles and the possibilities for their photofunctional applications as complex systems.

  9. Oxide-based inorganic/organic and nanoporous spherical particles: synthesis and functional properties.

    PubMed

    Shiba, Kota; Tagaya, Motohiro; Tilley, Richard D; Hanagata, Nobutaka

    2013-04-01

    This paper reviews the recent progress in the preparation of oxide-based and heteroatom-doped particles. Surfactant-templated oxide particles, e.g. silica and titania, are possible candidates for various potential applications such as adsorbents, photocatalysts, and optoelectronic and biological materials. We highlight nanoporous oxides of one element, such as silicon or titanium, and those containing multiple elements, which exhibit properties that are not achieved with individual components. Although the multicomponent nanoporous oxides possess a number of attractive functions, the origin of their properties is hard to determine due to compositional/structural complexity. Particles with a well-defined size and shape are keys for a quantitative and detailed discussion on the unique complex properties of the particles. From this viewpoint, we review the synthesis techniques of the oxide particles, which are functionalized with organic molecules or doped with heteroatoms, the physicochemical properties of the particles and the possibilities for their photofunctional applications as complex systems.

  10. Study of the Photo-oxidation and Photolysis of Unsaturated and Cross-linked Polyesters (UP) in the Presence of Photoactive or not Inorganic Fillers

    NASA Astrophysics Data System (ADS)

    Khalil, Zahi; Koubaissy, Bachar; Akil, Mariam

    Disturbances of the photochemical evolution involved in the photolysis and in the photo-oxidation at long wavelengths (ë?300 nm) of poly(propylene glycol-maleatophtalate cross-linked by the styrene (UP),caused by the addition of photo-active pigment such as zinc sulphide or black iron oxides,and no photoactive inorganic fillers such as calcium carbonate have been analysed by means of FTIR and U.V. spectrophotometry. The photo-oxidation observed by FTIR of the polymer UP in the presence of inorganic fillers leads to the same photoproducts such as ones of the photo-oxidation of the virgin polymer, but the oxidation rate is greatly affected by the nature and the percentage of the inorganic filler. Zinc sulfide and black iron are incorporated in the film of polymers, the absorption spectra of ZnS reveals that this pigment is not as absorbent as titanium oxide in a more limited field. On the other hand, with a very low inner filter effect, black iron oxides promote the formation of absorbing photoproducts. The addition of Calcium carbonate non- absorbing filler to the UP, causes a slight decrease in the evolution of the I.R

  11. Nitrous oxide emissions after sewage sludge and inorganic N-fertilization of a willow bio-energy plantation

    NASA Astrophysics Data System (ADS)

    Klemedtsson, Leif; Hedenrud, Anna; Rychlik, Sophie; Weslien, Per; Kasimir Klemedtsson, Åsa; Achberger, Christine; Lindroth, Anders

    2014-05-01

    The use of sewage sludge as fertilizer after harvest or inorganic N-fertilization of bio-energy plantations can give rise to high emissions of the greenhouse gas nitrous oxide (N2O). Plantations of e.g. willow (Salix) are today grown and used for bioenergy purposes. They could serve as carbon and nitrogen sinks, lowering greenhouse gas emissions and helping to mitigate a change in climate. However, since N2O is such a powerful greenhouse gas it can have a large impact on the total emission of greenhouse gases from a bio-energy plantation. The magnitude of N2O emissions after fertilization is therefore important to investigate. This study concerns N2O emissions from a conventionally grown bio-energy plantation of Salix. The aim of the study was to investigate the use of sewage sludge after harvest as well as inorganic N-fertilization in a growing plantation, and its effect on emissions of N2O from the soil ecosystem. The field site is a Salix plantation in south-western Sweden, a representative site in management practices and abiotic conditions. The site was divided into two areas, a larger field and smaller plots. The field was applied with sewage sludge after harvest 2013. Emissions of N2O were measured using the micrometeorological Eddy covariance technique, with a Quantum Cascade laser (Aerodyne). The fluxes of CO2 and H2O were measured using a LI-7200(Li-cor) instrument. The flux was calculated using the EddyPro software. On the plots, N2O emissions from inorganic N-fertilization (2013) were monitored using automatic chambers (height 1.05 m, volume 0.2625 m3) and a trace gas analyzer (TGA100, Campbell Scientific, USA) during approximately one (1) year. The N2O emissions from the plots (inorganic fertilizer) and field (sewage sludge) were compared with non-fertilized plots (controls) using the automatic chambers for both comparisons. The N2O emissions from the control plot for the inorganic fertilizer had an emission over the growing season that was 0.33 kg N2O

  12. Critical role of cellular glutathione homeostasis for trivalent inorganic arsenite-induced oxidative damage in human bronchial epithelial cells.

    PubMed

    Jiang, Xuejun; Chen, Chengzhi; Liu, Yuan; Zhang, Ping; Zhang, ZunZhen

    2014-08-01

    Trivalent inorganic arsenic (iAs(3+)) is a powerful carcinogen that enhances the risk of lung cancer. Paradoxically, iAs(3+) also shows substantial efficacy in the treatment of lung tumors. However, the exact molecular mechanisms underlying iAs(3+)-induced toxicity and therapeutic effect in lung remain unclear. In this study, the effects of iAs(3+), sodium arsenite (NaAsO2) and arsenic trioxide (As2O3), on cell viability, apoptosis, genotoxicity and oxidative stress in cultured human bronchial epithelial cells were observed. Our results showed that NaAsO2 and As2O3 exposure could result in defects in cell proliferation and greatly enhance the level of oxidative damage. To clarify the critical role of glutathione (GSH) homeostasis in oxidative damage induced by iAs(3+), we further measured the content of GSH, ratio of GSH to GSSG, and the activities of GSH-related enzymes involved in the process of GSH synthesis, recycling and utilization. Our data demonstrated that NaAsO2 and As2O3 disrupted the balance of GSH homeostasis, and NaAsO2- and As2O3-induced oxidative damage was closely associated with the imbalance in GSH synthesis, recycling and utilization. To better understand the physiologic significance of Nrf2 in maintaining GSH-homeostasis, the expression level of Nrf2 was measured after iAs(3+) exposure. We found that the protein expression levels of Nrf2 were increased in both NaAsO2- and As2O3-treated cells. Collectively, our findings suggest that disturbed Nrf2-regulated GSH-homeostasis is associated with the oxidative damage triggered by iAs(3+), and loss of GSH homeostasis might implicate in both the pathogenesis of iAs(3+)-induced lung diseases and anticancer activity of iAs(3+). Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Versatile Oxidation Methods for Organic and Inorganic Substrates Catalyzed by Platinum-Group Metals on Carbons.

    PubMed

    Sawama, Yoshinari; Asai, Shota; Monguchi, Yasunari; Sajiki, Hironao

    2016-02-01

    Platinum-group metals on activated carbon catalysts, represented by Pd/C, Ru/C, Rh/C, etc., are widely utilized to accomplish green and sustainable organic reactions due to their favorable features, such as easy handling, recoverability, and reusability. The efficient oxidation methods of various organic compounds using heterogeneous platinum-group metals on carbons with or without added oxidants are summarized in this Personal Account. The oxidation of internal alkynes into diketones was effectively catalyzed by Pd/C in the presence of dimethyl sulfoxide and molecular oxygen or pyridine N-oxide. The Pd/C-catalyzed mild combustion of gaseous hydrogen with molecular oxygen provided hydrogen peroxide, which could be directly utilized for the oxidation of sulfide derivatives into sulfoxides. Furthermore, the Ru/C-catalyzed aerobic oxidation of primary and secondary alcohols gave the corresponding aldehydes and ketones, respectively. On the other hand, the dehydrogenative oxidation of secondary alcohols into ketones was achieved using Rh/C in water, and primary alcohols were effectively dehydrogenated by Pd/C in water under mildly reduced pressure to produce carboxylic acids.

  14. Nanostructural surface engineering of grafted polymers on inorganic oxide substrates for membrane separations

    NASA Astrophysics Data System (ADS)

    Yoshida, Wayne Hiroshi

    Nanostructural engineering of inorganic substrates by free radical graft polymerization was studied with the goal of developing new membrane materials for pervaporation. Graft polymerization consisted of modification of surface hydroxyls with vinyl trimethoxysilane, followed by solution graft polymerization reaction using either vinyl acetate (VAc) or vinyl pyrrolidone (VP). The topology of the modified surfaces was studied by atomic force microscopy (AFM) on both atomically smooth silicon wafer substrates and microporous inorganic membrane supports in order to deduce the effects of modification on the nanostructural properties of the membrane. While unmodified wafers showed a root-mean-square (RMS) surface roughness of 0.21 +/- 0.03 nm, roughness increased to 3.15 +/- 0.23 nm upon silylation. Under poor solvent conditions (i.e., air), surfaces modified with higher poly(vinyl acetate) (PVAc) or poly(vinyl pyrrolidone) (PVP) polymer graft yields displayed lateral inhomogeneities in the polymer layer. Although RMS surface roughness was nearly identical (0.81--0.85 nm) for PVAc-modified surfaces grafted at different monomer concentrations, the skewness of the height distribution decreased from 2.22 to 0.78 as polymer graft yield increased from 0.8 to 3.5 mg/m2. The polymer-modified surfaces were used to create inorganic pervaporation membranes consisting of a single macromolecular separation layer formed by graft polymerization. PVAc grafted silica membranes (500A native pore size) were found selective for MTBE in the separation of 0.1--1% (v/v) MTBE from water, achieving MTBE enrichment factors as high as 371 at a permeate flux of 0.38 l/m2 hr and a Reynolds number of 6390; however, these membranes could not separate anhydrous organic mixtures. Pervaporative separation of methanol/MTBE mixtures was possible with PVAc and PVP-modified alumina supports of 50A native pore size, where the separation layer consisted of grafted polymer chains with estimated radius of

  15. Improved oxidation resistance of organic/inorganic composite atomic layer deposition coated cellulose nanocrystal aerogels

    SciTech Connect

    Smith, Sean W.; Matthews, David J.; Conley, John F.; Buesch, Christian; Simonsen, John

    2014-07-01

    Cellulose nanocrystal (CNC) aerogels are coated with thin conformal layers of Al{sub 2}O{sub 3} using atomic layer deposition to form hybrid organic/inorganic nanocomposites. Electron probe microanalysis and scanning electron microscopy analysis indicated the Al{sub 2}O{sub 3} penetrated more than 1500 μm into the aerogel for extended precursor pulse and exposure/purge times. The measured profile of coated fiber radius versus depth from the aerogel surface agrees well with simulations of precursor penetration depth in modeled aerogel structures. Thermogravimetric analysis shows that Al{sub 2}O{sub 3} coated CNC aerogel nanocomposites do not show significant thermal degradation below 295 °C as compared with 175 °C for uncoated CNC aerogels, an improvement of over 100 °C.

  16. Visibly transparent & radiopaque inorganic organic composites from flame-made mixed-oxide fillers

    NASA Astrophysics Data System (ADS)

    Mädler, Lutz; Krumeich, Frank; Burtscher, Peter; Moszner, Norbert

    2006-08-01

    Radiopaque composites have been produced from flame-made ytterbium/silica mixed oxide within a crosslinked methacrylate resin matrix. The refractive index of the filler powder increased with ytterbium oxide loading. A high transparency was achieved for a matching refractive index of the filler powder and the polymer in comparison to commercial materials with 52 wt% ceramic filling. It was demonstrated that powder homogeneity with regard to particle morphology and distribution of the individual metal atoms is essential to obtain a highly transparent composite. In contrast, segregation of crystalline single-oxide phases drastically decreased the composite transparency despite similar specific surface areas, refractive indices and overall composition. The superior physical strength, transparency and radiopacity compared to composites made from conventional silica based-fillers makes the flame-made mixed-oxide fillers especially attractive for dental restoration materials.

  17. Protective effects of propolis on inorganic mercury induced oxidative stress in mice.

    PubMed

    Zhao, Jun-Quan; Wen, Yi-Fei; Bhadauria, Monika; Nirala, Satendra Kumar; Sharma, Abhilasha; Shrivastava, Sadhana; Shukla, Sangeeta; Agrawal, Om Prakash; Mathur, Ramesh

    2009-04-01

    Protective potential of propolis was evaluated against mercury induced oxidative stress and antioxidant enzymatic alterations in mice liver. Exposure to mercuric chloride (HgCl2; 5 mg/kg; ip) induced oxidative stress by increasing lipid peroxidation and oxidized glutathione level along with concomitant decrease in glutathione and various antioxidant enzymes. Mercury intoxication deviated the activity of liver marker enzymes in serum. Conjoint treatment of propolis (200 mg/kg; po) inhibited lipid peroxidation and oxidized glutathione level, whereas increased glutathione level. Activities of antioxidants enzymes, i.e., superoxide dismutase, catalase, glutathione-S-transferase and glucose-6-phosphate dehydrogenase were also restored concomitantly towards control after propolis administration. Release of serum transaminases, alkaline phosphatase, lactate dehydrogenase and y-glutamyl transpeptidase were significantly restored towards control after propolis treatment. Results suggest that propolis augments the antioxidants defense against mercury induced toxicity and provides evidence that it has therapeutic potential as hepatoprotective agent.

  18. Heat Capacity of Hydrous Silicate Melts

    NASA Astrophysics Data System (ADS)

    Robert, G.; Whittington, A. G.; Stechern, A.; Behrens, H.

    2015-12-01

    We determined the heat capacities of four series of glasses and liquids of basaltic and basaltic andesite compositions including two natural remelts from Fuego volcano, Guatemala, and two Fe-free analogs. The samples are low-alkali, Ca- and Mg-rich aluminosilicates with non-bridging oxygen to tetrahedrally-coordinated cation ratios (NBO/T) ranging between 0.33 and 0.67. Differential scanning calorimetry measurements were performed at atmospheric pressure between room temperature and ≈100 K above the glass transition for hydrous samples and up to ≈1800 K for dry samples. The water contents investigated range up to 5.34 wt.% (16.4 mol%). Water does not measurably affect the heat capacity of glasses (T hydrous samples also occurs below the Dulong-Petit limit of 3R/g atom. We see little change in liquid heat capacity with increasing water content; hydrous liquid heat capacities are within 3-6% of the dry liquid, at low temperatures just above the glass transition. However, dry liquids show a decrease in heat capacity with increasing temperature above the glass transition, from supercooled to superliquidus temperatures. Liquid heat capacity values just above the glass transition range between 95-100 J/mol K, whereas liquid heat capacity values at superliquidus temperatures are between 85-91 J/mol K. Comparison with other studies of the heat capacity of hydrous glasses and liquids shows that the liquid heat capacity of strongly depolymerized samples (NBO/T ≥ 0.8) increases with increasing water content, whereas depolymerized samples (0.4 ≤ NBO/T ≤ 0.8) or polymerized samples (NBO/T ≤ 0.4) generally show little change or a moderate decrease in liquid heat capacity with increasing water content.

  19. Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

    NASA Astrophysics Data System (ADS)

    Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

    2015-05-01

    The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V2O5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V2O5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V2O5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/VxOx composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V2O5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing aid, such as the two cysteine-constrained peptides on the phage surface, and has potential for use in nanotechnology applications.

  20. Komatiites reveal a hydrous Archaean deep-mantle reservoir

    NASA Astrophysics Data System (ADS)

    Sobolev, Alexander V.; Asafov, Evgeny V.; Gurenko, Andrey A.; Arndt, Nicholas T.; Batanova, Valentina G.; Portnyagin, Maxim V.; Garbe-Schönberg, Dieter; Krasheninnikov, Stepan P.

    2016-03-01

    Archaean komatiites (ultramafic lavas) result from melting under extreme conditions of the Earth’s mantle. Their chemical compositions evoke very high eruption temperatures, up to 1,600 degrees Celsius, which suggests even higher temperatures in their mantle source. This message is clouded, however, by uncertainty about the water content in komatiite magmas. One school of thought holds that komatiites were essentially dry and originated in mantle plumes while another argues that these magmas contained several per cent water, which drastically reduced their eruption temperature and links them to subduction processes. Here we report measurements of the content of water and other volatile components, and of major and trace elements in melt inclusions in exceptionally magnesian olivine (up to 94.5 mole per cent forsterite). This information provides direct estimates of the composition and crystallization temperature of the parental melts of Archaean komatiites. We show that the parental melt for 2.7-billion-year-old komatiites from the Abitibi greenstone belt in Canada contained 30 per cent magnesium oxide and 0.6 per cent water by weight, and was depleted in highly incompatible elements. This melt began to crystallize at around 1,530 degrees Celsius at shallow depth and under reducing conditions, and it evolved via fractional crystallization of olivine, accompanied by minor crustal assimilation. As its major- and trace-element composition and low oxygen fugacities are inconsistent with a subduction setting, we propose that its high H2O/Ce ratio (over 6,000) resulted from entrainment into the komatiite source of hydrous material from the mantle transition zone. These results confirm a plume origin for komatiites and high Archaean mantle temperatures, and evoke a hydrous reservoir in the deep mantle early in Earth’s history.

  1. Komatiites reveal a hydrous Archaean deep-mantle reservoir.

    PubMed

    Sobolev, Alexander V; Asafov, Evgeny V; Gurenko, Andrey A; Arndt, Nicholas T; Batanova, Valentina G; Portnyagin, Maxim V; Garbe-Schönberg, Dieter; Krasheninnikov, Stepan P

    2016-03-31

    Archaean komatiites (ultramafic lavas) result from melting under extreme conditions of the Earth's mantle. Their chemical compositions evoke very high eruption temperatures, up to 1,600 degrees Celsius, which suggests even higher temperatures in their mantle source. This message is clouded, however, by uncertainty about the water content in komatiite magmas. One school of thought holds that komatiites were essentially dry and originated in mantle plumes while another argues that these magmas contained several per cent water, which drastically reduced their eruption temperature and links them to subduction processes. Here we report measurements of the content of water and other volatile components, and of major and trace elements in melt inclusions in exceptionally magnesian olivine (up to 94.5 mole per cent forsterite). This information provides direct estimates of the composition and crystallization temperature of the parental melts of Archaean komatiites. We show that the parental melt for 2.7-billion-year-old komatiites from the Abitibi greenstone belt in Canada contained 30 per cent magnesium oxide and 0.6 per cent water by weight, and was depleted in highly incompatible elements. This melt began to crystallize at around 1,530 degrees Celsius at shallow depth and under reducing conditions, and it evolved via fractional crystallization of olivine, accompanied by minor crustal assimilation. As its major- and trace-element composition and low oxygen fugacities are inconsistent with a subduction setting, we propose that its high H2O/Ce ratio (over 6,000) resulted from entrainment into the komatiite source of hydrous material from the mantle transition zone. These results confirm a plume origin for komatiites and high Archaean mantle temperatures, and evoke a hydrous reservoir in the deep mantle early in Earth's history.

  2. N2O production by ammonia oxidizing bacteria in an enriched nitrifying sludge linearly depends on inorganic carbon concentration.

    PubMed

    Peng, Lai; Ni, Bing-Jie; Ye, Liu; Yuan, Zhiguo

    2015-05-01

    The effect of inorganic carbon (IC) on nitrous oxide (N2O) production by ammonia oxidizing bacteria (AOB) was investigated over a concentration range of 0-12 mmol C/L, encompassing typical IC levels in a wastewater treatment reactors. The AOB culture was enriched along with nitrite-oxidizing bacteria (NOB) in a sequencing batch reactor (SBR) to perform complete nitrification. Batch experiments were conducted with continuous carbon dioxide (CO2) stripping or at controlled IC concentrations. The results revealed a linear relationship between N2O production rate (N2OR) and IC concentration (R(2) = 0.97) within the IC range studied, suggesting a substantial effect of IC on N2O production by AOB. Similar results were also obtained with an AOB culture treating anaerobic sludge digestion liquor. The fundamental mechanism responsible for this dependency is unclear; however, in agreement with previous studies, it was observed that the ammonia oxidation rate (AOR) was also influenced by the IC concentration, which could be well described by the Monod kinetics. These resulted in an exponential relationship between N2OR and AOR, as previously observed in experiments where AOR was altered by varying dissolved oxygen and ammonia concentrations. It is therefore possible that IC indirectly affected N2OR by causing a change in AOR. The observation in this study indicates that alkalinity (mostly contributed by IC) could be a significant factor influencing N2O production and should be taken into consideration in estimating and mitigating N2O emissions in wastewater treatment systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Influence of Inorganic Nitrogen Management Regime on the Diversity of Nitrite-Oxidizing Bacteria in Agricultural Grassland Soils

    PubMed Central

    Freitag, Thomas E.; Chang, Lisa; Clegg, Christopher D.; Prosser, James I.

    2005-01-01

    To assess links between the diversity of nitrite-oxidizing bacteria (NOB) in agricultural grassland soils and inorganic N fertilizer management, NOB communities in fertilized and unfertilized soils were characterized by analysis of clone libraries and denaturing gradient gel electrophoresis (DGGE) of 16S rRNA gene fragments. Previously uncharacterized Nitrospira-like sequences were isolated from both long-term-fertilized and unfertilized soils, but DGGE migration patterns indicated the presence of additional sequence types in the fertilized soils. Detailed phylogenetic analysis of Nitrospira-like sequences suggests the existence of one newly described evolutionary group and of subclusters within previously described sublineages, potentially representing different ecotypes; the new group may represent a lineage of noncharacterized Nitrospira species. Clone libraries of Nitrobacter-like sequences generated from soils under different long-term N management regimes were dominated by sequences with high similarity to the rhizoplane isolate Nitrobacter sp. strain PJN1. However, the diversity of Nitrobacter communities did not differ significantly between the two soil types. This is the first cultivation-independent study of nitrite-oxidizing bacteria in soil demonstrating that nitrogen management practices influence the diversity of this bacterial functional group. PMID:16332819

  4. New sol-gel synthetic route to transition and main-group metal oxide aerogels using inorganic salt precursors

    SciTech Connect

    Gash, A E; Tillotson, T M; Satcher Jr, J H; Hrubesh, L W; Simpson, R L

    2000-09-12

    We have developed a new sol-gel route to synthesize several transition and main-group metal oxide aerogels. The approach is straightforward, inexpensive, versatile, and it produces monolithic microporous materials with high surface areas. Specifically, we report the use of epoxides as gelation agents for the sol-gel synthesis of chromia aerogels and xerogels from simple Cr(III) inorganic salts. The dependence of both gel formation and its rate was studied by varying the solvent used, the Cr(III) precursor salt, the epoxide/Cr(III) ratio, as well as the type of epoxide employed. All of these variables were shown to affect the rate of gel formation and provide a convenient control of this parameter. Dried chromia aerogels were characterized by high-resolution transmission electron microscopy (HRTEM) and nitrogen adsorption/desorption analyses, results of which will be presented. Our studies have shown that rigid monolithic gels can be prepared from many different metal ions salts, provided the formal oxidation state of the metal ion is greater than or equal to +3. Conversely, when di-valent transition metal salts are used precipitated solids are the products.

  5. Superior inorganic ion cofactors of tetraborate species attaining highly efficient heterogeneous electrocatalysis for water oxidation on cobalt oxyhydroxide nanoparticles.

    PubMed

    Takeuchi, Ryouchi; Sato, Tetsuya; Tanaka, Kou; Aiso, Kaoru; Chandra, Debraj; Saito, Kenji; Yui, Tatsuto; Yagi, Masayuki

    2017-10-05

    A heterogeneous catalyst incorporating an inorganic ion cofactor for electrochemical water oxidation was exploited using a CoO(OH) nanoparticle layer-deposited electrode. The significant catalytic current for water oxidation was generated in a Na2B4O7 solution at pH 9.4 when applying at 0.94 V vs. Ag/AgCl in contrast to no catalytic current generation in the K2SO4 solution at the same pH. HB4O7- and B4O72- ions are indicated to act as key cofactors for the induced catalytic activity of the CoO(OH) layer. The Na2B4O7 concentration-dependence of Icat was analyzed based on a Michaelis-Menten type kinetics to provide affinity constant of cofactors to the active sites, Km = 28 mM and the maximum catalytic current density, Imax = 2.3 mA cm-2. The Imax value was 1.4 times higher than that (1.3 mA cm-2) for the previously-reported case of CO32- ions. This could be explained by the shorter-range proton transfer from the active site to the proton-accepting cofactor due to the larger size and more flexible conformation of HB4O7- and B4O72- ions compared with CO32- ions.

  6. Inorganic greywater matrix impact on photocatalytic oxidation: does flocculation of TiO2 nanoparticles impair process efficiency?

    PubMed

    Armanious, A; Ozkan, A; Sohmen, U; Gulyas, H

    2011-01-01

    This study was conducted in order to clarify whether photocatalyst flocculation--as observed in biologically pretreated greywater--contributes to photocatalytic oxidation (PCO) efficiency impairment. Aqueous solutions of tetraethyleneglycol dimethylether spiked with different inorganic salts in concentrations as found in biologically treated greywater were investigated with respect to TiO2 flocculation and PCO mineralisation kinetics. Flocculation of the photocatalyst primarily depended on pH (which was affected by the salts) and how close pH was to the point of zero charge (PZC). Photocatalyst agglomeration was maximum at pH 5.5. With salt concentrations >7 mmol L(-1), flocculation was strong even at pH far above PZC due to electric double layer compression. PCO rate constants were not unequivocally related to flocculation. Increasing pH was observed as the clearest factor deteriorating PCO efficiency. This was interpreted to result from impaired adsorbability of negatively charged oxidation intermediates as well as from enhanced CO2 absorption with increasing pH and subsequent formation of HCO3(-) anions which are OH radical scavengers.

  7. Synthesis of coral-like tantalum oxide films via anodization in mixed organic-inorganic electrolytes.

    PubMed

    Yu, Hongbin; Zhu, Suiyi; Yang, Xia; Wang, Xinhong; Sun, Hongwei; Huo, Mingxin

    2013-01-01

    We report a simple method to fabricate nano-porous tantalum oxide films via anodization with Ta foils as the anode at room temperature. A mixture of ethylene glycol, phosphoric acid, NH4F and H2O was used as the electrolyte where the nano-porous tantalum oxide could be synthesized by anodizing a tantalum foil for 1 h at 20 V in a two-electrode configuration. The as-prepared porous film exhibited a continuous, uniform and coral-like morphology. The diameters of pores ranged from 30 nm to 50 nm. The pores interlaced each other and the depth was about 150 nm. After calcination, the as-synthesized amorphous tantalum oxide could be crystallized to the orthorhombic crystal system. As observed in photocatalytic experiments, the coral-like tantalum oxide exhibited a higher photocatalytic activity for the degradation of phenol than that with a compact surface morphology, and the elimination rate of phenol increased by 66.7%.

  8. Synthesis of Coral-Like Tantalum Oxide Films via Anodization in Mixed Organic-Inorganic Electrolytes

    PubMed Central

    Yu, Hongbin; Zhu, Suiyi; Yang, Xia; Wang, Xinhong; Sun, Hongwei; Huo, Mingxin

    2013-01-01

    We report a simple method to fabricate nano-porous tantalum oxide films via anodization with Ta foils as the anode at room temperature. A mixture of ethylene glycol, phosphoric acid, NH4F and H2O was used as the electrolyte where the nano-porous tantalum oxide could be synthesized by anodizing a tantalum foil for 1 h at 20 V in a two–electrode configuration. The as-prepared porous film exhibited a continuous, uniform and coral-like morphology. The diameters of pores ranged from 30 nm to 50 nm. The pores interlaced each other and the depth was about 150 nm. After calcination, the as-synthesized amorphous tantalum oxide could be crystallized to the orthorhombic crystal system. As observed in photocatalytic experiments, the coral-like tantalum oxide exhibited a higher photocatalytic activity for the degradation of phenol than that with a compact surface morphology, and the elimination rate of phenol increased by 66.7%. PMID:23799106

  9. Easily processable multimodal spectral converters based on metal oxide/organic-inorganic hybrid nanocomposites.

    PubMed

    Julián-López, Beatriz; Gonell, Francisco; Lima, Patricia P; Freitas, Vânia T; André, Paulo S; Carlos, Luis D; Ferreira, Rute A S

    2015-10-09

    This manuscript reports the synthesis and characterization of the first organic-inorganic hybrid material exhibiting efficient multimodal spectral converting properties. The nanocomposite, made of Er(3+), Yb(3+) codoped zirconia nanoparticles (NPs) entrapped in a di-ureasil d-U(600) hybrid matrix, is prepared by an easy two-step sol-gel synthesis leading to homogeneous and transparent materials that can be very easily processed as monolith or film. Extensive structural characterization reveals that zirconia nanocrystals of 10-20 nm in size are efficiently dispersed into the hybrid matrix and that the local structure of the di-ureasil is not affected by the presence of the NPs. A significant enhancement in the refractive index of the di-ureasil matrix with the incorporation of the ZrO2 nanocrystals is observed. The optical study demonstrates that luminescent properties of both constituents are perfectly preserved in the final hybrid. Thus, the material displays a white-light photoluminescence from the di-ureasil component upon excitation at UV/visible radiation and also intense green and red emissions from the Er(3+)- and Yb(3+)-doped NPs after NIR excitation. The dynamics of the optical processes were also studied as a function of the lanthanide content and the thickness of the films. Our results indicate that these luminescent hybrids represent a low-cost, environmentally friendly, size-controlled, easily processed and chemically stable alternative material to be used in light harvesting devices such as luminescent solar concentrators, optical fibres and sensors. Furthermore, this synthetic approach can be extended to a wide variety of luminescent NPs entrapped in hybrid matrices, thus leading to multifunctional and versatile materials for efficient tuneable nonlinear optical nanodevices.

  10. Easily processable multimodal spectral converters based on metal oxide/organic—inorganic hybrid nanocomposites

    NASA Astrophysics Data System (ADS)

    Julián-López, Beatriz; Gonell, Francisco; Lima, Patricia P.; Freitas, Vânia T.; André, Paulo S.; Carlos, Luis D.; Ferreira, Rute A. S.

    2015-10-01

    This manuscript reports the synthesis and characterization of the first organic-inorganic hybrid material exhibiting efficient multimodal spectral converting properties. The nanocomposite, made of Er3+, Yb3+ codoped zirconia nanoparticles (NPs) entrapped in a di-ureasil d-U(600) hybrid matrix, is prepared by an easy two-step sol-gel synthesis leading to homogeneous and transparent materials that can be very easily processed as monolith or film. Extensive structural characterization reveals that zirconia nanocrystals of 10-20 nm in size are efficiently dispersed into the hybrid matrix and that the local structure of the di-ureasil is not affected by the presence of the NPs. A significant enhancement in the refractive index of the di-ureasil matrix with the incorporation of the ZrO2 nanocrystals is observed. The optical study demonstrates that luminescent properties of both constituents are perfectly preserved in the final hybrid. Thus, the material displays a white-light photoluminescence from the di-ureasil component upon excitation at UV/visible radiation and also intense green and red emissions from the Er3+- and Yb3+-doped NPs after NIR excitation. The dynamics of the optical processes were also studied as a function of the lanthanide content and the thickness of the films. Our results indicate that these luminescent hybrids represent a low-cost, environmentally friendly, size-controlled, easily processed and chemically stable alternative material to be used in light harvesting devices such as luminescent solar concentrators, optical fibres and sensors. Furthermore, this synthetic approach can be extended to a wide variety of luminescent NPs entrapped in hybrid matrices, thus leading to multifunctional and versatile materials for efficient tuneable nonlinear optical nanodevices.

  11. Interfacial Properties of Organic Semiconductor-Inorganic Magnetic Oxide Hybrid Spintronic Systems Fabricated Using Pulsed Laser Deposition.

    PubMed

    Majumdar, Sayani; Grochowska, Katarzyna; Sawczak, Miroslaw; Śliwiński, Gerard; Huhtinen, Hannu; Dahl, Johnny; Tuominen, Marjukka; Laukkanen, Pekka; Majumdar, Himadri S

    2015-10-14

    We report fabrication of a hybrid organic semiconductor-inorganic complex oxide interface of rubrene and La0.67Sr0.33MnO3 (LSMO) for spintronic devices using pulsed laser deposition (PLD) and investigate the interface structure and chemical bonding-dependent magnetic properties. Our results demonstrate that with proper control of growth parameters, thin films of organic semiconductor rubrene can be deposited without any damage to the molecular structure. Rubrene, a widely used organic semiconductor with high charge-carrier mobility and spin diffusion length, when grown as thin films on amorphous and crystalline substrates such as SiO2-glass, indium-tin oxide (ITO), and LSMO by PLD at room temperature and a laser fluence of 0.19 J/cm2, reveals amorphous structure. The Raman spectra verify the signatures of both Ag and Bg Raman active modes of rubrene molecules. X-ray reflectivity measurements indicate a well-defined interface formation between surface-treated LSMO and rubrene, whereas X-ray photoelectron spectra indicate the signature of hybridization of the electronic states at this interface. Magnetic measurements show that the ferromagnetic property of the rubrene-LSMO interface improves by >230% compared to the pristine LSMO surface due to this proposed hybridization. Intentional disruption of the direct contact between LSMO and rubrene by insertion of a dielectric AlOx layer results in an observably decreased ferromagnetism. These experimental results demonstrate that by controlling the interface formation between organic semiconductor and half-metallic oxide thin films, it is possible to engineer the interface spin polarization properties. Results also confirm that by using PLD for consecutive growth of different layers, contamination-free interfaces can be obtained, and this finding is significant for the well-controlled and reproducible design of spin-polarized interfaces for future hybrid spintronics devices.

  12. Inorganic nitrite attenuates NADPH oxidase-derived superoxide generation in activated macrophages via a nitric oxide-dependent mechanism.

    PubMed

    Yang, Ting; Peleli, Maria; Zollbrecht, Christa; Giulietti, Alessia; Terrando, Niccolo; Lundberg, Jon O; Weitzberg, Eddie; Carlström, Mattias

    2015-06-01

    Oxidative stress contributes to the pathogenesis of many disorders, including diabetes and cardiovascular disease. Immune cells are major sources of superoxide (O2(∙-)) as part of the innate host defense system, but exaggerated and sustained O2(∙-) generation may lead to progressive inflammation and organ injuries. Previous studies have proven organ-protective effects of inorganic nitrite, a precursor of nitric oxide (NO), in conditions manifested by oxidative stress and inflammation. However, the mechanisms are still not clear. This study aimed at investigating the potential role of nitrite in modulating NADPH oxidase (NOX) activity in immune cells. Mice peritoneal macrophages or human monocytes were activated by lipopolysaccharide (LPS), with or without coincubation with nitrite. O2(∙-) and peroxynitrite (ONOO(-)) formation were detected by lucigenin-based chemiluminescence and fluorescence techniques, respectively. The intracellular NO production was measured by DAF-FM DA fluorescence. NOX isoforms and inducible NO synthase (iNOS) expression were detected by qPCR. LPS increased both O2(∙-) and ONOO(-) production in macrophages, which was significantly reduced by nitrite (10µmol/L). Mechanistically, the effects of nitrite are (1) linked to increased NO generation, (2) similar to that observed with the NO donor DETA-NONOate, and (3) can be abolished by the NO scavenger carboxy-PTIO or by the xanthine oxidase (XO) inhibitor febuxostat. Nox2 expression was increased in activated macrophages, but was not influenced by nitrite. However, nitrite attenuated LPS-induced upregulation of iNOS expression. Similar to that observed in mice macrophages, nitrite also reduced O2(∙-) generation in LPS-activated human monocytes. In conclusion, XO-mediated reduction of nitrite attenuates NOX activity in activated macrophages, which may modulate the inflammatory response.

  13. Metallothionein Blocks Oxidative DNA Damage Induced by Acute Inorganic Arsenic Exposure

    PubMed Central

    Qu, Wei; Waalkes, Michael P.

    2014-01-01

    We studied how the protein metallothionein (MT) impacts arsenic-induced oxidative DNA damage (ODD) using cells that poorly express MT (MT-I/II double knockout embryonic cells; called MT-null cells) and wild-type (WT) MT competent cells. Arsenic (as NaAsO2) was less cytolethal over 24 h in WT cells (LC50 = 11.0 ± 1.3 µM; mean ± SEM) than in MT-null cells (LC50 = 5.6 ± 1.2 µM). ODD was measured by the immuno-spin trapping method. Arsenic (1 or 5 µM; 24 h) induced much less ODD in WT cells (121% and 141% of control, respectively) than in MT-null cells (202% and 260%). In WT cells arsenic caused concentration-dependent increases in MT expression (transcript and protein), and in the metal-responsive transcription factor-1 (MTF-1), which is required to induce the MT gene. In contrast, basal MT levels were not detectable in MT-null cells and unaltered by arsenic exposure. Transfection of MT-I into the MT-null cells markedly reduced arsenic-induced ODD levels. The transport genes, Abcc1 and Abcc2 were increased by arsenic in WT cells but either showed no or very limited increases in MT-null cells. Arsenic caused increases in oxidant stress defense genes HO-1 and GSTa2 in both WT and MT-null cells, but to much higher levels in WT cells. WT cells appear more adept at activating metal transport systems and oxidant response genes, although the role of MT in these responses is unclear. Overall, MT protects against arsenic-induced ODD in MT competent cells by potentially sequestration of scavenging oxidant radicals and/or arsenic. PMID:25485709

  14. Aqueous process to limit hydration of thin-film inorganic oxides

    NASA Astrophysics Data System (ADS)

    Perkins, Cory K.; Mansergh, Ryan H.; Park, Deok-Hie; Nanayakkara, Charith E.; Ramos, Juan C.; Decker, Shawn R.; Huang, Yu; Chabal, Yves J.; Keszler, Douglas A.

    2016-11-01

    Aqueous-processed aluminum oxide phosphate (AlPO) dielectric films were studied to determine how water desorbs and absorbs on heating and cooling, respectively. In-situ Fourier transform infrared spectroscopy showed a distinct, reversible mono- to bidentate phosphate structural change associated with water loss and uptake. Temperature programmed desorption measurements on a 1-μm thick AlPO film revealed water sorption was inhibited by an aqueous-processed HfO2 capping film only 11-nm thick. The HfO2 capping film prevents water resorption, thereby preserving the exceptional performance of AlPO as a thin-film dielectric.

  15. Metallothionein blocks oxidative DNA damage induced by acute inorganic arsenic exposure

    SciTech Connect

    Qu, Wei Waalkes, Michael P.

    2015-02-01

    We studied how protein metallothionein (MT) impacts arsenic-induced oxidative DNA damage (ODD) using cells that poorly express MT (MT-I/II double knockout embryonic cells; called MT-null cells) and wild-type (WT) MT competent cells. Arsenic (as NaAsO{sub 2}) was less cytolethal over 24 h in WT cells (LC{sub 50} = 11.0 ± 1.3 μM; mean ± SEM) than in MT-null cells (LC{sub 50} = 5.6 ± 1.2 μM). ODD was measured by the immuno-spin trapping method. Arsenic (1 or 5 μM; 24 h) induced much less ODD in WT cells (121% and 141% of control, respectively) than in MT-null cells (202% and 260%). In WT cells arsenic caused concentration-dependent increases in MT expression (transcript and protein), and in the metal-responsive transcription factor-1 (MTF-1), which is required to induce the MT gene. In contrast, basal MT levels were not detectable in MT-null cells and unaltered by arsenic exposure. Transfection of MT-I gene into the MT-null cells markedly reduced arsenic-induced ODD levels. The transport genes, Abcc1 and Abcc2 were increased by arsenic in WT cells but either showed no or very limited increases in MT-null cells. Arsenic caused increases in oxidant stress defense genes HO-1 and GSTα2 in both WT and MT-null cells, but to much higher levels in WT cells. WT cells appear more adept at activating metal transport systems and oxidant response genes, although the role of MT in these responses is unclear. Overall, MT protects against arsenic-induced ODD in MT competent cells by potential sequestration of scavenging oxidant radicals and/or arsenic. - Highlights: • Metallothionein blocks arsenic toxicity. • Metallothionein reduces arsenic-induced DNA damage. • Metallothionein may bind arsenic or radicals produced by arsenic.

  16. Inorganic Nitrate Supplementation in Young and Old Obese Adults Does Not Affect Acute Glucose and Insulin Responses but Lowers Oxidative Stress.

    PubMed

    Ashor, Ammar W; Chowdhury, Shakir; Oggioni, Clio; Qadir, Othman; Brandt, Kirsten; Ishaq, Abbas; Mathers, John C; Saretzki, Gabriele; Siervo, Mario

    2016-11-01

    Aging and obesity are associated with raised oxidative stress and a reduction of nitric oxide (NO) bioavailability, with subsequent decline in insulin sensitivity and endothelial function. Inorganic nitrate is converted into NO via a 2-step reduction process and may be an effective nutritional intervention to modify vascular and metabolic functions. This study tested whether inorganic nitrate supplementation improved glucose disposal and attenuated the acute effects of hyperglycemia on oxidative stress, inflammation, and vascular function in young and old obese participants. Ten young (aged 18-44 y) and 10 old (aged 55-70 y) obese participants consumed 75 g glucose followed by either potassium nitrate (7 mg/kg body weight) or potassium chloride (placebo) in a randomized, double-blind crossover design. Resting blood pressure (BP), endothelial function, and blood biomarkers were measured for 3 h postintervention. Biomarkers included plasma nitrate/nitrite (NOx), glucose, insulin, cyclic GMP, interleukin 6, 3-nitrotyrosine, E- and P-selectins, intercellular adhesion molecule 3 (ICAM-3), and thrombomodulin, as well as superoxide in freshly isolated peripheral blood mononuclear cells (PBMCs). Inorganic nitrate supplementation did not affect plasma glucose (P = 0.18) or insulin (P = 0.26) responses. The increase in plasma NOx concentrations 3 h after the administration of inorganic nitrate was significantly higher in young than in old participants (234% increase compared with 149% increase, respectively, P < 0.001). Plasma 3-nitrotyrosine concentrations declined significantly after inorganic nitrate supplementation compared with placebo (3 h postdose, 46% decrease compared with 27% increase, respectively, P = 0.04), and a similar nonsignificant trend was observed for superoxide concentrations (3 h postdose, 16% decrease compared with 23% increase, respectively, P = 0.06). Plasma cyclic GMP, ICAM-3, and thrombomodulin concentrations differed between young and old

  17. Flagellar filament bio-templated inorganic oxide materials - towards an efficient lithium battery anode

    NASA Astrophysics Data System (ADS)

    Beznosov, Sergei N.; Veluri, Pavan S.; Pyatibratov, Mikhail G.; Chatterjee, Abhijit; Macfarlane, Douglas R.; Fedorov, Oleg V.; Mitra, Sagar

    2015-01-01

    Designing a new generation of energy-intensive and sustainable electrode materials for batteries to power a variety of applications is an imperative task. The use of biomaterials as a nanosized structural template for these materials has the potential to produce hitherto unachievable structures. In this report, we have used genetically modified flagellar filaments of the extremely halophilic archaea species Halobacterium salinarum to synthesize nanostructured iron oxide composites for use as a lithium-ion battery anode. The electrode demonstrated a superior electrochemical performance compared to existing literature results, with good capacity retention of 1032 mAh g-1 after 50 cycles and with high rate capability, delivering 770 mAh g-1 at 5 A g-1 (~5 C) discharge rate. This unique flagellar filament based template has the potential to provide access to other highly structured advanced energy materials in the future.

  18. Flagellar filament bio-templated inorganic oxide materials - towards an efficient lithium battery anode.

    PubMed

    Beznosov, Sergei N; Veluri, Pavan S; Pyatibratov, Mikhail G; Chatterjee, Abhijit; MacFarlane, Douglas R; Fedorov, Oleg V; Mitra, Sagar

    2015-01-13

    Designing a new generation of energy-intensive and sustainable electrode materials for batteries to power a variety of applications is an imperative task. The use of biomaterials as a nanosized structural template for these materials has the potential to produce hitherto unachievable structures. In this report, we have used genetically modified flagellar filaments of the extremely halophilic archaea species Halobacterium salinarum to synthesize nanostructured iron oxide composites for use as a lithium-ion battery anode. The electrode demonstrated a superior electrochemical performance compared to existing literature results, with good capacity retention of 1032 mAh g(-1) after 50 cycles and with high rate capability, delivering 770 mAh g(-1) at 5 A g(-1) (~5 C) discharge rate. This unique flagellar filament based template has the potential to provide access to other highly structured advanced energy materials in the future.

  19. Parameters of oxidative stress variation depending on the concentration of inorganic zinc compounds

    PubMed Central

    Grigorescu, R; Gruia, MI; Nacea, V; Nitu, C

    2015-01-01

    Zinc deficiency is a problem faced by a large number of people, a U.S. study showing that only 46% of the population aged over 71 years has the best amount of zinc in the body. Due to the very complex role of zinc deficiency in this trace, it can occur through a variety of symptoms affecting multiple body functions. Zinc was demonstrated to have the ability to neutralize free radicals protecting the body from the harmful effects of these effects, ultimately leading to atherosclerosis and cardiovascular disease derived from premature aging, the immune and immune disorders and increased risk of cancer. The purpose of the paper is to identify the role of antioxidant systems, with Zn2+ ions in the center of defense and decrease oxidative stress in dynamic interaction with malignant transformed cells. PMID:26664468

  20. Improvement of device performance by using zinc oxide in hybrid organic-inorganic solar cells

    NASA Astrophysics Data System (ADS)

    Hayakawa, Akinobu; Sagawa, Takashi

    2016-02-01

    Zinc oxide (ZnO) nanopowder was applied to hybrid solar cells in combination with poly(3-hexylthiophene). Stability tests of the hybrid solar cell with or without encapsulation with glass and UV cut-off films were performed under 1 sun at 63 °C at a relative humidity of 50%. It was found that the sealed cell showed worse device performance in terms of the loss of the open-circuit voltage (Voc), whereas the unsealed cell exposed to air retained an almost constant Voc for more than 3 d under dark and atmospheric conditions. Placement in O2 atmosphere in the dark led to the recovery of Voc. Cation (Sn4+) doping into ZnO was performed, and the loss of Voc was effectively suppressed through the restraint of the supply of the excited electron from the valence band to the conduction band.

  1. Flagellar filament bio-templated inorganic oxide materials – towards an efficient lithium battery anode

    PubMed Central

    Beznosov, Sergei N.; Veluri, Pavan S.; Pyatibratov, Mikhail G.; Chatterjee, Abhijit; MacFarlane, Douglas R.; Fedorov, Oleg V.; Mitra, Sagar

    2015-01-01

    Designing a new generation of energy-intensive and sustainable electrode materials for batteries to power a variety of applications is an imperative task. The use of biomaterials as a nanosized structural template for these materials has the potential to produce hitherto unachievable structures. In this report, we have used genetically modified flagellar filaments of the extremely halophilic archaea species Halobacterium salinarum to synthesize nanostructured iron oxide composites for use as a lithium-ion battery anode. The electrode demonstrated a superior electrochemical performance compared to existing literature results, with good capacity retention of 1032 mAh g−1 after 50 cycles and with high rate capability, delivering 770 mAh g−1 at 5 A g−1 (~5 C) discharge rate. This unique flagellar filament based template has the potential to provide access to other highly structured advanced energy materials in the future. PMID:25583370

  2. Catalysis of peptide formation by inorganic oxides: high efficiency of alumina under mild conditions on the Earth-like planets.

    PubMed

    Basiuk, V A; Sainz-Rojas, J

    2001-01-01

    Amino acid condensation catalyzed by inorganic oxides is a widely recognized way for prebiotic peptide formation. Silica and alumina are widely distributed in the Earth-like planets' crust as minerals of different complexity, and thus are attractive model catalysts for the studies of abiotic peptide synthesis. Experiments performed in other laboratories have shown that this process can be efficient at > 80 degrees C, which is not easy to find on the planetary surface in combination with sufficient concentrations of amino acids and necessary catalysts. In the present work we tested catalytic activity of three forms of alumina (which proved to be an efficient catalyst for this process) in the intermolecular condensation of L-alanine. We expanded the temperature interval down to 55 degrees C and used the simplest permanent heating procedure, without employing fluctuating drying/wetting conditions. The most important finding is that even under the lowest temperature considered (i.e. 55 degrees C), short peptide formation can be detected already after 10-30 days of heating. This fact implies that the abiotic peptide formation might occur in a wide variety of planetary environments, without need for high temperatures, given the presence of amino acid building blocks and alumina-containing minerals. c2001 COSPAR. Published by Elsevier Science Ltd. All rights reserved.

  3. Oxide Semiconductor-Based Flexible Organic/Inorganic Hybrid Thin-Film Transistors Fabricated on Polydimethylsiloxane Elastomer.

    PubMed

    Jung, Soon-Won; Choi, Jeong-Seon; Park, Jung Ho; Koo, Jae Bon; Park, Chan Woo; Na, Bock Soon; Oh, Ji-Young; Lim, Sang Chul; Lee, Sang Seok; Chu, Hye Yong

    2016-03-01

    We demonstrate flexible organic/inorganic hybrid thin-film transistors (TFTs) on a polydimethysilox- ane (PDMS) elastomer substrate. The active channel and gate insulator of the hybrid TFT are composed of In-Ga-Zn-O (IGZO) and blends of poly(vinylidene fluoride-trifluoroethylene) [P(VDF- TrFE)] with poly(methyl methacrylate) (PMMA), respectively. It has been confirmed that the fabri- cated TFT display excellent characteristics: the recorded field-effect mobility, sub-threshold voltage swing, and I(on)/I(off) ratio were approximately 0.35 cm2 V(-1) s(-1), 1.5 V/decade, and 10(4), respectively. These characteristics did not experience any degradation at a bending radius of 15 mm. These results correspond to the first demonstration of a hybrid-type TFT using an organic gate insulator/oxide semiconducting active channel structure fabricated on PDMS elastomer, and demonstrate the feasibility of a promising device in a flexible electronic system.

  4. Synthesis of hybrid inorganic/organic nitric oxide-releasing silica nanoparticles for biomedical applications

    NASA Astrophysics Data System (ADS)

    Carpenter, Alexis Wells

    Nitric oxide (NO) is an endogenously produced free radical involved in a number of physiological processes. Thus, much research has focused on developing scaffolds that store and deliver exogenous NO. Herein, the synthesis of N-diazeniumdiolate-modified silica nanoparticles of various physical and chemical properties for biomedical applications is presented. To further develop NO-releasing silica particles for antimicrobial applications, a reverse microemulsion synthesis was designed to achieve nanoparticles of distinct sizes and similar NO release characteristics. Decreasing scaffold size resulted in improved bactericidal activity against Pseudomonas aeruginosa. Confocal microscopy revealed that the improved efficacy resulted from faster particle-bacterium association kinetics. To broaden the therapeutic potential of NO-releasing silica particles, strategies to tune NO release characteristics were evaluated. Initially, surface hydrophobicity and NO release kinetics were tuned by grafting hydrocarbon- and fluorocarbon-based silanes onto the surface of N-diazeniumdiolate-modified particles. The addition of fluorocarbons resulted in a 10x increase in the NO release half-life. The addition of short-chained hydrocarbons to the particle surface increased their stability in hydrophobic electrospun polyurethanes. Although NO release kinetics were longer than that of unmodified particles, durations were still limited to <7 days. An alternative strategy for increasing NO release duration involved directly stabilizing the N-diazeniumdiolate using O2-protecting groups. O2-Methoxymethyl 1-(4-(3-(trimethoxysilyl)propyl))piperazin-1-yl)diazen-1-ium-1,2-diolate (MOM-Pip/NO) was grafted onto mesoporous silica nanoparticles to yield scaffolds with an NO payload of 2.5 μmol NO/mg and an NO release half-life of 23 d. Doping the MOM-Pip/NO-modified particles into resin composites yielded antibacterial NO-releasing dental restorative materials. A 3-log reduction in viable adhered

  5. Arsenic inorganic compounds cause oxidative stress mediated by the transcription factor PHO4 in Candida albicans.

    PubMed

    Urrialde, Verónica; Alburquerque, Begoña; Guirao-Abad, José Pedro; Pla, Jesús; Argüelles, Juan Carlos; Alonso-Monge, Rebeca

    2017-10-01

    Arsenic is a toxic metalloid widespread in nature. Recently, it has been demonstrated a main role of the transcription factor Pho4 in the acquisition of tolerance to arsenic-derived compounds, arsenite and arsenate in Candida albicans. Here, the effect of these compounds on this pathogenic yeast has been analyzed. In wild type cells, both arsenite and arsenate induced a marked increase in the endogenous production of Reactive Oxygen Species (ROS), together with the accumulation of intracellular trehalose and the activation of catalase, suggesting their role as generators of oxidative stress in this yeast. However, a pho4 null mutant showed a minor increase of intracellular ROS and a different kinetics of catalase activation upon exposure to arsenite and arsenate. Interestingly, the enzymatic activity of glutathione reductase and superoxide dismutase were exclusively triggered by arsenite but not by arsenate. pho4 mutant cells were also found to be sensitive to azide but significantly resistant to arsenate through a process dependent on an active electron transport chain and the alternative oxidase system. Therefore, arsenic-derived compounds induce a strong antioxidant response in C.albicans via different mechanisms. Copyright © 2017 Elsevier GmbH. All rights reserved.

  6. Inorganic oxides with potential application in the preparation of a (68)Ge/(68)Ga generator system.

    PubMed

    Romero, E; Morcillo, M A

    2017-01-01

    The ion exchange properties of some tin and titanium oxides with potential application in the development of a (68)Ge/(68)Ga generator were determined. The best potential candidates, SnO2 and calcined SnO2, were further characterized by powder X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area analysis and its radiation stability was also determined. Two (68)Ge/(68)Ga pilot generators (1.85MBq) based on SnO2 and calcined SnO2 were developed and evaluated over 100 and 200 elution cycles respectively, using as eluent different concentrations of HCl. The generator based on calcined SnO2 showed higher (68)Ga elution yield and lower (68)Ge content in the eluate (75-80% and <3×10(-3)% respectively, 1-2M HCl) than the generator based on unheated SnO2 (60-65% and <1×10(-1)% respectively, 1-2M HCl). Nano-crystalline calcined SnO2 proved to be a promising sorbent; therefore it should be considered as an attractive candidate to develop (68)Ge/(68)Ga generators to produce gallium-68 for biomedical purposes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Biosensor made with organic-inorganic hybrid composite: cellulose-tin oxide

    NASA Astrophysics Data System (ADS)

    Mahadeva, Suresha K.; Nayak, Jyoti; Kim, Jaehwan

    2011-04-01

    Cellulose is the most abundant polymer found in nature, inexhaustible, low cost, easy processing, renewable, biodegradable and biocompatible. SnO2, is a known electrical conductor that is optically transparent in the visible spectrum with a wide band gap at room temperature. Thus, a hybrid nanocomposite of cellulose and SnO2can offer a unique property of cellulose combined with electrical properties of SnO2. These unique properties of cellulose- SnO2 hybrid nanocomposite can be capitalized to design flexible, biodegradable and low cost biosensors. Preparation and characterization of cellulose-SnO2 hybrid nanocomposite and its application as a flexible urea biosensor was demonstrated in this paper. It is observed sensitivity of cellulose-SnO2 hybrid nanocomposite urea biosensor was increased linearly with deposition time. As deposition time increased, amount of tin oxide deposited over cellulose surface also increases, so as to increase the amount of enzyme immobilization and attachment of analyte, attributes to large current output and high sensitivity of sensor. Increasing enzyme activity is observed, with increasing urea concentration. Experimental results suggested that, the proposed biosensor under study is suitable for urea detection below 50 mM.

  8. Biosensor made with organic-inorganic hybrid composite: cellulose-tin oxide

    NASA Astrophysics Data System (ADS)

    K. Mahadeva, Suresha; Nayak, Jyoti; Kim, Jaehwan

    2011-03-01

    Cellulose is the most abundant polymer found in nature, inexhaustible, low cost, easy processing, renewable, biodegradable and biocompatible. SnO2, is a known electrical conductor that is optically transparent in the visible spectrum with a wide band gap at room temperature. Thus, a hybrid nanocomposite of cellulose and SnO2can offer a unique property of cellulose combined with electrical properties of SnO2. These unique properties of cellulose- SnO2 hybrid nanocomposite can be capitalized to design flexible, biodegradable and low cost biosensors. Preparation and characterization of cellulose-SnO2 hybrid nanocomposite and its application as a flexible urea biosensor was demonstrated in this paper. It is observed sensitivity of cellulose-SnO2 hybrid nanocomposite urea biosensor was increased linearly with deposition time. As deposition time increased, amount of tin oxide deposited over cellulose surface also increases, so as to increase the amount of enzyme immobilization and attachment of analyte, attributes to large current output and high sensitivity of sensor. Increasing enzyme activity is observed, with increasing urea concentration. Experimental results suggested that, the proposed biosensor under study is suitable for urea detection below 50 mM.

  9. [Relationship between Arsenic (+3 Oxidation State) Methyltransferase Genetic Polymorphisms and Methylation Capacity of Inorganic Arsenic].

    PubMed

    Agusa, Tetsuro; Kunito, Takashi; Minh Tue, Nguyen; Thi Mai Lan, Vi; Binh Minh, Tu; Thi Kim Trang, Pham; Fujihara, Junko; Takeshita, Haruo; Takahashi, Shin; Hung Viet, Pham; Tanabe, Shinsuke; Iwata, Hisato

    2015-01-01

    Arsenic metabolism affects the susceptibility of humans to arsenic toxicity; therefore, clarification of the factors associated with individual variations in arsenic metabolism is an important task. Genetic polymorphisms such as single nucleotide polymorphisms (SNPs) in arsenic (+3 oxidation state) methyltransferase (AS3MT), which can methylate arsenic compounds using S-adenosyl-l-methionine (AdoMet), have been reported to modify arsenic methylation. In this review, we summarize studies conducted by us in Vietnam and by others on the association of AS3MT genetic polymorphisms with arsenic metabolism as well as human health effects. Most of the SNPs in AS3MT showed inconsistent results in terms of genotype-dependent differences in arsenic metabolism among the studies. However, AS3MT 12390 (rs3740393) and 14458 (rs11191439) were consistently related to arsenic methylation regardless of the study population: AS3MT 12390 (rs3740393) affected the second step of methylation of arsenic, whereas 14458 (rs11191439) affected the first methylation step.

  10. Probing Electronic, Structural, and Charge Transfer Properties of Organic Semiconductor/Inorganic Oxide Interfaces Using Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Spalenka, Josef Wade

    Interfaces between organic semiconductors and inorganic oxides provide the functionality for devices including field-effect transistors (FETs) and organic photovoltaics. Organic FETs are sensitive to the physical structure and electronic properties of the few molecular layers of material at the interface between the semiconducting channel and the gate dielectric, and provide quantitative information such as the field-effect mobility of charge carriers and the concentration of trapped charge. In this thesis, FET interfaces between organic small-molecule semiconductors and SiO2, and donor/acceptor interfaces between organic small-molecules and the wide bandgap semiconductor ZnO are studied using electrical measurements of field-effect transistor devices. Monolayer-scale films of dihexyl sexithiophene are shown to have higher hole mobility than other monolayer organic semiconductors, and the origin of the high mobility is discussed. Studies of the crystal structure of the monolayer using X-ray structural probes and atomic force microscopy reveal the crystal structure is different in the monolayer regime compared to thicker films and bulk crystals. Progress and remaining challenges are discussed for in situ X-ray diffraction studies of the dynamic changes in the local crystal structure in organic monolayers due to charge carriers generated during the application of electric fields from the gate electrode in working FETs. Studies were conducted of light sensitive organic/inorganic interfaces that are modified with organic molecules grafted to the surface of ZnO nanoparticles and thin films. These interfaces are models for donor/acceptor interfaces in photovoltaics. The process of exciton dissociation at the donor/acceptor interface was sensitive to the insulating or semiconducting molecules grafted to the ZnO, and the photoinduced charge transfer process is measured by the threshold voltage shift of FETs during illumination. Charge transfer between light sensitive donor

  11. Mechanisms of inorganic nitrous oxide production in soils during nitrification and their dependence on soil properties

    NASA Astrophysics Data System (ADS)

    Heil, Jannis; Liu, Shurong; Vereecken, Harry; Brüggemann, Nicolas

    2014-05-01

    Nitrous oxide (N2O) is an important anthropogenic greenhouse gas and today's single most ozone depleting substance. Soils have been identified as the major source of N2O. Microbial nitrification and denitrification are considered the major N2O emission sources. However, N2O production in soils, especially during nitrification, is far from being completely understood. Several abiotic reactions involving the nitrification intermediate hydroxylamine (NH2OH) have been identified leading to N2O emissions, but are being neglected in most current studies. However, it is known that NH2OH can be oxidized by several soil constituents to form N2O. For better mitigation strategies it is mandatory to understand the underlying processes of N2O production during nitrification and their controlling factors. We studied N2O emissions from different soils in laboratory incubation experiments. Soils covered a wide range of land use types from arable to grassland and forest. Soil incubations were conducted with and without the addition of NH2OH at conditions favorable for nitrification with non-sterile as well as with sterile samples. N2O and, additionally, CO2 evolution were analyzed using gas chromatography. To get insight into the dynamics of N2O formation, N2O production from NH2OH was quantified online using quantum cascade laser absorption spectroscopy. Furthermore, isotope ratio mass spectrometry was used to analyze the isotopic signature of the produced N2O (i.e. δ15N, δ18O, and 15N site preference). We observed large differences in N2O emissions between different soils upon the addition of NH2OH. While a forest soil sample with pH < 3 showed hardly any reaction to the addition of NH2OH, a very high and immediate formation of N2O was observed in a cropland soil sample at neutral pH. N2O production after NH2OH addition was also observed in autoclaved samples, which confirmed an abiotic production mechanism. Further, isotopic signatures of N2O could be used to differentiate

  12. Hosts of hydrogen in ALH 84001: Evidence for hydrous martian salts in the oldest martian meteorite?

    NASA Astrophysics Data System (ADS)

    Eiler, John M.; Kitchen, Nami; Leshin, Lauri; Strausberg, Melissa

    2002-03-01

    The Martian meteorite, ALH84001, contains D-rich hydrogen of plausible Martian origin (Leshin et al. 1996). The phase identity of the host(s) of this hydrogen are not well known and could include organic matter (McKay et al., 1996), phlogopite (Brearley 2000), glass (Mittlefehldt 1994) and/or other, unidentified components of this rock. Previous ion microprobe studies indicate that much of the hydrogen in ALH84001 as texturally associated with concretions of nominally anhydrous carbonates, glass and oxides (Boctor et al., 1998; Sugiura and Hoshino, 2000). We examined the physical and chemical properties of the host(s) of this hydrogen by stepped pyrolysis of variously pre-treated sub-samples. A continuous-flow method of water reduction and mass spectrometry (Eiler and Kitchen 2001) was used to permit detailed study of the small amounts of this hydrogen-poor sample available for study. We find that the host(s) of D-rich hydrogen released from ALH84001 at relatively low temperatures (~500 deg C) is soluble in orthophosphoric and dilute hydrochloric acids and undergoes near-complete isotopic exchange with water within hours at temperatures of 200 to 300 deg C. These characteristics are most consistent with the carrier phase(s) being a hydrous salt (e.g., carbonate, sulfate or halide); the thermal stability of this material is inconsistent with many examples of such minerals (e.g., gypsum) and instead suggests one or more relatively refractory hydrous carbonates (e.g., hydromagnesite). Hydrous salts (particularly hydrous carbonates) are common on the earth only in evaporite, sabkha, and hydrocryogenic-weathering environments; we suggest that much (if not all) of the 'Martian' hydrogen in ALH84001 was introduced in analogous environments on or near the martian surface rather than through biological activity or hydrothermal alteration of silicates in the crust.

  13. Decompression-Induced Crystallization of Hydrous Basalt

    NASA Astrophysics Data System (ADS)

    Teasdale, R.; Brooker, R. A.

    2014-12-01

    Decompression-induced crystallization of hydrous basalt during magma ascent from 1.5 kb (150 MPa) is quantified using isothermal decompression TZM experiments. The starting composition is a synthetic glass based on the 1921 Kilauea basalt, with 1% H2O added. In all cases, the liquidus phase is aluminous spinel, followed by clinopyroxene, then plagioclase. The plagioclase liquidus temperatures for isobaric (equilibrium) experiments range from 1175°C (at 1.5 kb) to 1217°C (at 200b), which are 35-75°C hotter than predicted by MELTS (Ghiorso & Sack 1995). Experiments were decompressed at 1kb/hr and quenched at 800, 400, 200, or 100b for three temperatures (1160°, 1150°, and 1140°C). Plagioclase crystals formed during decompression have long axes that range from less than 1 micron to 20 microns. Increasing decompression yields larger plagioclase crystal sizes and aspect ratios for experiments at equal temperatures. However, the number of crystals does not vary systematically, indicating that crystallization is dominated by growth rather than nucleation during decompression. Plagioclase compositions for experiments were measured with University of Bristol's Electron Microprobe and the Hyperprobe with Field Emission Gun. Plagioclase compositions from equilibrium experiments (An60-An80) span the range of those from decompression experiments (An60-An73). Equilibrium experiments generated higher An compositions at lower pressures (500b) than at higher pressure (1.5kb) but do not systematically vary with temperature. Variations in plagioclase compositions are minimal above H2O saturation (100-200°C, based on Papale et al., 2006). Below H2O saturation, An content decreases slightly, by approximately 4% An. One application of this work is better characterization of groundmass crystallization in hydrous basalt as it traverses the conduit during eruption. This work also provides a means of distinguishing groundmass plagioclase related to decompression from crystals

  14. Inorganic mercury causes pancreatic beta-cell death via the oxidative stress-induced apoptotic and necrotic pathways

    SciTech Connect

    Chen Yawen; Huang Chunfa; Yang Chingyao; Yen Chengchieh; Tsai Kehsung; Liu Shinghwa

    2010-03-15

    Mercury is a well-known highly toxic metal. In this study, we characterize and investigate the cytotoxicity and its possible mechanisms of inorganic mercury in pancreatic beta-cells. Mercury chloride (HgCl{sub 2}) dose-dependently decreased the function of insulin secretion and cell viability in pancreatic beta-cell-derived HIT-T15 cells and isolated mouse pancreatic islets. HgCl{sub 2} significantly increased ROS formation in HIT-T15 cells. Antioxidant N-acetylcysteine effectively reversed HgCl{sub 2}-induced insulin secretion dysfunction in HIT-T15 cells and isolated mouse pancreatic islets. Moreover, HgCl{sub 2} increased sub-G1 hypodiploids and annexin-V binding in HIT-T15 cells, indicating that HgCl{sub 2} possessed ability in apoptosis induction. HgCl{sub 2} also displayed several features of mitochondria-dependent apoptotic signals including disruption of the mitochondrial membrane potential, increase of mitochondrial cytochrome c release and activations of poly (ADP-ribose) polymerase (PARP) and caspase 3. Exposure of HIT-T15 cells to HgCl{sub 2} could significantly increase both apoptotic and necrotic cell populations by acridine orange/ethidium bromide dual staining. Meanwhile, HgCl{sub 2} could also trigger the depletion of intracellular ATP levels and increase the LDH release from HIT-T15 cells. These HgCl{sub 2}-induced cell death-related signals could be significantly reversed by N-acetylcysteine. The intracellular mercury levels were markedly elevated in HgCl{sub 2}-treated HIT-T15 cells. Taken together, these results suggest that HgCl{sub 2}-induced oxidative stress causes pancreatic beta-cell dysfunction and cytotoxicity involved the co-existence of apoptotic and necrotic cell death.

  15. Oxidative stress and genotoxicity of an organic and an inorganic nanomaterial to Eisenia andrei: SDS/DDAB nano-vesicles and titanium silicon oxide.

    PubMed

    Correia, Bruno; Lourenço, Joana; Marques, Sérgio; Nogueira, Verónica; Gavina, Ana; da Graça Rasteiro, Maria; Antunes, Filipe; Mendo, Sónia; Pereira, Ruth

    2017-06-01

    In the past few years the number of studies on the toxic effects of nanomaterials (NMs) in the environment increased significantly. Nonetheless, the data is still scarce, since there is a large number of NMs and new ones are being developed each day. Soils are extremely important for life, and are easily exposed to the released NMs, thus enhanced efforts are needed to study the impacts on soil biota. The objective of the present work was to determine if different concentrations of two NMs, one inorganic (TiSiO4) and other organic (nano-vesicles of sodium sodecyl sulfate/ didodecyl dimethylammonium bromide - SDS/DDAB), are genotoxic to soil invertebrates. Additionally, it was intended to understand whether, in the event of occurring, genotoxicity was caused by the incapability of the cells to deal with the oxidative stress caused by these NMs. With that purpose, Eisenia andrei were exposed for 30 days to the artificial OECD soil contaminated with different concentrations of the NMs being tested. After the exposure, coelomocytes were extracted from earthworms and DNA damage was measured by the comet assay. The activity of antioxidant enzymes (e.g. glutathione peroxidase, glutathione reductase and glutathione-S-Transferase) and lipid peroxidation were also assessed. The results showed that both NMs were genotoxic, particularly TiSiO4 for which significant DNA damages were recorded for concentrations above 444mg of TiSiO4-NM/kg of soildw. Since no statistically significant differences were found in the tested antioxidant enzymes and in lipid peroxidation, the mechanism of genotoxicity of these NMs seemed to be unrelated with oxidative stress. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. 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

    NASA Astrophysics Data System (ADS)

    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 (<5%), fresh, glassy obsidian samples with their post-eruptive (post-degassing) Fe2+ concentrations. Near-liquidus co-precipitation of two Fe-Ti oxides allows the pre-eruptive oxygen fugacity and temperature to be calculated in each rhyolite using the oxygen barometer and thermometer of Ghiorso and Evans (2008). Temperatures range from 793 (± 19) to 939 (± 15) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.4 to +1.4. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1991), which relates melt composition (not

  17. A note on the effects of inorganic seed aerosol on the oxidation state of secondary organic aerosol—α-Pinene ozonolysis

    NASA Astrophysics Data System (ADS)

    Huang, Dan Dan; Zhang, Xuan; Dalleska, Nathan F.; Lignell, Hanna; Coggon, Matthew M.; Chan, Chi-Ming; Flagan, Richard C.; Seinfeld, John H.; Chan, Chak K.

    2016-10-01

    We compare the oxidation state and molecular composition of α-pinene-derived secondary organic aerosol (SOA) by varying the types and surface areas of inorganic seed aerosol that are used to promote the condensation of SOA-forming vapors. The oxidation state of α-pinene SOA is found to increase with inorganic seed surface area, likely a result of enhanced condensation of low-volatility organic compounds on particles versus deposition on the chamber wall. α-Pinene SOA is more highly oxygenated in the presence of sodium nitrate (SN) seed than ammonium sulfate seed. The relative abundance of semivolatile monomers and low-volatility dimer components that account for more than half of α-pinene SOA mass is not significantly affected by the composition of seed aerosol. Enhanced uptake of highly oxidized small carboxylic acids onto SN seed particles is observed, which could potentially explain the observed higher SOA oxidation state in the presence of SN seed aerosol. Overall, our results demonstrate that a combined effect of seed aerosol composition and surface area leads to an increase in the O:C atomic ratio of α-pinene SOA by as much as a factor of 2.

  18. Inorganic Halogen Oxidizers

    DTIC Science & Technology

    evaluate both fluorination and oxygenation of substrates such as ClF3, Cl2O, and ClO2 . The reaction of solid FNO with excited fluorine was demonstrated at...196 C with the production of NF3O. Similar procedures were used in reacting Cl2O and ClO2 with F2.

  19. Inorganic Halogen Oxidizer Research.

    DTIC Science & Technology

    1980-03-17

    0 4.. *~~ 0 0 4 S a, 0 .- F_ I . 0 - n V t o C N 0 .0 C; 0 . 𔃺~~ V Oh Ix ca . VW W i-si I. 0 (0 UU Clo~~~*N 0 ( l 00 *Lf) 0 j ,) Z, U__ - (00 C6 0...Solubility products fora metathesis in iii [41: CS NiF + 2NF SbF F 2 CsShF 4 +(N i 2 6 𔃾 6 _ 780 6 (N 4)2 ; 6 R ( R8-1 3 H-owever, in cases where the

  20. Inorganic Halogen Oxidizer Research

    DTIC Science & Technology

    1979-02-16

    Christe, Inorg. Chem., 11, 1220 (1972). 22. "Iodine Trisperchlorate and Cesium Tetraperchlorato Iodate (III)," by K. 0. Christe and C. J. Schack...Applied Chemistry, Proceedings of XXIV Internat. Congress, 4, •S (1974). 40. " Cesium Bis(perchlorato)bromat, (I), Cs+ [Br(OCl0 3) 2 ] ," by K. 0...RocKxITDYxN , A DiVISION OF NOaRTH AxzRICAN ROcKWRLL, CANOGA PARK, CALUPORNLA 913M0 Iodine Tris(perchlorate) and Cesium Tetrakis(perchlorato)iodate(III) By

  1. Inorganic Halogen Oxidizer Research.

    DTIC Science & Technology

    1978-01-25

    fluoroborates in HF at -78’ Systena Composition of Product (weight %) NF 4BF 4 NF4XF 6 MXF 6 LiBF4 - NF4SbF6 81.7 8.4 9.9 LiRF 4 - NF4 BiF 6 86.7 5.9...all runs, except for the LiBF4 - NF4BiF 6 system, where approximately stoichiometric amounts of starting materials were used. expected, the...of Table III) the results obtained for the LiBF 4 - NF4SbF6 and the LiBF4 - NF4BiF 6 system are roughly comparable. RI/RD78-125 C-11 Oxonium

  2. Inorganic Halogen Oxidizer Research.

    DTIC Science & Technology

    1977-02-04

    Bougon, T. Bui Hluy, A. Cadet, P. Charpin, and R. Rousson, Inorg. Chem., 13, 690 (1974). 13. G. M. Begun and A. C. Rutenberg, Inorg. Chem., 6, 2212...Rocketdyne was inan- acta. 4A, 1795 (1968 . % cialy suppoted by the Odbce of Naval Research, Power [10] E.C. CumiSpectrochm Acaa,27A, *9n9(1971). Branch. Ti

  3. The formation and chemistry of low degree hydrous partial melt on top of the transition zone

    NASA Astrophysics Data System (ADS)

    Frost, Daniel J.; Mookherjee, Mainak

    2010-05-01

    There is some geophysical evidence for the presence of silicate melt on top of the 410 km seismic discontinuity. It has also been argued that the difference in the water storage capacity of upper mantle versus transition zone minerals may cause dehydration melting as material up-wells across the 410. Studies have proposed that hydrous partial melts may be neutrally buoyant in the mantle at these conditions. In order to assess these possibilities it is important to determine the likely composition of small degree hydrous melts at these conditions and to measure the H2O contents of mantle minerals coexisting with this melt phase. The composition of a hydrous melt in equilibrium with a mantle peridotite composition has been determined at conditions of the 410 and 1450°C. Sandwich experiments were performed where an 'initial-guess' hydrous melt composition was equilibrated with 50% anhydrous peridotite. The resulting melt composition was used to assemble a further melt, which was then equilibrated in the same way. After several iterations it was possible to derive a melt composition, which was in equilibrium with a mineral assemblage identical to that observed for an anhydrous peridotite composition at the same conditions. We assess whether this melt composition could be neutrally buoyant at 410km. The 410 km discontinuity may also correspond to a transition in redox state in the mantle from a reducing transition zone to a less reduced upper mantle. Volatiles may also collect and induce melting at this horizon due to the oxidation of a rising mobile reduced fluid phase containing CH4. Minerals in mantle upwelling out of a hydrous melt layer would be expected to have H2O contents close to saturation; however, this may not be the case if the melt layer also contains other volatile components such as CO2 or CH4, which further lower the H2O activity in the melt. We assess ranges of melt compositions that may be in equilibrium with minerals containing relatively low H2O

  4. Size-controlled synthesis and formation mechanism of manganese oxide OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids

    NASA Astrophysics Data System (ADS)

    Zhang, Qin; Cheng, Xiaodi; Qiu, Guohong; Liu, Fan; Feng, Xionghan

    2016-05-01

    This study presents a simplified approach for size-controlled synthesis of manganese oxide octahedral molecular sieve (OMS-2) nanowires using potassium permanganate (KMnO4) and different inorganic acids (HCl, HNO3, and H2SO4) under reflux conditions. The morphology and nanostructure of the synthesized products are characterized by X-ray diffraction, Ar adsorption, and electron microscopy analysis, in order to elucidate the controlling effects of acid concentration and type as well as the formation mechanism of OMS-2 nanowires. The concentration of inorganic acid is a crucial factor controlling the phase of the synthesized products. OMS-2 nanowires are obtained with HCl at the concentration ≥0.96 mol/L or with HNO3 and H2SO4 at the concentrations ≥0.72 mol/L. Differently, the type of inorganic acid effectively determines the particle size of OMS-2 nanowires. When the acid is changed from HCl to HNO3 and H2SO4 in the reflux system, the average length of OMS-2 declines significantly by 60-70% (1104-442 and 339 nm), with minor decreased in the average width (43-39 and 34 nm). The formation of OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids involves a two-step process, i.e., the initial formation of layered manganese oxides, and subsequent transformation to OMS-2 via a dissolution-recrystallization process under acidic conditions. The proposed reflux route provides an alternative approach for synthesizing OMS-2 nanowires as well as other porous nano-crystalline OMS materials.

  5. High Pressure Crystal Chemistry of Hydrous Ringwoodite

    NASA Astrophysics Data System (ADS)

    Holl, C. M.; Smyth, J. R.; Frost, D. J.; Jacobsen, S. D.

    2002-12-01

    Single crystals of hydrous Fo90 ringwoodite up to 800 μm in diameter have been synthesized in a multi-anvil press at 1400°C and 20 GPa. The crystals are deep blue in color and contain approximately 0.8 percent H2O by weight as measured by IR spectroscopy. The unit cell parameter of this material has been refined by single-crystal X-ray diffraction at 15 different pressures up to 3.8 GPa. Pressure was determined by refinement of the until cell volume of a standard quartz crystal. Preliminary values for the bulk modulus give a K0 = 172 +/- 9 GPa and K' = 5.1 +/- 1.6 over the range studied. The crystal structure of this material has been refined at six pressures up to 3.8 GPa. Refinements were obtained from an average of 13 unique data with values of Rf < 5%. Preliminary estimates of the polyhedral compressibilities are 1.0x10-2 GPa-1 (K = 100 GPa) for MgVI and 6.3x10-3 GPa-1 (K = 160 GPa) for SiIV. Comparison of the present data with previous results shows a systematic decrease in the bulk modulus of ringwoodite with H content. This decrease is larger than the effect of temperature within the allowable ranges of each so that an increase in H2O content of one percent would have an effect on the bulk modulus equivalent to raising the temperature by 500°C.

  6. A note on the effects of inorganic seed aerosol on the oxidation state of secondary organic aerosol — α-pinene ozonolysis

    NASA Astrophysics Data System (ADS)

    Huang, D.; Zhang, X.; Dalleska, N. F.; Lignell, H.; Coggon, M.; Chan, C. M.; Flagan, R. C.; Seinfeld, J.; Chan, C. K.

    2016-12-01

    We compare the molecular composition, oxidation state and aging of SOA from α-pinene ozonolysis in the presence of ammonium sulfate (AS) or sodium nitrate (SN) seed particles at a range of initial seed surface areas. The oxidation state () of α-pinene SOA is found to increase with inorganic seed surface area, likely a result of enhanced condensation of extremely low volatility organic compounds (ELVOCs) versus wall deposition. α-pinene SOA is more oxygenated in the presence of SN seed ( -0.32 - 0.13) than AS seed ( -0.53 - -0.33). Positive suggests the possible presence of highly oxygenated small acids in SOA, such as acetic acid, as detected in off-line samples. In small acid uptake experiments, SN particles exhibited a larger uptake than AS particles. Our study suggests that nitrate-containing salts can potentially promote SOA aging and increase SOA oxidation state by retaining highly oxygenated small acids.

  7. Characteristics of oxidative homolytic alkylation of imidazoles and organic-inorganic hybrid extended networks from large aromatic building blocks

    NASA Astrophysics Data System (ADS)

    Li, Kunhao

    The discovery of the dramatic in vitro antimalarial activity of 2-iodo-L-histidine and 2-fluoro-L-histidine, as well as their in vivo limitations, has prompted a systematic search for novel 2-substituted imidazoles and bioimidazoles as agents against human malaria. Previous research has shown that the regioselective alkyl free radical substitution on imidazoles and bioimidazoles could serve as a simple and efficient route to a wide variety of 2-alkylimidazoles. In this research, this methodology was successfully extended to include alkyl radicals substituted with various functional groups such as amide or ester. While this novel methodology should be of some synthetic utility when tertiary radicals are used, poorer yields are usually encountered in the cases of primary radicals. In the second part of this dissertation, a series of novel ligands containing multiple ortho-bis(organothio) groups were synthesized and their coordination and network forming properties were studied in the context of crystalline organic-inorganic hybrid extended networks. For the syntheses of HRTTs [2,3,6,7,10,11-hexakis(alkylthio)triphenylenes], a simpler, safer and higher yielding one-pot process was developed. Quenching the hexa-anions (formed when sodium methylthiolate was refluxed with hexabromotriphenylene) with alkyl halides or acid chlorides afforded HRTTs. This newly developed process was also successfully expanded to the pyrene system. In the syntheses of unsymmetrically substituted triphenlyenes, it was shown for the first time that the oxidative cyclization process is applicable to thioether containing systems, pointing to a novel strategy for the preparation of this type of unsymmetrically substituted triphenlyenes. Treating these novel ligands with various metal salts [i.e. bismuth(III) chloride and bismuth(III) bromide] under carefully controlled conditions resulted in a series of air-stable semiconductive coordination networks. Their single crystal structures were

  8. Elasticity of Hydrous Phases in Subduction Zones- Geophysical Implications

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Mainprice, D.

    2014-12-01

    Globally, subduction zones are region associated with earthquakes and volcanic activities, both involving risk to local populations. These processes are intimately related to the thermodynamic stability and instabilty of hydrous phases that are subducted with the down going slab. These phases sequestrate several wt % of water in their crystallographic structure and can account for significant proportion of the hydrogen budget of the upper mantle , transition zone and perhaps the top of the lower mantle. In order to quantify the degree of mantle hydration, we need to have a good understanding of the elastic properties of layered hydrous phases, the effects of temperature, and pressure and relate them to seismological observables, such as the velocity and its anisotropy. Using first principle simulations, we have investigated several layered hydrous phases, including the important minerals antigorite, talc, and chlorite. These results are complementary to the recent experimental Brillouin Scattering results at ambient conditions. Based on the full elastic constant tensor we note that these hydrous phases have significant shear wave anisotropy and often have unusual pressure dependence of the anisotropy. Together with elasticity data, thermodynamic predictions of phase stability and experimental plastic deformation studies it is apparent that these layered hydrous phases could account for the large delay times observed in certain subduction zone settings, such as Ryukyu trench. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477). MM acknowledges computing resources (request # EAR130015) from the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number OCI-1053575.

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

    NASA Astrophysics Data System (ADS)

    Panić, V. V.; Dekanski, A. B.; Stevanović, R. M.

    Hydrous ruthenium oxide/carbon black nanocomposites were prepared by impregnation of the carbon blacks by differently aged inorganic RuO 2 sols, i.e. of different particle size. Commercial Black Pearls 2000 ® (BP) and Vulcan ® XC-72 R (XC) carbon blacks were used. Capacitive properties of BP/RuO 2 and XC/RuO 2 composites were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in H 2SO 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.

  10. Crystallization Response of Hydrous Granitic Liquids

    NASA Astrophysics Data System (ADS)

    London, D.; Morgan, G. B.; Evensen, J. M.

    2006-05-01

    Preconditioning of hydrous haplogranite liquid (200 MPa eutectic composition Ab38Or28Qz34) at 100° C above the liquidus temperature for 72 hr is sufficient to eliminate any vestiges of the initial structural states of vitreous or crystalline starting materials. Experimental crystallization of this composition in the presence of aqueous vapor begins by nucleation in the vapor space, following which crystal growth advances into supercooled melt. The minimum in nucleation delay (~ 200 hrs) and maximum in nucleation density and growth rate occur at liquidus undercooling (ΔT) of 200° C. Crystallization does not exceed 10% in experiments up to 600 hrs at any value of ΔT, and no crystallization occurs within 50° C of the liquidus up to 700 hrs. Though the melt composition is invariant (eutectic), and no compositional gradients are discernable by EMPA in quenched glasses, the crystallization response is sequential: at ΔT = 200° C, coarsely skeletal K-feldspar nucleates and grows first, followed by graphic to spherulitic quartz-sodic alkali feldspar intergrowths, and lastly in some experiments, monophase quartz blebs. Once formed, crystals or clusters tend not to grow larger, but rather, new centers of nucleation and growth appear. The result is a sequential history of uniform crystal texture (size and habit). At comparable ΔT, the nucleation delay decreases as the bulk composition is displaced (by choosing a composition) farther from the eutectic. At comparable ΔT, fluxes (P, F) serve to increase the nucleation delay and decrease the nucleation density but do not notably change either growth rates or crystal habits. Diffusion of alkalis through melt is rapid, such that any gradients in alkalis that should result from non-eutectic crystallization are erased in minutes or hours over distances of 5 mm and down to ΔT = 350° C, in the field of glass. These relations of undercooling (ΔT) to time (t) apply only to H2O-oversaturated systems. We do not have data for the

  11. Creation of giant two-dimensional crystal of zinc oxide nanodisk by method of single-particle layer of organo-modified inorganic fine particles.

    PubMed

    Meng, Qi; Honda, Nanami; Uchida, Saki; Hashimoto, Kazuaki; Shibata, Hirobumi; Fujimori, Atsuhiro

    2015-09-01

    In this study, the formation and structure of a single-particle layer of organo-zinc oxide are investigated using surface-pressure-area (π-A) isotherms, out-of-plane X-ray diffraction (XRD) analysis, and atomic force microscopy (AFM). Further, techniques for achieving the solubilization of inorganic fine particles in general solvents have been proposed, and a single-particle layer has been formed using such an inorganic solution as a "spreading solution" for an interfacial film. Surface modification of ZnO is performed using a long-chain carboxylic acid. Accordingly, a regular arrangement of ZnO can be easily achieved in order to overcome the relatively weak van der Walls interactions between inorganic materials. A condensed Langmuir monolayer of these particles is also formed. A multiparticle layered structure is constructed by the Langmuir-Blodgett (LB) technique. Out-of-plane XRD measurement results for a single-particle layer of organo-ZnO clearly show a sharp peak at 42 Å. This peak is attributed to the distance between ZnO layers. The AFM image of this single-particle layer of organo-ZnO shows a particle assembly with a uniform height of 60 nm. These aggregated particles form large two-dimensional crystals. In other words, a regular periodic structure along the c-axis and a condensed single-particle layer had been fabricated using Langmuir and LB techniques.

  12. Bioinspired heme, heme/nonheme diiron, heme/copper, and inorganic NOx chemistry: *NO((g)) oxidation, peroxynitrite-metal chemistry, and *NO((g)) reductive coupling.

    PubMed

    Schopfer, Mark P; Wang, Jun; Karlin, Kenneth D

    2010-07-19

    The focus of this Forum Article highlights work from our own laboratories and those of others in the area of biochemical and biologically inspired inorganic chemistry dealing with nitric oxide [nitrogen monoxide, *NO((g))] and its biological roles and reactions. The latter focus is on (i) oxidation of *NO((g)) to nitrate by nitric oxide dioxygenases (NODs) and (ii) reductive coupling of two molecules of *NO((g)) to give N(2)O(g). In the former case, NODs are described, and the highlighting of possible peroxynitrite/heme intermediates and the consequences of this are given by a discussion of recent works with myoglobin and a synthetic heme model system for NOD action. Summaries of recent copper complex chemistries with *NO((g)) and O(2)(g), leading to peroxynitrite species, are given. The coverage of biological reductive coupling of *NO((g)) deals with bacterial nitric oxide reductases (NORs) with heme/nonheme diiron active sites and on heme/copper oxidases such as cytochrome c oxidase, which can mediate the same chemistry. Recently designed protein and synthetic model compounds (heme/nonheme/diiron or heme/copper) as functional mimics are discussed in some detail. We also highlight examples from the chemical literature, not necessarily involving biologically relevant metal ions, that describe the oxidation of *NO((g)) to nitrate (or nitrite) and possible peroxynitrite intermediates or reductive coupling of *NO((g)) to give nitrous oxide.

  13. Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

    PubMed

    Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

    2017-08-21

    Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH4 )n [MMo6 O18 (OH)6 ] (M=Cu(2+) ; Fe(3+) ; Co(3+) ; Ni(2+) ; Zn(2+) , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo(VI) centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Introduction to Homogenous Catalysis with Ruthenium-Catalyzed Oxidation of Alcohols: An Experiment for Undergraduate Advanced Inorganic Chemistry Students

    ERIC Educational Resources Information Center

    Miecznikowski, John R.; Caradonna, John P.; Foley, Kathleen M.; Kwiecien, Daniel J.; Lisi, George P.; Martinez, Anthony M.

    2011-01-01

    A three-week laboratory experiment, which introduces students in an advanced inorganic chemistry course to air-sensitive chemistry and catalysis, is described. During the first week, the students synthesize RuCl[subscript 2](PPh[subscript 3])[subscript 3]. During the second and third weeks, the students characterize the formed coordination…

  15. Introduction to Homogenous Catalysis with Ruthenium-Catalyzed Oxidation of Alcohols: An Experiment for Undergraduate Advanced Inorganic Chemistry Students

    ERIC Educational Resources Information Center

    Miecznikowski, John R.; Caradonna, John P.; Foley, Kathleen M.; Kwiecien, Daniel J.; Lisi, George P.; Martinez, Anthony M.

    2011-01-01

    A three-week laboratory experiment, which introduces students in an advanced inorganic chemistry course to air-sensitive chemistry and catalysis, is described. During the first week, the students synthesize RuCl[subscript 2](PPh[subscript 3])[subscript 3]. During the second and third weeks, the students characterize the formed coordination…

  16. Role of inorganic nitrate and nitrite in driving nitric oxide-cGMP-mediated inhibition of platelet aggregation in vitro and in vivo.

    PubMed

    Apostoli, G L; Solomon, A; Smallwood, M J; Winyard, P G; Emerson, M

    2014-11-01

    Nitric oxide (NO) is a critical negative regulator of platelets that is implicated in the pathology of thrombotic diseases. Platelets generate NO, but the presence and functional significance of NO synthase (NOS) in platelets is unclear. Inorganic nitrate/nitrite is increasingly being recognized as a source of bioactive NO, although its role in modulating platelets during health and vascular dysfunction is incompletely understood. We investigated the functional significance and upstream sources of NO-cGMP signaling events in platelets by using established methods for assessing in vitro and in vivo platelet aggregation, and assessed the bioconversion of inorganic nitrate to nitrite during deficiency of endothelial NOS (eNOS). The phosphodiesterase 5 (PDE5) inhibitor sildenafil inhibited human platelet aggregation in vitro. This inhibitory effect was abolished by a guanylyl cyclase inhibitor and NO scavengers, but unaffected by NOS inhibition. Inorganic nitrite drove cGMP-mediated inhibition of human platelet aggregation in vitro and nitrate inhibited platelet function in eNOS(-/-) mice in vivo in a model of thromboembolic radiolabeled platelet aggregation associated with an enhanced plasma nitrite concentration as compared with wild-type mice. Platelets generate transient, endogenous cGMP signals downstream of NO that are primarily independent of NOS and may be enhanced by inhibition of PDE5. Furthermore, nitrite can generate transient NO-cGMP signals in platelets. The absence of eNOS leads to enhanced plasma nitrite levels following nitrate administration in vivo, which negatively impacts on platelet function. Our data suggest that inorganic nitrate exerts an antiplatelet effect during eNOS deficiency, and, potentially, that dietary nitrate may reduce platelet hyperactivity during endothelial dysfunction. © 2014 International Society on Thrombosis and Haemostasis.

  17. A systematic study of transfection efficiency and cytotoxicity in HeLa cells using iron oxide nanoparticles prepared with organic and inorganic bases.

    PubMed

    Calmon, Marilia Freitas; de Souza, Aryane Tofanello; Candido, Natalia Maria; Raposo, Maria Irene Bartolomeu; Taboga, Sebastião; Rahal, Paula; Nery, Jose G

    2012-12-01

    Magnetic iron oxide nanoparticles (magnetite) (MNPs) were prepared using different organic and inorganic bases. Strong inorganic base (KOH) and organic bases (NH(4)OH and 1,4-diazabicyclo[2.2.2]octane (DABCO)) were used in the syntheses of the MNPs. The MNPs were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR) and magnetization measurements. MNPs prepared with strong inorganic base yielded an average size of 100 nm, whereas the average size of the MNPs prepared with the organic bases was 150 nm. The main competitive phase for MNPs prepared with the strong inorganic and organic bases was maghemite; however, syntheses with KOH yielded a pure magnetite phase. The transfection study performed with the MNPs revealed that the highest transfection rate was obtained with the MNPs prepared with KOH (74%). The correlation between the magnetic parameters and the transfection ratio without transfection agents indicated that MNPs prepared with KOH were a better vector for possible applications of these MNPs in biomedicine. HeLa cells incubated with MNP-KOH at 10 μg/mL for 24 and 48 h exhibited a decrease in population in comparison with the control cells and it was presumably related to the toxicity of the MNPs. However, the cells incubated with MNP-KOH at 50 and 100 μg/mL presented a very small difference in the viability between the cell populations studied at 24 and 48 h. These data illustrate the viability of HeLa cells treated with MNP-KOH and suggest the potential use of these MNPs in biomedical applications. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Steady-State Growth under Inorganic Carbon Limitation Conditions Increases Energy Consumption for Maintenance and Enhances Nitrous Oxide Production in Nitrosomonas europaea

    PubMed Central

    Giguere, Andrew; Chaplen, Frank; Bottomley, Peter J.

    2016-01-01

    ABSTRACT Nitrosomonas europaea is a chemolithoautotrophic bacterium that oxidizes ammonia (NH3) to obtain energy for growth on carbon dioxide (CO2) and can also produce nitrous oxide (N2O), a greenhouse gas. We interrogated the growth, physiological, and transcriptome responses of N. europaea to conditions of replete (>5.2 mM) and limited inorganic carbon (IC) provided by either 1.0 mM or 0.2 mM sodium carbonate (Na2CO3) supplemented with atmospheric CO2. IC-limited cultures oxidized 25 to 58% of available NH3 to nitrite, depending on the dilution rate and Na2CO3 concentration. IC limitation resulted in a 2.3-fold increase in cellular maintenance energy requirements compared to those for NH3-limited cultures. Rates of N2O production increased 2.5- and 6.3-fold under the two IC-limited conditions, increasing the percentage of oxidized NH3-N that was transformed to N2O-N from 0.5% (replete) up to 4.4% (0.2 mM Na2CO3). Transcriptome analysis showed differential expression (P ≤ 0.05) of 488 genes (20% of inventory) between replete and IC-limited conditions, but few differences were detected between the two IC-limiting treatments. IC-limited conditions resulted in a decreased expression of ammonium/ammonia transporter and ammonia monooxygenase subunits and increased the expression of genes involved in C1 metabolism, including the genes for RuBisCO (cbb gene cluster), carbonic anhydrase, folate-linked metabolism of C1 moieties, and putative C salvage due to oxygenase activity of RuBisCO. Increased expression of nitrite reductase (gene cluster NE0924 to NE0927) correlated with increased production of N2O. Together, these data suggest that N. europaea adapts physiologically during IC-limited steady-state growth, which leads to the uncoupling of NH3 oxidation from growth and increased N2O production. IMPORTANCE Nitrification, the aerobic oxidation of ammonia to nitrate via nitrite, is an important process in the global nitrogen cycle. This process is generally dependent

  19. Hydrous silica coatings: occurrence, speciation of metals, and environmental significance.

    PubMed

    Schindler, Michael; Durocher, Jennifer L; Abdu, Yassir; Hawthorne, Frank C

    2009-12-01

    Si-enriched coatings form on the surface of silicate minerals under acidic conditions. Although they are often only a few nanometers thick, their large specific surface area may control the interaction between silicate minerals in acidic soils, aquifers, and mine tailings. Micrometer thick, hydrous-silica coatings occur on the surface of a granite outcrop in contact with acidic pond water at the Coppercliff mine-tailings area in the Greater City of Sudbury, Ontario, and are ideal to study the concentration and speciation of metals and metalloids inside Si-enriched coatings. These coatings have higher average concentrations of Cr, Mn, Co, Ni, Cu, Zn, and Pb than coatings composed of schwertmannite, Fe(8)O(8)(OH)(4.4)(SO(4))(1.8) (H(2)O)(8.4). Microscopic and spectroscopic examination of the hydrous-silica coating indicates the occurrence of Fe- and Cu-Zn-oxy-hydroxide particles, tetrahedrally coordinated Fe(3+) and a high proportion of M-O-Si bonds (M = metal). These observations suggest that metals occur either finely distributed in the hydrous-silica matrix or in oxy-hydroxide particles. The latter particles are products of the diffusion of metals into the hydrous silica and the subsequent nucleation of oxy-hydroxide phases.

  20. Reproductive toxicity of inorganic mercury exposure in adult zebrafish: Histological damage, oxidative stress, and alterations of sex hormone and gene expression in the hypothalamic-pituitary-gonadal axis.

    PubMed

    Zhang, Qun-Fang; Li, Ying-Wen; Liu, Zhi-Hao; Chen, Qi-Liang

    2016-08-01

    Mercury (Hg) is a prominent environmental contaminant that causes a variety of adverse effects on aquatic organisms. However, the mechanisms underlying inorganic Hg-induced reproductive impairment in fish remains largely unknown. In this study, adult zebrafish were exposed to 0 (control), 15 and 30μg Hg/l (added as mercuric chloride, HgCl2) for 30days, and the effects on histological structure, antioxidant status and sex hormone levels in the ovary and testis, as well as the mRNA expression of genes involved in the hypothalamic-pituitary-gonadal (HPG) axis were analyzed. Exposure to Hg caused pathological lesions in zebrafish gonads, and changed the activities and mRNA levels of antioxidant enzymes (catalase (CAT), superoxide dismutase (SOD) and glutathione peroxidase (GPx)) as well as the content of glutathione (GSH) and malondialdehyde (MDA). In females, although ovarian 17β-estradiol (E2) content remained relatively stable, significant down-regulation of lhβ, gnrh2, gnrh3, lhr and erα were observed. In males, testosterone (T) levels in the testis significantly decreased after Hg exposure, accompanied by down-regulated expression of gnrh2, gnrh3, fshβ and lhβ in the brain as well as fshr, lhr, ar, cyp17 and cyp11b in the testis. Thus, our study indicated that waterborne inorganic Hg exposure caused histological damage and oxidative stress in the gonads of zebrafish, and altered sex hormone levels by disrupting the transcription of related HPG-axis genes, which could subsequently impair the reproduction of fish. Different response of the antioxidant defense system, sex hormone and HPG-axis genes between females and males exposed to inorganic Hg indicated the gender-specific regulatory effect by Hg. To our knowledge, this is the first time to explore the effects and mechanisms of inorganic Hg exposure on reproduction at the histological, enzymatic and molecular levels, which will greatly extend our understanding on the mechanisms underlying of reproductive

  1. The heat capacity of hydrous cordierite above 295 K

    NASA Astrophysics Data System (ADS)

    Carey, J. William

    1993-04-01

    The heat capacity of synthetic hydrous cordierite (Mg2Al4Si5O18·nH2O) has been determined by differential scanning calorimetry (DSC) from 295 to 425 K as a function of H2O content. Six samples with H2O contents ranging from 0 to 0.82 per formula unit were examined. The partial molar heat capacity of H2O in cordierite over the measured temperature interval is independent of composition and temperature within experimental uncertainty and is equal to 43.3 ±0.8 J/mol/ K. This value exceeds the molar heat capacity of gaseous H2O by 9.7 J/mol/K, but is significantly smaller than the heat capacity of H2O in several zeolites and liquid H2O. A statistical-mechanical model of the heat capacity of adsorbed gas species (Barrer 1978) is used to extrapolate the heat capacity of hydrous cordierite to temperatures greater than 425 K. In this model, the heat capacity of hydrous cordierite (Crd·nH2O) is represented as follows: Cp(Crd · nH2O) = Cp(Crd)+ n{Cp(H2O, gas)+ R(gas constant)} (1) An examination of calorimetric data for hydrous beryl, analcime, mordenite, and clinoptilolite (Hemingway et al. 1986; Johnson et al. 1982, 1991, 1992) demonstrates the general applicability of the statistical-mechanical model for the extrapolation of heat capacity data of zeolitic minerals. The heat capacity data for cordierite are combined with the data of Carey and Navrotsky (1992) to obtain the molar enthalpy of formation and enthalpy of hydration of hydrous cordierite as a function of temperature.

  2. Adsorption of Isoxaflutole Degradates to Hydrous Metal Oxide Surfaces

    USDA-ARS?s Scientific Manuscript database

    Isoxaflutole (IXF) is a pre-emergence herbicide that is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and, subsequently, DKN can be degraded to a benzoic acid derivative (BA) within soil. Due to the short half-life (t1/2) of IXF and the signif...

  3. Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides

    USDA-ARS?s Scientific Manuscript database

    Isoxaflutole (IXF) is a pre-emergence herbicide that has been marketed as a substitute for atrazine. It is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and, subsequently, DKN can be further degraded to a benzoic acid derivative (BA) within so...

  4. Ultra-hydrous stishovite obtained by hydrothermal treatment of SiO2

    NASA Astrophysics Data System (ADS)

    Spektor, K.; Nylen, J.; Stoyanov, E.; Navrotsky, A.; Hervig, R. L.; Leinenweber, K.; Holland, G. P.; Haussermann, U.

    2011-12-01

    Stishovite (SiO2) is an important high pressure mineral occurring in silica rich parts of subducted oceanic slabs and crustal fragments in the Earth's mantle. This silica polymorph adopts the rutile structure with octahedrally coordinated silicon and is generally considered to be nearly anhydrous with a maximum of 30 ppm H2O. In the presence of Al2O3, stishovite is capable of incorporating up to 0.3 wt.% of H2O. This research shows the possibility of synthesizing ultra-hydrous stishovite containing 1.3±0.2% of water without the presence of aluminum. Hydrous stishovite was unexpectedly obtained during hydrothermal treatments of either silica glass or coesite in a multi-anvil high pressure device at 10 GPa and 8 hours isothermal heating, at temperatures between 300 °C and 550 °C. Employed silica - water mixtures averaged a molar ratio of 1:1. At temperatures above 400 °C pure samples of stishovite were obtained. Optical and SEM observations showed that silica glass transforms via coesite into stishovite. Thermogravimetric analysis (TGA) and secondary ion mass spectrometry (SIMS) results were in good agreement, giving 1.3(2) wt.% of incorporated H2O for hydrous stishovite samples obtained at 450 °C. Hydrous stishovite has a slightly larger unit cell volume compared to conventionally prepared, dry, stishovite (0.5 to 0.8%). Infrared spectra (IR) showed intense OH stretching bands in 2500-3500 cm-1 region. Oxide melt drop solution calorimetry results show very modest (< 10 kJ per mole of SiO2) energetic destabilization associated with the observed H2O incorporation. On the other hand, the pV term at room temperature and 10 GPa is estimated to be about - 7 kJ/mol and thus can overcome the destabilizing enthalpy at atmospheric pressure. NMR data on the hydrous stishovite indicates that an octahedral Si vacancy is balanced by a cluster of 4 H atoms in a hydrogarnet-type defect. 1H NMR shows clustering of the hydrogen nuclei where the H-H distances are below 3 Å. 29Si

  5. Microfluidics in inorganic chemistry.

    PubMed

    Abou-Hassan, Ali; Sandre, Olivier; Cabuil, Valérie

    2010-08-23

    The application of microfluidics in chemistry has gained significant importance in the recent years. Miniaturized chemistry platforms provide controlled fluid transport, rapid chemical reactions, and cost-saving advantages over conventional reactors. The advantages of microfluidics have been clearly established in the field of analytical and bioanalytical sciences and in the field of organic synthesis. It is less true in the field of inorganic chemistry and materials science; however in inorganic chemistry it has mostly been used for the separation and selective extraction of metal ions. Microfluidics has been used in materials science mainly for the improvement of nanoparticle synthesis, namely metal, metal oxide, and semiconductor nanoparticles. Microfluidic devices can also be used for the formulation of more advanced and sophisticated inorganic materials or hybrids.

  6. Abundance retrieval of hydrous minerals around the Mars Science Laboratory landing site in Gale crater, Mars

    NASA Astrophysics Data System (ADS)

    Lin, Honglei; Zhang, Xia; Shuai, Tong; Zhang, Lifu; Sun, Yanli

    2016-02-01

    The detection of hydrous minerals on Mars is of great importance for revealing the early water environment as well as possible biotic activity. However, few studies focus on abundance retrieval of hydrous minerals for some difficulties. In this paper, we studied the area around the Mars Science Laboratory (MSL) landing site, to identify hydrous minerals and retrieve their abundance. Firstly, the distribution of hydrous minerals was extracted using their hydration features. Then, a sparse unmixing algorithm was applied along with the CRISM spectral library to retrieve the abundance of hydrous minerals in this area. As a result, seven hydrous minerals were retrieved, i.e. actinolite, montmorillonite, saponite, jarosite, halloysite, szomolnokite and magnesite and, the total concentration of all hydrous minerals was as high as 40 vol% near the lower reaches of Mount Sharp. Our results were consistent with results from related research and the in-situ analysis of the MSL rover Curiosity.

  7. Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol

    NASA Astrophysics Data System (ADS)

    Phillips, Cory Bernard

    1999-11-01

    This work deals with the synthesis of isobutylene from a hydrous ethanol feedstock over zeolites. The synthesis is accomplished in three steps: (1) low-temperature direct ethanol conversion to ethylene on H-ZSM-5 zeolite, (2) ethylene conversion to butene products over metal-exchanged zeolites, and (3) butene skeletal rearrangement to isobutylene over FER zeolites. The key to understanding and optimizing each synthesis step lies in the ability to control and regulate the zeolite acidity (Bronsted and Lewis)---both strength and number. Therefore, the continuous temperature programmed amine desorption (CTPAD) technique was further developed to simultaneously count the Bronsted acid sites and quantitatively characterize their strength. The adsorption of ethanol, reaction products, amines, coke and ethanol-derived residue (EDR) were monitored gravimetrically using the highly sensitive, novel Tapered Element Oscillating Microreactor (TEOM) apparatus. The TEOM was also used also in conjunction with CTPAD to characterize Bronsted acidity which is a new application for the instrument. For the first synthesis step, a parallel reaction exists which simultaneously produces diethyl ether and ethylene directly over H-ZSM-5. The reaction rates for each pathway were measured directly using a differential reactor operating at low temperatures (<473 K). Water in the ethanol feed enhances the rate of ethylene formation. A mechanism and kinetic expression are proposed for this reaction over H-ZSM-5, with diethyl-ether desorption and ethylene formation as the rate limiting steps. Heat of adsorption values measured from the independent microcalorimetry work reported in the literature are incorporated into the kinetic analysis which reduces the number of regressed parameters. For the remaining synthesis steps, several zeolite structures (ZSM-5, Y, FER) partially exchanged with Pd, Ti, Ni and Au were prepared and tested. It was determined from this screening study that the zeolites

  8. Influence of crustal dust and sea spray supermicron particle concentrations and acidity on inorganic NO3− aerosol during the 2013 Southern Oxidant and Aerosol Study

    DOE PAGES

    Allen, H. M.; Draper, D. C.; Ayres, B. R.; ...

    2015-09-25

    Inorganic aerosol composition was measured in the southeastern United States, a region that exhibits high aerosol mass loading during the summer, as part of the 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. Measurements using a Monitor for AeRosols and GAses (MARGA) revealed two periods of high aerosol nitrate (NO3−) concentrations during the campaign. These periods of high nitrate were correlated with increased concentrations of supermicron crustal and sea spray aerosol species, particularly Na+ and Ca2+, and with a shift towards aerosol with larger (1 to 2.5 μm) diameters. We suggest this nitrate aerosol forms by multiphase reactions of HNO3more » and particles, reactions that are facilitated by transport of crustal dust and sea spray aerosol from a source within the United States. The observed high aerosol acidity prevents the formation of NH4NO3, the inorganic nitrogen species often dominant in fine-mode aerosol at higher pH. In addition, calculation of the rate of the heterogeneous uptake of HNO3 on mineral aerosol supports the conclusion that aerosol NO3− is produced primarily by this process, and is likely limited by the availability of mineral cation-containing aerosol surface area. Modeling of NO3− and HNO3 by thermodynamic equilibrium models (ISORROPIA II and E-AIM) reveals the importance of including mineral cations in the southeastern United States to accurately balance ion species and predict gas–aerosol phase partitioning.« less

  9. Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO2 production

    USGS Publications Warehouse

    Chapelle, F.H.; McMahon, P.B.

    1991-01-01

    A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO2 production. Although sulfate concentrations are low (approximately 0.05-0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4-20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Fick's Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO2 production (about 10-5 mmoll-1 year-1), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2-6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments. ?? 1991.

  10. Synthesis and characterizations of anion exchange organic-inorganic hybrid materials based on poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)

    SciTech Connect

    Zhang Shaoling; Wu Cuiming; Xu Tongwen . E-mail: twxu@ustc.edu.cn; Gong Ming; Xu Xiaolong

    2005-07-15

    A series of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid materials for anion exchange were prepared through sol-gel process of polymer precursors PPO-Si(OCH{sub 3}){sub 3}. PPO-Si(OCH{sub 3}){sub 3} were obtained from the reaction of bromomethylated PPO with 3-aminopropyl-trimethoxysilane (A1110). These polymer precursors then underwent hydrolysis and condensation with additional A1110 to generate hybrid materials. The reaction to produce polymer precursors was identified by FTIR; while FTIR, TGA, XRD, SEM, as well as conventional ion exchange capacity (IEC) measurements were conducted for the structures and properties of the prepared hybrids. TGA results show that this series of hybrid materials possess high thermal stability; XRD and SEM indicate that the prepared hybrid materials are amorphous and the inorganic and organic contents show good compatibility if the ratio between them is proper. The IEC values of the hybrid materials due to the amine groups range from 1.13 mmol/gBPPO (material i) to 4.80 mmol/gBPPO (material iv)

  11. Improvement of charge injection efficiency in organic-inorganic hybrid solar cells by chemical modification of metal oxides with organic molecules

    SciTech Connect

    Kudo, Naomi; Honda, Satoshi; Shimazaki, Yuta; Ohkita, Hideo; Ito, Shinzaburo; Benten, Hiroaki

    2007-04-30

    The effect of chemical modification of metal oxide surface with dye molecules in organic-inorganic hybrid solid solar cells was studied by using double layered cells consisting of poly(3-hexylthiophene) (P3HT) and a flat layer of dense TiO{sub 2}. The external quantum efficiency of the chemically modified cell was nearly double that expected from the photosensitizing effect of the dye molecules. The additional increase shows that the chemical modification with dye molecules can serve not only as a photosensitizer but mainly as an energy funnel and/or an electronic mediator to significantly improve the electron injection efficiency from P3HT to TiO{sub 2}.

  12. Growth and Filling Regularities of Filamentary Channels in Non-Metallic Inorganic Coatings Under Anodic Oxidation of Valve Metals. Mathematical Modeling

    NASA Astrophysics Data System (ADS)

    Mamaev, A. I.; Mamaeva, V. A.; Kolenchin, N. F.; Chubenko, A. K.; Kovalskaya, Ya. B.; Dolgova, Yu. N.; Beletskaya, E. Yu.

    2015-12-01

    Theoretical models are developed for growth and filling processes in filamentary channels of nanostructured non-metallic coatings produced by anodizing and microplasma oxidation. Graphical concentration distributions are obtained for channel-reacting anions, cations, and sparingly soluble reaction products depending on the time of electric current transmission and the length of the filamentary channel. Graphical distributions of the front moving velocity for the sparingly soluble compound are presented. The resulting model representation increases the understanding of the anodic process nature and can be used for a description and prediction of porous anodic film growth and filling. It is shown that the character of the filamentary channel growth and filling causes a variety of processes determining the textured metal - nonmetallic inorganic coating phase boundary formation.

  13. A novel control method for nitritation: The domination of ammonia-oxidizing bacteria by high concentrations of inorganic carbon in an airlift-fluidized bed reactor.

    PubMed

    Tokutomi, Takaaki; Shibayama, Chizu; Soda, Satoshi; Ike, Michihiko

    2010-07-01

    A novel nitritation method based on the addition of inorganic carbon (IC) was verified using an airlift-fluidized bed reactor packed with sponge cubes. A continuous-treatment experiment demonstrated that the type of nitrification-nitrite or nitrate accumulation-could be controlled by the addition of different alkalinity sources (NaHCO(3) or NaOH, respectively). The maximum rate of ammonia oxidation at 30 degrees C was 2.47kg-N/(m(3) d), with nitrate formation of less than 0.5% of the converted ammonia. Nitrite accumulation of over 90% was maintained stably over 250 days at 30 degrees C and was achieved even at 19 degrees C. Qualitative and quantitative shifts of nitrifying bacteria in the biofilm were monitored by real-time PCR and T-RFLP analysis. Ammonia-oxidizing bacteria (AOB) were dominant but nitrite-oxidizing bacteria (NOB) were eliminated in the reactor when NaHCO(3) was used as the alkalinity source. From the kinetic data, we inferred that high IC concentrations drive stable nitritation by promoting a higher growth rate for AOB than for NOB.

  14. Sulfate Saturated Hydrous Magmas Associated with Hydrothermal Gold Ores

    NASA Astrophysics Data System (ADS)

    Chambefort, I.; Dilles, J. H.; Kent, A. J.

    2007-12-01

    -ICP-MS. Yanacocha anhydrite, hosted by amphiboles, are enriched in FeO (up to 0.6 wt%) and present positive anomalies in Eu and SrO (up to 8000ppm in anhydrite blebs hosted by high Al amphibole of the sample RC6). Anhydrite hosted by clinopyroxene (CPx) and low Al amphibole present higher Ce2O3 content (up to 2000ppm in CPx). In comparison, hydrothermal anhydrite analyzed from El Salvador, Butte and Ajo ore deposits contain less SrO (~ 2000 ppm) and no FeO. Pinatubo anhydrite phenocrysts and inclusions from the 1991 Pinatubo dacite yield low FeO contents, except anhydrite included in amphibole. These data suggest FeO in anhydrite is a product of subsolidus diffusion from the host. The breakdown of abundant anhydrite crystals "stored" in the magma may source of SO2-rich hydrothermal fluids that produced the sulfur enrichment (>500 M Tonnes) observed the Yanacocha hydrothermal gold deposits. The two populations of amphibole are evidence of magma mixing in the Yanacocha magmatic rocks. A sulfate-saturated oxidized dacitic magma chamber resided at about 4 to 8 km depth and 800°C was periodically underplated or fed by hydrous sulfate-rich oxidized basaltic-andesite magma. The shape of the irregular anhydrite blebs suggest that these inclusions could have been trapped as an immiscible sulfate- phosphate rich melt, despite the fact that anhydrite normally has a liquidus temperature of 1450°C and the host amphiboles crystallized at no more than 1050°C based on experiments on andesites and dacites.

  15. The Identity of Hydrous Defects Controlling the Rheology of Olivine

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    The reduction of the creep strength of minerals due to the presence of water is well established. The nature of the relevant hydrous defect(s) is perhaps less well understood. Standard treatments examine intrinsic defects of a pure crystal, but impurity-related defects are not usually considered. Natural olivine contains monovalent (Na) and trivalent (e.g. Al) trace elements in concentrations that exceed the concentration of intrinsic defects by up to an order of magnitude. They therefore are potentially important as agents for water-weakening. Hydrated defects - both intrinsic and impurity-related - systematically affect infrared absorption spectra, which can therefore be used for their identification and quantification. Experiments with olivine in contact with a range of buffer assemblages (e.g. MgO and enstatite) have shown that the infrared spectra of natural olivine can only be reproduced experimentally in the presence of titanium. Doping with a range of trivalent cations shows systematics in the infrared spectra related to the ionic radius of the dopants, confirming that the spectra are sensitive to the bonding environment and can be used to identify particular defects. To investigate the relationship between hydrous, titanium-related defects and creep strength we conducted deformation experiments on synthetic Fo90 olivine that was buffered by enstatite and doped with titanium. The infrared spectra of the deformed samples show absorption bands at the same wave numbers and relative intensity as natural olivine, indicating that the experimental samples contain the same hydrous defects. Fitting the creep data from samples with a range of water contents determined from these absorption bands shows a near linear relationship between strain rate and water content, consistent with published observations. The experiments therefore show that the rheology of hydrous olivine is determined by hydrated impurity-related defects rather than intrinsic point defects.

  16. Structure and stability of hydrous minerals at high pressure

    NASA Technical Reports Server (NTRS)

    Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

    1994-01-01

    The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

  17. Structure and stability of hydrous minerals at high pressure

    NASA Technical Reports Server (NTRS)

    Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

    1994-01-01

    The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

  18. Structure and stability of hydrous minerals at high pressure

    NASA Astrophysics Data System (ADS)

    Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

    The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

  19. Oxidative treatment of bromide-containing waters: formation of bromine and its reactions with inorganic and organic compounds--a critical review.

    PubMed

    Heeb, Michèle B; Criquet, Justine; Zimmermann-Steffens, Saskia G; von Gunten, Urs

    2014-01-01

    Bromide (Br(-)) is present in all water sources at concentrations ranging from ≈ 10 to >1000 μg L(-1) in fresh waters and about 67 mg L(-1) in seawater. During oxidative water treatment bromide is oxidized to hypobromous acid/hypobromite (HOBr/OBr(-)) and other bromine species. A systematic and critical literature review has been conducted on the reactivity of HOBr/OBr(-) and other bromine species with inorganic and organic compounds, including micropollutants. The speciation of bromine in the absence and presence of chloride and chlorine has been calculated and it could be shown that HOBr/OBr(-) are the dominant species in fresh waters. In ocean waters, other bromine species such as Br2, BrCl, and Br2O gain importance and may have to be considered under certain conditions. HOBr reacts fast with many inorganic compounds such as ammonia, iodide, sulfite, nitrite, cyanide and thiocyanide with apparent second-order rate constants in the order of 10(4)-10(9)M(-1)s(-1) at pH 7. No rate constants for the reactions with Fe(II) and As(III) are available. Mn(II) oxidation by bromine is controlled by a Mn(III,IV) oxide-catalyzed process involving Br2O and BrCl. Bromine shows a very high reactivity toward phenolic groups (apparent second-order rate constants kapp ≈ 10(3)-10(5)M(-1)s(-1) at pH 7), amines and sulfamides (kapp ≈ 10(5)-10(6)M(-1)s(-1) at pH 7) and S-containing compounds (kapp ≈ 10(5)-10(7)M(-1)s(-1) at pH 7). For phenolic moieties, it is possible to derive second-order rate constants with a Hammett-σ-based QSAR approach with [Formula in text]. A negative slope is typical for electrophilic substitution reactions. In general, kapp of bromine reactions at pH 7 are up to three orders of magnitude greater than for chlorine. In the case of amines, these rate constants are even higher than for ozone. Model calculations show that depending on the bromide concentration and the pH, the high reactivity of bromine may outweigh the reactions of chlorine during

  20. Assessment of the formation of inorganic oxidation by-products during the electrocatalytic treatment of ammonium from landfill leachates.

    PubMed

    Pérez, G; Saiz, J; Ibañez, R; Urtiaga, A M; Ortiz, I

    2012-05-15

    This work investigates the formation of oxidation by-products during the electrochemical removal of ammonium using BDD electrodes from wastewaters containing chlorides. The influence of the initial chloride concentration has been experimentally analyzed first, working with model solutions with variable ammonium concentration and second, with municipal landfill leachates. Two different levels of chloride concentration were studied, i) low chloride concentrations ranging between 0 and 2000 mg/L and, ii) high chloride concentrations ranging between 5000 and 20,000 mg/L. Ammonium removal took place mainly via indirect oxidation leading to the formation of nitrogen gas and nitrate as the main oxidation products; at high chloride concentration the formation of nitrogen gas and the rate of ammonium removal were both favored. However, chloride was also oxidized during the electrochemical treatment leading to the formation of free chlorine responsible of the ammonium oxidation, together with undesirable products such as chloramines, chlorate and perchlorate. Chloramines appeared during the treatment but they reached a maximum and then started decreasing, being totally removed when high chloride concentrations were used. With regard to the formation of chlorate and perchlorate once again the concentration of chloride exerted a strong influence on the formation kinetics of the oxidation by-products and whereas at low chloride concentrations, chlorate appeared like an intermediate compound leading to the formation of perchlorate, at high chloride concentrations chlorate formation was delayed significantly and perchlorate was not detected during the experimental time. Thus this work contributes first to the knowledge of the potential hazards of applying the electro-oxidation technology as an environmental technology to deal with ammonium oxidation under the presence of chloride and second it reports efficient conditions that minimize or even avoid the formation of undesirable

  1. First principles investigation of the vibrational properties of hydrous wadsleyite

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Jun

    2017-04-01

    Wadsleyite is the primary constituent mineral in the upper part of the Earth's transition zone and this phase can be a significant water reservoir in the Earth. There have been large numbers of reports about the structure, stability, and physical properties of hydrous wadsleyite. The vibrational measurements such as FTIR and Raman are the most commonly used for investigating the OH defects in wadsleyite. There are major and minor doublets of OH stretching bands in hydrous wadsleyite, the former exist around 3300 cm-1 with dν/dP˜-10 cm-1 and the latter around 3600 cm-1 with almost no pressure dependence. There is a broad consensus that main absorption band is interpreted as the OH stretching modes existing in the M3 vacancy. On the other hand, the minor OH band is not well constrained so far. Since the stable hydrogen defects are usually less mobile in wadsleyite crystal, the determination of minor and metastable hydrogen defects are more important for investigating the transport properties including the electrical conductivity and the deformation properties. Here I investigated the structural and vibrational properties of hydrous wadsleyite using first principles techniques in order to clarify the minor metastable hydrogen positions under high-pressure.

  2. Heat capacity, configurational heat capacity and fragility of hydrous magmas

    NASA Astrophysics Data System (ADS)

    Di Genova, D.; Romano, C.; Giordano, D.; Alletti, M.

    2014-10-01

    The glassy and liquid heat capacities of four series of dry and hydrous natural glasses and magma as a function of temperature and water content (up to 19.9 mol%) were investigated using differential scanning calorimetry (DSC). The analyzed compositions are basalt, latite, trachyte and pantellerite. The results of this study indicate that the measured heat capacity of glasses (Cpg) is a linear function of composition and is well reproduced by the empirical model of Richet (1987). For the investigated glasses, the partial molar heat capacity of water can be considered as independent of composition, in agreement with Bouhifd et al. (2006). For hydrous liquids, the heat capacity (Cpliq) decreases nonlinearly with increasing water content. Previously published models, combined with the partial molar heat capacity of water from the literature, are not able to reproduce our experimental data in a satisfactory way. We estimated the partial molar heat capacity of water (CpH2O) in hydrous magma over a broad compositional range. The proposed value is 41 ± 3 J mol-1 K-1. Water strongly affects the configurational heat capacity at the glass transition temperature [Cpconf (Tg)]. An increases of Cpconf (Tg) with water content was measured for the polymerized liquids (trachyte and pantellerite), while the opposite behavior was observed for the most depolymerized liquids (basalt and latite). Structural and rheological implications of this behavior are discussed in light of the presented results.

  3. Arsenic, inorganic

    Integrated Risk Information System (IRIS)

    Arsenic , inorganic ; CASRN 7440 - 38 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinoge

  4. The Chassigny meteorite - A cumulate dunite with hydrous amphibole-bearing melt inclusions

    NASA Technical Reports Server (NTRS)

    Floran, R. J.; Prinz, M.; Hlava, P. F.; Keil, K.; Nehru, C. E.; Hinthorne, J. R.

    1978-01-01

    The Chassigny meteorite, an iron-rich dunite (Fo 68), is a moderately shocked olivine achondrite or chassignite with features indicative of a cumulate origin with some subsolidus annealing. The evidence that the meteorite experienced shock pressures of approximately 150-200 kbar is described. Kaersutitic amphibole, found only in melt inclusions, represents the first extraterrestrial occurence of hydrous amphibole and the first meteoritic amphibole type other than fluorichterite. Fractionation data indicate that Chassigny formed under relatively more oxidizing conditions than most other achondrites, which implies that its parental melt could not have been directly derived from a chondritic composition in a simple single-stage process. Similarities and differences with the Brachina meteorite, the only other meteorite of the Chassigny type, are considered.

  5. In situ hydrothermal oxidative destruction of DNAPLS in a creosote contaminated site

    SciTech Connect

    Leif, R. N., LLNL

    1998-02-27

    Hydrous Pyrolysis / Oxidation (HPO) is an in situ thermal remediation technology that uses hot, oxygenated groundwater to completely mineralize a wide range of organic pollutants. A field demonstration of HPO was performed at a creosote contaminated site during the summer of 1997. The groundwater was heated by steam injections and oxygen was added by coinjection of compressed air. The remediation was monitored from multiple groundwater monitoring wells. Dissolved organic carbon levels increased in response to steam injections as a result of the enhanced dissolution and mobilization of the creosote into the heated groundwater. Elevated concentrations of partially oxidized organic compounds (i.e. phenols, benzoic acid, fluorenone, anthrone and 9,10- anthracenedione), decreased levels of dissolved oxygen and isotopic shifts in the dissolved inorganic pool were indicators of partial to complete oxidative destruction of the creosote in the heated aquifer as a result of the HPO process.

  6. Inorganic mercury exposure: toxicological effects, oxidative stress biomarkers and bioaccumulation in the tropical freshwater fish matrinxã, Brycon amazonicus (Spix and Agassiz, 1829).

    PubMed

    Monteiro, Diana Amaral; Rantin, Francisco Tadeu; Kalinin, Ana Lúcia

    2010-01-01

    Alterations in the antioxidant cellular system have often been proposed as biomarkers of pollutant-mediated toxicity. This study evaluated the effects of mercury on oxidative stress biomarkers and bioaccumulation in the liver, gills, white muscle and heart of the freshwater fish matrinxã, Brycon amazonicus, exposed to a nominal and sub-lethal concentration (~20% of 96 h-LC(50)) of 0.15 mg L(-1) of mercury chloride (HgCl(2)) for 96 h in a static system. Increases in superoxide dismutase, catalase, glutathione peroxidase (GPx), glutathione S-transferase (GST) and glutathione reductase (GR) were observed in all tissues after HgCl(2) exposure, except for white muscle GR activity and hepatic GPx. In the liver and gills, the exposure to HgCl(2) also induced significant increases in reduced glutathione (GSH). Conversely, exposure to HgCl(2) caused a significant decrease in the GSH levels and an increase in the oxidized glutathione (GSSG) content in the white muscle, while both GSH and GSSG levels increased significantly in the heart muscle. Metallothionein concentrations were significantly high after HgCl(2) exposure in the liver, gills and heart, but remained at control values in the white muscle. HgCl(2) exposure induced oxidative damage, increasing the lipid peroxidation and protein carbonyl content in all tissues. Mercury accumulated significantly in all the fish tissue. The pattern of accumulation follows the order gills > liver > heart > white muscle. In conclusion, these data suggest that oxidative stress in response to inorganic mercury exposure could be the main pathway of toxicity induced by this metal in fish.

  7. Oxidations of Organic and Inorganic Substrates by Superoxo-, hydroperoxo-, and oxo-compounds of the transition metals.

    SciTech Connect

    Vasbinder, Michael John

    2006-01-01

    Chapters 1 and 2 dealt with the chemistry of superoxo-, hydroperoxo-, and oxo- complexes of chromium, rhodium and cobalt. Chapter 3 dealt with the mechanism of oxygen-atom transfer catalyzed by an oxo-complex of rhenium. In Chapter 1, it was shown that hydroperoxometal complexes of cobalt and rhodium react with superoxochromium and chromyl ions, generating reduced chromium species while oxidizing the hydroperoxometal ions to their corresponding superoxometal ions. It was shown that the chromyl and superoxochromium ions are the more powerful oxidants. Evidence supports hydrogen atom transfer from the hydroperoxometal ion to the oxidizing superoxochromium or chromyl ion as the reaction mechanism. There is a significant H/D kinetic isotope effect. Comparisons to the rate constants of other known hydrogen atom transfer reactions show the expected correlation with bond dissociation energies. In Chapter 2, it was found that the superoxometal complexes Cr{sub aq}OO2+ and Rh(NH3)4(H2O)OO2+ oxidize stable nitroxyl radicals of the TEMPO series with rate constants that correlate with the redox potentials of both the oxidant and reductant. These reactions fit the Marcus equation for electron transfer near the theoretical value. Acid catalysis is important to the reaction, especially the thermodynamically limited cases involving Rh(NH3)4(H2O)OO2+ as the oxidant. The rate constants are notably less than those measured in the reaction between the same nitroxyl radicals and other strong free-radical oxidants, an illustration of the delocalized and stabilized nature of the superoxometal ions. Chapter 3 showed that oxo-rhenium catalysts needed a nucleophile to complete the catalytic oxygen-atom transfer from substituted pyridine-N-oxides to triphenylphosphine. The reaction was studied by introducing various pyridine-derived nucleophiles and monitoring their effect on the rate, then

  8. Effects of oxide electron transport layer on quantum dots light emitting diode with an organic/inorganic hybrid structure

    NASA Astrophysics Data System (ADS)

    Kim, Jiwan; Park, Yu Jin; Kim, Yohan; Kim, Yong-Hoon; Han, Chul Jong; Han, Jeong In; Oh, Min Suk

    2013-11-01

    We report on the effects of an oxide semiconductor as an electron transport layer (ETL) on a quantum dots light emitting diode (QD-LED). To improve the properties of QD-LED, we optimized the process parameters for the deposition and post-annealing steps of an oxide ETL. When zinc tin oxide (ZTO) was deposited by radio-frequency magnetron sputtering in a gas mixture of argon and oxygen (Ar : O2 = 2 : 1) and then annealed under 760 Torr O2 for 10 min, our QD-LED showed improved luminescence characteristics. Additionally, to overcome the problem of non-uniform luminescence, we optimized the concentration and process conditions of colloidal quantum dot materials. Finally, we fabricated QD-LED devices with luminescence of 4,874 cd/m2 and luminous efficiency of 2.68 cd/A.

  9. [AFM study on microtopography of NOM and newly formed hydrous manganese dioxide adsorbed on mica].

    PubMed

    Guo, Jin; Ma, Jun; Shi, Xue-hua

    2006-05-01

    With the methods of mica adsorbing, the microtopography of the newly formed hydrous manganese dioxide was perfectly captured. The tapping mode AFM study results revealed that the newly formed hydrous manganese dioxide possesses a perforated sheet (with a thickness of 0-1.75 nm) as well as some spheric particle structures compared with the hydrous manganese dioxide with 2 h aging time, which demonstrated that the newly formed hydrous manganese dioxide have a large surface area and adsorption capacity. When 1 mmol/L newly formed hydrous manganese dioxide was added, the microtopography of NOM molecules shifted from loosely dispersed pancake shape (with adsorption height of 5-8.5 nm) to densely dispersed and uniform spheric structure. NOM was prone to adsorb on the surface of the newly formed hydrous manganese dioxide, which provided a valid proof for the coagulation-aid mechanism of permanganate preoxidation.

  10. Oxidative cell damage in Kat-sod assay of oxyhalides as inorganic disinfection by-products and their occurrence by ozonation.

    PubMed

    Ueno, H; Oishi, K; Sayato, Y; Nakamuro, K

    2000-01-01

    Nine oxyhalides as possible inorganic disinfection by-products were tested for oxidative cell damage by Kat-sod assay with E. coli mutant strains deficient in the active oxygen-scavenging enzymes. Chlorine dioxide, chlorite, and iodate were highly cytotoxic, whereas in the presence of cysteine, bromate (BrO3-) and metaperiodate (IO4-) showed more growth inhibition toward the superoxide dismutase-deficient strains than the wild strain. BrO3- also showed oxidative mutagenicity with cysteine or glutathione ethyl ester in S. typhimurium TA 100. To identify oxyhalides formed by ozonation of raw water containing sea water, the occurrence of ozonation by-products of bromide and iodide was investigated. The results indicate that BrO3- is toxicologically one of the most remarkable oxyhalides detectable in drinking water because IO4- was not detected in the ozonated solution of iodide, and the ozonation condition to lower BrO3- is to keep it neutral in the presence of ammonium ion.

  11. Effects of soil moisture, temperature, and inorganic nitrogen on nitric oxide emissions from acidic tropical savannah soils

    SciTech Connect

    Cardenas, L.; Sanhueza, E.; Rondon, A.; Johansson, C.

    1993-08-20

    NO fluxes from soils with a wide range of soil moistures, soil inorganic-N concentrations, and soil temperatures were measured during the wet and the dry season at a Venezuelan savannah site. Maximum NO emissions ({approximately} 12 ngN m{sup {minus}2} s{sup {minus}1}) were observed at soil gravimetric moistures between 10% and 18%. Deviation from this optimum range results in decreased NO fluxes; very low emissions (< 2 ngN m{sup {minus}2} s{sup {minus}1}) were recorded at low (< 2%) and high (< 25%) soil moistures. Both NO production in soil and its transport within the soil play important roles in the emission of NO to the atmosphere. Under most conditions no temperature effect was observed. NO emission was strongly stimulated by the addition of NO{sub 3}{sup {minus}} and only very weakly by the addition of NH{sub 4}{sup +}; at low and moderate soil moistures, soil nitrate and the NO flux were positively correlated. At low (natural) soil nitrate content and comparable soil moisture and temperature, NO emissions were greater during the dry season than during the rainy season, suggesting that other factors (i.e., soil physical structure) may also govern NO flux from savannah soil. 29 refs., 6 figs., 3 tabs.

  12. Effect Of Inorganic, Synthetic And Naturally Occurring Chelating Agents On Fe(II) Mediated Advanced Oxidation Of Chlorophenols

    EPA Science Inventory

    This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H...

  13. Respiration-dependent proton translocation in Nitrosomonas europaea and its apparent absence in Nitrobacter agilis during inorganic oxidations.

    PubMed Central

    Hollocher, T C; Kumar, S; Nicholas, D J

    1982-01-01

    Oxygen pulse experiments were carried out with the nitrifying bacteria Nitrosomonas europaea and Nitrobacter agilis and with spheroplasts and everted vesicles prepared from Nitrobacter agilis. In addition to thiocyanate, the salting-in anions perchlorate and trichloroacetate proved to be permeant and effective in allowing respiration-dependent proton translocation with Nitrosomonas europaea. Valinomycin-K+, however, was generally ineffective in this respect with Nitrosomonas europaea. The observed leads to H+/O ratio for ammonium ion oxidation by Nitrosomonas europaea was 3.4; that for hydroxylamine and hydrazine cation oxidation was 4.4. These values, when corrected for production of stoichiometric protons and for the fact that the first step in ammonium ion oxidation (hydroxylamine production) is mediated by a monooxygenase, give effective leads to H+/O ratios of about 4 for these three substrates. This value compares favorably with those obtained with other aerobes. No convincing evidence was obtained for operation of a respiratory proton pump in Nitrobacter agilis during nitrite oxidation. Implications of this unexpected result are discussed. PMID:6277846

  14. Effect Of Inorganic, Synthetic And Naturally Occurring Chelating Agents On Fe(II) Mediated Advanced Oxidation Of Chlorophenols

    EPA Science Inventory

    This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H...

  15. Graphene oxide-TiO2 composite solid phase extraction combined with graphite furnace atomic absorption spectrometry for the speciation of inorganic selenium in water samples.

    PubMed

    Zhang, Yanan; Chen, Beibei; Wu, Shaowei; He, Man; Hu, Bin

    2016-07-01

    In this paper, a method of graphene oxide (GO)-TiO2 composite solid phase extraction followed by graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the speciation of inorganic selenium in environmental waters. The adsorption behavior of inorganic Se(IV) and Se(VI) on the GO-TiO2(1:1) composite was investigated. It was found that Se(IV) was quantitatively retained on the GO-TiO2 composites within a wide pH range of 0.5-10, while Se(VI) was quantitatively adsorbed on GO-TiO2(1:1) composite at pH 0.5-2, and no obvious adsorption of Se(VI) within the pH range of 4-10 was found. By selecting pH 6.0, Se(IV) could be easily determined. After reduction of Se(VI), total Se was determined by the proposed method, and Se(VI) was calculated as the difference between the total Se and Se(IV). The factors affecting the separation/preconcentration of Se(IV) and Se(VI) were studied. Under the optimum conditions, the isothermal adsorption of Se(IV) on the GO-TiO2(1:1) composite fitted Langmuir model; a linear range over 0.1-12ngmL(-1) was obtained. The limit of detection (LOD) and precision of the method for Se(IV) was 0.04ngmL(-1) and 9.4% (cSe(IV)=0.5ngmL(-1), n=7), respectively. In order to verify the accuracy of the method, a standard water sample (GSBZ50031-94) was analyzed, and the determined value was in a good agreement to the certified value. The established method was applied to inorganic Se speciation in environmental water samples and the recovery of 87.4-102% was obtained for the spiked samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Reactive uptake of N2O5 to internally mixed inorganic and organic particles: the role of organic carbon oxidation state and inferred organic phase separations

    NASA Astrophysics Data System (ADS)

    Gaston, C. J.; Thornton, J. A.; Ng, N. L.

    2014-06-01

    We measured N2O5 reactive uptake onto mixed organic/inorganic submicron particles using organic compounds with a variety of oxidation states (using mainly atomic O : C ratios as a proxy) and molecular weights. The organic mass fraction, organic molecular composition, and relative humidity (RH) were varied to assess their effects separately on the N2O5 uptake coefficient, γ(N2O5). At a constant RH, mixtures of organic components having an O : C < 0.5 with ammonium bisulfate significantly suppressed the uptake of N2O5(g) compared to pure ammonium bisulfate, even at small organic mass fractions (e.g., ≤ 15%). The effect of the organic component became less pronounced at higher RH. In general, highly oxygenated organic components (O : C > 0.8) had a smaller or even negligible impact on N2O5(g) uptake at all RHs probed; however, a few exceptions were observed. Notably, γ(N2O5) for mixtures of ammonium bisulfate with polyethylene glycol (PEG), PEG-300 (O : C = 0.56), decreased nearly linearly as the PEG mass fraction increased at constant RH until leveling off at the value measured for pure PEG. The response of γ(N2O5) to increasing PEG mass fraction was similar to that measured on ambient atmospheric particles as a function of organic mass fraction. The effects of the organic mass fraction on γ(N2O5), for mixtures having an O : C < ~0.8, were best described using a standard resistor model of reactive uptake assuming the particles had an RH-dependent inorganic core-organic shell morphology. This model suggests that the N2O5 diffusivity and/or solubility in the organic layer is up to a factor of 20 lower compared to aqueous solution particles, and that the diffusivity, solubility, and reactivity of N2O5 within organic coatings and particles depend upon both RH and the molecular composition of the organic medium. We use these dependencies and ambient measurements of organic aerosol from the global aerosol mass spectrometry (AMS) database to show that the typical

  17. The Fouling of Zirconium(IV) Hydrous Oxide–Polyacrylate Dynamically Formed Membranes during the Nanofiltration of Lactic Acid Solutions

    PubMed Central

    Polom, Ewa

    2013-01-01

    The results of investigations of flux decline during nanofiltration (NF) of lactic acid solutions using dynamically formed zirconium(IV) hydrous oxide/polyacrylate membranes (Zr(IV)/PAA) under conditions resulting in low and high lactic acid rejection are reported. The experimental permeate flux versus time curves were analyzed in the frame of resistance in a series model with the aim of developing the characteristic of resistances. Analysis of experimental data and results of calculations showed that the reduction of fouling effects in the investigated system could be achieved due to appropriate hydrodynamic process conditions and regular rinsing with deionized water. PMID:24957066

  18. Cs{sup +} ion exchange kinetics in complex electrolyte solutions using hydrous crystalline silicotitanates

    SciTech Connect

    Gu, D.; Nguyen, L.; Philip, C.V.; Huckman, M.E.; Anthony, R.G.; Miller, J.E.; Trudell, D.E.

    1997-12-01

    TAM-5 is a hydrous crystalline sodium silicotitanate inorganic ion exchanger with a high selectivity for Cs{sup +}. The kinetics of Cs{sup +}-Na{sup +} ion exchange using TAM-5 in multicomponent electrolyte solutions were determined using batch experiments. For the powder, which is composed of crystals, a single-phase, homogeneous model fit the data best. For the granules, which were prepared from the powder, a two-phase, heterogeneous model resulted in an excellent fit of the data. Macropore and crystal diffusivities were determined by fitting the model to experimental data collected on the powder and the granules. Intracrystalline diffusivities were concentration dependent and were on the order of 10{sup {minus}19} m{sup 2}/s. Macropore diffusivities were on the order of 10{sup {minus}10} m{sup 2}/s. Resistance to diffusion in the macropores was not significant for granules with diameters less than 15 {micro}m. A two-phase, homogeneous model, where liquid within the pores is in equilibrium with the solid, was also evaluated for the granules. Surprisingly, for the granules, an excellent fit of the data was obtained; however, the effective macropore diffusivity was 1.1 {times} 10{sup {minus}11} m{sup 2}/s, an order of magnitude smaller than the macropore diffusivity found using the two-phase, heterogeneous model.

  19. Comparative short-term inhalation toxicity of five organic diketopyrrolopyrrole pigments and two inorganic iron-oxide-based pigments

    PubMed Central

    Hofmann, Thomas; Ma-Hock, Lan; Strauss, Volker; Treumann, Silke; Rey Moreno, Maria; Neubauer, Nicole; Wohlleben, Wendel; Gröters, Sibylle; Wiench, Karin; Veith, Ulrich; Teubner, Wera; van Ravenzwaay, Bennard; Landsiedel, Robert

    2016-01-01

    Abstract Diketopyrrolopyrroles (DPP) are a relatively new class of organic high-performance pigments. The present inhalation and particle characterization studies were performed to compare the effects of five DPP-based pigments (coarse and fine Pigment Red 254, coarse and fine meta-chloro DPP isomer and one form of mixed chlorinated DPP isomers) and compare it to coarse and fine inorganic Pigment Red 101. Wistar rats were exposed head-nose to atmospheres of the respective materials for 6 h/day on 5 consecutive days. Target concentrations were 30 mg/m3 as high dose for all compounds and selected based occupational exposure limits for respirable nuisance dust. Toxicity was determined after end of exposure and after 3-week recovery using broncho-alveolar lavage fluid (BALF) and microscopic examinations of the entire respiratory tract. Mixed chlorinated DPP isomers and coarse meta-chloro DPP isomer caused marginal changes in BALF, consisting of slight increases of polymorphonuclear neutrophils, and in case of coarse meta-chloro DPP increased MCP-1 and osteopontin levels. Mixed chlorinated DPP isomers, Pigment Red 254, and meta-chloro DPP caused pigment deposits and phagocytosis by alveolar macrophages, slight hypertrophy/hyperplasia of the bronchioles and alveolar ducts, but without evidence of inflammation. In contrast, only pigment deposition and pigment phagocytosis were observed after exposure to Pigment Red 101. All pigments were tolerated well and caused only marginal effects in BALF or no effects at all. Only minor effects were seen on the lung by microscopic examination. There was no evidence of systemic inflammation based on acute-phase protein levels in blood. PMID:27387137

  20. Inhibition of Recombinant Aldose-6-Phosphate Reductase from Peach Leaves by Hexose-Phosphates, Inorganic Phosphate and Oxidants.

    PubMed

    Hartman, Matías D; Figueroa, Carlos M; Arias, Diego G; Iglesias, Alberto A

    2017-01-01

    Glucitol, also known as sorbitol, is a major photosynthetic product in plants from the Rosaceae family. This sugar alcohol is synthesized from glucose-6-phosphate by the combined activities of aldose-6-phosphate reductase (Ald6PRase) and glucitol-6-phosphatase. In this work we show the purification and characterization of recombinant Ald6PRase from peach leaves. The recombinant enzyme was inhibited by glucose-1-phosphate, fructose-6-phosphate, fructose-1,6-bisphosphate and orthophosphate. Oxidizing agents irreversibly inhibited the enzyme and produced protein precipitation. Enzyme thiolation with oxidized glutathione protected the enzyme from insolubilization caused by diamide, while incubation with NADP+ (one of the substrates) completely prevented enzyme precipitation. Our results suggest that Ald6PRase is finely regulated to control carbon partitioning in peach leaves. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  1. Ultrasonic-assisted degradation of phenazopyridine with a combination of Sm-doped ZnO nanoparticles and inorganic oxidants.

    PubMed

    Eskandarloo, Hamed; Badiei, Alireza; Behnajady, Mohammad A; Ziarani, Ghodsi Mohammadi

    2016-01-01

    Pure and samarium doped ZnO nanoparticles were synthesized by a sonochemical method and characterized by TEM, SEM, EDX, XRD, Pl, and DRS techniques. The average crystallite size of pure and Sm-doped ZnO nanoparticles was about 20 nm. The sonocatalytic activity of pure and Sm-doped ZnO nanoparticles was considered toward degradation of phenazopyridine as a model organic contaminant. The Sm-doped ZnO nanoparticles with Sm concentration of 0.4 mol% indicated a higher sonocatalytic activity (59%) than the pure ZnO (51%) and other Sm-doped ZnO nanoparticles. It was believed that Sm(3+) ion with optimal concentration (0.4 mol%) can act as superficial trapping for electrons in the conduction band of ZnO and delayed the recombination of charge carriers. The influence of the nature and concentration of various oxidants, including periodate, hydrogen peroxide, peroxymonosulfate, and peroxydisulfate on the sonocatalytic activity of Sm-doped ZnO nanoparticles was studied. The influence of the oxidants concentration (0.2-1.4 g L(-1)) on the degradation rate was established by the 3D response surface and the 2D contour plots. The results demonstrated that the utilizing of oxidants in combination with Sm-doped ZnO resulting in rapid removal of contaminant, which can be referable to a dual role of oxidants; (i) scavenging the generated electrons in the conduction band of ZnO and (ii) creating highly reactive radical species under ultrasonic irradiation. It was found that the Sm-doped ZnO and periodate combination is the most efficient catalytic system under ultrasonic irradiation.

  2. Inorganic Graphene Analogs

    NASA Astrophysics Data System (ADS)

    Rao, C. N. R.; Maitra, Urmimala

    2015-07-01

    In the last four to five years, there has been a great resurgence of research on two-dimensional inorganic materials, partly because of the impetus received from graphene research. Unlike graphene, which is a gap-less material, most inorganic layered materials are semiconductors or insulators. Some of them, as exemplified by MoS2, exhibit unexpected properties, not unlike graphene, with possible applications. Thus, layered metal chalcogenides are being explored intensely, and MoS2 is emerging as a wonder material. In this article, we present the synthesis and properties of nanosheets composing single or few layers of these fascinating materials. Besides metal chalcogenides, boron nitride, borocarbonitrides (BxCyNz), metal oxides, and metal-organic frameworks are also discussed.

  3. A Random Network Model of Electrical Conduction in Hydrous Rock

    NASA Astrophysics Data System (ADS)

    Fujita, K.; Seki, M.; Katsura, T.; Ichiki, M.

    2011-12-01

    To evaluate the variation in conductivity of hydrous rock during the dehydration, it is essential to comprehend the mechanism of electrical conduction network in rock. In the recent past, several attempts have been made to demonstrate the mechanism of electrical conduction network in hydrous rock. However, realistic conduction mechanism within the crustal rock and mineral is unknown and relevant theories have not been successful. The aim of our study is to quantify the electrical conduction network in the rock and/or mineral. We developed a cell-type lattice network model to evaluate the electrical conduction mechanism of fluid-mineral interaction. Using cell-type lattice model, we simulated the various electrical paths and connectivity in the rock and/or mineral sample. First, we assumed a network model consists of 100 by 100 elementary cells as matrix configuration. We also settled the current input and output layers at the edge of the lattice model. Second, we randomly generated and put the conductive and resistive cells using the scheme of Mersenne Twister. Third, we applied the current for this model and performed a great number of realization on each mineral distribution patterns explaining realistic conduction network model. Considering fractal dimensions, our model has been compared with images from Electron Probe Micro Analysis. To evaluate the distribution pattern of conductive and resistive cells quantitatively, we have determined fractal dimensions by box-counting method. Assessing the bulk conductivity change as a function of conductor ratio in the hydrous rock, the model has been examined successfully both against simulated data and experimental data.

  4. Seismic signature of a hydrous mantle transition zone

    NASA Astrophysics Data System (ADS)

    Thio, Vincent; Cobden, Laura; Trampert, Jeannot

    2016-01-01

    Although water has a major influence on tectonic and other geodynamic processes, little is known about its quantity and distribution within the deep Earth. In the last few decades, laboratory experiments on nominally anhydrous minerals (NAMs) of the transition zone have shown that these minerals can contain significant amounts of water, up to 3.3 wt%. In this study, we investigate if it is possible to use seismic observations to distinguish between a hydrous and anhydrous transition zone. We perform an extensive literature search of mineral experimental data, to generate a compilation of the water storage capacities, elastic parameters and phase boundary data for potentially hydrous minerals in the transition zone, and use thermodynamic modelling to compute synthetic seismic profiles of density, VP and VS at transition zone temperatures and pressures. We find that large uncertainties on the mineral phase equilibria (ca. 2 GPa) and elastic properties produce a wide range of seismic profiles. In particular, there is a lack of data at temperatures corresponding to those along a 1300 °C adiabat or hotter, which may be expected at transition zone pressures. Comparing our hydrous transition zone models with equivalent profiles at anhydrous conditions, we see that the depths of the 410 and 660 discontinuities cannot at present be used to map the water content of the transition zone due to these uncertainties. Further, while average velocities and densities inside the transition zone clearly decrease with increasing water content, there is a near-perfect trade-off with increases in temperature. It is therefore difficult to distinguish thermal from water effects, and the conventional view of a slow and thick transition zone for water and slow and thin transition zone for high temperature should be regarded with caution. A better diagnostic for water may be given by the average velocity gradients of the transition zone, which increase with increasing water content (but

  5. Hydrous species in eclogitic omphacite: Implication for metamorphic dehydration during exhumation

    NASA Astrophysics Data System (ADS)

    Sheng, Ying-Ming; Gong, Bing

    2017-09-01

    Water contents were analyzed by infrared spectroscopy for structural hydroxyl in randomly oriented cuboids and doubly polished wafers of single crystal omphacite from an ultrahigh-pressure eclogite in the Dabie orogen. The results are quantitatively compared with bulk water contents measured by the TC/EA-MS continuous flow technique. This enables recognition of various hydrous species in omphacite and their bearings on metamorphic dehydration during continental subduction. The two cuboids yield constant maximal structural water contents of ∼378 ppm (H2O wt.) using the omphacite-specific infrared absorption coefficient, which are much lower than the bulk water contents of ∼1496 ppm. The excessive water is contributed by the presence of other hydrous species in the form of hydrous mineral inclusions, hydrous symplectite and submicron fluid inclusions. Since the hydrous mineral and/or fluid inclusions may be captured at different metamorphic stages during subduction and exhumation of continental crust and the hydrous symplectite is the secondary rather than the primary, it is suggested that the bulk water contents represent a mixing of various hydrous species with distinct origins. In this regard, it is critical to examine whether water in these secondary hydrous species is of internal origin; if not, it has nothing to do with the transport capacity of water in deeply subducted crustal rocks. Upon stepwise heating up to 700 °C, omphacite exhibits a gradual decrease in bulk water contents but an increase in δD values, indicating the preferential loss of D-depleted hydrous species as a whole due to the decompressional dehydration of UHP metamorphic rocks during exhumation. Therefore, the D-depleted hydrous species may be dominated in the hydrous symplectite and inclusion water.

  6. The research progress of Li-ion battery separators with inorganic oxide nanoparticles by electrospinning: A mini review

    NASA Astrophysics Data System (ADS)

    Chen, Hong-Li; Jiao, Xiao-Ning; Zhou, Jin-Tao

    2016-09-01

    The technology of Lithium-ion battery (LIB) separator has become more and more mature. But there are still many problems that needed to be resolved. For example, its mechanical strength is low relatively, thermal stability is bad and the porosity and electrochemical performance are imperfect. This paper introduces modification of electrospinning LIB separator from the way of adding nanoparticles, including SiO2, TiO2, Al2O3 and copper titanate oxide, etc. And addition methods include dissolving in dispersant, dissolving in polymer solution, coating and in situ method. The modified membranes possess higher ionic conductivity which can reach to the level of 10-3s/cm.

  7. Evaluation of phagocytic activity and nitric oxide generation by molluscan haemocytes as biomarkers of inorganic arsenic exposure.

    PubMed

    Chakraborty, Sudipta; Ray, Mitali; Ray, Sajal

    2009-12-01

    The natural habitats of the freshwater bivalve Lamellidens marginalis face the risk of contamination by the toxic metalloid arsenic. Haemocyte-mediated non-self phagocytosis and generation of nitric oxide (NO) as reactive nitrogen intermediate were examined to establish the reliability of the parameters as biomarkers of sodium arsenite-induced stress on the animal at sublethal concentrations. The studies suggest imposition of a remarkable immune compromise/immune suppression on the animal by the natural contaminant. The animal expressed partial recovery in its phagocytic potential and NO generation over a period of 30 days. Quantitation of phagocytic efficiency and intrahaemocyte NO generation indicates the possibility of the parameters be accepted as cellular biomarkers to estimate and characterize the vulnerability of the freshwater organisms to sodium arsenite-induced stress.

  8. Efficient automatic screening for Li ion conductive inorganic oxides with bond valence pathway models and percolation algorithm

    NASA Astrophysics Data System (ADS)

    Nakayama, Masanobu; Kimura, Mayumi; Jalem, Randy; Kasuga, Toshihiro

    2016-01-01

    Fast ion conductive solid oxide electrolytes are urgently needed because of the development of batteries, fuel cells, and sensors. Ab initio density functional theory can predict ionic conductivities with high accuracy, although it often requires large computational resources and time. In this paper, we use empirical bond valence relations [Adams et al., Phys. Status Solidi A 208, 1746 (2011)] and a percolation algorithm for fast, efficient, fully automated evaluation of migration energies for Li ion conduction in 14 olivine-type LiMXO4 compounds. The results showed a high correlation coefficient with the ab initio density functional theory (DFT) approach, indicating that our method could be attractive for identifying fast ion conductors in databases of numerous candidates.

  9. Effect of inorganic carbon concentration on the stability and nitrite-oxidizing bacteria community structure of the CANON process in a membrane bioreactor.

    PubMed

    Zhang, Xiaojing; Zhou, Yue; Ma, Yongpeng; Zhang, Nan; Zhao, Siyu; Zhang, Rongrong; Zhang, Jun; Zhang, Hongzhong

    2017-03-30

    In the completely autotrophic nitrogen removal over nitrite (CANON) process, the nitrite-oxidizing bacteria (NOB) should be effectively suppressed or thoroughly washed out. In this study, the nitrate production and the structure of NOB community under different inorganic carbon (IC) concentrations were investigated using denaturing gradient gel electrophoresis (DGGE) in a membrane bioreactor (MBR). Results showed that IC decrease correspondingly lowered the nitrogen removal, and simultaneously induced the nitrate production by NOB. DGGE results indicated the IC deficit led to the biodiversity increasing of both Nitrobacter-like NOB and Nitrospira-like NOB. An equation fitted between the ratio of nitrate production to ammonia consumption ([Formula: see text]) and the ratio of influent IC to ammonia concentration ([Formula: see text]) indicated the influent [Formula: see text] should be controlled between 1.6 and 2.3 to ensure the stable operation of the CANON process. A small amount addition of organic material could be used as an effective strategy to suppress NOB when the [Formula: see text] ratio was not appropriate.

  10. Utilization of titanium oxide-like compound as an inorganic phosphate adsorbent for the control of serum phosphate level in chronic renal failure.

    PubMed

    Tamagawa, Kazuhiko; Nakayama-Imaohji, Haruyuki; Wakimoto, Shin; Ichimura, Minoru; Kuwahara, Tomomi

    2010-08-01

    Hyperphosphatemia adversely affects the prognosis of patients with chronic renal failure (CRF). We synthesized a titanium oxide-like compound (TAP) as a phosphate adsorbent for treatment of hyperphosphatemia in CFR patients. We evaluated the ability of TAP to adsorb inorganic phosphate in vitro and in vivo. TAP was shown to contain sulfate and hydroxyl groups by thermal analysis, which probably involved in phosphate adsorption through an ionic exchange mechanism. TAP constantly adsorbed phosphate (66.20-72.84 mg/g TAP) over a wide pH range (1.22-7.27) in vitro. To evaluate the phosphate binding potential of TAP in vivo, adenine-induced CRF rats were fed AIN-76 diet containing 3% TAP, 10% TAP, 3% sevelamer hydrochloride (clinical phosphate adsorbent), or 3% calcium carbonate, and serum levels of phosphate and calcium and urinary phosphate were compared with those in untreated CRF rats. Orally administered TAP showed the inhibitory effect on serum phosphate level in adenine-induced CRF rats, which was equivalent to that of sevelamer hydrochloride. These results indicate that TAP is a useful alternative phosphate-binder with fewer side effects than sevelamer hydrochloride and calcium carbonate.

  11. Hydrous mantle transition zone indicated by ringwoodite included within diamond.

    PubMed

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

    2014-03-13

    The ultimate origin of water in the Earth's hydrosphere is in the deep Earth--the mantle. Theory and experiments have shown that although the water storage capacity of olivine-dominated shallow mantle is limited, the Earth's transition zone, at depths between 410 and 660 kilometres, could be a major repository for water, owing to the ability of the higher-pressure polymorphs of olivine--wadsleyite and ringwoodite--to host enough water to comprise up to around 2.5 per cent of their weight. A hydrous transition zone may have a key role in terrestrial magmatism and plate tectonics, yet 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 transition zone contains abundant water remains highly controversial. Here we report X-ray diffraction, Raman and infrared spectroscopic data that provide, to our knowledge, the first evidence for the terrestrial occurrence of any higher-pressure polymorph of olivine: we find ringwoodite included in a diamond from Juína, Brazil. The water-rich nature of this inclusion, indicated by infrared absorption, along with the preservation of the ringwoodite, is direct evidence that, at least locally, the transition zone is hydrous, to about 1 weight per cent. The finding also indicates that some kimberlites must have their primary sources in this deep mantle region.

  12. Electrical conductivity of hydrous andesitic melts pertinent to subduction zones

    NASA Astrophysics Data System (ADS)

    Guo, Xuan; Li, Bin; Ni, Huaiwei; Mao, Zhu

    2017-03-01

    Andesitic magmatism and rocks are widespread at convergent plate boundaries. Electrically conductive bodies beneath subduction zone arc volcanoes, such as the Uturuncu Volcano, Bolivia, may correspond to active reservoirs of H2O-bearing andesitic magma. Laboratory measurements of electrical conductivity of hydrous andesitic melts are required to constrain the physicochemical conditions of these magma reservoirs in combination with magnetotelluric data. This experimental study investigates electrical conductivity of andesitic melts with 0.01-5.9 wt % of H2O at 1164-1573 K and 0.5-1.0 GPa in a piston cylinder apparatus using sweeping-frequency impedance spectroscopy. Electrical conductivity of andesitic melt increases with increasing temperature and H2O concentration but decreases with pressure. Across the investigated range of H2O concentration, electrical conductivity varies by 1.2-2.4 log units, indicating stronger influence of H2O for andesitic melt than for rhyolitic and dacitic melts. Using the Nernst-Einstein equation, the principal charge carrier is inferred to be Na in anhydrous melt but divalent cations in hydrous andesitic melts. The experimental data are regressed into a general electrical conductivity model for andesitic melt accounting for the pressure-temperature-H2O dependences altogether. Modeling results show that the conductive layer at >20 km depths beneath the surface of the Uturuncu Volcano could be interpreted by the presence of less than 20 vol % of H2O-rich andesitic melt (with 6-9 wt % H2O).

  13. Creep behavior of Fe-bearing olivine under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Tasaka, Miki; Zimmerman, Mark E.; Kohlstedt, David L.

    2015-09-01

    To understand the effect of iron content on the creep behavior of olivine, (MgxFe(1 - x))2SiO4, under hydrous conditions, we have conducted tri-axial compressive creep experiments on samples of polycrystalline olivine with Mg contents of x = 0.53, 0.77, 0.90, and 1. Samples were deformed at stresses of 25 to 320 MPa, temperatures of 1050° to 1200°C, a confining pressure of 300 MPa, and a water fugacity of 300 MPa using a gas-medium high-pressure apparatus. Under hydrous conditions, our results yield the following expression for strain rate as a function of iron content for 0.53 ≤ x ≤ 0.90 in the dislocation creep regime: ɛ˙=ɛ˙0.90((1-x/0.1))1/2exp[226×1030.9-x/RT]. In this equation, the strain rate of San Carlos olivine, ɛ˙0.90, is a function of T, σ, and fH2O. As previously shown for anhydrous conditions, an increase in iron content directly increases creep rate. In addition, an increase in iron content increases hydrogen solubility and therefore indirectly increases creep rate. This flow law allows us to extrapolate our results to a wide range of mantle conditions, not only for Earth's mantle but also for the mantle of Mars.

  14. Adsorption of natural dissolved organic matter at the oxide/water interface

    USGS Publications Warehouse

    Davis, James A.

    1982-01-01

    Natural organic matter is readily adsorbed by alumina and kaolinite in the pH range of natural waters. Adsorption occurs by complex formation between surface hydroxyls and the acidic functional groups of the organic matter. Oxides with relatively acidic surface hydroxyls, e.g. silica, do not react strongly with the organic matter. Under conditions typical for natural waters, almost complete surface coverage by adsorbed organic matter may be expected for alumina, hydrous iron oxides and the edge sites of aluminosilicates. Potentiometric titration and electrophoresis indicate that most of the acidic functional groups of the adsorbed organic matter are neutralized by protons from solution. The organic coating is expected to have a great influence on subsequent adsorption of inorganic cations and anions.

  15. Temperature dependence of rat liver mitochondrial respiration with uncoupling of oxidative phosphorylation by fatty acids. Influence of inorganic phosphate.

    PubMed

    Samartsev, V N; Chezganova, S A; Polishchuk, L S; Paydyganov, A P; Vidyakina, O V; Zeldi, I P

    2003-06-01

    The respiration rate of liver mitochondria in the course of succinate oxidation depends on temperature in the presence of palmitate more strongly than in its absence (in state 4). In the Arrhenius plot, the temperature dependence of the palmitate-induced stimulation of respiration has a bend at 22 degrees C which is characterized by transition of the activation energy from 120 to 60 kJ/mol. However, a similar dependence of respiration in state 4 is linear over the whole temperature range and corresponds to the activation energy of 17 kJ/mol. Phosphate partially inhibits the uncoupling effect of palmitate. This effect of phosphate is increased on decrease in temperature. In the presence of phosphate the temperature dependence in the Arrhenius plot also has a bend at 22 degrees C, and the activation energy increases from 128 to 208 kJ/mol in the range from 13 to 22 degrees C and from 56 to 67 kJ/mol in the range from 22 to 37 degrees C. Mersalyl (10 nmol/mg protein), an inhibitor of the phosphate carrier, similarly to phosphate, suppresses the uncoupling effect of laurate, and the effects of mersalyl and phosphate are not additive. The recoupling effects of phosphate and mersalyl seem to show involvement of the phosphate carrier in the uncoupling effect of fatty acids in liver mitochondria. Possible mechanisms of involvement of the phosphate carrier in the uncoupling effect of fatty acids are discussed.

  16. Calcium controls the assembly of the photosynthetic water-oxidizing complex: a cadmium(II) inorganic mutant of the Mn4Ca core

    PubMed Central

    Bartlett, John E; Baranov, Sergei V; Ananyev, Gennady M; Dismukes, G. Charles

    2007-01-01

    Perturbation of the catalytic inorganic core (Mn4Ca1OxCly) of the photosystem II-water-oxidizing complex (PSII-WOC) isolated from spinach is examined by substitution of Ca2+ with cadmium(II) during core assembly. Cd2+ inhibits the yield of reconstitution of O2-evolution activity, called photoactivation, starting from the free inorganic cofactors and the cofactor-depleted apo-WOC-PSII complex. Ca2+ affinity increases following photooxidation of the first Mn2+ to Mn3+ bound to the ‘high-affinity’ site. Ca2+ binding occurs in the dark and is the slowest overall step of photoactivation (IM1→IM1* step). Cd2+ competitively blocks the binding of Ca2+ to its functional site with 10- to 30-fold higher affinity, but does not influence the binding of Mn2+ to its high-affinity site. By contrast, even 10-fold higher concentrations of Cd2+ have no effect on O2-evolution activity in intact PSII-WOC. Paradoxically, Cd2+ both inhibits photoactivation yield, while accelerating the rate of photoassembly of active centres 10-fold relative to Ca2+. Cd2+ increases the kinetic stability of the photooxidized Mn3+ assembly intermediate(s) by twofold (mean lifetime for dark decay). The rate data provide evidence that Cd2+ binding following photooxidation of the first Mn3+, IM1→IM1*, causes three outcomes: (i) a longer intermediate lifetime that slows IM1 decay to IM0 by charge recombination, (ii) 10-fold higher probability of attaining the degrees of freedom (either or both cofactor and protein d.f.) needed to bind and photooxidize the remaining 3 Mn2+ that form the functional cluster, and (iii) increased lability of Cd2+ following Mn4 cluster assembly results in (re)exchange of Cd2+ by Ca2+ which restores active O2-evolving centres. Prior EPR spectroscopic data provide evidence for an oxo-bridged assembly intermediate, Mn3+(μ-O2−)Ca2+, for IM1*. We postulate an analogous inhibited intermediate with Cd2+ replacing Ca2+. PMID:17954439

  17. Calcium controls the assembly of the photosynthetic water-oxidizing complex: a cadmium(II) inorganic mutant of the Mn4Ca core.

    PubMed

    Bartlett, John E; Baranov, Sergei V; Ananyev, Gennady M; Dismukes, G Charles

    2008-03-27

    Perturbation of the catalytic inorganic core (Mn4Ca1OxCly) of the photosystem II-water-oxidizing complex (PSII-WOC) isolated from spinach is examined by substitution of Ca2+ with cadmium(II) during core assembly. Cd2+ inhibits the yield of reconstitution of O2-evolution activity, called photoactivation, starting from the free inorganic cofactors and the cofactor-depleted apo-WOC-PSII complex. Ca2+ affinity increases following photooxidation of the first Mn2+ to Mn3+ bound to the 'high-affinity' site. Ca2+ binding occurs in the dark and is the slowest overall step of photoactivation (IM1-->IM1* step). Cd2+ competitively blocks the binding of Ca2+ to its functional site with 10- to 30-fold higher affinity, but does not influence the binding of Mn2+ to its high-affinity site. By contrast, even 10-fold higher concentrations of Cd2+ have no effect on O2-evolution activity in intact PSII-WOC. Paradoxically, Cd2+ both inhibits photoactivation yield, while accelerating the rate of photoassembly of active centres 10-fold relative to Ca2+. Cd2+ increases the kinetic stability of the photooxidized Mn3+ assembly intermediate(s) by twofold (mean lifetime for dark decay). The rate data provide evidence that Cd2+ binding following photooxidation of the first Mn3+, IM1-->IM1*, causes three outcomes: (i) a longer intermediate lifetime that slows IM1 decay to IM0 by charge recombination, (ii) 10-fold higher probability of attaining the degrees of freedom (either or both cofactor and protein d.f.) needed to bind and photooxidize the remaining 3 Mn2+ that form the functional cluster, and (iii) increased lability of Cd2+ following Mn4 cluster assembly results in (re)exchange of Cd2+ by Ca2+ which restores active O2-evolving centres. Prior EPR spectroscopic data provide evidence for an oxo-bridged assembly intermediate, Mn3+(mu-O2(-))Ca2+, for IM1*. We postulate an analogous inhibited intermediate with Cd2+ replacing Ca2+.

  18. Analysis of Mineral Assemblages Containing Unstable Hydrous Phases

    NASA Astrophysics Data System (ADS)

    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

  19. Geochemical signatures of thermochemical sulfate reduction in controlled hydrous pyrolysis experiments

    USGS Publications Warehouse

    Zhang, T.; Ellis, G.S.; Walters, C.C.; Kelemen, S.R.; Wang, K.-s.; Tang, Y.

    2008-01-01

    A series of gold tube hydrous pyrolysis experiments was conducted in order to investigate the effect of thermochemical sulfate reduction (TSR) on gas generation, residual saturated hydrocarbon compositional alteration, and solid pyrobitumen formation. The intensity of TSR significantly depends on the H2O/MgSO4 mole ratio, the smaller the ratio, the stronger the oxidizing conditions. Under highly oxidizing conditions (MgSO4/hydrocarbon wt/wt 20/1 and hydrocarbon/H2O wt/wt 1/1), large amounts of H2S and CO2 are generated indicating that hydrocarbon oxidation coupled with sulfate reduction is the dominant reaction. Starting with a mixture of C21-C35 n-alkanes, these hydrocarbons are consumed totally at temperatures below the onset of hydrocarbon thermal cracking in the absence of TSR (400 ??C). Moreover, once the longer chain length hydrocarbons are oxidized, secondarily formed hydrocarbons, even methane, are oxidized to CO2. Using whole crude oils as the starting reactants, the TSR reaction dramatically lowers the stability of hydrocarbons leading to increases in gas dryness and gas/oil ratio. While their concentrations decrease, the relative distributions of n-alkanes do not change appreciably from the original composition, and consequently, are non-diagnostic for TSR. However, distinct molecular changes related to TSR are observed, Pr/n-C17 and Ph/n-C18 ratios decrease at a faster rate under TSR compared to thermal chemical alteration (TCA) alone. TSR promotes aromatization and the incorporation of sulfur and oxygen into hydrocarbons leading to a decrease in the saturate to aromatic ratio in the residual oil and in the generation of sulfur and oxygen rich pyrobitumen. These experimental findings could provide useful geochemical signatures to identify TSR in settings where TSR has occurred in natural systems. ?? 2008 Elsevier Ltd. All rights reserved.

  20. Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

    USGS Publications Warehouse

    Amrani, A.; Lewan, M.D.; Aizenshtat, Zeev

    2005-01-01

    Hydrous pyrolysis experiments at 200 to 365??C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2 S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2??? in 34S during thermal maturation compared with the initial ??34S values. The ??34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1??? of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21??? lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the ??34S-enriched secondary pyrite decomposes above 300??C resulting in a corresponding decrease in the ??34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen ??34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The

  1. Science Update: Inorganic Chemistry.

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1981-01-01

    Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

  2. Science Update: Inorganic Chemistry.

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1981-01-01

    Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

  3. Nitric oxide generated by nitrate reductase increases nitrogen uptake capacity by inducing lateral root formation and inorganic nitrogen uptake under partial nitrate nutrition in rice

    PubMed Central

    Sun, Huwei; Li, Jiao; Song, Wenjing; Tao, Jinyuan; Huang, Shuangjie; Chen, Si; Hou, Mengmeng; Xu, Guohua; Zhang, Yali

    2015-01-01

    Increasing evidence shows that partial nitrate nutrition (PNN) can be attributed to improved plant growth and nitrogen-use efficiency (NUE) in rice. Nitric oxide (NO) is a signalling molecule involved in many physiological processes during plant development and nitrogen (N) assimilation. It remains unclear whether molecular NO improves NUE through PNN. Two rice cultivars (cvs Nanguang and Elio), with high and low NUE, respectively, were used in the analysis of NO production, nitrate reductase (NR) activity, lateral root (LR) density, and 15N uptake under PNN, with or without NO production donor and inhibitors. PNN increased NO accumulation in cv. Nanguang possibly through the NIA2-dependent NR pathway. PNN-mediated NO increases contributed to LR initiation, 15NH4 +/15NO3 – influx into the root, and levels of ammonium and nitrate transporters in cv. Nanguang but not cv. Elio. Further results revealed marked and specific induction of LR initiation and 15NH4 +/15NO3 – influx into the roots of plants supplied with NH4 ++sodium nitroprusside (SNP) relative to those supplied with NH4 + alone, and considerable inhibition upon the application of cPTIO or tungstate (NR inhibitor) in addition to PNN, which is in agreement with the change in NO fluorescence in the two rice cultivars. The findings suggest that NO generated by the NR pathway plays a pivotal role in improving the N acquisition capacity by increasing LR initiation and the inorganic N uptake rate, which may represent a strategy for rice plants to adapt to a fluctuating nitrate supply and increase NUE. PMID:25784715

  4. Nitric oxide generated by nitrate reductase increases nitrogen uptake capacity by inducing lateral root formation and inorganic nitrogen uptake under partial nitrate nutrition in rice.

    PubMed

    Sun, Huwei; Li, Jiao; Song, Wenjing; Tao, Jinyuan; Huang, Shuangjie; Chen, Si; Hou, Mengmeng; Xu, Guohua; Zhang, Yali

    2015-05-01

    Increasing evidence shows that partial nitrate nutrition (PNN) can be attributed to improved plant growth and nitrogen-use efficiency (NUE) in rice. Nitric oxide (NO) is a signalling molecule involved in many physiological processes during plant development and nitrogen (N) assimilation. It remains unclear whether molecular NO improves NUE through PNN. Two rice cultivars (cvs Nanguang and Elio), with high and low NUE, respectively, were used in the analysis of NO production, nitrate reductase (NR) activity, lateral root (LR) density, and (15)N uptake under PNN, with or without NO production donor and inhibitors. PNN increased NO accumulation in cv. Nanguang possibly through the NIA2-dependent NR pathway. PNN-mediated NO increases contributed to LR initiation, (15)NH₄(+)/(15)NO₃(-) influx into the root, and levels of ammonium and nitrate transporters in cv. Nanguang but not cv. Elio. Further results revealed marked and specific induction of LR initiation and (15)NH₄(+)/(15)NO₃(-) influx into the roots of plants supplied with NH₄(+)+sodium nitroprusside (SNP) relative to those supplied with NH₄(+) alone, and considerable inhibition upon the application of cPTIO or tungstate (NR inhibitor) in addition to PNN, which is in agreement with the change in NO fluorescence in the two rice cultivars. The findings suggest that NO generated by the NR pathway plays a pivotal role in improving the N acquisition capacity by increasing LR initiation and the inorganic N uptake rate, which may represent a strategy for rice plants to adapt to a fluctuating nitrate supply and increase NUE. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  5. Association Between Variants in Arsenic (+3 Oxidation State) Methyltranserase (AS3MT) and Urinary Metabolites of Inorganic Arsenic: Role of Exposure Level.

    PubMed

    Xu, Xiaofan; Drobná, Zuzana; Voruganti, V Saroja; Barron, Keri; González-Horta, Carmen; Sánchez-Ramírez, Blanca; Ballinas-Casarrubias, Lourdes; Cerón, Roberto Hernández; Morales, Damián Viniegra; Terrazas, Francisco A Baeza; Ishida, María C; Gutiérrez-Torres, Daniela S; Saunders, R Jesse; Crandell, Jamie; Fry, Rebecca C; Loomis, Dana; García-Vargas, Gonzalo G; Del Razo, Luz M; Stýblo, Miroslav; Mendez, Michelle A

    2016-09-01

    Variants in AS3MT, the gene encoding arsenic (+3 oxidation state) methyltranserase, have been shown to influence patterns of inorganic arsenic (iAs) metabolism. Several studies have suggested that capacity to metabolize iAs may vary depending on levels of iAs exposure. However, it is not known whether the influence of variants in AS3MT on iAs metabolism also vary by level of exposure. We investigated, in a population of Mexican adults exposed to drinking water As, whether associations between 7 candidate variants in AS3MT and urinary iAs metabolites were consistent with prior studies, and whether these associations varied depending on the level of exposure. Overall, associations between urinary iAs metabolites and AS3MT variants were consistent with the literature. Referent genotypes, defined as the genotype previously associated with a higher percentage of urinary dimethylated As (DMAs%), were associated with significant increases in the DMAs% and ratio of DMAs to monomethylated As (MAs), and significant reductions in MAs% and iAs%. For 3 variants, associations between genotypes and iAs metabolism were significantly stronger among subjects exposed to water As >50 versus ≤50 ppb (water As X genotype interaction P < .05). In contrast, for 1 variant (rs17881215), associations were significantly stronger at exposures ≤50 ppb. Results suggest that iAs exposure may influence the extent to which several AS3MT variants affect iAs metabolism. The variants most strongly associated with iAs metabolism-and perhaps with susceptibility to iAs-associated disease-may vary in settings with exposure level. © The Author 2016. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  6. Micro-Raman studies of hydrous ferrous sulfates and jarosites.

    PubMed

    Chio, Chi Hong; Sharma, Shiv K; Muenow, David W

    2005-08-01

    Ferrous sulfates of various hydration states (FeSO(4) X xH(2)O; x=7, 4, 1) and jarosites (MFe(3)(SO(4))(2)(OH)(6); M=Na or K) were synthesized and studied by micro-Raman spectroscopy between 295 and 8K. Spectral analyses of the sulfate and water/hydroxyl vibrational modes are presented. Fingerprint regions attributed to the symmetric (nu(1)) and antisymmetric (nu(3)) stretching vibrations of the sulfate group are found to vary with the degree of hydration in hydrous ferrous sulfate. In jarosites, the Raman shift of the OH stretching mode is related to the type of alkali metal present between the tetrahedral and octahedral layers. The Raman technique can thus unambiguously identify ferrous sulfate of various hydration states and jarosites bearing different alkali metal ions.

  7. Nitrogen Isotopic Anomalies in a Hydrous Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Smith, J. B.; Dai, Z. R.; Weber, P. K.; Graham, G. A.; Hutcheon, I. D.; Bajt, S.; Ishii, H.; Bradley, J. P.

    2005-01-01

    Interplanetary dust particles (IDPs) collected in the stratosphere are the fine-grained end member (5 - 50 microns in size) of the meteoritic material available for investigation in the laboratory. IDPs are derived from either cometary or asteroidal sources. Some IDPs contain cosmically primitive materials with isotopic signatures reflecting presolar origins. Recent detailed studies using the NanoSIMS have shown there is a wide variation of isotopic signatures within individual IDPs; grains with a presolar signature have been observed surrounded by material with a solar isotopic composition. The majority of IDPs studied have been anhydrous. We report here results from integrated NanoSIMS/FIB/TEM/Synchrotron IR studies of a hydrous IDP, focused on understanding the correlations between the isotopic, mineralogical and chemical compositions of IDPs.

  8. Optimizing the electron microprobe analysis of hydrous alkali aluminosilicate glasses

    SciTech Connect

    Morgan, G.B. VI; London, D.

    1996-09-01

    The time-dependent loss of NaK{alpha} X-ray intensity during electron-beam irradiation of hydrous alkali aluminosilicate glasses is apparently more significant during the initial few seconds of beam exposure than it is for anhydrous glasses, and it is pronounced for incident beam currents >2-5 nA (using 15-20 {mu}m beam diameters). Exponential fits of NaK{alpha} intensity vs. time show a progressive decrease in the apparent zero-time intercepts for incident beams from 2 to 20 nA, and thus methods for correcting Na concentrations solely on the basis of curve fitting and extrapolation to zero-time values may underestimate Na contents by almost 10% (relative) for higher beam currents. Similar exponential fits to the intensity-time data for AlK{alpha} and SiK{alpha} show that {open_quotes}grow-in{close_quotes} is greater for Al than for Si. For incident currents {ge}5 nA, the magnitudes of all intensity changes also increase with total H{sub 2}O content of glass. On the basis of these observations, the optimal conditions for analysis of hydrous alkali aluminosilicate glasses include a 2 nA beam with 20 {mu}m diameter and counting times of 20-40 s for the analysis of alkali aluminosilicate components, with Na and Al analyzed first (simultaneously, if possible). These methods minimize Na loss and grow-in for Al and Si to the point that little or no correction is needed, provide good statistical accuracy, and work with a wide variety of standard materials (i.e., glass standards with compositions and H{sub 2}O contents comparable to the unknowns are not needed). 19 refs., 6 figs., 2 tabs.

  9. Single-crystal elasticity of hydrous wadsleyite by Brillouin scattering

    NASA Astrophysics Data System (ADS)

    Mao, Z.; Jiang, F.; Jacobsen, S. D.; Smyth, J. R.; Holl, C.; Duffy, T. S.; Frost, D. J.

    2006-12-01

    Wadsleyite (β-Mg2SiO4) is the high-pressure polymorph of olivine that is expected to be a dominant mineral in the transition zone from 410 km to 520 km depth in the mantle. The elasticity of wadsleyite is crucial to constrain the mineralogy of the transition zone. Previous studies show wadsleyite can incorporate variable amounts of water up to 3.3 wt% of water (Kohlstedt et al. 1996; Inoue et al. 1995; Smyth et al. 1987, 1994). The effect of water on the bulk modulus of wadsleyite was studied by x-ray diffraction (Yusa and Inoue, 1997; Smyth et al. 2005) but no constraints on the shear modulus exist. We have measured the single-crystal elastic constants of hydrous wadsleyite with varying water content using Brillouin spectroscopy at ambient conditions. We carried out measurements for samples containing 0.3 wt%, 0.6 wt% and 1.6 wt% water using at least 2 crystal planes for each sample. By computing the aggregate elastic properties, we find that the bulk (K0S) and shear modulus (G0) of hydrous wadsleyite decrease linearly with water content according to the following relations: K0S=169.0-11.8X_W; G0=115.1-12.5X_W; where X_W is the water H2O weight percent. Compared with anhydrous wadsleyite, 1 wt% of water will lead to 7.0% decrease in bulk modulus, 10.9% decrease in shear modulus. Water has a greater effect on the elastic moduli of wadsleyite than that of olivine or ringwoodite. The olivine to wadsleyite phase transition is believed to be the origin of the seismic discontinuity near 410 km. Using these new results, the possible effect of water content on the velocity contrast across the 410-km discontinuity will be examined.

  10. Amino acid, mineral and vitamin levels in hydrous faeces obtained from coprophagy-prevented rats.

    PubMed

    Sukemori, S; Ikeda, S; Kurihara, Y; Ito, S

    2003-06-01

    Amino acid, mineral and vitamin levels in hydrous faeces obtained from coprophagy-prevented rats were examined. Two experiments were conducted with rats of different age, 4 weeks and 10 weeks. Six rats each were fed under coprophagy-prevented and coprophagy-allowed (conventional feeding) conditions, respectively. In the first experiment using 4-week-old rats, amino acid values were determined for hydrous faeces and usual faeces obtained in the above-mentioned conditions. In the second experiment using 10-week-old rats, mineral values were determined for both types of faeces. Vitamin values were determined in both experiments. In a comparison of amino acid values and their patterns, specific kinds of amino acids in hydrous faeces were not recognized as growth factors. Sodium and potassium levels in hydrous faeces were significantly higher than those for usual faeces, but those levels were 1/(18-20) of those derived from feed. Although cyanocobalamin and folic acid levels in hydrous faeces were two to three times higher than those for usual faeces, folic acid supplements from coprophagy were 1/8 of those derived from feed. Cyanocobalamin supplements from hydrous faeces were five times larger than those from feed. Therefore, it appears that cyanocobalamin was supplied by the ingestion of hydrous faeces and that this cyanocobalamin supports conventional growth in rats.

  11. Formation of orthopyroxenite by reaction between peridotite and hydrous basaltic melt: an experimental study

    NASA Astrophysics Data System (ADS)

    Wang, Chunguang; Liang, Yan; Dygert, Nick; Xu, Wenliang

    2016-09-01

    The consequences of hydrous basaltic melts and peridotite interaction were examined experimentally in Au-Pd, Pt, and graphite capsules using the reaction couple method. Reactions between a hydrous basaltic andesite (4 wt% H2O) and dunite or lherzolite in an Au-Pd capsule at 1 GPa and 1200 °C produce a melt-bearing orthopyroxenite-dunite sequence. Reactions between a hydrous ferro-basalt and lherzolite in Pt or Au-Pd capsules at 0.8-2 GPa and 1250-1385 °C produce a melt-bearing orthopyroxenite-harzburgite sequence. Reactions between the ferro-basalt and lherzolite in graphite capsules (not designed to retain water) result in a melt-bearing dunite-harzburgite sequence at 1 GPa and a melt-bearing harzburgite-lherzolite sequence at 2 GPa. The orthopyroxenite from the hydrous reaction experiments has a high porosity, and it is separated by a sharp lithological interface from the dunite or harzburgite. Orthopyroxenes in the orthopyroxenite are large in size with resorbed olivine inclusions. Formation of the high-porosity orthopyroxenite in the hydrous melt-rock reaction experiments is determined by the liquidus phase relation of the interface reacting melt and reaction kinetics. Reaction between orthopyroxene-saturated hydrous melt and olivine at melt-rock interface produces orthopyroxenite. Water infiltration induces hydrous melting of the lherzolite, producing a dunite or an orthopyroxene-depleted harzburgite. Efficient diffusive exchange between the partial melt and the hydrous reacting melt promotes orthopyroxene-oversaturation around the melt-rock interfacial region. The simplified experiments reveal end-member processes for understanding the formation of orthopyroxenite in the upper mantle. The presence of orthopyroxenites in mantle samples is a strong indication of hydrous melt and peridotite interaction.

  12. The use of anthracene as a model compound in a comparative study of hydrous pyrolysis methods for industrial waste remediation.

    PubMed

    Nkansah, Marian Asantewah; Christy, Alfred A; Barth, Tanja

    2011-07-01

    Polycyclic aromatic hydrocarbons are very stable compounds and tend to bioaccumulate in the environment due to their high degree of conjugation and aromaticity. Hydrous pyrolysis is explored as a technique for the treatment of industrial water containing PAH, using anthracene as a model compound. The reactivity of anthracene under a range of temperatures and durations are studied in this paper. Aliquots of 1.0-10.0mg of anthracene in a range of 1.0-5.0 mL of H(2)O are subjected to hydrous pyrolysis under varied conditions of temperature, reagents and duration. The conditions include oxidising systems comprising distilled water, hydrogen peroxide and Nafion-SiO(2) solid catalyst in water; and reducing systems of formic acid and formic acid/Nafion-SiO(2)/Pd-C catalysts to assess a range of redox reaction conditions. Oxygen in air played a role in some of the reaction conditions. Pyrolysed products were identified and quantified by the use of Gas Chromatography-Mass Spectrometry (GC-MS). The major products were anthrone, anthraquinone, xanthone from oxidation; and multiple hydro-anthracene derivatives from reductive hydogenation. The nature of reaction conditions influenced the extent of anthracene degradation. The products formed are more reactive (less stable) as compared to anthracene the starting material and will therefore be less persistent in the environment.

  13. Plasma chemistry for inorganic materials

    NASA Technical Reports Server (NTRS)

    Matsumoto, O.

    1980-01-01

    Practical application of plasma chemistry to the development of inorganic materials using both low temperature and warm plasmas are summarized. Topics cover: the surface nitrification and oxidation of metals; chemical vapor deposition; formation of minute oxide particles; the composition of oxides from chloride vapor; the composition of carbides and nitrides; freezing high temperature phases by plasma arc welding and plasma jet; use of plasma in the development of a substitute for petroleum; the production of silicon for use in solar cell batteries; and insulating the inner surface of nuclear fusion reactor walls.

  14. Implication on Aqueous History of Mars as Revealed by Hydrous Minerals in Southwest Melas Chasma

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Glotch, T. D.

    2014-07-01

    We made new detections of hydrous minerals in southwest Melas Chasma including poly- and mono-hydrated sulfates, jarosite, and Fe/Mg smectites, and explored their possible formation mechanisms and implications on martian aqueous history.

  15. Viscosity of Anhydrous and Hydrous Basalt Melts at High Pressures

    NASA Astrophysics Data System (ADS)

    Tinker, D.; Lesher, C. E.; Baxter, G. M.; Uchida, T.; Wang, Y.; Zhao, Y.

    2004-12-01

    We performed in situ falling-sphere experiments to determine the viscosity of anhydrous and hydrous basaltic (48 wt% SiO2) melts from 1.5 to 5.3 GPa between 1600 and 1840 K, using the T-25 MA8 multianvil apparatus at the GSECARS 13-ID-D beamline at the Advanced Photon Source, Argonne National Lab. These falling-sphere experiments included monitoring the simultaneous settling of Pt and Mo spheres, an approach that provides redundant viscosity measurements for individual experiments and offers the opportunity to recover simultaneously melt density. Our results show that the viscosity of anhydrous basalt melt decreases with pressure up to 5.3 GPa, with an activation volume for viscous flow of -8.1 to -9.5 cm3/mol between 2 and 5.3 GPa. The addition of a few wt. % water reduces melt viscosity by roughly 0.5 log units; however, there is no resolvable influence on activation volume. This negative pressure dependence is consistent with previous results for basaltic melts up to 3 GPa [1, 2], while the activation volume at low pressure is indistinguishable from the activation volume for O self-diffusion in the same bulk composition [3]. Application of the Eyring equation using O self-diffusion data for basaltic melt [3] predicts anhydrous melt viscosities that are 30-90% of the values determined in this study. This result is in stark contrast with our recent results for dacitic melt (68 wt% SiO2) melt [4], in which the Eyring equation overestimates viscosity by as much as 40% at pressures < 5 GPa. The limited utility of the Eyring equation for naturally-occurring silicate melts illustrates the difficulties in relating O self-diffusion to viscous flow in polymerized liquids. Adam-Gibbs theory [5] provides a means for addressing structural controls on these transport properties. The negative pressure dependence for anhydrous and hydrous basalt viscosity suggests that the extraction of partial melts from mantle source regions will be enhanced with pressure to 5.3 GPa. Future

  16. Late Holocene hydrous mafic magmatism at the Paint Pot Crater and Callahan flows, Medicine Lake Volcano, N. California and the influence of H2O in the generation of silicic magmas

    USGS Publications Warehouse

    Kinzler, R.J.; Donnelly-Nolan, J. M.; Grove, T.L.

    2000-01-01

    This paper characterizes late Holocene basalts and basaltic andesites at Medicine Lake volcano that contain high pre-eruptive H2O contents inherited from a subduction related hydrous component in the mantle. The basaltic andesite of Paint Pot Crater and the compositionally zoned basaltic to andesitic lavas of the Callahan flow erupted approximately 1000 14C years Before Present (14C years B.P.). Petrologic, geochemical and isotopic evidence indicates that this late Holocene mafic magmatism was characterized by H2O contents of 3 to 6 wt% H2O and elevated abundances of large ion lithophile elements (LILE). These hydrous mafic inputs contrast with the preceding episodes of mafic magmatism (from 10,600 to ~3000 14C years B.P.) that was characterized by the eruption of primitive high alumina olivine tholeiite (HAOT) with low H2O (< 0.2 wt%), lower LILE abundance and different isotopic characteristics. Thus, the mantle-derived inputs into the Medicine Lake system have not always been low H2O, primitive HAOT, but have alternated between HAOT and hydrous subduction related, calc-alkaline basalt. This influx of hydrous mafic magma coincides temporally and spatially with rhyolite eruption at Glass Mountain and Little Glass Mountain. The rhyolites contain quenched magmatic inclusions similar in character to the mafic lavas at Callahan and Paint Pot Crater. The influence of H2O on fractional crystallization of hydrous mafic magma and melting of pre-existing granite crust beneath the volcano combined to produce the rhyolite. Fractionation under hydrous conditions at upper crustal pressures leads to the early crystallization of Fe-Mg silicates and the suppression of plagioclase as an early crystallizing phase. In addition, H2O lowers the saturation temperature of Fe and Mg silicates, and brings the temperature of oxide crystallization closer to the liquidus. These combined effects generate SiO2-enrichment that leads to rhyodacitic differentiated lavas. In contrast, low H2O HAOT

  17. Fractional crystallization of primitive, hydrous arc magmas: an experimental study at 0.7 GPa

    NASA Astrophysics Data System (ADS)

    Nandedkar, Rohit H.; Ulmer, Peter; Müntener, Othmar

    2014-06-01

    Differentiation of mantle-derived, hydrous, basaltic magmas is a fundamental process to produce evolved intermediate to SiO2-rich magmas that form the bulk of the middle to shallow continental and island arc crust. This study reports the results of fractional crystallization experiments conducted in a piston cylinder apparatus at 0.7 GPa for hydrous, calc-alkaline to arc tholeiitic magmas. Fractional crystallization was approached by synthesis of starting materials representing the liquid composition of the previous, higher temperature experiment. Temperatures ranged from near-liquidus at 1,170 °C to near-solidus conditions at 700 °C. H2O contents varied from 3.0 to more than 10 wt%. The liquid line of descent covers the entire compositional range from olivine-tholeiite (1,170 °C) to high-silica rhyolite (700 °C) and evolves from metaluminous to peraluminous compositions. The following crystallization sequence has been established: olivine → clinopyroxene → plagioclase, spinel → orthopyroxene, amphibole, titanomagnetite → apatite → quartz, biotite. Anorthite-rich plagioclase and spinel are responsible for a marked increase in SiO2-content (from 51 to 53 wt%) at 1,040 °C. At lower temperatures, fractionation of amphibole, plagioclase and Fe-Ti oxide over a temperature interval of 280 °C drives the SiO2 content continuously from 53 to 78 wt%. Largest crystallization steps were recorded around 1,040 °C and at 700 °C. About 40 % of ultramafic plutonic rocks have to crystallize to generate basaltic-andesitic liquids, and an additional 40 % of amphibole-gabbroic cumulate to produce granitic melts. Andesitic liquids with a liquidus temperature of 1,010 °C only crystallize 50 % over an 280 °C wide range to 730 °C implying that such liquids form mobile crystal mushes (<50 % crystals) in long-lived magmatic systems in the middle crust, allowing for extensive fractionation, assimilation and hybridization with periodic replenishment of more mafic magmas

  18. Ionic liquid-based zinc oxide nanofluid for vortex assisted liquid liquid microextraction of inorganic mercury in environmental waters prior to cold vapor atomic fluorescence spectroscopic detection.

    PubMed

    Amde, Meseret; Liu, Jing-Fu; Tan, Zhi-Qiang; Bekana, Deribachew

    2016-01-01

    Zinc oxide nanofluid (ZnO-NF) based vortex assisted liquid liquid microextraction (ZnO-NF VA-LLME) was developed and employed in extraction of inorganic mercury (Hg(2+)) in environmental water samples, followed by cold vapor atomic fluorescence spectrometry (CV-AFS). Unlike other dispersive liquid liquid microextraction techniques, ZnO-NF VA-LLME is free of volatile organic solvents and dispersive solvent consumption. Analytical signals were obtained without back-extraction from the ZnO-NF phase prior to CV-AFS determination. Some essential parameters of the ZnO-NF VA-LLME and cold vapor generation such as composition and volume of the nanofluid, vortexing time, pH of the sample solution, amount of the chelating agent, ionic strength and matrix interferences have been studied. Under optimal conditions, efficient extraction of 1ng/mL of Hg(2+) in 10mL of sample solution was achieved using 50μL of ZnO-NF. The enrichment factor before dilution, detection limits and limits of quantification of the method were about 190, 0.019 and 0.064ng/mL, respectively. The intra and inter days relative standard deviations (n=8) were found to be 4.6% and 7.8%, respectively, at 1ng/mL spiking level. The accuracy of the current method was also evaluated by the analysis of certified reference materials, and the measured Hg(2+) concentration of GBW08603 (9.6ng/mL) and GBW(E)080392 (8.9ng/mL) agreed well with their certified value (10ng/mL). The method was applied to the analysis of Hg(2+) in effluent, influent, lake and river water samples, with recoveries in the range of 79.8-92.8% and 83.6-106.1% at 1ng/mL and 5ng/mL spiking levels, respectively. Overall, ZnO-NF VA-LLME is fast, simple, cost-effective and environmentally friendly and it can be employed for efficient enrichment of the analyte from various water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Evans-Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic-Organic Hybrid Compounds with Copper-Organic Coordination Complexes: Synthesis and Oxidation Catalysis.

    PubMed

    An, Haiyan; Hou, Yujiao; Wang, Lin; Zhang, Yumeng; Yang, Wei; Chang, ShenZhen

    2017-10-02

    Four new hybrid architectures containing a [Co2Mo10H4O38](6-) polyoxoanion, (en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O (1), (Hbim)2[{Cu(bim)2(H2O)2}2{Co2Mo10H4O38}]·5H2O (2), H2[Cu(dpdo)3(H2O)4][{Cu2(dpdo)3(H2O)4(CH3CN)}2{Co2Mo10H4O38}2]·9H2O (3), and (H2bpp)4[{Cu(H2O)2}{NaCo2Mo10H4O38}2]·10H2O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [Co2Mo10H4O38](6-) as the guest. Compound 2 is constructed from [Co2Mo10H4O38](6-) polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [Co2Mo10H4O38](6-) polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [Co2Mo10H4O38](6-) polyoxoanions joined together by Na(+) and Cu(2+) cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.

  20. Deformation of olivine in torsion under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Demouchy, Sylvie; Tommasi, Andréa; Barou, Fabrice; Mainprice, David; Cordier, Patrick

    2012-08-01

    We performed torsional deformation experiments on pre-hydrated fine-grained olivine aggregates using an innovative experimental assembly to investigate water weakening in mantle rocks at high shear strains. San Carlos olivine powder was cold-pressed and then hot-pressed under hydrous conditions, producing aggregates with average grain sizes of 7 or 15 μm. Deformation experiments were performed in a high-resolution gas-medium apparatus equipped with a torsional actuator, under a confining pressure of 300 MPa, a temperature of 1200 °C, and constant shear strain rates ranging from 8 × 10-5 to 1.4 × 10-4 s-1. Maximum shear stresses range from 150 to 195 MPa. These values are 30% lower relative to those determined in previous torsion experiments on dry, fined-grained dunites under similar conditions. Textures and microstructures of the starting and deformed specimens were characterized by scanning and transmission electron microscopy. All deformed aggregates exhibit a shape-preferred orientation marking a foliation and lineation, as well as a reduction in mean grain size from 15 μm down to 3-4 μm due to dynamic recrystallization. Olivine crystallographic fabrics developed rapidly (γ < 0.1), but their strength, characterized by the J-index, is low compared to naturally deformed peridotites or to polycrystalline olivine deformed at similar finite shear strains under dry conditions. The crystallographic fabrics are consistent with deformation by a dislocation accommodated creep mechanism with activation of multiple {0 k l}[1 0 0] systems, among which the (0 1 0)[1 0 0] slip system is dominant, and minor participation of the (0 1 0)[0 0 1] slip system. Transmission electron microscopy confirmed the occurrence of dislocations with [1 0 0] and [0 0 1] Burgers vectors in most grains. Analysis of unpolarized infrared spectra indicates that hydrogen concentration in the olivine lattice is below the saturation level of 18 ppm wt H2O, which is similar to those typically

  1. Petrological features of anhydrous and hydrous mantle xenoliths from Harrow Peaks, Antarctica

    NASA Astrophysics Data System (ADS)

    Pelorosso, Beatrice; Bonadiman, Costanza; Coltorti, Massimo; Giacomoni, Pier Paolo; Ntaflos, Theodoros

    2014-05-01

    enrichment in iron contents, accompanied (opx1 rim) by relevant depletion in Al2O3 and CaO. Primary and unmetasomatized portions of spongy cpx preserve primary residual chemical features in terms of mg#(89.19-90.87) and Al2O3(3.50-4.50 wt%), whereas TiO2 is anomalously high (0.47-0.6 wt%). In spongy and secondary cpx, effects of metasomatism at depth is evidenced by relatively higher mg# and low to very low TiO2 and Al2O3 contents, while the interaction with the host basalts univocally is testified by a coherent trend of the same elements. Sp follow the expected negative correlation between cr# [= Cr/(Cr+Al)*100 mol] and mg#, beside the strong textural evidence of matrix/melt interaction. Amphibole are pargasites (mg# 87.2-89.5) relatively homogeneous in composition with TiO2 ranging from 1.65 to 2.53 wt%. The few data so far available indicate T in the range 940 -1194 °C and relatively low condition of Δlog FMQ (-1.11; -0.25),comparable to the nearby hydrous xenolith locality of Baker Rocks. As already suggested by Bonadiman et al.(2014)the presence of amphibole do not necessarily mean high oxidation conditions. References: Bonadiman et al., (2014) CMP, in press Coltorti et. al., (2004) Lithos 75, 115-139

  2. Density of Hydrous Ultramafic Silicate Melt under the Earth's Deep Upper Mantle Conditions

    NASA Astrophysics Data System (ADS)

    Jing, Z.; Matsukage, K. N.; Karato, S.

    2005-12-01

    between hydrous melts and the surrounding solids at 410 km were determined for different water content, temperature, and partial molar volume of water. Results showed that the critical water content is ~6wt% for T=1800K and V̅H2O=8cm3/mol, although the uncertainties are still large. We recognize, however, that these initial results likely underestimated the melt density in Earth's mantle. The low-pressure data indicate that oxygen fugacity has important effects on melt density (e.g., Kress & Carmichael, 1991). In our experiments, we used a rhenium capsule to minimize the chemical reaction, which defines a relatively high oxygen fugacity. At lower oxygen fugacities, the oxidation state of iron is likely different, which will increase the density of melts. Calculations showed that at room pressure the density difference between sample buffered by Re-ReO2 and by Mo-MoO2 is ~0.5-2%, which is important to determine the conditions for density crossover. We will report on new results on the influence of oxygen fugacity on melt density which will provide a better estimate for the conditions for density cross-over.

  3. Bromine speciation in hydrous haplogranitic melts up to 7 GPa

    NASA Astrophysics Data System (ADS)

    Cochain, B.; de Grouchy, C.; Crepisson, C.; Kantor, I.; Irifune, T.; Sanloup, C.

    2013-12-01

    Halogens are minor volatiles in the Earth's mantle and crust, but they have significant and specific influences on magmatic and degassing processes. They also provide insights about subsurface magma movement and eruption likelihood in subduction-related volcanism. Their speciation in silicate melts affects volatile exsolution, rheology, and the thermodynamic properties of the melts but still remains relatively unknown. A few studies have explored halogen speciation at room conditions, i.e. in glasses but no firm conclusion has yet been reached. Furthermore, halogen speciation remains unexplored at high pressures and temperatures. In this work we investigate the speciation of Br in subduction-related melt (hydrous haplogranite melt) up to 1200°C and 7 GPa using X-ray absorption spectroscopy (XANES and EXAFS) at the Br K-edge. High P-T conditions were generated by the Paris-Edinburgh press. The use of nanocrystalline diamond capsules enabled us to avoid glitches in the EXAFS spectra. The results provide valuable information on Br speciation and its evolution with pressure. It gives insights into solubility mechanisms for halogens in magmas at depth and on their degassing from the melt. In addition, we were able to identify quench effects on the atomic environment of Br by comparison of high P-T in-situ spectra and ex-situ spectra recorded on quenched samples.

  4. Diffusion of hydrous species in model basaltic melt

    NASA Astrophysics Data System (ADS)

    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.

  5. Toxicity of inorganic nanomaterials in biomedical imaging.

    PubMed

    Li, Jinxia; Chang, Xueling; Chen, Xiaoxia; Gu, Zhanjun; Zhao, Feng; Chai, Zhifang; Zhao, Yuliang

    2014-01-01

    Inorganic nanoparticles have shown promising potentials as novel biomedical imaging agents with high sensitivity, high spatial and temporal resolution. To translate the laboratory innovations into clinical applications, their potential toxicities are highly concerned and have to be evaluated comprehensively both in vitro and in vivo before their clinical applications. In this review, we first summarized the in vivo and in vitro toxicities of the representative inorganic nanoparticles used in biomedical imagings. Then we further discuss the origin of nanotoxicity of inorganic nanomaterials, including ROS generation and oxidative stress, chemical instability, chemical composition, the surface modification, dissolution of nanoparticles to release excess free ions of metals, metal redox state, and left-over chemicals from synthesis, etc. We intend to provide the readers a better understanding of the toxicology aspects of inorganic nanomaterials and knowledge for achieving optimized designs of safer inorganic nanomaterials for clinical applications. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Remote Monitoring, Inorganic Monitoring

    EPA Science Inventory

    This chapter provides an overview of applicability, amenability, and operating parameter ranges for various inorganic parameters:this chapter will also provide a compilation of existing and new online technologies for determining inorganic compounds in water samples. A wide vari...

  7. Remote Monitoring, Inorganic Monitoring

    EPA Science Inventory

    This chapter provides an overview of applicability, amenability, and operating parameter ranges for various inorganic parameters:this chapter will also provide a compilation of existing and new online technologies for determining inorganic compounds in water samples. A wide vari...

  8. D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

    USGS Publications Warehouse

    Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

    1999-01-01

    Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected

  9. An Assessment of the Environmental Impacts from the Discharge of Bilge Water in the Norfolk Naval Station Harbor

    DTIC Science & Technology

    1991-08-01

    between the metal ion and specific surface sites. The hydrous metal oxides, clays and carbonates were typically the most common [ inorganic adsorbents... Hydrous metal oxides have the greatest affinity for ions because of their charged surface sites and high surface area. Hydrous metal oxides were...often present as coatings on particles such as organic " matter and clays. The dominant hydrous metal oxides in natural systems were the oxides of iron

  10. Phase H: A new high pressure phase of dense hydrous magnesium silicates in the lower mantle

    NASA Astrophysics Data System (ADS)

    Tsuchiya, J.; Tsuchiya, T.; Nishi, M.; Mookherjee, M.

    2014-12-01

    It has been believed that water is carried into the deep Earth's interior by hydrous minerals such as the dense hydrous magnesium silicates (DHMSs) in the descending cold plate. Recently, the new high pressure phase of DHMSs is theoretically predicted (Tsuchiya 2013) and experimentally confirmed in lower mantle pressure conditions above ~45 GPa (Nishi et al. 2014). This phase has MgSiO4H2 chemical composition and named as phase H. At the lower mantle pressure conditions, Al and H-bearing SiO2, δ-AlOOH, ɛ-FeOOH and phase H may be the potential hydrous phases in the subducting slabs. Interestingly, the crystal structure of these hydrous phases are almost same and have CaCl2 type structure. This suggests that these hydrous phases may be able to make the wide range of solid solution. Some experimental studies already reported that Al preferentially partitioned into phase H and the stability of phase H drastically increased by incorporation of Al (Nishi et al. 2014, Ohira et al. 2014). The density of subducted MORB is reported to be denser than that of pyrolite in the lower mantle. Therefore, there is a possibility that phase H containing Al and Fe in subducted MORB survive down to the bottom of lower mantle and the melting of phase H at the core mantle boundary may contribute to the cause of ultra-low velocity zones. In this study, we report the effects of Al and Fe on the stability of phase H, elasticity and seismic anisotropy of this new hydrous mineral using first principles calculation techniques and discuss the possible effects of this hydrous phase at the bottom of lower mantle.

  11. The density of dry and hydrous granitic magmas

    NASA Astrophysics Data System (ADS)

    Malfait, W. J.; Sanchez-Valle, C.; Seifert, R.; Petitgirard, S.; Perrillat, J.

    2011-12-01

    Large volumes of granitic magmas form through partial melting of the lower crust and are subsequently emplaced in the higher crustal levels [1]. In addition, granite-like liquids may form through partial melting of subducted sediments [2] or as an end-product of magmatic differentiation [3]. Moreover, water rich magmas of granitic composition are a major source of explosive volcanism. The physical properties of granitic melts, and particularly their density, are key controls on the migration rate and emplacement depth of granitic intrusions. However, because of the high viscosity of granitic liquids, density and compressibility measurements with the sink/float method and sound velocity measurements are challenging. As a result, the density and compressibility of dry and volatile-bearing granitic liquids is poorly constrained, particularly for the pressure-temperature conditions relevant for their formation and emplacement. In this study, we present in situ experimental data on the density of dry and hydrous haplogranitic melts (5 and 10 wt% water) at pressure and temperature conditions relevant for the crust and the subducting slab (1.0-2.7 GPa, 1350-1720 K). The experiments were performed with a panoramic Paris-Edinburgh press installed at the ID27 beamline of ESRF. The samples were contained in a cylindrical diamond capsule, capped with a platinum disk on either side, surrounded by hexagonal boron nitride (hBN) and placed inside a graphite heater and boron epoxy gasket. Pressure and temperature were determined from the X-ray diffraction patterns of hBN and platinum using the double-isochore method [4]. The density of the melts was determined from the X-ray absorption contrast between the sample and the diamond capsule (Mo edge, 20 keV). The molten state of the sample at the condition of the density measurements was verified by X-ray diffraction. The run products were analyzed by electron microprobe and infrared spectroscopy to verify the chemical composition and

  12. Mantle hydrous-fluid interaction with Archaean granite.

    NASA Astrophysics Data System (ADS)

    Słaby, E.; Martin, H.; Hamada, M.; Śmigielski, M.; Domonik, A.; Götze, J.; Hoefs, J.; Hałas, S.; Simon, K.; Devidal, J.-L.; Moyen, J.-F.; Jayananda, M.

    2012-04-01

    Water content/species in alkali feldspars from late Archaean Closepet igneous bodies as well as growth and re-growth textures, trace element and oxygen isotope composition have been studied (Słaby et al., 2011). Both processes growth and re-growth are deterministic, however they differ showing increasing persistency in element behaviour during interaction with fluids. The re-growth process fertilized domains and didn't change their oxygen-isotope signature. Water speciation showed persistent behaviour during heating at least up to 600oC. Carbonate crystals with mantle isotope signature are associated with the recrystallized feldspar domains. Fluid-affected domains in apatite provide evidence of halide exchange. The data testify that the observed recrystallization was a high-temperature reaction with fertilized, halide-rich H2O-CO2 mantle-derived fluids of high water activity. A wet mantle being able to generate hydrous plumes, which appear to be hotter during the Archean in comparison to the present time is supposed by Shimizu et al. (2001). Usually hot fluids, which can be strongly carbonic, precede asthenospheric mantle upwelling. They are supposed to be parental to most recognized compositions, which can be derived by their immiscible separation into saline aqueous-silicic and carbonatitic members (Klein-BenDavid et al., 2007). The aqueous fractions are halogen-rich with a significant proportion of CO2. Both admixed fractions are supposed to be fertile. The Closepet granite emplaced in a major shear zone that delimitates two different terrains. Generally such shear zones, at many places, are supposed to be rooted deep into the mantle. The drain, that favoured and controlled magma ascent and emplacement, seemed to remain efficient after granite crystallization. In the southern part of the Closepet batholiths an evidence of intensive interaction of a lower crust fluid (of high CO2 activity) is provided by the extensive charnockitization of amphibolite facies (St

  13. The redox conditions of anhydrous and hydrous xenoliths of suprasubduction and intraplate lithospheric mantle

    NASA Astrophysics Data System (ADS)

    Bonadiman, C.; Coltorti, M.

    2012-12-01

    The oxidation state of the upper mantle, its relationship with C-H-O fluids speciation and tectonic settings has been debated for decades and the various modelling have considered the prevalent role of the hydrous minerals over nominally anhydrous minerals (and the opposite) as well as the dissolution of silicate minerals (as providers of Fe3+ to the system) as directly related to water activity and oxygen fugacity. Each of these modelling has different implications for mantle rheology, seismic structure, and the evolution of the lithosphere (i.e.: Karato and Jung, 1998, Hirshmann, 2006). Upper mantle is the only part of the Earth's mantle where the oxygen fugacity can be directly measured, its values/variation being dependent on various processes such as partial melting and metasomatism often operating in time and space without solution of continuity. Recent general reviews of oxygen thermobarometry measurements (Forst & McCammon, 2008; Foley, 2011) indicate that the oxygen fugacity at the top of the upper mantle falls within ±2 log units of the fayalite-magnetite-quartz (FMQ) oxygen buffer. There is also a general consensus in considering H2O as the strongest oxidizing agent in mantle metasomatic fluids, its activity leading to the formation of amphibole and raising the mantle redox state. This contribution presents fO2 and water activity results from three spinel-bearing mantle xenolith localities and distinct geodynamic settings: Ichinomegata (Japan) amphibole-bearing peridotites entrained in calc-alkaline basalts and Cerro Fraile (South Patagonia, Argentina), mostly anhydrous lherzolites and pirossenites brought up to the surface by alkaline basalts representing fragments of sub-arc mantle and Baker Rocks, Victoria Land (Antarctica), amphibole-bearing lherzolites representing portion of intraplate subcontinental lithospheric mantle. The three mantle sectors records fO2 values in the range of -1.9 to +0.8 log units of the FQM buffer. and low to very low aH2O

  14. Predicted model for hydrous modified olivine (HyM-α)

    NASA Astrophysics Data System (ADS)

    Kudoh, Y.

    A possible structure for hydrous modified olivine (HyM-α) has been obtained by the subtraction of Mg3SiO5 from forsterite by crystallographic shear along a direction parallel to the [010] direction of olivine. The subtraction of Mg3SiO5 results in the subtraction of MgO from bulk chemistry (-Mg3SiO5=-Mg2SiO4-MgO). A possible structure for HyM-α thus obtained has the chemical formula Mg9Si5H2O20 (= 5 × Mg1.8SiH0.4O4) with monoclinic unit cell a=4.754 Å, b=10.19 Å, c=29.90 Å, ρ=3.126 g cm-3, and space group=Ac2m (no. 39). Since the X-ray powder diffraction pattern of HyM-α proposed in this study is very close to that of clinohumite, there is the possibility of this phase having been undiscovered. The humite group minerals and HyM-α proposed in this study make a homologous series as recombination structures: Mg(2m+n)SimH2nO2(2m+n) for the humite group and Mg(2m+n)Si(m+n)H2nO4(m+n) for HyM-α A characteristic feature is that Mg/Si > 2 for the humite group and Mg/Si < 2 for HyM-α. Forsterite specimens containing around 100 ppm H2O reported in mantle xenoliths might be the disordered case with n=1 and m=1200 of the humite group or HyM-α.

  15. Hydrous pyrolysis of crude oil in gold-plated reactors

    USGS Publications Warehouse

    Curiale, J.A.; Lundegard, P.D.; Kharaka, Y.K.

    1992-01-01

    Crude oils from Iraq and California have been pyrolyzed under hydrous conditions at 200 and 300??C for time periods up to 210 days, in gold-plated reactors. Elemental (vanadium, nickel), stable isotopic (carbon), and molecular (n-alkanes, acyclic isoprenoids, steranes, terpanes and aromatic steroid hydrocarbons) analyses were made on the original and pyrolyzed oils. Various conventional crude oil maturity parameters, including 20S/(20S + 20R)-24-ethylcholestane ratios and the side-chain-length distribution of aliphatic and aromatic steroidal hydrocarbons, were measured in an effort to assess the modification of molecular maturity parameters in clay-free settings, similar to those encountered in "clean" reservoirs. Concentrations of vanadium and nickel in the Iraq oil decrease significantly and the V/(V + Ni) ratio decreases slightly, with increasing pyrolysis time/temperature. Whole oil carbon isotope ratios remain fairly constant during pyrolysis, as do hopane/sterane ratios and carbon number distribution of 5??(H),14??(H),17??(H),20R steranes. These latter three parameters are considered maturity-invariant. The ratios of short side-chain components to long side-chain components of the regular steranes [C21/(C21 + C29R)] and the triaromatic steroid hydrocarbons [C21/(C21 + C28)] vary systematically with increasing pyrolysis time, indicating that these parameters may be useful as molecular maturity parameters for crude oils in clay-free reservoir rocks. In addition, decreases in bisnorhopane/hopane ratio with increasing pyrolysis time, in a clay-free and kerogen-free environment, suggest that the distribution of these compounds is controlled by either differential thermal stabilities or preferential release from a higher-molecular weight portion of the oil. ?? 1992.

  16. The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans.

    PubMed

    Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

    2017-01-01

    The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the -35 (or -24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed.

  17. Inorganic nanomedicine--part 1.

    PubMed

    Sekhon, Bhupinder S; Kamboj, Seema R

    2010-08-01

    Inorganic nanomedicine refers to the use of inorganic or hybrid nanomaterials and nanosized objects to achieve innovative medical breakthroughs for drug and gene discovery and delivery, discovery of biomarkers, and molecular diagnostics. Potential uses for fluorescent quantum dots include cell labeling, biosensing, in vivo imaging, bimodal magnetic-luminescent imaging, and diagnostics. Biocompatible quantum dot conjugates have been used successfully for sentinel lymph node mapping, tumor targeting, tumor angiogenesis imaging, and metastatic cell tracking. Magnetic nanowires applications include biosensing and construction of nucleic acids sensors. Magnetic cell therapy is used for the repair of blood vessels. Magnetic nanoparticles (MNPs) are important for magnetic resonance imaging, drug delivery, cell labeling, and tracking. Superparamagnetic iron oxide nanoparticles are used for hyperthermic treatment of tumors. Multifunctional MNPs applications include drug and gene delivery, medical imaging, and targeted drug delivery. MNPs could have a vital role in developing techniques to simultaneously diagnose, monitor, and treat a wide range of common diseases and injuries. From the clinical editor: This review serves as an update about the current state of inorganic nanomedicine. The use of inorganic/hybrid nanomaterials and nanosized objects has already resulted in innovative medical breakthroughs for drug/gene discovery and delivery, discovery of biomarkers and molecular diagnostics, and is likely to remain one of the most prolific fields of nanomedicine.

  18. Temperature-stable and optically transparent thin-film zinc oxide aerogel electrodes as model systems for 3D interpenetrating organic-inorganic heterojunction solar cells.

    PubMed

    Krumm, Michael; Pawlitzek, Fabian; Weickert, Jonas; Schmidt-Mende, Lukas; Polarz, Sebastian

    2012-12-01

    Novel, nanostructured electrode materials comprising porous ZnO films with aerogel morphology are presented. Almost any substrate including polymers, metals, or ceramics can be coated using a method that is suitable for mass production. The thin, porous films can be prepared from the wet gels via conventional drying, supercritical drying is not necessary. The filigree ZnO network is thermally very stable and exhibits sufficient electrical conductivity for advanced electronic applications. The latter was tested by realizing a highly desired architecture of organic-inorganic hybrid solar cells. After sensitizing of the ZnO with a purely organic squarine dye (SQ2), a nanostructured, interpenetrating 3D network of the inorganic semiconductor (ZnO) and organic semiconductor (P3HT) was prepared. The solar cell device was tested under illumination with AM 1.5G solar light (100 mW/cm(2)) and exhibited an energy conversion efficiency (η(eff)) of 0.69%.

  19. Polyaspartic acid facilitates oxolation within iron(iii) oxide pre-nucleation clusters and drives the formation of organic-inorganic composites

    NASA Astrophysics Data System (ADS)

    Scheck, J.; Drechsler, M.; Ma, X.; Stöckl, M. T.; Konsek, J.; Schwaderer, J. B.; Stadler, S. M.; De Yoreo, J. J.; Gebauer, D.

    2016-12-01

    The interplay between polymers and inorganic minerals during the formation of solids is crucial for biomineralization and bio-inspired materials, and advanced material properties can be achieved with organic-inorganic composites. By studying the reaction mechanisms, basic questions on organic-inorganic interactions and their role during material formation can be answered, enabling more target-oriented strategies in future synthetic approaches. Here, we present a comprehensive study on the hydrolysis of iron(iii) in the presence of polyaspartic acid. For the basic investigation of the formation mechanism, a titration assay was used, complemented by microscopic techniques. The polymer is shown to promote precipitation in partly hydrolyzed reaction solutions at the very early stages of the reaction by facilitating iron(iii) hydrolysis. In unhydrolyzed solutions, no significant interactions between the polymer and the inorganic solutes can be observed. We demonstrate that the hydrolysis promotion by the polymer can be understood by facilitating oxolation in olation iron(iii) pre-nucleation clusters. We propose that the adsorption of olation pre-nucleation clusters on the polymer chains and the resulting loss in dynamics and increased proximity of the reactants is the key to this effect. The resulting composite material obtained from the hydrolysis in the presence of the polymer was investigated with additional analytical techniques, namely, scanning and transmission electron microscopies, light microscopy, atomic force microscopy, zeta potential measurements, dynamic light scattering, and thermogravimetric analyses. It consists of elastic, polydisperse nanospheres, ca. 50-200 nm in diameter, and aggregates thereof, exhibiting a high polymer and water content.

  20. Effect of Hydrous Mantle on a Coupled Core-Mantle Evolution

    NASA Astrophysics Data System (ADS)

    Nakagawa, T.; Iwamori, H.

    2014-12-01

    The water in the mantle is also important for dynamics, evolution, composition and structure of deep Earth's interior [e.g. Karato, 2011]. However, the hydrous mantle was not assumed for thermo-chemical evolution model in numerical mantle convection simulations [e.g. Nakagawa and Tackley, 2014]. To assess the effect of hydrous mantle in thermo-chemical evolution of deep Earth's interior, we develop a coupled core-mantle evolution model including water transportation system based on Iwamori [1998; 2004]. The important ingredient of this model is the rheological property of hydrous mantle and dehydration processes. Here we assume this taken from deformation experiments on hydrous olivine [e.g. Mei and Kohlsteadt, 2000; Korenaga and Karato, 2008; Fei et al., 2013], which ranges from weak to extremely strong viscosity dependence due to the water content. We also assume the reduction of solidus temperature of mantle minerals based on Katz et al. [2003]. Preliminary results suggested that the best-fit scenario of thermo-chemical evolution of Earth's mantle and core could be found in the weak rheological dependence due to the water content. In the successful model, the lower mantle would be close to water-saturated situation less than 1.0 Gyrs from initial condition assuming the completely dry mantle. In the presentation, we will also discuss the possibility on hydrous basalt in the lowermost mantle and geochemical evolution in the deep mantle.

  1. Density and seismic velocity of hydrous melts under crustal and upper mantle conditions

    NASA Astrophysics Data System (ADS)

    Ueki, Kenta; Iwamori, Hikaru

    2016-05-01

    We present a new model for calculating the density of hydrous silicate melts as a function of P, T, H2O concentration, and melt composition. We optimize VPr,Tr, ∂V/∂T, ∂V/∂P, ∂V2/∂T∂P, and K' of H2O end-member components in hydrous silicate melts, as well as K' of anhydrous silicate melts, using previously reported experimental results. The parameter set for H2O end-member component in silicate melt optimized in this study is internally consistent with the parameter values for the properties of anhydrous silicate melt reported by Lange and Carmichael (1987, 1990). The model calculation developed in this study reproduces the experimentally determined densities of various hydrous melts, and can be used to calculate the relationships between pressures, temperatures, and H2O concentrations of various hydrous melts from ultramafic to felsic compositions at pressures of 0-4.29 GPa. Using the new parameter set, we investigate the effects of H2O content on the seismic velocity of hydrous melts, as well as seismic velocities in partially molten regions of subduction zones. The results show that water content in silicate melt plays a key role in determining seismic velocity structure, and therefore must be taken into account when interpreting seismic tomography.

  2. Adsorption mechanisms of selenium oxyanions at the aluminum oxide/water interface.

    PubMed

    Peak, Derek

    2006-11-15

    Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO4(2-) and selenite (SeO3(2-) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum (alpha-Al2O3) was studied to determine if adsorption mechanisms change as the aluminum oxide surface structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and alpha-Me2O3.

  3. U-Pb Geochronology of Hydrous Silica (Siebengebirge, Germany)

    NASA Astrophysics Data System (ADS)

    Tomaschek, Frank; Nemchin, Alexander; Geisler, Thorsten; Heuser, Alexander; Merle, Renaud

    2015-04-01

    Low-temperature, hydrous weathering eventually leads to characteristic products such as silica indurations. Elevated U concentrations and the ability of silica to maintain a closed system permits silica to be dated by the U-Pb method, which, in turn, will potentially allow constraining the timing of near-surface processes. To test the feasibility of silica U-Pb geochronology, we sampled opal and chalcedony from the Siebengebirge, Germany. This study area is situated at the terminus of the Cenozoic Lower Rhine Basin on the Rhenish Massif. The investigated samples include silicified gravels from the Mittelbachtal locality, renowned for the embedded wood opal. Structural characterization of the silica phases (Raman spectroscopy) was combined with in situ isotopic analyses, using ion microprobe and LA-ICPMS techniques. In the Siebengebirge area fluviatile sediments of Upper Oligocene age were covered by an extended trachyte tuff at around 25 Ma. Silica is known to indurate some domains within the tuff and, in particular, certain horizons within the subjacent fluviatile sediments ('Tertiärquarzite'). Cementation of the gravels occurred during at least three successive growth stages: early paracrystalline silica (opal-CT), fibrous chalcedony, and late microcrystalline quartz. It has traditionally been assumed that this silica induration reflects intense weathering, more or less synchronous with the deposition of the volcanic ashes. Results from U-Pb geochronology returned a range of discrete 206Pb-238U ages, recording a protracted silicification history. For instance, we obtained 22 ± 1 Ma for opal-CT cement from a silicified tuff, 16.6 ± 0.5 Ma for silicified wood and opal-CT cement in the fluviatile gravels, as well as 11 ± 1 Ma for texturally late chalcedony. While silicification of the sampled tuff might be contemporaneous with late-stage basalts, opaline silicification of the subjacent sediments and their wood in the Mittelbachtal clearly postdates active

  4. Optical Absorption Spectra of Hydrous Wadsleyite to 32 GPa

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Goncharov, A. F.; Jacobsen, S. D.; Bina, C. R.; Frost, D. J.

    2009-05-01

    Optical absorption spectra of high-pressure minerals can be used as indirect tools to calculate radiative conductivity of the Earth's interior [e.g., 1]. Recent high-pressure studies show that e.g. ringwoodite, γ-(Mg,Fe)2SiO4, does not become opaque in the near infrared and visible region, as previously assumed, but remains transparent to 21.5 GPa [2]. Therefore, it has been concluded that radiative heat transfer does not necessarily become blocked at high pressures of the mantle and ferromagnesian minerals actually could contribute to the heat flow in the Earth's interior [2]. In this study we use gem-quality single-crystals of hydrous Fe-bearing wadsleyite, β-(Mg,Fe)2SiO4, that were synthesized at 18 GPa and 1400 °C in a multianvil apparatus. Crystals were analyzed by Mössbauer and Raman spectroscopy, electron microprobe analysis and single-crystal X-ray diffraction. For absorption measurements a double-polished 50 μm sized single-crystal of wadsleyite was loaded in a diamond-anvil cell with neon as pressure medium. Optical absorption spectra were recorded at ambient conditions as well as up to 32 GPa from 400 to 50000 cm-1. At ambient pressure the absorption spectrum reveals two broad bands at - 10000 cm-1 and -15000 cm-1, and an absorption edge in the visible-ultraviolet range. With increasing pressure the absorption spectrum changes, both bands continuously shift to higher frequencies as has been observed for ringwoodite [2], but is contrary to earlier presumptions for wadsleyite [3]. Here, we will discuss band assignment along with the influence of iron, compare our results to previous absorption studies of mantle materials [2], and analyze possible implications for radiative conductivity of the transition zone. References: [1] Goncharov et al. (2008), McGraw Yearbook Sci. Tech., 242-245. [2] Keppler & Smyth (2005), Am. Mineral., 90 1209-1212. [3] Ross (1997), Phys. Chem. Earth, 22 113-118.

  5. Diamond Synthesis and Carbon Solubility in a Hydrous Granitoid System

    NASA Astrophysics Data System (ADS)

    Renfro, A.; Dobrzhinetskaya, L. P.

    2004-12-01

    An increasing number of UHP metamorphic terranes incorporated in collisional orogenic belts have been identified since the first discovery of diamonds within felsic metamorphic rocks of Kokchetav massif, Kazakhstan, extending up to ˜4000 km in length in the Dabie-SuLu-Qinling belt of China. Some have suggested that all orogenic belt diamonds formed from a carbonate or calc-alkaline melt similar to those derived from kimberlitic pipes, or alternatively that they formed from a carbon-enriched silicate melt with a granitoid bulk chemistry composition. Another group has suggested that orogenic belt diamonds crystallized from a COH-rich supercritical fluid. While the diversity of the minor components accompanying the SiO2-dominated inclusions from Kokchetav diamonds, as well as the presence of cavities bearing traces of a former fluid, suggest the idea of diamond growth from a COH fluid, a Si-rich melt as a source for diamond formation cannot be ruled out. Although many experiments were performed on diamond synthesis and on the petrology of diamond-bearing rocks, no consensus has been reached as to which of the mentioned growth media is correct to explain orogenic belt diamond formation. We report here the results of an experimental program undertaken to determine the critical point of the Si-Al-K-C-H2O system (and thus, to distinguish a melt environment from a fluid one) and to provide an understanding of how diamond is crystallized in hydrous subducted felsic continental crust. Carbon solubility in these systems was qualitatively determined based on the observed diamond growth rates. Experiments were performed at in a Walker-style multianvil apparatus at P=7 GPa and T=1500-1700° C with SiO2 ranging from 90 wt. %, imitating diamondiferous quartzite, to 62 wt. %, imitating a wide range of feldspathic diamondiferous gneisses. An additional parameter, oxygen fugacity, was also varied to test its affects on the solubility of carbon in Si-rich melt/fluid.

  6. Fabricating porous materials using interpenetrating inorganic-organic composite gels

    DOEpatents

    Seo, Dong-Kyun; Volosin, Alex

    2016-06-14

    Porous materials are fabricated using interpenetrating inorganic-organic composite gels. A mixture or precursor solution including an inorganic gel precursor, an organic polymer gel precursor, and a solvent is treated to form an inorganic wet gel including the organic polymer gel precursor and the solvent. The inorganic wet gel is then treated to form a composite wet gel including an organic polymer network in the body of the inorganic wet gel, producing an interpenetrating inorganic-organic composite gel. The composite wet gel is dried to form a composite material including the organic polymer network and an inorganic network component. The composite material can be treated further to form a porous composite material, a porous polymer or polymer composite, a porous metal oxide, and other porous materials.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. FORUM: Bioinspired Heme, Heme/non-heme Diiron, Heme/copper and Inorganic NOx Chemistry: ·NO(g) Oxidation, Peroxynitrite-Metal Chemistry and ·NO(g) Reductive Coupling

    PubMed Central

    Schopfer, Mark P.; Wang, Jun; Karlin, Kenneth D.

    2010-01-01

    The focus of this Forum review highlights work from our own laboratories and those of others in the area of biochemical and biologically inspired inorganic chemistry dealing with nitric oxide (nitrogen monoxide, ·NO(g)) and its biological roles and reactions. The latter focus is on (i) oxidation of ·NO(g) to nitrate by nitric oxide dioxygenases (NOD’s), and (ii) reductive coupling of two molecules of ·NO(g) to give N2O(g). In the former case, NOD’s are described and the highlighting of possible peroxynitrite-heme intermediates and consequences of this are given by discussion of recent works with myoglobin and a synthetic heme model system for NOD action. Summaries of recent copper complex chemistries with ·NO(g) and O2(g) leading to peroxynitrite species are given. The coverage of biological reductive coupling of ·NO(g) deals with bacterial nitric oxide reductases (NOR’s) with heme/non-heme diiron active sites, and on heme/Cu oxidases such as cytochrome c oxidase which can mediate the same chemistry. Recent designed protein and synthetic model compound (heme/non-heme diiron or heme/copper) as functional mimics are discussed in some detail. We also highlight examples from the chemical literature, not necessarily involving biologically relevant metal ions, which describe the oxidation of ·NO(g) to nitrate (or nitrite) and possible peroxynitrite intermediates, or reductive coupling of ·NO(g) to give nitrous oxide. PMID:20666386

  9. Inorganic Nanomaterials as Carriers for Drug Delivery.

    PubMed

    Chen, Shizhu; Hao, Xiaohong; Liang, Xingjie; Zhang, Qun; Zhang, Cuimiao; Zhou, Guoqiang; Shen, Shigang; Jia, Guang; Zhang, Jinchao

    2016-01-01

    For safe and effective therapy, drugs must be delivered efficiently and with minimal systemic side effects. Nanostructured drug carriers enable the delivery of small-molecule drugs as well as nucleic acids and proteins. Inorganic nanomaterials are ideal for drug delivery platforms due to their unique physicochemical properties, such as facile preparation, good storage stability and biocompatibility. Many inorganic nanostructure-based drug delivery platforms have been prepared. Although there are still many obstacles to overcome, significant advances have been made in recent years. This review focuses on the status and development of inorganic nanostructures, including silica, quantum dots, gold, carbon-based and magnetic iron oxide-based nanostructures, as carriers for chemical and biological drugs. We specifically highlight the extensive use of these inorganic drug carriers for cancer therapy. Finally, we discuss the most important areas in the field that urgently require further study.

  10. Origin of hydrous alkali feldspar-silica intergrowth in spherulites from intra-plate A2-type rhyolites at the Jabal Shama, Saudi Arabia

    NASA Astrophysics Data System (ADS)

    Surour, Adel A.; El-Nisr, Said A.; Bakhsh, Rami A.

    2016-03-01

    Miocene rhyolites (19.2 ± 0.9 Ma) at the Jabal Shama in western Saudi Arabia represent an example of rift-related silicic volcanism that took place during the formation of the Red Sea. They mostly consist of tuffaceous varieties with distinct flow banding, and pea-sized spherulites, obsidian and perlitized rhyolite tuffs. Although they have the geochemical signature of A2-type rhyolites, these silicic rocks are not typically alkaline but alkali-calcic to calc-alkaline. They developed in a within-plate regime and possibly derived from a recycled mafic subducted slab in depleted sub-continental mantle beneath the western Arabian plate. The Jabal Shama rhyolites are younger in age than their Miocene counterparts in Yemen and Ethiopia. The Jabal Shama spherulites consist of hydrous alkali feldspar-silica radial intergrowths with an occasional brown glass nucleus. Carbonate- and glass-free spherulites give up to 4.45 wt% L.O.I. The hydrous nature of these silicates and the absence of magnetite in the spherulites is a strong indication of oxidizing conditions. The spherulites contain hydrous feldspars with up to ∼6 wt% H2O, and they develop by diffusion and devitrification of glass in the rhyolite tuff at ∼800 °C. Owing to higher undercooling due to supersaturation, the radial hydrous phases within spherulites might grow faster and led to coagulation. The polygonal contacts between spherulites and the ∼120° dihedral angle suggest solid-state modification and recrystallization as the process of devitrification proceeds as low as ∼300 °C. The sum of FeO + MgO is positively correlated with total alkalies along with magnetite oxidation in the matrix to Fe-oxyhydroxides, and to the incorporation of OH- into silicates within the spehrulites themselves. Structural H2O in glass of the Jabal Shama perlite (obsidian) is considerable (∼9-12 wt%) with 3.72-5.6 wt% L.O.I. of the whole-rock. The presence of deleterious silica impurities would lower the ore grade due to

  11. Method for plating with metal oxides

    SciTech Connect

    Silver, Gary L.; Martin, Frank S.

    1994-08-23

    A method of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate.

  12. Method for plating with metal oxides

    SciTech Connect

    Silver, G.L.; Martin, F.S.

    1994-08-23

    A method is disclosed of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate. 1 fig.

  13. Method for plating with metal oxides

    DOEpatents

    Silver, G.L.; Martin, F.S.

    1994-08-23

    A method is disclosed of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate. 1 fig.

  14. Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

    PubMed

    Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; You, Shao-hong; Hu, Xi; Tan, Xiao-fei; Chen, An-wei; Guo, Fang-ying

    2015-05-01

    The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal.

  15. Inorganic contents of peats

    SciTech Connect

    Raymond, R. Jr.; Bish, D.L.; Cohen, A.D.

    1988-02-01

    Peat, the precursor of coal, is composed primarily of plant components and secondarily of inorganic matter derived from a variety of sources. The elemental, mineralogic, and petrographic composition of a peat is controlled by a combination of both its botanical and depositional environment. Inorganic contents of peats can vary greatly between geographically separated peat bogs as well as vertially and horizontally within an individual bog. Predicting the form and distribution of inorganic matter in a coal deposit requires understanding the distribution and preservation of inorganic matter in peat-forming environments and diagenetic alterations affecting such material during late-stage peatification and coalification processes. 43 refs., 4 figs., 3 tabs.

  16. Selective inorganic thin films

    SciTech Connect

    Phillips, M.L.F.; Pohl, P.I.; Brinker, C.J.

    1997-04-01

    Separating light gases using membranes is a technology area for which there exists opportunities for significant energy savings. Examples of industrial needs for gas separation include hydrogen recovery, natural gas purification, and dehydration. A membrane capable of separating H{sub 2} from other gases at high temperatures could recover hydrogen from refinery waste streams, and facilitate catalytic dehydrogenation and the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction. Natural gas purification requires separating CH{sub 4} from mixtures with CO{sub 2}, H{sub 2}S, H{sub 2}O, and higher alkanes. A dehydrating membrane would remove water vapor from gas streams in which water is a byproduct or a contaminant, such as refrigeration systems. Molecular sieve films offer the possibility of performing separations involving hydrogen, natural gas constituents, and water vapor at elevated temperatures with very high separation factors. It is in applications such as these that the authors expect inorganic molecular sieve membranes to compete most effectively with current gas separation technologies. Cryogenic separations are very energy intensive. Polymer membranes do not have the thermal stability appropriate for high temperature hydrogen recovery, and tend to swell in the presence of hydrocarbon natural gas constituents. The authors goal is to develop a family of microporous oxide films that offer permeability and selectivity exceeding those of polymer membranes, allowing gas membranes to compete with cryogenic and adsorption technologies for large-scale gas separation applications.

  17. Melting the hydrous, subarc mantle: the origin of primitive andesites

    NASA Astrophysics Data System (ADS)

    Mitchell, Alexandra L.; Grove, Timothy L.

    2015-08-01

    This experimental study is the first comprehensive investigation of the melting behavior of an olivine + orthopyroxene ± spinel—bearing fertile mantle (FM) composition as a function of variable pressure and water content. The fertile composition was enriched with a metasomatic slab component of ≤0.5 % alkalis and investigated from 1135 to 1470 °C at 1.0-2.0 GPa. A depleted lherzolite with 0.4 % alkali addition was also studied from 1225 to 1240 °C at 1.2 GPa. Melts of both compositions were water-undersaturated: fertile lherzolite melts contained 0-6.4 wt% H2O, and depleted lherzolite melts contained ~2.5 wt% H2O. H2O contents of experimental glasses are measured using electron microprobe, secondary ion mass spectrometry, and synchrotron-source reflection Fourier transform infrared spectroscopy, a novel technique for analyzing H2O in petrologic experiments. Using this new dataset in conjunction with results from previous hydrous experimental studies, a thermobarometer and a hygrometer-thermometer are presented to determine the conditions under which primitive lavas were last in equilibration with the mantle. These predictive models are functions of H2O content and pressure, respectively. A predictive melting model is also presented that calculates melt compositions in equilibrium with an olivine + orthopyroxene ± spinel residual assemblage (harzburgite). This model quantitatively predicts the following influences of H2O on mantle lherzolite melting: (1) As melting pressure increases, melt compositions become more olivine-normative, (2) as melting extent increases, melt compositions become depleted in the normative plagioclase component, and (3) as melt H2O content increases, melts become more quartz-normative. Natural high-Mg# [molar Mg/(Mg + Fe2+)], high-MgO basaltic andesite and andesite lavas—or primitive andesites (PAs)—contain high SiO2 contents at mantle-equilibrated Mg#s. Their compositional characteristics cannot be readily explained by melting

  18. Increased recovery rates of phosphocreatine and inorganic phosphate after isometric contraction in oxidative muscle fibers and elevated hepatic insulin resistance in homozygous carriers of the A-allele of FTO rs9939609.

    PubMed

    Grunnet, Louise G; Brøns, Charlotte; Jacobsen, Stine; Nilsson, Emma; Astrup, Arne; Hansen, Torben; Pedersen, Oluf; Poulsen, Pernille; Quistorff, Bjørn; Vaag, Allan

    2009-02-01

    Recent studies identified the rs9939609 A-allele of the FTO (fat mass and obesity associated) gene as being associated with obesity and type 2 diabetes. We studied the role of the A-allele in the regulation of peripheral organ functions involved in the pathogenesis of obesity and type 2 diabetes. Forty-six young men underwent a hyperinsulinemic euglycemic clamp with excision of skeletal muscle biopsies, an iv glucose tolerance test, 31phosphorous magnetic resonance spectroscopy, and 24-h whole body metabolism was measured in a respiratory chamber. The FTO rs9939609 A-allele was associated with elevated fasting blood glucose and plasma insulin, hepatic insulin resistance, and shorter recovery half-times of phosphocreatine and inorganic phosphate after exercise in a primarily type I muscle. These relationships--except for fasting insulin--remained significant after correction for body fat percentage. The risk allele was not associated with fat distribution, peripheral insulin sensitivity, insulin secretion, 24-h energy expenditure, or glucose and fat oxidation. The FTO genotype did not influence the mRNA expression of FTO or a set of key nuclear or mitochondrially encoded genes in skeletal muscle during rest. Increased energy efficiency--and potentially increased mitochondrial coupling--as suggested by faster recovery rates of phosphocreatine and inorganic phosphate in oxidative muscle fibers may contribute to the increased risk of obesity and type 2 diabetes in homozygous carriers of the FTO A-risk allele. Hepatic insulin resistance may represent the key metabolic defect responsible for mild elevations of fasting blood glucose associated with the FTO phenotype.

  19. Mineralogical, Spectral, and Compositional Changes During Heating of Hydrous Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Nakamura, T.; Matsuoka, M.; Yamashita, S.; Sato, Y.; Mogi, K.; Enokido, Y.; Nakata, A.; Okumura, S.; Furukawa, Y.; Zolensky, M.

    2017-01-01

    Hydrous carbonaceous chondrites experienced hydration and subsequent dehydration by heating, which resulted in a variety of mineralogical and spectral features [e. g., 1-6]. The degree of heating is classified according to heating stage (HS) II to IV based on mineralogy of phyllosilicates [2], because they change, with elevating temperature, to poorly crystal-line phases and subsequently to aggregates of small secondary anhydrous silicates of mainly olivine. Heating of hydrous carbonaceous chondrites also causes spectral changes and volatile loss [3-6]. Experimental heating of Murchison CM chondrite showed flattening of whole visible-near infrared spectra, especially weakening of the 3µm band strength [1, 4, 7]. In order to understand mineralogical, spectral, and compositional changes during heating of hydrous carbonaceous chondrites, we have carried out systematic investigation of mineralogy, reflectance spectra, and volatile composition of hydrated and dehydrated carbonaceous chondrites as well as experimentally-heated hydrous carbonaceous chondrites. In addition, we investigated reflectance spectra of tochilinite that is a major phase of CM chondrites and has a low dehydration temperature (250degC).

  20. Infrared diffuse reflectance spectra of carbonaceous chondrites: Amount of hydrous minerals

    NASA Technical Reports Server (NTRS)

    Miyamoto, M.; Zolensky, M. E.

    1994-01-01

    Infrared diffuse reflectance spectra (2.53-25 microns) of some carbonaceous (C) chondrites were measured. The integrated intensity of the absorption bands near 3 microns caused by hydrous minerals were compared with the modal content of hydrous minerals for the meteorites. The CM and CI chondrites show larger values of the intergated intensity than those of the unique C chondrites Y82162, Y86720 and B7904, suggesting that the amount of hydrous minerals in the CM and CI chondrites is larger, which supports the contention that hydrous minerals were dehydrated by thermal metamorphism in the unique chondrites. Orgueil (CI) has the largest value of the integrated intensity among the C chondrites we measured and shows a sharp absorption band at 3685/cm (2.71 microns) that is not seen in the spectra of the CM chondrites. There is an excellent correlation between the observed hydrogen content in C chondrites and the integrated intensity. The CM chondrites show a wide variation in the strength of absorption bands at 1470/cm (6.8 microns), despite the similarity in absorption features near 3 micron for all CM chondites. The 1470/cm band could be due to the presence of some hydrocarbons but may also be a result of terrestrial alteration processes.

  1. SEM Observation of Hydrous Superabsorbent Polymer Pretreated with Room-Temperature Ionic Liquids

    PubMed Central

    Tsuda, Tetsuya; Mochizuki, Eiko; Kishida, Shoko; Iwasaki, Kazuki; Tsunashima, Katsuhiko; Kuwabata, Susumu

    2014-01-01

    Room-temperature ionic liquid (RTIL), which is a liquid salt at or below room temperature, shows peculiar physicochemical properties such as negligible vapor pressure and relatively-high ionic conductivity. In this investigation, we used six types of RTILs as a liquid material in the pretreatment process for scanning electron microscope (SEM) observation of hydrous superabsorbent polymer (SAP) particles. Very clear SEM images of the hydrous SAP particles were obtained if the neat RTILs were used for the pretreatment process. Of them, tri-n-butylmethylphosphonium dimethylphosphate ([P4, 4, 4, 1][DMP]) provided the best result. On the other hand, the surface morphology of the hydrous SAP particles pretreated with 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) was damaged. The results of SEM observation and thermogravimetry analysis of the hydrous SAP pretreated with the RTILs strongly suggested that most water in the SAP particles are replaced with RTIL during the pretreatment process. PMID:24621609

  2. Low-Mr hydrocarbons generated during hydrous and dry pyrolysis of kerogen.

    PubMed

    Tannenbaum, E; Kaplan, I R

    1985-10-24

    The validity of applying laboratory pyrolysis experiments to simulating the maturation of organic matter in sedimentary basins has been vigorously debated. We report here results from the generation of hydrocarbons of low relative molecular mass (Mr) in both hydrous and dry pyrolysis. A principal difference is that under dry conditions in the presence of montmorillonite, catalysis occurs with respect to generation of low-Mr hydrocarbons but no such effect is evident for hydrous conditions, probably because of a reduction in the clay's acidity. In addition, olefins which were previously reported as not being present in the products of hydrous pyrolyses were found to be produced in the C2-C6 range in comparable amounts under both hydrous and dry pyrolyses at 300 degrees C and may form in the course of kerogen catagenesis in nature but disappear with geologic time due to their instability. These studies have relevance to understanding the interactions between kerogen and minerals in sedimentary rocks and to processes in the formation of natural gas.

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

    PubMed

    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.

  4. The Effect of Disorder on Hydrous Mineral Stability at High Pressure

    NASA Astrophysics Data System (ADS)

    Rytel, A. L.; Pigott, J. S.; Panero, W. R.

    2014-12-01

    The water storage capacity in the Earth's deep interior and its transport between reservoirs is in part dependent upon the stability of high-pressure phases of hydrous minerals. Prediction of mineral stability in the Earth's mantle is dependent upon accurately calculating the Gibbs free energy of each phase as a function of pressure, temperature, and composition. Contributions from crystallographic disorder to the configurational entropy can extend the stability field of minerals at high temperatures. In certain hydrous and anhydrous aluminum and magnesium silicates such as ringwoodite, some degree of disorder is favored at mantle pressure and temperature conditions. This study constrains the water storage capacity of the mantle by examining the effects of cation disorder on the structure and energetics of hydrous and anhydrous aluminum and magnesium silicates (kyanite, topaz-OH, phase egg, phase D, and δ-AlOOH) as a function of Si and Al coordination. We present the energetics of disorder at mantle pressure and temperature conditions from static lattice energy minimizations using interatomic potentials and complementary first-principles calculations coupled with modeling of configurational entropy. This work assesses the applicability of the aluminum avoidance principle in high-pressure hydrous aluminosilicates.

  5. Comparison of artificial maturation of lignite in hydrous and nonhydrous conditions

    USGS Publications Warehouse

    Behar, F.; Lewan, M.D.; Lorant, F.; Vandenbroucke, M.

    2003-01-01

    The objectives of the study are to compare product compositions and yields generated from lignite artificially matured by open nonhydrous pyrolysis, closed nonhydrous pyrolysis, and hydrous pyrolysis. The pyrolysis products were fractionated into CO2, H2O, CH4, C2-C5, C8-C14, C14+ saturates, C14+ aromatics and NSOs (resins+asphaltenes). All three methods generated high and similar quantities of water during pyrolysis that ranged between 14.6 and 15.2 wt.% of the original lignite. As a result of this high water content generated by the lignite, the experiments with no added water are referred to as nonhydrous rather than anhydrous. Rock-Eval pyrolysis and elemental analyses were conducted on the recovered lignite after solvent extraction to determine their residual hydrocarbon generation potential and to plot their position in a van Krevelen diagram, respectively. Residual lignite from the closed nonhydrous and hydrous experiments showed relationships between vitrinite reflectance (%Ro) values and atomic H/C ratios that occurred within the fields observed for natural maturation of coal. Although no significant differences in the atomic H/C ratios were observed between closed nonhydrous and hydrous pyrolysis, the vitrinite reflectance values were on the average 0.2% Ro lower in the residual lignite from the nonhydrous experiments. The remaining hydrocarbon generation potential as determined by Rock-Eval pyrolysis of the residual lignite showed that the nonhydrous residuals had on the average 16 mg more hydrocarbon potential per gram of original lignite than the hydrous residuals. This suggests there is a better release of the pyrolysis products from the lignite network in the hydrous experiments once generation occurs. For gas generation, at maximum yields, open nonhydrous pyrolysis generates the most hydrocarbon gas (21.0 mg/g original lignite), which is 20% more than closed nonhydrous pyrolysis and 29% more than hydrous pyrolysis. Closed nonhydrous pyrolysis

  6. Biosynthetic inorganic chemistry.

    PubMed

    Lu, Yi

    2006-08-25

    Inorganic chemistry and biology can benefit greatly from each other. Although synthetic and physical inorganic chemistry have been greatly successful in clarifying the role of metal ions in biological systems, the time may now be right to utilize biological systems to advance coordination chemistry. One such example is the use of small, stable, easy-to-make, and well-characterized proteins as ligands to synthesize novel inorganic compounds. This biosynthetic inorganic chemistry is possible thanks to a number of developments in biology. This review summarizes the progress in the synthesis of close models of complex metalloproteins, followed by a description of recent advances in using the approach for making novel compounds that are unprecedented in either inorganic chemistry or biology. The focus is mainly on synthetic "tricks" learned from biology, as well as novel structures and insights obtained. The advantages and disadvantages of this biosynthetic approach are discussed.

  7. Investigations of inorganic and hybrid inorganic-organic nanostructures

    NASA Astrophysics Data System (ADS)

    Kam, Kinson Chihang

    This thesis focuses on the exploratory synthesis and characterization of inorganic and hybrid inorganic-organic nanomaterials. In particular, nanostructures of semiconducting nitrides and oxides, and hybrid systems of nanowire-polymer composites and framework materials, are investigated. These materials are characterized by a variety of techniques for structure, composition, morphology, surface area, optical properties, and electrical properties. In the study of inorganic nanomaterials, gallium nitride (GaN), indium oxide (In2O3), and vanadium dioxide (VO2) nanostructures were synthesized using different strategies and their physical properties were examined. GaN nanostructures were obtained from various synthetic routes. Solid-state ammonolysis of metastable gamma-Ga2O 3 nanoparticles was found to be particularly successful; they achieved high surface areas and photoluminescent study showed a blue shift in emission as a result of surface and size defects. Similarly, In2O3 nanostructures were obtained by carbon-assisted solid-state syntheses. The sub-oxidic species, which are generated via a self-catalyzed vapor-liquid-solid mechanism, resulted in 1D nanostructures including nanowires, nanotrees, and nanobouquets upon oxidation. On the other hand, hydrothermal methods were used to obtain VO2 nanorods. After post-thermal treatment, infrared spectroscopy demonstrated that these nanorods exhibit a thermochromic transition with temperature that is higher by ˜10°C compared to the parent material. The thermochromic behavior indicated a semiconductor-to-metal transition associated with a structural transformation from monoclinic to rutile. The hybrid systems, on the other hand, enabled their properties to be tunable. In nanowire-polymer composites, zinc oxide (ZnO) and silver (Ag) nanowires were synthesized and incorporated into polyaniline (PANI) and polypyrrole (PPy) via in-situ and ex-situ polymerization method. The electrical properties of these composites are

  8. Flow behavior and microstructures of hydrous olivine aggregates at upper mantle pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Ohuchi, Tomohiro; Kawazoe, Takaaki; Higo, Yuji; Suzuki, Akio

    2017-08-01

    Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5-9.8 GPa, temperatures of 1223-1800 K, and strain rates ranging from 0.8 × 10-5 to 7.5 × 10-5 s-1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm3 mol-1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323-1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323-1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633-1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm3 mol-1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol-1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth's upper mantle.

  9. Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis

    USGS Publications Warehouse

    Lewan, M.D.; Ruble, T.E.

    2002-01-01

    This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 ??C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-US kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.

  10. Effect of thermal maturation on the K-Ar, Rb-Sr and REE systematics of an organic-rich New Albany Shale as determined by hydrous pyrolysis

    USGS Publications Warehouse

    Clauer, Norbert; Chaudhuri, Sambhudas; Lewan, M.D.; Toulkeridis, T.

    2006-01-01

    Hydrous-pyrolysis experiments were conducted on an organic-rich Devonian-Mississippian shale, which was also leached by dilute HCl before and after pyrolysis, to identify and quantify the induced chemical and isotopic changes in the rock. The experiments significantly affect the organic-mineral organization, which plays an important role in natural interactions during diagenetic hydrocarbon maturation in source rocks. They produce 10.5% of volatiles and the amount of HCl leachables almost doubles from about 6% to 11%. The Rb-Sr and K-Ar data are significantly modified, but not just by removal of radiogenic 40Ar and 87Sr, as described in many studies of natural samples at similar thermal and hydrous conditions. The determining reactions relate to alteration of the organic matter marked by a significant change in the heavy REEs in the HCl leachate after pyrolysis, underlining the potential effects of acidic fluids in natural environments. Pyrolysis induces also release from organics of some Sr with a very low 87Sr/86Sr ratio, as well as part of U. Both seem to have been volatilised during the experiment, whereas other metals such as Pb, Th and part of U appear to have been transferred from soluble phases into stable (silicate?) components. Increase of the K2O and radiogenic 40Ar contents of the silicate minerals after pyrolysis is explained by removal of other elements that could only be volatilised, as the system remains strictly closed during the experiment. The observed increase in radiogenic 40Ar implies that it was not preferentially released as a volatile gas phase when escaping the altered mineral phases. It had to be re-incorporated into newly-formed soluble phases, which is opposite to the general knowledge about the behavior of Ar in supergene natural environments. Because of the strictly closed-system conditions, hydrous-pyrolysis experiments allow to better identify and even quantify the geochemical aspects of organic-inorganic interactions, such as

  11. Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

    NASA Astrophysics Data System (ADS)

    Li, Yuan

    2014-11-01

    Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ-2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750-1500 for Cu; 600-1200 for Ni; 35-42 for Co; 35-53 for Pb; and 1-2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380-500 for Cu; 520-750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3-6 for Pb; 0.1-2 for As; 1-2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu-Au deposits and magmatic sulfide deposits. I show that the metasomatized arc mantle may no longer contain sulfide after >10-14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions. Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO2 > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10-14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and

  12. New inorganic materials

    SciTech Connect

    Birchall, J.D.; Kelly, A.

    1983-05-01

    Inorganic chemistry is preparing to contribute to the conservation of energy and of hydrocarbons by manipulating inorganic chemical compounds at low temperature. In this regard cement preparation and qualities are extensively discussed. Related techniques with regard to glasses are mentioned. The manipulation of inorganic compounds at low temperature is being aided by advances in the understanding of material properties such as porosity. Interestingly, the importance of the control of porosity had not emerged from all the previous work on high-temperature methods of fabrication. It may be too early to speak of a new Neolithic age, but its beginnings are clearly with us.

  13. New composites of nanoparticle Cu (I) oxide and titania in a novel inorganic polymer (geopolymer) matrix for destruction of dyes and hazardous organic pollutants.

    PubMed

    Falah, Mahroo; MacKenzie, Kenneth J D; Knibbe, Ruth; Page, Samuel J; Hanna, John V

    2016-11-15

    New photoactive composites to efficiently remove organic dyes from water are reported. These consist of Cu2O/TiO2 nanoparticles in a novel inorganic geopolymer matrix modified by a large tertiary ammonium species (cetyltrimethylammonium bromide, CTAB) whose presence in the matrix is demonstrated by FTIR spectroscopy. The CTAB does not disrupt the tetrahedral geopolymer structural silica and alumina units as demonstrated by (29)Si and (27)Al MAS NMR spectroscopy. SEM/EDS, TEM and BET measurements suggest that the Cu2O/TiO2 nanoparticles are homogenously distributed on the surface and within the geopolymer pores. The mechanism of removal of methylene blue (MB) dye from solution consists of a combination of adsorption (under dark conditions) and photodegradation (under UV radiation). MB adsorption in the dark follows pseudo second-order kinetics and is described by Freundlich-Langmuir type isotherms. The performance of the CTAB-modified geopolymer based composites is superior to composites based on unmodified geopolymer hosts, the most effective composite containing 5wt% Cu2O/TiO2 in a CTAB-modified geopolymer host. These composites constitute a new class of materials with excellent potential in environmental protection applications.

  14. Experiments on phase equilibria in hydrous tholeiitic systems: implications for the genesis of oceanic plagiogranites

    NASA Astrophysics Data System (ADS)

    Koepke, J.; Berndt, J.; Feig, S. T.

    2003-04-01

    For the genesis of oceanic plagiogranites at mid-ocean spreading systems, two models are under discussion: (1) Late-stage differentiation of a MORB-type melt and (2) partial melting of pre-existing gabbros within high-temperature shear zones. In this study, we have applied recent experimental data of the experimental lab in Hannover to the plagiogranite petrogenesis in order to test both models. The role of water during the genesis of these rocks (presence of amphibole as mafic phase in natural plagiogranites) was assessed by including water to the systems. Crystallization experiments were performed in a MORB system doped with different water contents at different redox conditions at 200 MPa (Berndt, 2002), and hydrous partial melting experiments were performed at 200 MPa on typical oceanic gabbros (Feig et al., this volume). For the experiments we have used an internally heated pressure vessel for high temperatures (up to 1250°C) equipped with a rapid-quench system and a hydrogen membrane for controlling the oxygen fugacity. Liquid lines of descent obtained via crystallization experiments are mainly controlled by oxygen fugacity and only to a little extent by water activity. SiO2-rich residual melts can be obtained under both oxidizing and reducing redox condition at low temperatures, but at least one fractionation step is required to reach high-silicic plagiogranites (SiO2 > 70 wt%). The partial melting of typical oceanic gabbro leads at low temperatures also to plagiogranitic melts. At 940°C, the normalized SiO2 contents of the experimental melts of the three investigated systems range between 60 and 61 wt%, and at 900°C from 63 and 68 wt%. These melts coexist with orthopyroxene, amphibole, plagioclase and in one sample also with olivine. The experimental melt compositions are compared with those of natural plagiogranites of different tectonic settings and show in general a broad compositional overlap with those. Our experiments imply, in concordance with the

  15. Influence of crustal dust and sea spray supermicron particle concentrations and acidity on inorganic NO3 aerosol during the 2013 Southern Oxidant and Aerosol Study

    SciTech Connect

    Allen, H. M.; Draper, D. C.; Ayres, B. R.; Ault, A.; Bondy, A.; Takahama, S.; Modini, R. L.; Baumann, K.; Edgerton, E.; Knote, C.; Laskin, A.; Wang, B.; Fry, J. L.

    2015-09-25

    Inorganic aerosol composition was measured in the southeastern United States, a region that exhibits high aerosol mass loading during the summer, as part of the 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. Measurements using a Monitor for AeRosols and GAses (MARGA) revealed two periods of high aerosol nitrate (NO3) concentrations during the campaign. These periods of high nitrate were correlated with increased concentrations of supermicron crustal and sea spray aerosol species, particularly Na+ and Ca2+, and with a shift towards aerosol with larger (1 to 2.5 μm) diameters. We suggest this nitrate aerosol forms by multiphase reactions of HNO3 and particles, reactions that are facilitated by transport of crustal dust and sea spray aerosol from a source within the United States. The observed high aerosol acidity prevents the formation of NH4NO3, the inorganic nitrogen species often dominant in fine-mode aerosol at higher pH. In addition, calculation of the rate of the heterogeneous uptake of HNO3 on mineral aerosol supports the conclusion that aerosol NO3 is produced primarily by this process, and is likely limited by the availability of mineral cation-containing aerosol surface area. Modeling of NO3 and HNO3 by thermodynamic equilibrium models (ISORROPIA II and E-AIM) reveals the importance of including mineral cations in the southeastern United States to accurately balance ion species and predict gas–aerosol phase partitioning.

  16. Analytical methods for SiO2 and other inorganic oxides in titanium dioxide or certain silicates for food additive specifications.

    PubMed

    Mutsuga, Motoh; Sato, Kyoko; Hirahara, Yoshichika; Kawamura, Yoko

    2011-04-01

    An analytical method has been developed for the detection of SiO(2) and other oxides in titanium dioxide and certain silicates used in food additives using inductively coupled plasma (ICP) atomic emission spectrometry without hydrofluoric acid. SiO(2) and other oxides in titanium dioxide or certain silicates were resolved by alkali fusion with KOH and boric acid and then dissolved in dilute hydrochloric acid as a test solution for ICP. The recovery of SiO(2) and Al(2)O(3) added at 0.1 and 1.0%, respectively, in TiO(2) was 88-104%; coefficient of variation was <4%. The limit of determination of SiO(2) and Al(2)O(3) was about 0.08%, and the accuracy of the ICP method was better than that of the Joint FAO/WHO Expert Committee on Food Additives (JECFA) test method. The recovery of SiO(2) and other oxides in silicates was 95-107% with a coefficient of variation of <4%. Using energy dispersive X-ray fluorescence spectrometry (EDX) with fundamental parameter determination, the content of SiO(2) and other oxide in titanium dioxide and silicate showed good agreement with the ICP results. ICP with alkali fusion proved suitable as a test method for SiO(2), Al(2)O(3) and other oxides in titanium dioxide and certain silicates, and EDX proves useful for screening such impurities in titanium dioxide and componential analysis of certain silicates.

  17. Science Update: Inorganic Chemistry

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1978-01-01

    This first in a series of articles describing the state of the art of various branches of chemistry reviews inorganic chemistry, including bioinorganic, photochemistry, organometallic, and solid state chemistries. (SL)

  18. Science Update: Inorganic Chemistry

    ERIC Educational Resources Information Center

    Rawls, Rebecca

    1978-01-01

    This first in a series of articles describing the state of the art of various branches of chemistry reviews inorganic chemistry, including bioinorganic, photochemistry, organometallic, and solid state chemistries. (SL)

  19. Silica modified with zirconium oxide for on-line determination of inorganic arsenic using a hydride generation-atomic absorption system.

    PubMed

    Macarovscha, Greice T; Bortoleto, Gisele G; Cadore, Solange

    2007-02-28

    In the present work, an on-line pre-concentration system, using SiO(2)/ZrO(2) as solid phase adsorbent, for the determination of low concentrations of arsenic was developed. In this procedure, total inorganic arsenic present in the sample is reduced to As (III) with l-cysteine and the solution is passed into a glass column (varphi(i)=3mm; h=35mm) containing 70mg of SiO(2)/ZrO(2) (100-230 mesh) to retain the As (III), with the solution flowing at 3.2mLmin(-1). After 2min, the concentrated species are eluted with 3molL(-1) HCl (3.2mLmin(-1)) loading a 150muL loop while a 1.0% (m/v) sodium borohydride solution loads the other loop of a FI-HG AAS system. The elution step is carried out during 7s and, at the same time, the SiO(2)/ZrO(2) phase is regenerated for the next concentration cycle. The arsine generated is carried with N(2) (flow rate=90mLmin(-1)) to a quartz cell where the electrothermal atomization process occurs. Under these conditions, a 20-fold enrichment factor is obtained considering the increase of sensitivity in the analytical curve after the concentration step. The limits of detection and quantification were 0.05 and 0.35mugL(-1), respectively, with an injection frequency of about 28h(-1) and relative standard deviation lower than 8%. Four metallurgical reference materials were analyzed with the proposed method after their acid dissolution. The results obtained were in good agreement with certified values.

  20. The role of Nrf2/Keap1 signaling in inorganic mercury induced oxidative stress in the liver of large yellow croaker Pseudosciaena crocea.

    PubMed

    Zeng, Lin; Zheng, Jia-Lang; Wang, Yong-Hong; Xu, Mei-Ying; Zhu, Ai-Yi; Wu, Chang-Wen

    2016-10-01

    The aim of the present study was to evaluate the effects of acute inorganic Hg exposure (0, 32 and 64μgHgL(-1)) on lipid peroxidation, activities and gene expression of antioxidant enzymes (Cu/Zn-SOD, CAT, GPx, GR and GST), and mRNA levels of the Keap1-Nrf2 signaling molecules at different exposure times (6h, 12h, 24h, 48h, and 96h) in the liver of large yellow croaker Pseudosciaena crocea. The results showed that lipid peroxidation was sharply reduced by 32μg Hg L(-1) during 6-12h before returning to control levels. Similarly, lipid peroxidation was significantly reduced during 6-12h followed by a sharp increase towards the end of the exposure in the 64μgHgL(-1) group. There was a negative relationship between lipid peroxidation and antioxidant enzyme activities, and positive relationship between activities and gene expression of antioxidant enzymes, suggesting that the changes at a molecular level may underlie enzymatic level and accordingly affect hepatic lipid peroxidation. Obtained results also showed a coordinated transcriptional regulation of antioxidant genes, suggesting that Nrf2 is required for the protracted induction of these genes. Furthermore, a negative relationship between the mRNA levels of Nrf2 and Keap1 indicated that Keap1 may play an important role in switching off the Nrf2 response. In conclusion, this is the first study to elucidate effects of waterborne Hg on antioxidant system in large yellow croaker through the Keap1-Nrf2 pathway, which will aid our understanding of the molecular mechanisms of waterborne heavy metal on antioxidant responses in fish.

  1. Inorganic and organic structures as interleavers among [bis(1-methyl-3-(p-carboxylatephenyl)triazenide 1-oxide)Ni(II)] complexes to form supramolecular arrangements

    NASA Astrophysics Data System (ADS)

    Santos, Aline Joana Rolina Wohlmuth Alves; dos Santos Hackbart, Helen Cristina; Giacomini, Gabriela Xavier; Bersch, Patrícia; Paraginski, Gustavo Luiz; Hörner, Manfredo

    2016-12-01

    Alternative compounds to capture metal ions are triazenes 1-oxide since they are basic compounds O(N) with negative charge in the deprotonated form. The proximity of both coordination sites (O and N) enables these compounds to have good chelating ability and a tendency to stabilize in the formation of rings with soft and hard transition metal ions. The structure analysis by single crystal X-ray diffraction of compounds (1) and (2) demonstrate the formation of 3D supramolecular arrangements through ion-ion, ion-dipolo and dipolo-dipolo interactions. In one of them, there are [(H2O)2(CH3CH3SO)K2]2+ as linkers of polymerization and, in another complex, there are [(H2O)(CH3CH3SO)Ni(H2O)6]2+ as a linker of polymerization. These linkers act in the polymerization of the novel mononuclear complex [bis(1-methyl (p-carboxylatephenyl) triazenide 1-oxide) NiII] (3). The crystallography analysis of (1) and (2) showed distorted quadratic geometry for Ni (II), thus, there are two axial positions available in Ni (II) to be used in catalysis studies and as sensor or biosensor. In addition, this study shows the support of this novel mononuclear complex of Ni (II) (3) on protonated chitosan chains (4). The compounds (3) and (4) were characterized by spectroscopic analysis, infrared (IR) and energy dispersive X-ray detector (EDS), and by differential scanning calorimetry analysis (DSC). The specificity of ligand 1-methyl (p-carboxyphenyl) triazene 1-oxide to capture potassium and nickel ions will be tested at different pH values, as well as the capacity of the triazenide 1-oxide of Ni (II) complex, supported on chitosan polymer, or not, to act as a catalyst for organic reactions and biomimetic organic reactions.

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

    NASA Astrophysics Data System (ADS)

    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

  3. Evidence for the late formation of hydrous asteroids from young meteoritic carbonates.

    PubMed

    Fujiya, Wataru; Sugiura, Naoji; Hotta, Hideyuki; Ichimura, Koji; Sano, Yuji

    2012-01-17

    The accretion of small bodies in the Solar System is a fundamental process that was followed by planet formation. Chronological information of meteorites can constrain when asteroids formed. Secondary carbonates show extremely old (53)Mn-(53)Cr radiometric ages, indicating that some hydrous asteroids accreted rapidly. However, previous studies have failed to define accurate Mn/Cr ratios; hence, these old ages could be artefacts. Here we develop a new method for accurate Mn/Cr determination, and report a reliable age of 4,563.4+0.4/-0.5 million years ago for carbonates in carbonaceous chondrites. We find that these carbonates have identical ages, which are younger than those previously estimated. This result suggests the late onset of aqueous activities in the Solar System. The young carbonate age cannot be explained if the parent asteroid accreted within 3 million years after the birth of the Solar System. Thus, we conclude that hydrous asteroids accreted later than differentiated and metamorphosed asteroids.

  4. Sensibility of hydrous ethanol adulteration detection using ultrasonic parameters validated in a metrological base

    NASA Astrophysics Data System (ADS)

    K-K Figueiredo, Monique; Costa-Felix, Rodrigo P. B.; Maggi, Luis E.; Alvarenga, André V.; Romeiro, Gilberto A.

    2011-02-01

    The aim of this study is to identify possible changes in fuels, in this case hydrous ethanol, through ultrasonic parameters such as attenuation and propagation speed. The system setup and method were implemented at Inmetro's Laboratory of Ultrasound. Experiments and method uncertainties were assessed accordingly to ISO/IEC Guide 98 1:2009 (Uncertainty of measurement - Part 1: Introduction to the expression of uncertainty in measurement). Mixtures of ethanol and water varying from 90% to 94% of alcohol in mass were used as testing samples. Attenuation and propagation speed were accurately measured and uncertainties evaluated. The accordingly to Brazilian biofuel regulations, the concentration of water in hydrous ethanol can be accepted at a maximum concentration of 93.8 and minimum of 92.6 of alcohol in mass. To achieve that figure, a functional combination of tested parameters should be implemented. Those results could be used as a tool to identify adulteration of biofuel, even in analysis performed on site.

  5. Hydrous ethanol injection system. Final report/project accomplishments summary, CRADA Number 95-KCP-1017

    SciTech Connect

    Carr, M.E.

    1997-03-01

    This CRADA effort applies AlliedSignal Federal Manufacturing and Technologies (FM and T) expertise and facilities together with FMD`s knowledge of diesel emissions control as a design team to create a practical Hydrous Ethanol Injection and Fuel Management System which will significantly reduce particulate and NOx emissions and improve fuel economy. FM and T`s knowledge of high reliability electronic design and packaging gained from traditional business was used to assist in this design process. The combination of these capabilities with the experience in bringing a product from initial concept through development and into full production complemented FMD design and product experience. This collaborative design team effort between FM and T and FMD has resulted in the development of a practical Hydrous Ethanol Injection and Fuel Management System.

  6. Water Speciation and properties of hydrous model basalt melt at high pressure

    NASA Astrophysics Data System (ADS)

    Bajgain, S. K.; Karki, B. B.

    2013-12-01

    Silicate melts in the Earth's interior are known/expected to be hydrous. Water can make major impact on physical properties including the structure, density, and mobility of melts. The behavior of relevant hydrous melts over most of the mantle pressure regime is poorly constrained. Water solubility increases rapidly with increasing pressure at low pressure [1] and a complete miscibility of liquid MgSiO3 and H2O has been suggested based on high-pressure simulations [2]. We have recently performed first principle molecular dynamics simulations of hydrous model basalt melt at high pressure. Our results show that with increasing pressure, the partial molar volume of water in the melt asymptotically approaches to that of pure water, and both the volumes become identical after certain point. Water is predicted to dissolve in the form of hydroxyls and water molecules at low pressure and as more extended structures at high pressure. The simulated basalt-H2O system commences to behave ideally at pressures above 10 GPa. In contrast, the simulated SiO2-H2O and MgSiO3-H2O systems approach to an ideal limit at much higher pressures of 50 GPa or above. These results imply an unlimited solubility of water in in silicate melts and the water solubility rather appears to be insensitive of composition at high pressure. Existence of water-rich silicate melts over most of the mantle in early history could have made substantial contribution to the origin of hydrosphere [3]. [1] Shen, A. H., and H. Keppler (1997), Direct observation of complete miscibility in the Albite-H2O system, Nature, 385, 710-712. [2] Mookherjee, M., L. Stixrude, and B. Karki (2008), Hydrous silicate melt at high pressure, Nature, 452, 983-986. [3] Matsui, T., and Y. Abe (1986), Evolution of an impact-induced atmosphere and magma ocean on the accreting Earth, Nature, 319, 303-305.

  7. Experimental Insights into the Stability and Composition of Hydrous Phases in the Metasomatized Mantle Lithosphere

    NASA Astrophysics Data System (ADS)

    Mandler, B. E.; Grove, T. L.

    2014-12-01

    Mantle xenoliths and exhumed peridotite bodies from all tectonic settings record pervasive metasomatism of the mantle lithosphere by volatile-rich fluids. These fluids commonly enrich the lithospheric mantle not only in H2O but also K2O and Na2O as well as other minor elements. As a result, alkali-bearing hydrous phases (amphibole and biotite) become an important part of the mineralogy of mantle lithosphere. We have performed high-pressure-temperature experiments on alkali-enriched fertile and depleted mantle with low bulk H2O (0.65 wt.%) from 950 - 1150°C and 2 - 4 GPa to determine the stability fields and composition of these hydrous phases in the mantle as a function of temperature, pressure and bulk composition. We find that our stability field for amphibole at 0.65 wt.% H2O is similar to that of (1) and (2). This stability for amphibole extends to higher pressures and temperatures than that found by (3), indicating that bulk H2O content exercises an important control on hydrous mineral phase stability (4). We also find that metasomatic compositional changes induce other mineralogical changes. The stability and composition of other phases, particularly the typical aluminous phases spinel and garnet, are significantly affected by the formation of Al-bearing amphibole. We combine our experimental results with those of other experimental studies to more rigorously assess and quantify the influence of compositional changes in the lithospheric mantle on hydrous and anhydrous phase stability. (1) Niida & Green (1999) CMP 135, 18-40; (2) Fumagalli et al. (2009) CMP 158, 723-737; (3) Grove et al. (2006) EPSL 249, 74-89; (4) Green et al. (2010) Nature 448-451.

  8. Detectability of hydrous minerals using ONC-T camera onboard the Hayabusa2 spacecraft

    NASA Astrophysics Data System (ADS)

    Kameda, S.; Suzuki, H.; Cho, Y.; Koga, S.; Yamada, M.; Nakamura, T.; Hiroi, T.; Sawada, H.; Honda, R.; Morota, T.; Honda, C.; Takei, A.; Takamatsu, T.; Okumura, Y.; Sato, M.; Yasuda, T.; Shibasaki, K.; Ikezawa, S.; Sugita, S.

    2015-10-01

    The Hayabusa2 spacecraft has three framing cameras (ONC-T, ONC-W1, and ONC-W2) for optical navigation to asteroid 1999 JU3. The ONC-T is a telescopic camera with seven band-pass filters in the visible and near-infrared range. These filters are placed on a wheel, which rotates to put a selected filter for different observations, enabling multiband imaging. Previous ground-based observations suggesting that hydrous materials may be present on the surface of 1999 JU3 and distributed in relatively limited areas. The presence of hydrous minerals indicates that this asteroid experienced only low to moderate temperatures during its formation, suggesting that primordial materials are preserved. In order to find the best sampling sites, we will perform reflectance spectroscopic observations using the ONC-T near the asteroid after arrival. Finding regions rich in hydrous minerals is the key for this remote sensing observation. In preparation for this, we conducted ground-based experiments for the actual ONC-T flight model to confirm the detectability of the absorption band of Fe-rich serpentine. As a result, we detected the absorption band near 0.7 μm by reflectance spectroscopy of CM2 chondrites, such as Murchison and Nogoya, which are known to contain the Fe-rich serpentine, and did not detect any 0.7 μm absorption in Jbilet Winselwan CM2 chondrite with decomposed Fe-rich serpentine.

  9. Inorganic Phosphor Materials for Lighting.

    PubMed

    Lin, Yuan-Chih; Karlsson, Maths; Bettinelli, Marco

    2016-04-01

    This chapter addresses the development of inorganic phosphor materials capable of converting the near UV or blue radiation emitted by a light emitting diode to visible radiation that can be suitably combined to yield white light. These materials are at the core of the new generation of solid-state lighting devices that are emerging as a crucial clean and energy saving technology. The chapter introduces the problem of white light generation using inorganic phosphors and the structure-property relationships in the broad class of phosphor materials, normally containing lanthanide or transition metal ions as dopants. Radiative and non-radiative relaxation mechanisms are briefly described. Phosphors emitting light of different colors (yellow, blue, green, and red) are described and reviewed, classifying them in different chemical families of the host (silicates, phosphates, aluminates, borates, and non-oxide hosts). This research field has grown rapidly and is still growing, but the discovery of new phosphor materials with optimized properties (in terms of emission efficiency, chemical and thermal stability, color, purity, and cost of fabrication) would still be of the utmost importance.

  10. Inorganic separator technology program

    NASA Technical Reports Server (NTRS)

    Smatko, J. S.; Weaver, R. D.; Kalhammer, F. R.

    1973-01-01

    Testing and failure analyses of silver zinc cells with largely inorganic separators were performed. The results showed that the wet stand and cycle life objective of the silver-zinc cell development program were essentially accomplished and led to recommendations for cell composition, design, and operation that should yield further improvement in wet and cycle life. A series of advanced inorganic materials was successfully developed and formulated into rigid and semiflexible separator samples. Suitable screening tests for evaluation of largely inorganic separators were selected and modified for application to the separator materials. The results showed that many of these formulations are potentially superior to previously used materials and permitted selection of three promising materials for further evaluation in silver-zinc cells.

  11. Intermediate-depth earthquake generation: what hydrous minerals can tell us

    NASA Astrophysics Data System (ADS)

    Deseta, N.; Ashwal, L.; Andersen, T. B.

    2012-04-01

    Subduction zone seismicity has commonly been causally related to the dehydration of minerals within the subducting slab(Hacker et al. 2004, Jung et al. (2004), Dobson et al. 2002, Rondenay et al. 2008). Other models for release of intermediate- and deep earthquakes include spontaneous reaction(s) affecting large rock-bodies along overstepped phase boundaries ( e.g. Green and Houston, 1995) and various shear heating-localization models (e.g. Kelemen and Hirth 2007, John et al. 2009). These concepts are principally reliant on seismic and thermo-petrological modeling; both of which are indirect methods of analysis. Recent discoveries of pseudotachylytes (PST) formed under high pressure conditions (Ivrea-Verbano Zone, Italy, Western Gneiss Region, Norway and Corsica) provide the first tangible opportunity to evaluate these models (Austrheim and Andersen, 2004, Lund and Austrheim, 2003, Obata and Karato, 1995, Jin et al., 1998). This case study focuses on observations based on ultramafic and mafic PST within the Ligurian Ophiolite of the high pressure-low temperature metamorphic (HP-LT) 'Shistes Lustres' complex in Cima di Gratera, Corsica (Andersen et al. 2008). These PST have been preserved in pristine lenses of peridotite and gabbro surrounded by schistose serpentinites. The PST range in thickness from 1mm to 25 cm (Andersen and Austrheim, 2006). Petrography and geochemistry on PST from the peridotite and gabbro samples indicates that total/near-total fusion of the local host rock mineral assemblage occurred; bringing up the temperature of shear zone from 350° C to 1400 - 1700° C; depending on the host rock (Andersen and Austrheim, 2006). The composition of the PST is highly variable, even at the thin section scale and this has been attributed to the coarse-grained nature of the host rock, its small scale inhomogeneity and poor mixing of the fusion melt. Almost all the bulk analyses of the PST are hydrous; the peridotitic PST is always hydrous (H2O content from 3

  12. pH dependence of Fenton reagent generation and As(III) oxidation and removal by corrosion of zero valent iron in aerated water.

    PubMed

    Katsoyiannis, Ioannis A; Ruettimann, Thomas; Hug, Stephan J

    2008-10-01

    Corrosion of zerovalent iron (ZVI) in oxygen-containing water produces reactive intermediates that can oxidize various organic and inorganic compounds. We investigated the kinetics and mechanism of Fenton reagent generation and As(III) oxidation and removal by ZVI (0.1m2/g) from pH 3-11 in aerated water. Observed half-lives for the oxidation of initially 500 microg/L As(III) by 150 mg Fe(0)/L were 26-80 min at pH 3-9. At pH 11, no As(III) oxidation was observed during the first two hours. Dissolved Fe(III) reached 325, 140, and 6 microM at pH 3, 5, and 7. H2O2 concentrations peaked within 10 min at 1.2, 0.4, and < 0.1 microM at pH 3, 5, and 7, and then decreased to undetectable levels. Addition of 2,2'-bipyridine (1-3 mM), prevented Fe(II) oxidation by O2 and H2O2 and inhibited As(III)oxidation. 2-propanol (14 mM), scavenging OH-radicals, quenched the As(III) oxidation at pH 3, but had almost no effect at pH 5 and 7. Experimental data and kinetic modeling suggest that As(III) was oxidized mainly in solution by the Fenton reaction and removed by sorption on newly formed hydrous ferric oxides. OH-radials are the main oxidant for As(III) at low pH, whereas a more selective oxidant oxidizes As(III) at circumneutral pH.

  13. Inorganic and Organometallic Polymers

    NASA Astrophysics Data System (ADS)

    Chandrasekhar, Vadapalli

    This textbook is intended to give an understanding of the basic principles that constitute the field of non-conventional polymers containing inorganic and organometalic units as the repeating units. Each chapter will be self-explanatory with a good background so that it can be easily understood at the senior undergraduate level. The principles involved in the preparation of these polymers, their characterisation and their applications will be discussed. Basic inorganic chemistry required for the understanding of each topic is presented so that the content of the chapter is readily understood.

  14. Cationic polyelectrolyte induced separation of some inorganic contaminants and their mixture (zirconium silicate, kaolin, K-feldspar, zinc oxide) as well as of the paraffin oil from water.

    PubMed

    Ghimici, Luminita

    2016-03-15

    The flocculation efficiency of a cationic polyelectrolyte with quaternary ammonium salt groups in the backbone, namely PCA5 was evaluated on zirconium silicate (kreutzonit), kaolin, K- feldspar and zinc oxide (ZnO) suspensions prepared either with each pollutant or with their mixture. The effect of several parameters such as settling time, polymer dose and the pollutant type on the separation efficacy was evaluated and followed by optical density and zeta potential measurements. Except for ZnO, the interactions between PCA5 and suspended particles led to low residual turbidity values (around 4% for kreutzonit, 5% for kaolin and 8% for K-feldspar) as well as to the reduction of flocs settling time (from 1200 min to 30 min and 120 min in case of kaolinit and K-feldspar, respectively), that meant a high efficiency in their separation. The negative value of the zeta potential and flocs size measurements, at the optimum polymer dose, point to contribution from charge patch mechanism for the particles flocculation. A good efficiency of PCA5 in separation of paraffin oil (a minimum residual turbidity of 9.8%) has been also found. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Direct laser writing of micro-supercapacitors on thick graphite oxide films and their electrochemical properties in different liquid inorganic electrolytes.

    PubMed

    Kumar, Rajesh; Joanni, Ednan; Singh, Rajesh K; da Silva, Everson T S G; Savu, Raluca; Kubota, Lauro T; Moshkalev, Stanislav A

    2017-08-03

    In this article we demonstrate a simple approach to fabricate interdigitated in-plane electrodes for flexible micro-supercapacitors (MSCs). A nanosecond ultraviolet laser treatment is used to reduce and pattern the electrodes on thick graphite oxide (GO) freestanding films. These laser-treated regions obtained by direct writing provide the conducting channels for electrons in the capacitors. The electrochemical performance of the MSCs was evaluated in the presence of two different electrolytes and they exhibit characteristics of nearly electrical double layer capacitors. The MSCs have areal capacitances as 2.40, 2.23 and 1.62μF/cm(2) for NaOH, Na2SO4 and KCl electrolytes respectively, for measurements performed at the scan rate of 50mV/s. They retain ∼93.1% of their initial capacitances after 3500 cycles (scan rate=80mV/s) in NaOH electrolyte. The proposed laser treatment approach enables facile and fast fabrication of flexible MSCs without the need for tedious processing methods such as photolithographic micro-patterning and deposition of porous carbon or metallic current collectors. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Impacts of organic and inorganic fertilizers on nitrification in a cold climate soil are linked to the bacterial ammonia oxidizer community.

    PubMed

    Fan, Fenliang; Yang, Qianbao; Li, Zhaojun; Wei, Dan; Cui, Xi'an; Liang, Yongchao

    2011-11-01

    The microbiology underpinning soil nitrogen cycling in northeast China remains poorly understood. These agricultural systems are typified by widely contrasting temperature, ranging from -40 to 38°C. In a long-term site in this region, the impacts of mineral and organic fertilizer amendments on potential nitrification rate (PNR) were determined. PNR was found to be suppressed by long-term mineral fertilizer treatment but enhanced by manure treatment. The abundance and structure of ammonia-oxidizing bacterial (AOB) and archaeal (AOA) communities were assessed using quantitative polymerase chain reaction and denaturing gradient gel electrophoresis techniques. The abundance of AOA was reduced by all fertilizer treatments, while the opposite response was measured for AOB, leading to a six- to 60-fold reduction in AOA/AOB ratio. The community structure of AOA exhibited little variation across fertilization treatments, whereas the structure of the AOB community was highly responsive. PNR was correlated with community structure of AOB rather than that of AOA. Variation in the community structure of AOB was linked to soil pH, total carbon, and nitrogen contents induced by different long-term fertilization regimes. The results suggest that manure amendment establishes conditions which select for an AOB community type which recovers mineral fertilizer-suppressed soil nitrification.

  17. Synthesis of porous inorganic hollow fibers without harmful solvents.

    PubMed

    Shukla, Sushumna; de Wit, Patrick; Luiten-Olieman, Mieke W J; Kappert, Emiel J; Nijmeijer, Arian; Benes, Nieck E

    2015-01-01

    A route for the fabrication of porous inorganic hollow fibers with high surface-area-to-volume ratio that avoids harmful solvents is presented. The approach is based on bio-ionic gelation of an aqueous mixture of inorganic particles and sodium alginate during wet spinning. In a subsequent thermal treatment, the bio-organic material is removed and the inorganic particles are sintered. The method is applicable to the fabrication of various inorganic fibers, including metals and ceramics. The route completely avoids the use of organic solvents, such as N-methyl-2-pyrrolidone, and additives associated with the currently used fiber fabrication methods. In addition, it inherently avoids the manifestation of so-called macro voids and allows the facile incorporation of additional metal oxides in the inorganic hollow fibers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A Review of Clinical Translation of Inorganic Nanoparticles.

    PubMed

    Anselmo, Aaron C; Mitragotri, Samir

    2015-09-01

    Inorganic nanoparticles are widely used for therapeutic and diagnostic purposes as they offer unique features as compared with their organic and polymeric counterparts. As such, inorganic nanoparticles represent an exciting opportunity to develop drug delivery and imaging systems that are poised to tackle unique challenges which are currently unaddressed in clinical settings. Despite these clear advantages, very few inorganic nanoparticle systems have entered the clinic. Here, we review the current clinical landscape of inorganic nanoparticle systems and their opportunities and challenges, with particular emphasis on gold-, iron-oxide- and silica-based nanoparticle systems. Key examples of inorganic nanoparticles that are currently being investigated in the clinic (e.g., trials which are recruiting or currently active but not completed) are highlighted, along with the preclinical work that these examples have leveraged to transition from the lab to the clinic.

  19. Hybrid inorganic-organic materials: Novel poly(propylene oxide)-based ceramers, abrasion-resistant sol-gel coatings for metals, and epoxy-clay nanocomposites, with an additional chapter on: Metallocene-catalyzed linear polyethylene

    NASA Astrophysics Data System (ADS)

    Jordens, Kurt

    1999-12-01

    The sol-gel process has been employed to generate hybrid inorganic-organic network materials. Unique ceramers were prepared based on an alkoxysilane functionalized soft organic oligomer, poly(propylene oxide (PPO), and tetramethoxysilane (TMOS). Despite the formation of covalent bonds between the inorganic and organic constituents, the resulting network materials were phase separated, composed of a silicate rich phase embedded in a matrix of the organic oligomer chains. The behavior of such materials was similar to elastomers containing a reinforcing filler. The study focused on the influence of initial oligomer molecular weight, functionality, and tetramethoxysilane, water, and acid catalyst content on the final structure, mechanical and thermal properties. The sol-gel approach has also been exploited to generate thin, transparent, abrasion resistant coatings for metal substrates. These systems were based on alkoxysilane functionalized diethylenetriamine (DETA) with TMOS, which generated hybrid networks with very high crosslink densities. These materials were applied with great success as abrasion resistant coatings to aluminum, copper, brass, and stainless steel. In another study, intercalated polymer-clay nanocomposites were prepared based on various epoxy networks montmorillonite clay. This work explored the influence of incorporated clay on the adhesive properties of the epoxies. The lap shear strength decreased with increasing day content This was due to a reduction in the toughness of the epoxy. Also, the delaminated (or exfoliated) nanocomposite structure could not be generated. Instead, all nanocomposite systems possessed an intercalated structure. The final project involved the characterization of a series of metallocene catalyzed linear polyethylenes, produced at Phillips Petroleum. Polyolefins synthesized with such new catalyst systems are becoming widely available. The influence of molecular weight and thermal treatment on the mechanical, rheological

  20. Experimental constraints on the genesis of hydrous arc dacites

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    Shallow, pre-eruptive storage conditions are well known for dacitic magmas of the Cascade arc through melt inclusions, FeTi oxides, and experiments. Zircon ages indicate protracted (>105 yrs) incubation for some Cascade dacites, but their origins in the deep crust have not been established. Accordingly, we report experimental results identifying the P-T-H2O conditions under which such liquids could segregate from (hornblende-) gabbroic sources. Two compositions were investigated: (1) MSH-Yn dacite (SiO2: 65 wt%) from Mount St. Helens' voluminous Yn tephra, and (2) MSH-Yn + 10% cpx to force saturation with cpx and locate the cpx + melt = amphibole peritectic. H2O-undersaturated (3-9 wt% H2O) piston cylinder experiments were conducted at pressures, temperatures, and fO2 appropriate for the lower to middle crust (400 to 900 MPa, 825 to 1100°C, and ReReO2). Results for MSH-Yn indicate near-liquidus equilibrium with a cpx-free hornblende-gabbro residue (amphibole, plagioclase, magnetite, +/- opx and ilmeno-hematite) with 6-7 wt% H2O, 925°C, and 700-900 MPa. Opx disappears down-temperature consistent with the reaction opx + melt = amphibole. Cpx-added phase relations are similar in that once ~10% cpx crystallizes, multiple saturation is attained with cpx, amphibole, and plagioclase, +/- opx, at 6-7 wt% H2O, 950°C, and 700-900 MPa. Plagioclase-amphibole-cpx saturated liquids diverge from plagioclase-amphibole-opx saturated liquids, consistent with the MSH-Yn dacite composition marking a (pseudo-invariant) distributary reaction point where amphibole appears down-temperature and opx + cpx cease to coexist. Liquid compositions and temperatures stall at reaction points, irrespective of whether the source is crystallizing or melting, accounting for the compositional and thermal uniformity of voluminous dacites that feed into the shallow storage regions of arc volcanoes.

  1. Protection from inorganic mercury effects on the in vivo dopamine release by ionotropic glutamate receptor antagonists and nitric oxide synthase inhibitors.

    PubMed

    Vidal, Lucía; Durán, Rafael; Faro, Lilian F; Campos, Francisco; Cervantes, Rosa C; Alfonso, Miguel

    2007-09-05

    The possible role of ionotropics glutamate receptors on the HgCl(2)-induced dopamine (DA) release from rat striatum was investigated by using in vivo brain microdialysis technique after administration of selective NMDA and AMPA/Kainate receptors antagonists dizocilpine (MK-801), D (-)-2-amino-5-phoshonopentanoic acid (AP5), and 6-cyano-7-nitroquinoxaline-2,3-dione (CNQX). Moreover, we have also studied the effects of nitric oxide synthase (NOS) inhibitors L-nitro-arginine methyl ester (L-NAME) and 7-nitro-indazol (7-NI) on HgCl(2)-induced DA release. Intraestriatal infusion of 1mM HgCl(2) increased striatal DA to 1717.2+/-375.4% respect to basal levels. Infusion of 1mM HgCl(2) in 400 microM MK-801 pre-treated animals produced an increase on striatal DA levels 61% smaller than that induced in non-pre-treated animals. In the case of AP5, this treatment reduced 92% the increase produced by HgCl(2) as compared to non-pre-treated rats. Nevertheless, the administration of CNQX did not produce any effect on HgCl(2)-induced dopamine release. Intrastriatal infusion of 1mM HgCl(2) in 100 microM L-NAME pre-treated animals produced an increase on extracellular DA levels 82% smaller than produced by HgCl(2) alone. In addition, the pre-treatment with 7-NI reduced 90% the increase produced by infusion of HgCl(2) alone in rats. Thus, HgCl(2)-induced DA release could be produced at last in part, by overstimulation of NMDA receptors with NO production, since administration of NMDA receptor antagonists and NOS inhibitors protected against HgCl(2) effects on DA release.

  2. Lead and compounds (inorganic)

    Integrated Risk Information System (IRIS)

    Lead and compounds ( inorganic ) ; CASRN 7439 - 92 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

  3. Geological and Inorganic Materials.

    ERIC Educational Resources Information Center

    Jackson, L. L.; And Others

    1989-01-01

    Presents a review focusing on techniques and their application to the analysis of geological and inorganic materials that offer significant changes to research and routine work. Covers geostandards, spectroscopy, plasmas, microbeam techniques, synchrotron X-ray methods, nuclear activation methods, chromatography, and electroanalytical methods.…

  4. Inorganic High Energy Oxidisers,

    DTIC Science & Technology

    properties may contribute significantly to the energy of the whole system. A book entitled ’Inorganic High - Energy Oxidisers’ by E.W. Lawless and I.C. Smith is the subject of this Essay Review by W.E. Batty.

  5. Polyhedra in (inorganic) chemistry.

    PubMed

    Alvarez, Santiago

    2005-07-07

    A systematic description of polyhedra with varying degrees of regularity is illustrated with examples of chemical structures, mostly from different fields of Inorganic Chemistry. Also the geometrical relationships between different polyhedra are highlighted and their application to the analysis of complex structures is discussed.

  6. ADSORPTION OF THE ISOXAFLUTOLE DEGRADATES TO ALUMINUM AND IRON HYDROUS OXIDES

    USDA-ARS?s Scientific Manuscript database

    Isoxaflutole is relatively new herbicide which rapidly hydrolyzes to a diketonitrile (DKN) degradate after field application. Subsequently, DKN is degraded to form a benzoic acid (BA) derivative and other inactive degradates. However, our understanding of soil solid phases influencing or governing t...

  7. Precipitation and conversion of basic cupric sulfate to cupric hydrous oxide

    SciTech Connect

    Marani, D.

    1992-01-01

    The mechanism of conversion of posnjakite (CuSO[sub 4].3Cu(OH)[sub 2] H[sub 2]O) to tenorite (CuO) has been investigated. Posnjakite is a kinetic precursor of brochantite (CuSO[sub 4].3Cu(OH)[sub 2]). Both basic sulfates are likely to precipitate as intermediate phases during the alkaline treatment of copper and sulfate-bearing wastewaters. Upon aging in its mother liquor, posnjakite slowly dehydrates to brochantite. The [delta]G[degrees] value of the dehydration reaction measured in this work is comparable with previously reported data. In alkaline media posnjakite converts to tenorite. The conversion mechanism has been investigated with batch tests performed at constant pH and constant temperature. Scanning electron microscopy and X-ray diffraction measurements suggest that conversion takes place through incongruent dissolution, including transport of OH- to the surface of posnjakite platelets, dissolution of posnjakite, transport of soluble CU(II) species through the liquid phase, and nucleation and growth of tenorite needles. Conversion rates are initially increasing, remain constant for a large portion of the process, and finally decrease toward the end of the process. This trend suggests a sequence of at least two rate-limiting steps. Initially, the conversion process seems to be controlled by nucleation and growth of tenorite (increasing rate), and then by the dissolution of posnjakite (constant conversion rate). Following the mechanistic scheme described above, the effects of pH and temperature on the constant conversion rate were studied to investigate the mechanism of posnjakite dissolution. The fractional order dependence of steady conversion rates on pH suggests that posnjakite dissolution is surface reaction-controlled. This hypothesis is supported by the values of activation energy, activation enthalpy, and activation entropy calculated from the effect of temperature on steady constant conversion rates.

  8. SEQUENTIAL EXTRACTIONS FOR PARTITIONING OF ARSENIC ON HYDROUS IRON OXIDES AND IRON SULFIDES

    EPA Science Inventory

    The objective of this study was to use model solids to test solutions designed to extract arsenic from relatively labile solid phase fractions. The use of sequential extractions provides analytical constraints on the identification of mineral phases that control arsenic mobility...

  9. Chiral Inorganic Nanostructures.

    PubMed

    Ma, Wei; Xu, Liguang; de Moura, André F; Wu, Xiaoling; Kuang, Hua; Xu, Chuanlai; Kotov, Nicholas A

    2017-06-28

    The field of chiral inorganic nanostructures is rapidly expanding. It started from the observation of strong circular dichroism during the synthesis of individual nanoparticles (NPs) and their assemblies and expanded to sophisticated synthetic protocols involving nanostructures from metals, semiconductors, ceramics, and nanocarbons. Besides the well-established chirality transfer from bioorganic molecules, other methods to impart handedness to nanoscale matter specific to inorganic materials were discovered, including three-dimentional lithography, multiphoton chirality transfer, polarization effects in nanoscale assemblies, and others. Multiple chiral geometries were observed with characteristic scales from ångströms to microns. Uniquely high values of chiral anisotropy factors that spurred the development of the field and differentiate it from chiral structures studied before, are now well understood; they originate from strong resonances of incident electromagnetic waves with plasmonic and excitonic states typical for metals and semiconductors. At the same time, distinct similarities with chiral supramolecular and biological systems also emerged. They can be seen in the synthesis and separation methods, chemical properties of individual NPs, geometries of the nanoparticle assemblies, and interactions with biological membranes. Their analysis can help us understand in greater depth the role of chiral asymmetry in nature inclusive of both earth and space. Consideration of both differences and similarities between chiral inorganic, organic, and biological nanostructures will also accelerate the development of technologies based on chiroplasmonic and chiroexcitonic effects. This review will cover both experiment and theory of chiral nanostructures starting with the origin and multiple components of mirror asymmetry of individual NPs and their assemblies. We shall consider four different types of chirality in nanostructures and related physical, chemical, and

  10. Partitioning of protactinium, uranium, thorium and other trace elements between columbite and hydrous silicate melt

    NASA Astrophysics Data System (ADS)

    Huang, F.; Schmidt, M. W.; Günther, D.; Eikenberg, J.

    2009-12-01

    U-series disequilibria are a unique powerful tool to constrain the time-scales and processes of magmatism in mid-ocean ridge, intra-plate, and convergent margin settings. 235U-231Pa is one of the important parent-daughter pairs (231Pa half life = 33 kyr) because protactinium is normally much more incompatible than U during magmatism and thus the ubiquitously observed 231Pa excess in young igneous rocks most likely reflects melting processes. However, because of the extreme incompatibility of protactinium in most silicate minerals (mineral/meltDPa < 10-5), it is quite challenging to experimentally investigate partition coefficient of Pa. Furthermore, it is unclear whether Pa is always +5 or possibly more reduced at natural magmatic conditions, in particular in a reduced mantle. This significantly limits our understanding of the chemical behavior of Pa and applications of U-series disequilibrium data to the study of magmatism. Columbite (Mn(Nb,Ta)2O6) is a mineral with Nb5+ and Ta5+ as major elements, and occurs in per-aluminous granites and pegmatites. Because protactinium is expected to be +5 charged at crustal oxygen fugacities, and Pa5+ has an ionic radius close to Nb5+ and Ta5+, Nb and Ta have been used as proxy elements to constrain partitioning of Pa between minerals and melt using lattice strain modeling. Nb and Ta are strongly compatible in columbite (columbite/meltDNb-Ta ~ 10), and lattice strain modeling based on physical characteristics of the Nb-Ta site where Pa should be incorporated predicts that columbite/meltDPa5+ should be around 0.2, high enough to be experimentally determined at the permissible Pa doping level of 10 ppm (bulk). Experiments were run in a piston cylinder apparatus at 0.5 GPa and 1115 oC using Pt double capsules with NNO or FMQ as external fO2 buffers. The starting material is a hydrous per-aluminous granitic composition, doped with Pa solution in the Paul Scherrer Institute and also contains other trace elements including U, Th, REE

  11. Crystal chemistry of hydrous phases in the Al2O3-Fe2O3-H2O system: implications for water cycle in the deep lower mantle

    NASA Astrophysics Data System (ADS)

    Zhang, L.

    2016-12-01

    Hydrous minerals play an important role in the transportation and storage of water in the Earth's interior. Recently a pyrite-structured iron oxide (FeO2) (P-phase) was found stable at 76 GPa and 1800 K [1] and this discovery has brought new insights into the H2-O2 cycles in the deep mantle. In this study, we perform in situ synchrotron X-ray experiments in the Al2O3-Fe2O3-H2O system in a laser-heated diamond anvil cell (DAC) at P-T conditions in the deep lower mantle. The new results added more complexity to the H2-O2/H2O cycles in the deep lower mantle. The symmetry and unit-cell parameters of each phase in the run products were determined using the multigrain approach [2]. On the other hand, the d-H solid solution AlOOH-MgSiO2(OH)2 is the stable hydrous phase coexisting with bridgmanite or post-perovskite under equilibrium P-T conditions to the deepest lower mantle [3]. The detailed crystal chemistry of the newly found hydrous phases and its relations to the d-H phase have been investigated using both first-principles calculations and experiments, providing new understanding to the hydration mechanism and water storage in the deep mantle. It is worth mentioning that recent development in high pressure multigrain method has realized separation of each individual phase in a multiphase assemblage and even allowed in situ crystal structure determination of a minor phase in the assemblage contained in a DAC [4]. [1] Q. Hu, D. Y. Kim, W. Yang, L. Yang, Y. Meng, L. Zhang, and H. K. Mao, Nature 534, 241 (2016). [2] H. O. Sørensen et al., Zeitschrift für Kristallographie 227, 63 (2012). [3] I. Ohira, E. Ohtani, T. Sakai, M. Miyahara, N. Hirao, Y. Ohishi, and M. Nishijima, Earth and Planetary Science Letters 401, 12 (2014). [4] L. Zhang, D. Popov, Y. Meng, J. Wang, C. Ji, B. Li, and H.-k. Mao, American Mineralogist 101, 231 (2016).

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

    PubMed

    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.

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

    PubMed Central

    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

  14. Geological Sequestration of CO2 by Hydrous Carbonate Formation with Reclaimed Slag

    SciTech Connect

    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.

  15. Al-bearing dense hydrous minerals under mantle transition zone and uppermost lower mantle conditions

    NASA Astrophysics Data System (ADS)

    Inoue, T.; Hayashi, K.; Yurimoto, H.

    2013-12-01

    Subducting slabs are supplying water into the deep mantle, and some hydrous minerals may be present in the mantle transition zone and even in the uppermost lower mantle. The water storage capacities of mantle minerals are supposed to be significantly coupled with Al by a substitution with Mg2+, Si4+ or Mg2+ + Si4+, because Al3+ is the trivalent cation, and H+ is the monovalent cation. In this study, we have examined the effect of Al for the water content and the stability of some hydrous phases in the system MgO - Al2O3 - SiO2 - H2O in the mantle transition zone and the uppermost lower mantle condition. The experiments were conducted at 20 - 25 GPa and 1873 - 2273K by MA8-type (KAWAI-type) high pressure apparatus. The samples were sealed by AuPd capsule to prevent the loss of water, and the temperatures were measured by WRe thermocouple. The charges were heated for 1 hour in the desired P-T conditions, and then quenched at the rate of ~1000K/sec by tuning off the electric power supply. After releasing the press load for several hours, the run products were recovered, and then the recovered samples were polished to measure the chemical composition and the H2O contents.. We succeeded to synthesize the Al-bearing hydrous minerals (Al-bearing phase B, Al-bearing superhydrous phase B, Mg-Si bearing δ-AlOOH), and found that the significant coupling of H and Al were occurred in these minerals. The chemical compositions and the lattice parameters are examined by SEM-EDS and microfocus-XRD, and the H2O contents were measured by SIMS. The present chemical formula and the lattice parameters were compared to discuss about the difference between the pure chemical forms. Still more, the substitution mechanisms were considered basically by the chemical compositions and the information of the crystal structures. Our study suggests that water can be stored in the mantle transition zone and the uppermost lower mantle in the form of Al-bearing hydrous minerals or nominally anhydrous

  16. Stability of Pure Hydrous Silica at Geotherm Temperatures up to 70 GPa

    NASA Astrophysics Data System (ADS)

    Nisr, C.; Shim, S. H.; Leinenweber, K. D.; Hervig, R. L.; Prakapenka, V.; Meng, Y.; Liu, Z.

    2015-12-01

    Stishovite, in the rutile structure with octahedrally coordinated silicon, is expected to exist in silica rich parts of subducted oceanic slabs and crustal fragments in the Earth's mantle, and has been considered for a long time to be essentially anhydrous. However, Spektor et al., (2011) have shown that ~1.3 wt% can be incorporated into pure Al-free stishovite at 10 GPa and 723 K. Yet, the stability and physical properties of hydrous silica at mantle related pressures and temperatures are unknown. We have synthesized hydrous silica samples in the multi anvil press at 9-20 GPa and 700-900 K, and in the laser-heated diamond anvil cell at 17-70 GPa and 1400-2100 K. Three different sample setups have been used: dry silica gel in an H2O medium, anhydrous stishovite in an H2O medium, and hydrous silica gel in a Ne or Ar medium. The presence of percent level of water was found by Secondary Ion Mass Spectrometry, and Raman and Infrared spectroscopy measurements. X-ray diffraction patterns show that the unit-cell volumes of the recovered stishovite samples are greater by 0.2-3.9 % compared with anhydrous stishovite at 1 bar. The unit-cell volumes show strong linear correlation with their c/a ratio suggesting that the same OH substitution mechanism persists for a wide range of water content. Based on unit-cell volumes vs water content calibration by Spektor et al., (2011), our samples contain 0.3-7.9 wt% H2O. We found that pure silica is capable of containing as much as 4.9 wt% of H2O at temperatures close to those of the mantle geotherm (e.g., sample synthesized at ~1997 K and ~67 GPa). The highest water contents were found at the highest pressures, suggesting that the pressure stabilizes OH in dense silica. X-ray diffraction patterns have also shown several new diffraction lines upon compression and heating which appear from 45 GPa (1500-2100 K) and are observed up to 100 GPa. The peaks appear to belong to a new hydrous silica phase stable at higher pressures and

  17. [Hydrous and photosynthetic adaptations of common and durum wheat to saline stress].

    PubMed

    Alem, Chakib; Labhilili, Mustapha; Brahmi, Kouider; Jlibene, Mohamed; Nasrallah, Nasralhaq; Filali-Maltouf, Abdelkarim

    2002-11-01

    Seven varieties of bred wheat and seven varieties of durum wheat were cultivated in three different sites from the area of Errachidia (southeastern Morocco). These sites differ by the degree of salinity in the irrigation water. Results obtained showed that the reduction in leaf area is the principal strategy that makes it possible to attenuate the effects of the reduction in the availability of water under saline stress. Bread wheat, which limited the reduction in the leaf area, with the risk to undergo some hydrous problems, seems to better preserve its photosynthetic potentialities and grain productivity.

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

    NASA Astrophysics Data System (ADS)

    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 re