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Sample records for metal phosphates sulfides

  1. Metal sulfide and rare-earth phosphate nanostructures and methods of making same

    Science.gov (United States)

    Wong, Stanislaus; Zhang, Fen

    2014-05-13

    The present invention provides a method of producing a crystalline metal sulfide nanostructure. The metal is a transitional metal or a Group IV metal. In the method, a porous membrane is placed between a metal precursor solution and a sulfur precursor solution. The metal cations of the metal precursor solution and sulfur ions of the sulfur precursor solution react, thereby producing a crystalline metal sulfide nanostructure.

  2. Metal-phosphate binders

    Science.gov (United States)

    Howe, Beth Ann [Lewistown, IL; Chaps-Cabrera, Jesus Guadalupe [Coahuila, MX

    2009-05-12

    A metal-phosphate binder is provided. The binder may include an aqueous phosphoric acid solution, a metal-cation donor including a metal other than aluminum, an aluminum-cation donor, and a non-carbohydrate electron donor.

  3. Sulfidation kinetics of silver nanoparticles reacted with metal sulfides.

    Science.gov (United States)

    Thalmann, Basilius; Voegelin, Andreas; Sinnet, Brian; Morgenroth, Eberhard; Kaegi, Ralf

    2014-05-06

    Recent studies have documented that the sulfidation of silver nanoparticles (Ag-NP), possibly released to the environment from consumer products, occurs in anoxic zones of urban wastewater systems and that sulfidized Ag-NP exhibit dramatically reduced toxic effects. However, whether Ag-NP sulfidation also occurs under oxic conditions in the absence of bisulfide has not been addressed, yet. In this study we, therefore, investigated whether metal sulfides that are more resistant toward oxidation than free sulfide, could enable the sulfidation of Ag-NP under oxic conditions. We reacted citrate-stabilized Ag-NP of different sizes (10-100 nm) with freshly precipitated and crystalline CuS and ZnS in oxygenated aqueous suspensions at pH 7.5. The extent of Ag-NP sulfidation was derived from the increase in dissolved Cu(2+) or Zn(2+) over time and linked with results from X-ray absorption spectroscopy (XAS) analysis of selected samples. The sulfidation of Ag-NP followed pseudo first-order kinetics, with rate coefficients increasing with decreasing Ag-NP diameter and increasing metal sulfide concentration and depending on the type (CuS and ZnS) and crystallinity of the reacting metal sulfide. Results from analytical electron microscopy revealed the formation of complex sulfidation patterns that seemed to follow preexisting subgrain boundaries in the pristine Ag-NP. The kinetics of Ag-NP sulfidation observed in this study in combination with reported ZnS and CuS concentrations and predicted Ag-NP concentrations in wastewater and urban surface waters indicate that even under oxic conditions and in the absence of free sulfide, Ag-NP can be transformed into Ag2S within a few hours to days by reaction with metal sulfides.

  4. Nanostructured metal sulfides for energy storage.

    Science.gov (United States)

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-07

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  5. Single-layer transition metal sulfide catalysts

    Science.gov (United States)

    Thoma, Steven G [Albuquerque, NM

    2011-05-31

    Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

  6. Synthesis of arsenic transition metal sulfides and metal arsenides

    Energy Technology Data Exchange (ETDEWEB)

    Singhal, G.H.; Brown, L.D.; Ryan, D.F. [Exxon Research & Development Labs, Baton Rouge, LA (United States)

    1993-12-31

    One of the chief problems in upgrading shale oil is the presence of inherent arsenic which is known to poison downstream catalysts. Highly dispersed transition metal sulfides formed in situ from the decomposition of dithiocarbamate (DTC) complexes of transition metals show excellent potential as dearsenation agents. The authors have studied the reaction of these sulfides with various arsenic compositions and characterized the metal arsenides and arsenic metal sulfides formed as well as the ease of their formation. Thus, the reaction of bis(butyldithiocarbamato)Ni, (NiBuDTC) with model compounds was very facile and gave NiAs, NiAsS, and NiAs2=xSx. In general the effectiveness of the sulfides for dearsenation followed the sequence Ni>Mo{much_gt}Co, while iron sulfides were totally ineffective. Based upon these results, tests were run in autoclaves (as well as a fixed-bed flow-through unit) with NiBuDTC and shale oil having 73 ppm inherent As. Under optimum conditions, dearsenation down to les than 1 ppm was obtained.

  7. Layered metal sulfides capture uranium from seawater.

    Science.gov (United States)

    Manos, Manolis J; Kanatzidis, Mercouri G

    2012-10-03

    Uranium is the main source for nuclear energy but also one of the most toxic heavy metals. The current methods for uranium removal from water present limitations, such as narrow pH operating range, limited tolerance to high salt concentrations, or/and high cost. We show here that a layered sulfide ion exchanger K(2)MnSn(2)S(6) (KMS-1) overcomes these limitations and is exceptionally capable in selectively and rapidly sequestering high (ppm) as well as trace (ppb) quantities of UO(2)(2+) under a variety of conditions, including seawater. KMS-1 can efficiently absorb the naturally occurring U traces in seawater samples. The results presented here reveal the exceptional potential of sulfide-based ion-exchangers for remediating of uranium-containing wastes and groundwater and for extracting uranium from the sea.

  8. Synthesis and characterization of metal sulfide clusters for toxicological studies.

    Science.gov (United States)

    Bowles, L C; Bell, Russell A; Ernste, Michael J; Kramer, James R; Manolopoulos, Helen; Ogden, Nancy

    2002-04-01

    Zinc sulfide clusters were synthesized and characterized at low micromolar concentrations to assess the effect of metal-sulfide ligands on metal toxicity to aquatic organisms in oxic environments. Recommended preparation times are greater than 2 h initial reaction of equimolar sodium sulfide and zinc nitrate, followed by oxic aeration for 3 d. Ionic strength, pH, and anoxic stabilization time were found to be relatively unimportant in controlling the final yield. Adsorptive losses of zinc sulfide (ZnS) clusters to surfaces, however, were significant for a variety of vessel materials and membrane filters. Ionic strength and pH were found to be important factors controlling the extent of adsorptive losses with minimal loss for pHs greater than 9 and for soft waters. The Ag(I), Cu(II), and Hg(II) as metal sulfides completely suppress the analysis of sulfide, whereas Pb(II), Mn(II), and Co(II) partially suppress the analysis of sulfide by the methylene blue technique. Ultraviolet and fluorescence spectra are shown for synthesized ZnS clusters.

  9. Platinum Metals in Magmatic Sulfide Ores

    Science.gov (United States)

    Naldrett, A. J.; Duke, J. M.

    1980-06-01

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example.

  10. Metal sulfide electrodes and energy storage devices thereof

    Energy Technology Data Exchange (ETDEWEB)

    Chiang, Yet-Ming; Woodford, William Henry; Li, Zheng; Carter, W. Craig

    2017-02-28

    The present invention generally relates to energy storage devices, and to metal sulfide energy storage devices in particular. Some aspects of the invention relate to energy storage devices comprising at least one flowable electrode, wherein the flowable electrode comprises an electroactive metal sulfide material suspended and/or dissolved in a carrier fluid. In some embodiments, the flowable electrode further comprises a plurality of electronically conductive particles suspended and/or dissolved in the carrier fluid, wherein the electronically conductive particles form a percolating conductive network. An energy storage device comprising a flowable electrode comprising a metal sulfide electroactive material and a percolating conductive network may advantageously exhibit, upon reversible cycling, higher energy densities and specific capacities than conventional energy storage devices.

  11. Separation of platinum metals by theirs extraction as sulfides

    International Nuclear Information System (INIS)

    Pilipenko, A.T.; Ryabushko, O.P.; Ty Van Mak

    1978-01-01

    Separation of platinum metals by means of their sediment in the form of sulfides with subsequent extraction is studied. The optimum conditions of metal sulfide extraction are determined, the metal output dependence from acidness and aqueous phase composition and also the organic solvent nature are investigated. Ruthenium concentration was determined photometrically. Ruthenium sulfide is extracted by butyl spirit from 1-4 normal hydrochloric acid. The maximum extraction grade of 63% is reached in 3.2-normal acid. When the mixture of acetic and hydrochloric acids (2:1) is used for decomposition of ruthenium tiosalts, the grade of ruthenium extraction by amyl spirit or the mixture of anyl and butyl spirits (1:1) constitutes 100%

  12. Magnetite-sulfide-metal complexes in the Allende meteorite

    Science.gov (United States)

    Haggerty, S. E.; Mcmahon, B. M.

    1979-01-01

    A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

  13. Transition Metal Sulfide Hydrogen Evolution Catalysts for Hydrobromic Acid Electrolysis

    NARCIS (Netherlands)

    Ivanovskaya, Anna; Singh, Nirala; Liu, Ru-Fen; Kreutzer, Haley; Baltrusaitis, Jonas; Nguyen, Trung Van; Metiu, Horia; McFarland, Eric

    2013-01-01

    Mixed metal sulfides containing combinations of W, Fe, Mo, Ni, and Ru were synthesized and screened for activity and stability for the hydrogen evolution reaction (HER) in aqueous hydrobromic acid (HBr). Co- and Ni-substituted RuS2 were identified as potentially active HER electrocatalysts by

  14. Uranium and heavy metals in phosphate fertilizers

    International Nuclear Information System (INIS)

    Khater, A.E.M.

    2008-01-01

    Agricultural applications of chemical fertilizers are a worldwide practice. The specific activity of uranium-238 and heavy metals in phosphate fertilizers depends on the phosphate ore from which the fertilizer produced and on the chemical processing of the ore. Composite phosphate fertilizers samples where collected and the uranium-238 specific activity, in Bq/kg, and As, Cd, Cu, Pb, Se concentration, in ppm, were measured. The annual addition of these elements in soil due to fertilization were calculated and discussed. (author)(tk)

  15. Preparation of transition metal sulfide nanoparticles via hydrothermal route

    International Nuclear Information System (INIS)

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Tze-Khong, L.; Mohd Ambar Yarmo; Nay-Ming, H.

    2010-01-01

    Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesised via a simple hydrothermal method. Sodium thiosulfate pentahydrate (Na 2 S 2 O 3 ·5H 2 O) and hydroxylamine sulfate ((H 3 NO) 2 ·H 2 SO 4 ) were used as the starting materials and reacted with the transition metal source at 200 degree Celsius for 90 min. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR). Spherical shape CuS and FeS 2 nanoparticles with high crystallinity were successfully produced. The transmission electron micrographs revealed the well-dispersibility of the produced nanoparticles. Scanning electron micrograph showed the MoS 2 nanoparticles possessed a spherical shape with sheet-like structure covering on the outer surface of the particles. (author)

  16. Volcanic sulfur degassing and the role of sulfides in controlling volcanic metal emissions

    Science.gov (United States)

    Edmonds, M.; Liu, E.

    2017-12-01

    Volcanoes emit prodigious quantities of sulfur and metals, their behaviour inextricably linked through pre-eruptive sulfide systematics and through degassing and speciation in the volcanic plume. Fundamental differences exist in the metal output of ocean island versus arc volcanoes, with volcanoes in Hawaii and Iceland outgassing large fluxes of gaseous and particulate chalcophiles; and arc volcanoes' plumes, in contrast, enriched in Zn, Cu, Tl and Pb. Metals and metalloids partition into a magmatic vapor phase from silicate melt at crustal pressures. Their abundance in magmatic vapor is influenced strongly by sulfide saturation and by the composition of the magmatic vapor phase, particularly with respect to chloride. These factors are highly dependent on tectonic setting. Metal outgassing is controlled by magma water content and redox: deep saturation in vapor and minimal sulfide in arc basalts yields metal-rich vapor; shallow degassing and resorption of sulfides feeds the metal content of volcanic gas in ocean islands. We present a detailed study of the sulfide systematics of the products of the 2014-2015 Holuhraun basaltic fissure eruption (Bárðarbunga volcanic system, Iceland) to illustrate the interplay between late water and sulfur outgassing; sulfide saturation and breakdown; and metal partitioning into a vapor phase. Sulfide globules, representing quenched droplets of an immiscible sulfide liquid, are preserved within erupted tephra. Sulfide globules in rapidly quenched tephra are preserved within both matrix glass and as inclusions in crystals. The stereologically-corrected 3D size distribution of sulfide globules ranges from eruption and co-existed with an immiscible sulfide liquid throughout much of ol-cpx-plag crystallisation. Individual globules are associated with locally elevated dissolved sulfur concentrations, with concentration gradients away from sulfides preserved over distances of 10-40 µm from the melt-sulfide interfaces. We discuss the

  17. Sahara 03505 sulfide-rich iron meteorite: Evidence for efficient segregation of sulfide-rich metallic melt during high-degree impact melting of an ordinary chondrite

    Science.gov (United States)

    Orazio, M. D.; Folco, L.; Chaussidon, M.; Rochette, P.

    2009-03-01

    The Sahara 03505 meteorite is a 65 g sulfide-rich iron found in an undisclosed locality of the Sahara. It consists of roughly equal volumetric proportion of polycrystalline troilite (crystal size 1.5-7.5 mm) enclosing cellular/dendritic metallic Fe-Ni (width of the dendrite arms, ~100 µm). The mineral assemblage is completed by sparse skeletal crystals of chromite, abundant droplets, 5- 100 µm in size, of anhydrous Fe-, Fe-Na-, and Fe-Mn-Mg-Ca-Na-K-phosphates, tiny crystals of schreibersite, and particles of metallic Cu. The medium- to fine-grained quench texture, and cooling modeling suggest that Sahara 03505 formed through crystallization of a sulfur-rich metallic melt under rapid cooling conditions (1- 4 °C s-1). The low troilite/metallic Fe-Ni ratio (~0.6 by weight) shows that this liquid was generated at much higher temperatures (>1300 °C) with respect to the FeS-Fe,Ni cotectic liquids. Based on bulk chemistry and oxygen isotope composition of chromite, we propose that Sahara 03505 formed by extensive impact melting of an ordinary chondrite lithology, followed by the efficient segregation of the immiscible silicate and metallic liquids. The sulfur-rich metallic liquid rapidly cooled either by radiation into space as a small lump, or by conduction to a chondrite country rock as a vein intruded into the walls of an impact crater. Sahara 03505 belongs to a small group of sulfide-rich iron meteorites which are characterized by medium- to fine-grained quench textures and by bulk chemistry that is different from the other iron meteorite groups. We propose here to use the descriptive term “sulfide-irons” for this meteorite group, by analogy with the stony-irons.

  18. Some problems of synthesis of coordination compounds - the molecular predecessors of metal sulfides

    International Nuclear Information System (INIS)

    Larionov, S.V.

    1996-01-01

    Processes of metal sulfide preparations which require preliminary synthesis of coordination compounds o the metals (Cd, In, etc.) with organic sulfur-containing ligands have been considered. The promising trends in the synthesis are as follows: synthesis of chelate compounds and salts with rationally selected anions; synthesis of different-ligand compounds; synthesis of precursors for complex sulfides preparation. 14 refs

  19. Remediation of Cd-contaminated soil around metal sulfide mines

    Science.gov (United States)

    Lu, Xinzhe; Hu, Xuefeng; Kang, Zhanjun; Luo, Fan

    2017-04-01

    The mines of metal sulfides are widely distributed in the southwestern part of Zhejiang Province, Southeast China. The activities of mining, however, often lead to the severe pollution of heavy metals in soils, especially Cd contamination. According to our field investigations, the spatial distribution of Cd-contaminated soils is highly consistent with the presence of metal sulfide mines in the areas, further proving that the mining activities are responsible for Cd accumulation in the soils. To study the remediation of Cd-contaminated soils, a paddy field nearby large sulfide mines, with soil pH 6 and Cd more than 1.56 mg kg-1, five times higher than the national recommended threshold, was selected. Plastic boards were deeply inserted into soil to separate the field and make experimental plots, with each plot being 4 m×4 m. Six treatments, TK01˜TK06, were designed to study the effects of different experimental materials on remediating Cd-contaminated soils. The treatment of TK01 was the addition of 100 kg zeolites to the plot; TK02, 100 kg apatites; TK03, 100 kg humid manure; TK04, 50 kg zeolites + 50 kg apatites; TK05, 50 kg zeolites + 50 kg humid manure; TK06 was blank control (CK). One month after the treatments, soil samples at the plots were collected to study the possible change of chemical forms of Cd in the soils. The results indicated that these treatments reduced the content of available Cd in the soils effectively, by a decreasing sequence of TK04 (33%) > TK02 (25%) > TK01 (23%) > TK05 (22%) > TK03 (15%), on the basis of CK. Correspondingly, the treatments also reduced the content of Cd in rice grains significantly, by a similar decreasing sequence of TK04 (83%) > TK02 (77%) > TK05 (63%) > TK01 (47%) > TK03 (27%). The content of Cd in the rice grains was 0.071 mg kg-1, 0.094 mg kg-1, 0.159 mg kg-1, 0.22 mg kg-1 and 0.306 mg kg-1, respectively, compared with CK, 0.418 mg kg-1. This experiment suggested that the reduction of available Cd in the soils is

  20. Ceramic/metal seals. [refractory materials for hermetic seals for lighium-metal sulfide batteries

    Science.gov (United States)

    Bredbenner, A. M.

    1977-01-01

    Design criteria are discussed for a hermetic seal capable of withstanding the 450 C operating temperature of a lithium-metal sulfide battery system. A mechanical seal consisting of two high strength alloy metal sleeves welded or brazed to a conductor assembly and pressed onto a ceramic is described. The conductor center passes through the ceramic but is not sealed to it. The seal is effected on the outside of the taper where the tubular part is pressed down over and makes contact.

  1. The metal-rich sulfides and phosphides of the early transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Franzen, H.F. [Ames Lab., IA (United States)]|[Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

    1996-06-01

    Early work on the preparation of refractory metal-rich compounds of the early transition metals resulted in the understanding that metal-metal bonding results in a structural variety that plays an important role in the high-temperature chemistry of these systems. The binary metal-rich systems have been thoroughly studied at high temperatures, and the structures of most, if not all, of the refractory sulfides and phosphides are known. More recently new ternary phases have been discovered, and these have been shown to result from distributed fractional site occupation of metal atom sites in complex structures. The extent of metal-metal bonding has been quantified by Extended-Hueckel Tight-Bonding calculations using Mullikan Overlap Populations. Correlations of site occupancy with MOP based upon the DFSO model have been observed. 44 refs.

  2. Precipitation of heavy metals from coal ash leachate using biogenic hydrogen sulfide generated from FGD gypsum.

    Science.gov (United States)

    Jayaranjan, Madawala Liyanage Duminda; Annachhatre, Ajit P

    2013-01-01

    Investigations were undertaken to utilize flue gas desulfurization (FGD) gypsum for the treatment of leachate from the coal ash (CA) dump sites. Bench-scale investigations consisted of three main steps namely hydrogen sulfide (H(2)S) production by sulfate reducing bacteria (SRB) using sulfate from solubilized FGD gypsum as the electron acceptor, followed by leaching of heavy metals (HMs) from coal bottom ash (CBA) and subsequent precipitation of HMs using biologically produced sulfide. Leaching tests of CBA carried out at acidic pH revealed the existence of several HMs such as Cd, Cr, Hg, Pb, Mn, Cu, Ni and Zn. Molasses was used as the electron donor for the biological sulfate reduction (BSR) process which produced sulfide rich effluent with concentration up to 150 mg/L. Sulfide rich effluent from the sulfate reduction process was used to precipitate HMs as metal sulfides from CBA leachate. HM removal in the range from 40 to 100% was obtained through sulfide precipitation.

  3. Bioactive calcium phosphate coatings on metallic implants

    Science.gov (United States)

    Sedelnikova, M. B.; Komarova, E. G.; Sharkeev, Yu. P.; Tolkacheva, T. V.; Khlusov, I. A.; Sheikin, V. V.

    2017-09-01

    Biocomposites based on bioinert metals or alloys and bioactive calcium phosphate coatings are a promising tendency of the new-generation implants development. In recent years, the approach of regenerative medicine based on the use of biodegradable biomaterials has been priority direction. Such materials are capable of initiating the bone tissue regeneration and replaced by the newly formed bone. The microarc oxidation (MAO) method allows obtaining the bioactive coatings with a porous structure, special functional properties, and modified by the essential elements. During the last decade, the investigations in the field of the nanostructured biocomposites based on bioinert Ti, Zr, Nb and their alloys with a calcium phosphate coatings deposited by the MAO method have been studied in the Institute of Strength Physics and Materials Science SB RAS, Tomsk. In this article the possibility to produce the bioactive coatings with high antibacterial and osseoconductive properties due to the introduction in the coatings of Zn, Cu, Ag, La, Si elements and wollastonite CaSiO3 was shown. The high hydrophilic and bioresorbed coatings stimulate the processes of osseointegration of the implant into the bone tissue. A promising direction in the field of the medical material science is a development of the metallic implants with good biomechanical compatibility to the bone, such as Ti-Nb alloys with a low elastic modulus that can be classified as biomaterials of the second generation. Zr and its alloys are promising materials for the dentistry and orthopedic surgery due to their high strength and corrosion resistance. Biodegradable Mg alloys are biomaterials of third generation. Such materials can dissolve with a certain speed in human body and excreted from the body thereby excluding the need for reoperation. This article presents the analysis of the study results of bioactive MAO coatings on Ti, Ti-Nb, Zr-Nb and Mg alloys and their promising medical application.

  4. Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides.

    Science.gov (United States)

    Zhou, Xiuquan; Eckberg, Christopher; Wilfong, Brandon; Liou, Sz-Chian; Vivanco, Hector K; Paglione, Johnpierre; Rodriguez, Efrain E

    2017-05-01

    Inspired by naturally occurring sulfide minerals, we present a new family of iron-based superconductors. A metastable form of FeS known as the mineral mackinawite forms two-dimensional sheets that can be readily intercalated by various cationic guest species. Under hydrothermal conditions using alkali metal hydroxides, we prepare three different cation and metal hydroxide-intercalated FeS phases including (Li 1- x Fe x OH)FeS, [(Na 1- x Fe x )(OH) 2 ]FeS, and K x Fe 2- y S 2 . Upon successful intercalation of the FeS layer, the superconducting critical temperature T c of mackinawite is enhanced from 5 K to 8 K for the (Li 1- x Fe x OH) δ + intercalate. Layered heterostructures of [(Na 1- x Fe x )(OH) 2 ]FeS resemble the natural mineral tochilinite, which contains an iron square lattice interleaved with a hexagonal hydroxide lattice. Whilst heterostructured [(Na 1- x Fe x )(OH) 2 ]FeS displays long-range magnetic ordering near 15 K, K x Fe 2- y S 2 displays short range antiferromagnetism.

  5. Metal Phosphides and Phosphates-based Electrodes for Electrochemical Supercapacitors.

    Science.gov (United States)

    Li, Xin; Elshahawy, Abdelnaby M; Guan, Cao; Wang, John

    2017-10-01

    Phosphorus compounds, such as metal phosphides and phosphates have shown excellent performances and great potential in electrochemical energy storage, which are demonstrated by research works published in recent years. Some of these metal phosphides and phosphates and their hybrids compare favorably with transition metal oxides/hydroxides, which have been studied extensively as a class of electrode materials for supercapacitor applications, where they have limitations in terms of electrical and ion conductivity and device stability. To be specific, metal phosphides have both metalloid characteristics and good electric conductivity. For metal phosphates, the open-framework structures with large channels and cavities endow them with good ion conductivity and charge storage capacity. In this review, we present the recent progress on metal phosphides and phosphates, by focusing on their advantages/disadvantages and potential applications as a new class of electrode materials in supercapacitors. The synthesis methods to prepare these metal phosphides/phosphates are looked into, together with the scientific insights involved, as they strongly affect the electrochemical energy storage performance. Particular attentions are paid to those hybrid-type materials, where strong synergistic effects exist. In the summary, the future perspectives and challenges for the metal phosphides, phosphates and hybrid-types are proposed and discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Translocation of metal phosphate via the phosphate inorganic transport system of Escherichia coli

    NARCIS (Netherlands)

    van Veen, H.W; Abee, T.; Kortstee, G.J J; Konings, W.N; Zehnder, A.J B

    1994-01-01

    P-i transport via the phosphate inorganic transport system (Pit) of Escherichia coil was studied in natural and artificial membranes. P-i uptake via Pit is dependent on the presence of divalent cations, like Mg2+, Ca2+, Co2+, or Mn2+, which form a soluble, neutral metal phosphate (MeHPO(4)) complex.

  7. Sythesis of metal sulfide nanomaerials via thermal decomposition of single-source percursors

    Energy Technology Data Exchange (ETDEWEB)

    Jen-La Plante, Ilan; Zeid, Tahani W.; Yang, Peidong; Mokari, Taleb

    2010-06-03

    In this report, we present a synthetic method for the formation of cuprous sulfide (Cu2S) and lead sulfide (PbS) nanomaterials directly on substrates from the thermolysis of single-source precursors. We find that the final morphology and arrangement of the nanomaterials may be controlled through the concentration of the dissolved precursors and choice of solvent. One-dimensional (1-D) morphologies may also be grown onto substrates with the addition of a metal catalyst layer through solution-liquid-solid (SLS) growth. These synthetic techniques may be expanded to other metal sulfide materials.

  8. Spatial variation of metals and acid volatile sulfide in floodplain lake sediment

    NARCIS (Netherlands)

    Griethuysen, van C.; Meijboom, E.W.; Koelmans, A.A.

    2003-01-01

    In risk assessment of aquatic sediments, much attention is paid to the immobilizing effect of acid volatile sulfide (AVS) on trace metals. The difference of AVS and simultaneously extracted metals (SEM) gives an indication of metal availability. In floodplain sediments, where changing redox

  9. Metal-organic frameworks for the storage and delivery of biologically active hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Allan, Phoebe K; Wheatley, Paul S; Aldous, David; Mohideen, M Infas; Tang, Chiu; Hriljac, Joseph A; Megson, Ian L; Chapman, Karena W; De Weireld, Guy; Vaesen, Sebastian; Morris, Russell E [St Andrews

    2012-04-02

    Hydrogen sulfide is an extremely toxic gas that is also of great interest for biological applications when delivered in the correct amount and at the desired rate. Here we show that the highly porous metal-organic frameworks with the CPO-27 structure can bind the hydrogen sulfide relatively strongly, allowing the storage of the gas for at least several months. Delivered gas is biologically active in preliminary vasodilation studies of porcine arteries, and the structure of the hydrogen sulfide molecules inside the framework has been elucidated using a combination of powder X-ray diffraction and pair distribution function analysis.

  10. Iron phosphate compositions for containment of hazardous metal waste

    Science.gov (United States)

    Day, D.E.

    1998-05-12

    An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P{sub 2}O{sub 5} and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe{sup 3+} provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided. 21 figs.

  11. Synthesis and Characterization of Metal Phosphates for Photocatalytic Applications

    KAUST Repository

    Al-Sabban, Bedour

    2012-07-01

    Solar energy is the most abundant efficient and important source of renewable energy. The objective of this study is to develop highly efficient visible light responsive photocatalysts for overall water splitting. This is done by using silver or copper containing materials. Phosphate compounds have caught much attention due to their rigid structure, thermal stability and resistance to chemical attacks. Solid phosphates can be prepared by direct solid-state reaction between metal cations and phosphate anions at high temperatures. Double metal phosphates of the Nasion-type structure had shown further technological importance. It has been reported that well-crystallized double metal phosphate particles have excellent ordering and cationic conduction channels in the Nasicon framework. In this study, several Nasion-type structured materials have been synthesized by solid-state method (e.g. CuTi2(PO4)3 and AgTi2(PO4)3) heated up under different temperatures (400–1100C) in N2 or air atmosphere. These materials were characterized by XRD, SEM, DR-UV-Vis spectroscopy and tested for photocatalytic applications. A new method for direct synthesis of photoelectrode on Ti Plate had been demonstrated. Further investigations on controlling the size and morphology for better performance of single and double metal phosphates will be done.

  12. A combined sodium phosphate and sodium sulfide pretreatment for enhanced enzymatic digestibility and delignification of corn stover.

    Science.gov (United States)

    Qing, Qing; Zhou, Linlin; Guo, Qi; Huang, Meizi; He, Yucai; Wang, Liqun; Zhang, Yue

    2016-10-01

    Na3PO4 and Na2S were employed as efficient alkaline catalysts for the pretreatment of corn stover. To systematically obtain optimal conditions, the effects of critical pretreatment parameters including sodium phosphate concentration (1-4%), sulfidity (0-20%), pretreatment temperature (100-120°C), and reaction time (20-60min) on the reducing sugar yield of pretreated substrates were evaluated in a lab-scale using the response surface methodology. Pretreated under the sodium phosphate concentration of 4%, sulfidity of 10%, temperature of 120°C, and reaction time of 40min, the reducing sugar yield and glucose yield of the pretreated corn stover achieved 91.11% and 64.01%, respectively, with a moderate enzyme loading of 30FPU/g substrate. Additionally, a strong correlation (R(2)=0.971 and R(2)=0.954) between the delignification and the reducing sugar yield (or glucose yield) was observed by this pretreatment method. These results evidently support that the combined Na3PO4-Na2S pretreatment is an effective and feasible method for processing lignocellulosic biomass. Copyright © 2016. Published by Elsevier Ltd.

  13. Metal Phosphates as Intermediate Temperature Proton Conducting Electrolytes

    DEFF Research Database (Denmark)

    Huang, Yunjie; Li, Q.F.; Pan, Chao

    2012-01-01

    A series of metal phosphates were synthesized and screened as potential proton conductor electrolytes for fuel cells and electrolysers operational at intermediate temperatures. Among the selected, niobium and bismuth phosphates exhibited a proton conductivity of 10-2 and 10-7 S cm-1, respectively......, under the anhydrous atmosphere at 250 °C, showing close correlation with the presence of hydroxyl groups in the phosphate phases. At the water partial pressure of above 0.6 atm, both phosphates possessed a proton conductivity to a level of above 3 x 10-2 S cm-1. Reasonable stability of the proton...... conductivity was observed under either a constant low water partial pressure or under a humidity cycling test within a period of more than 80 hours....

  14. Production of aluminum metal by electrolysis of aluminum sulfide

    Science.gov (United States)

    Minh, N.Q.; Loutfy, R.O.; Yao, N.P.

    1982-04-01

    Metallic aluminum may be produced by the electrolysis of Al/sub 2/S/sub 3/ at 700 to 800/sup 0/C in a chloride melt composed of one or more alkali metal chlorides, and one or more alkaline earth metal chlorides and/or aluminum chloride to provide improved operating characteristics of the process.

  15. Solid-phase synthesis of multivalent metal phosphates

    International Nuclear Information System (INIS)

    Konstant, Z.A.

    1984-01-01

    Some multivalent metals (Mg, Zn, Mn, Co, Ni, Sc, Ti, V, Cr, Fe, Ce) are used as examples for considering certain general problems (mechanism, phase formation) of solid-phase synthesis of phosphates from metal oxides and ammonium dihydrophosphate (t=200-1500 deg C). It is noted that the observed phenomena, such as parallel reactionS, formation of several modifications of one compound is characteristic of solid-phase synthesis of condensed phosphates when condensation is determined by the metal-phosphorus ratio, potential cation coordination and thermodynamic characteristics of polymers being prepared. The possibility of oxidation-reduction reactions with multiple changes in the valence of elements is also very important. Complex schemes of interactions, phase diagrams of the systems are presented

  16. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  17. Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2009-12-01

    Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.

  18. From Metal Thiobenzoates to Metal Sulfide Nanocrystals: An Experimental and Theoretical Investigation

    Directory of Open Access Journals (Sweden)

    Fenfang Yin

    2012-04-01

    Full Text Available A simple preparation of metal sulfide nanoparticles via the decomposition of thiobenzoate precursors at room temperature is presented and discussed. Long chain alkylamines were found to mediate the breakdown of metal thiobenzoates, such as those containing Ag, Cu, In and Cd, to produce uniform Ag2S, Cu2−xS, In2S3 and CdS nanoparticles respectively. The long chain amines are assumed to play dual roles as the nucleophilic reagent and the capping agent. It was found that sizes of the nanoparticles can be controlled by changing the type of amine used, as well as the molar ratio between amine and the precursor. We performed DFT calculations on a proposed mechanism involving an initial nucleophilic addition of amine molecule onto the thiocarboxylates. The proposed reaction was also confirmed through the analysis of by-products via infrared spectroscopy. On the basis of this understanding, we propose to manipulate the stability of the precursors by coordination with suitable stabilizing groups, such that the reaction kinetics can be modified to generate different nanostructures of interest.

  19. From Metal Thiobenzoates to Metal Sulfide Nanocrystals: An Experimental and Theoretical Investigation

    Science.gov (United States)

    Zhang, Zhihua; Lim, Wen Pei; Wong, Chiong Teck; Xu, Hairuo; Yin, Fenfang; Chin, Wee Shong

    2012-01-01

    A simple preparation of metal sulfide nanoparticles via the decomposition of thiobenzoate precursors at room temperature is presented and discussed. Long chain alkylamines were found to mediate the breakdown of metal thiobenzoates, such as those containing Ag, Cu, In and Cd, to produce uniform Ag2S, Cu2−xS, In2S3 and CdS nanoparticles respectively. The long chain amines are assumed to play dual roles as the nucleophilic reagent and the capping agent. It was found that sizes of the nanoparticles can be controlled by changing the type of amine used, as well as the molar ratio between amine and the precursor. We performed DFT calculations on a proposed mechanism involving an initial nucleophilic addition of amine molecule onto the thiocarboxylates. The proposed reaction was also confirmed through the analysis of by-products via infrared spectroscopy. On the basis of this understanding, we propose to manipulate the stability of the precursors by coordination with suitable stabilizing groups, such that the reaction kinetics can be modified to generate different nanostructures of interest. PMID:28348299

  20. A General Route for Growing Metal Sulfides onto Graphene Oxide and Exfoliated Graphite Oxide.

    Science.gov (United States)

    Lopes, Joana L; Estrada, Ana C; Fateixa, Sara; Ferro, Marta; Trindade, Tito

    2017-08-31

    Graphene-based materials are elective materials for a number of technologies due to their unique properties. Also, semiconductor nanocrystals have been extensively explored due to their size-dependent properties that make them useful for several applications. By coupling both types of materials, new applications are envisaged that explore the synergistic properties in such hybrid nanostructures. This research reports a general wet chemistry method to prepare graphene oxide (GO) sheets decorated with nanophases of semiconductor metal sulfides. This method allows the in situ growth of metal sulfides onto GO by using metal dialkyldithiocarbamate complexes as single-molecule precursors. In particular, the role of GO as heterogeneous substrate for the growth of semiconductor nanocrystals was investigated by using Raman spectroscopic and imaging methods. The method was further extended to other graphene-based materials, which are easily prepared in a larger scale, such as exfoliated graphite oxide (EGO).

  1. Phosphate Favors the Biosynthesis of CdS Quantum Dots inAcidithiobacillus thiooxidansATCC 19703 by Improving Metal Uptake and Tolerance.

    Science.gov (United States)

    Ulloa, Giovanni; Quezada, Carolina P; Araneda, Mabel; Escobar, Blanca; Fuentes, Edwar; Álvarez, Sergio A; Castro, Matías; Bruna, Nicolás; Espinoza-González, Rodrigo; Bravo, Denisse; Pérez-Donoso, José M

    2018-01-01

    Recently, we reported the production of Cadmium sulfide (CdS) fluorescent semiconductor nanoparticles (quantum dots, QDs) by acidophilic bacteria of the Acidithiobacillus genus. Here, we report that the addition of inorganic phosphate to Acidithiobacillus thiooxidans ATCC 19703 cultures favors the biosynthesis of CdS QDs at acidic conditions (pH 3.5). The effect of pH, phosphate and cadmium concentrations on QDs biosynthesis was studied by using Response Surface Methodology (RSM), a multivariate technique for analytical optimization scarcely used in microbiological studies to date. To address how phosphate affects intracellular biosynthesis of CdS QDs, the effect of inorganic phosphate on bacterial cadmium-uptake was evaluated. By measuring intracellular levels of cadmium we determined that phosphate influences the capacity of cells to incorporate this metal. A relation between cadmium tolerance and phosphate concentrations was also determined, suggesting that phosphate participates in the adaptation of bacteria to toxic levels of this metal. In addition, QDs-biosynthesis was also favored by the degradation of intracellular polyphosphates. Altogether, our results indicate that phosphate contributes to A. thiooxidans CdS QDs biosynthesis by influencing cadmium uptake and cadmium tolerance. These QDs may also be acting as a nucleation point for QDs formation at acidic pH. This is the first study reporting the effect of phosphates on QDs biosynthesis and describes a new cadmium-response pathway present in A. thiooxidans and most probably in other bacterial species.

  2. Phosphate Favors the Biosynthesis of CdS Quantum Dots in Acidithiobacillus thiooxidans ATCC 19703 by Improving Metal Uptake and Tolerance

    Science.gov (United States)

    Ulloa, Giovanni; Quezada, Carolina P.; Araneda, Mabel; Escobar, Blanca; Fuentes, Edwar; Álvarez, Sergio A.; Castro, Matías; Bruna, Nicolás; Espinoza-González, Rodrigo; Bravo, Denisse; Pérez-Donoso, José M.

    2018-01-01

    Recently, we reported the production of Cadmium sulfide (CdS) fluorescent semiconductor nanoparticles (quantum dots, QDs) by acidophilic bacteria of the Acidithiobacillus genus. Here, we report that the addition of inorganic phosphate to Acidithiobacillus thiooxidans ATCC 19703 cultures favors the biosynthesis of CdS QDs at acidic conditions (pH 3.5). The effect of pH, phosphate and cadmium concentrations on QDs biosynthesis was studied by using Response Surface Methodology (RSM), a multivariate technique for analytical optimization scarcely used in microbiological studies to date. To address how phosphate affects intracellular biosynthesis of CdS QDs, the effect of inorganic phosphate on bacterial cadmium-uptake was evaluated. By measuring intracellular levels of cadmium we determined that phosphate influences the capacity of cells to incorporate this metal. A relation between cadmium tolerance and phosphate concentrations was also determined, suggesting that phosphate participates in the adaptation of bacteria to toxic levels of this metal. In addition, QDs-biosynthesis was also favored by the degradation of intracellular polyphosphates. Altogether, our results indicate that phosphate contributes to A. thiooxidans CdS QDs biosynthesis by influencing cadmium uptake and cadmium tolerance. These QDs may also be acting as a nucleation point for QDs formation at acidic pH. This is the first study reporting the effect of phosphates on QDs biosynthesis and describes a new cadmium-response pathway present in A. thiooxidans and most probably in other bacterial species. PMID:29515535

  3. Phosphate Favors the Biosynthesis of CdS Quantum Dots in Acidithiobacillus thiooxidans ATCC 19703 by Improving Metal Uptake and Tolerance

    Directory of Open Access Journals (Sweden)

    Giovanni Ulloa

    2018-02-01

    Full Text Available Recently, we reported the production of Cadmium sulfide (CdS fluorescent semiconductor nanoparticles (quantum dots, QDs by acidophilic bacteria of the Acidithiobacillus genus. Here, we report that the addition of inorganic phosphate to Acidithiobacillus thiooxidans ATCC 19703 cultures favors the biosynthesis of CdS QDs at acidic conditions (pH 3.5. The effect of pH, phosphate and cadmium concentrations on QDs biosynthesis was studied by using Response Surface Methodology (RSM, a multivariate technique for analytical optimization scarcely used in microbiological studies to date. To address how phosphate affects intracellular biosynthesis of CdS QDs, the effect of inorganic phosphate on bacterial cadmium-uptake was evaluated. By measuring intracellular levels of cadmium we determined that phosphate influences the capacity of cells to incorporate this metal. A relation between cadmium tolerance and phosphate concentrations was also determined, suggesting that phosphate participates in the adaptation of bacteria to toxic levels of this metal. In addition, QDs-biosynthesis was also favored by the degradation of intracellular polyphosphates. Altogether, our results indicate that phosphate contributes to A. thiooxidans CdS QDs biosynthesis by influencing cadmium uptake and cadmium tolerance. These QDs may also be acting as a nucleation point for QDs formation at acidic pH. This is the first study reporting the effect of phosphates on QDs biosynthesis and describes a new cadmium-response pathway present in A. thiooxidans and most probably in other bacterial species.

  4. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Science.gov (United States)

    Qian, Xiaoshuang; Qin, Hongmei; Meng, Tao; Lin, Yi; Ma, Zhen

    2014-01-01

    Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2) have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO4)6(OH)2, denoted as Ca-P-O here) also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La) catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP) atomic emission spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), CO2 temperature-programmed desorption (CO2-TPD), X-ray photoelectron spectroscopy (XPS), and H2 temperature-programmed reduction (H2-TPR). This work furnishes a new catalyst system for CO oxidation and other possible reactions. PMID:28788293

  5. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  6. Ternary metal-rich sulfide with a layered structure

    Science.gov (United States)

    Franzen, Hugo F.; Yao, Xiaoqiang

    1993-08-17

    A ternary Nb-Ta-S compound is provided having the atomic formula, Nb.sub.1.72 Ta.sub.3.28 S.sub.2, and exhibiting a layered structure in the sequence S-M3-M2-M1-M2-M3-S wherein S represents sulfur layers and M1, M2, and M3 represent Nb/Ta mixed metal layers. This sequence generates seven sheets stacked along the [001] direction of an approximate body centered cubic crystal structure with relatively weak sulfur-to-sulfur van der Waals type interactions between adjacent sulfur sheets and metal-to-metal bonding within and between adjacent mixed metal sheets.

  7. Functional metal sulfides and selenides for the removal of hazardous dyes from Water.

    Science.gov (United States)

    Shamraiz, Umair; Hussain, Raja Azadar; Badshah, Amin; Raza, Bareera; Saba, Sonia

    2016-06-01

    Water contamination by organic dyes, is among the most alarming threats to healthy green environment. Complete removal of organic dyes is necessary to make water healthy for drinking, cooking, and for other useful aspects. Recently use of nanotechnology for removing organic dyes, became fruitful because of high surface to volume ratio and adsorption properties. Among these materials, metal chalcogenides emerge as new class of active materials for water purification. In this review article, we gathered information related to sulfide and selenide based nanomaterials which include metal sulfides and selenides, their binary composites, and use of different capping agents and dopants for enhancing photocatalysis. We have discussed in detail, about adsorption power of different dyes, relative percentage degradation, reaction time and concentration. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Metal sulfide nanoparticles synthesized via enzyme treatment of biopolymer stabilized nanosuspensions

    Science.gov (United States)

    Kim, Yi-Yeoun; Walsh, Dominic

    2010-02-01

    Nanoparticles of CuS, CuxS, Ag2S and CdS were successfully prepared using a novel general and green synthetic process to give dextran biopolymer stabilised metal sulfifde nanosuspensions. Following preparation, dextranase enzyme was used to remove the bulk of the bound dextran to give pure stable metal sulfide nanocrystals for application in for example aspects of medicine, photonics and solar cells. Particles of good homogeneity were obtained and the CuS nanoparticle size was controlled to 9-27 nm by adjusting the reaction conditions. Cu2S nanoparticles were 14 nm, Ag2S nanoparticles were 20-50 nm and CdS nanoparticles were 9 nm is size. The complexing mechanism of nanoparticle sulfides to dextrans was further studied using carboxylmethyl dextran as a complexing agent and crosslinked Sephadex (dextran) `beads as substrate. Particles were characterized by TEM, XRD, TGA, FT-IR and zeta-potential measurement, and their UV-vis spectroscopic absorption properties were determined. Stabilization of the sulfide nanoparticles with soluble hydroxylated biopolymers such as dextran is previously unreported and is here interpreted in terms of viscosity, pH of the system and weak polar S-H or S(metal)OH2+ interactions with dextran depending on the material. Notably, the complexing mechanism appears to differ significantly from that taking place in known dextran-metal oxide systems. The process shown here has good potential for scale-up as a biosynthetic route for a range of functional sulfide nanoparticles.Nanoparticles of CuS, CuxS, Ag2S and CdS were successfully prepared using a novel general and green synthetic process to give dextran biopolymer stabilised metal sulfifde nanosuspensions. Following preparation, dextranase enzyme was used to remove the bulk of the bound dextran to give pure stable metal sulfide nanocrystals for application in for example aspects of medicine, photonics and solar cells. Particles of good homogeneity were obtained and the CuS nanoparticle size

  9. Hydrogen evolution on nano-particulate transition metal sulfides

    DEFF Research Database (Denmark)

    Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.

    2008-01-01

    The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal...

  10. A computational study of adhesion between rubber and metal sulfides at rubber–brass interface

    International Nuclear Information System (INIS)

    Ling, Chian Ye; Hirvi, Janne T.; Suvanto, Mika; Bazhenov, Andrey S.; Ajoviita, Tommi; Markkula, Katriina; Pakkanen, Tapani A.

    2015-01-01

    Highlights: • An atomic level model for brass–rubber interactions has been presented. • The main adhesion force has been tracked to the rubber sulfur–brass zinc or brass copper interaction. • The model gives new understanding of the adhesion and can be used for further developments of the system. - Abstract: Computational study at level of density functional theory has been carried out in order to investigate the adhesion between rubber and brass plated steel cord, which has high importance in tire manufacturing. Adsorption of natural rubber based adsorbate models has been studied on zinc sulfide, ZnS(1 1 0), and copper sulfide, Cu 2 S(1 1 1) and CuS(0 0 1), surfaces as the corresponding phases are formed in adhesive interlayer during rubber vulcanization. Saturated hydrocarbons exhibited weak interactions, whereas unsaturated hydrocarbons and sulfur-containing adsorbates interacted with the metal atoms of sulfide surfaces more strongly. Sulfur-containing adsorbates interacted with ZnS(1 1 0) surface stronger than unsaturated hydrocarbons, whereras both Cu 2 S(1 1 1) and CuS(0 0 1) surfaces showed opposite adsorption preference as unsaturated hydrocarbons adsorbed stronger than sulfur-containing adsorbates. The different interaction strength order can play role in rubber–brass adhesion with different relative sulfide concentrations. Moreover, Cu 2 S(1 1 1) surface exhibits higher adsorption energies than CuS(0 0 1) surface, possibly indicating dominant role of Cu 2 S in the adhesion between rubber and brass

  11. The Formation and Chronology of the PAT 91501 Impact-Melt L-Chondrite with Vesicle-Metal-Sulfide Assemblages

    Science.gov (United States)

    Benedix, G. K.; Ketcham, R. A.; Wilson, L.; McCoy, T. J.; Bogard, D. D.; Garrison, D. H.; Herzog, G. F.; Xue, S.; Klein, J.; Middleton, R.

    2007-01-01

    The L chondrite Patuxent Range (PAT) 41 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up approximately 2 vol.% and exhibit a similar orientation of long axes. Ar-39-Ar-40 measurements date the time of impact at 4.461 +/- 0.008 Gyr B.P. Cosmogenic noble gases and Be-10 and Al-2l activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S2 (approximately 15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over approximately 2 hours. During this time, approximately 90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501.

  12. A kinetic approach to evaluate the association of acid volatile sulfide and simultaneously extracted metals in aquatic sediments

    NARCIS (Netherlands)

    Poot, A.; Meerman, E.; Gillissen, F.; Koelmans, A.A.

    2009-01-01

    The acid volatile sulfide (AVS) and simultaneously extracted metals (¿SEM) method is widely used for evaluating potential bioavailability of heavy metals in soil and sediment. It is also criticized, because the requirement that AVS and SEM metals (i.e., Cd, Cu, Ni, Pb, and Zn) are associated in the

  13. Synthesis of free-standing metal sulfide nanoarrays via anion exchange reaction and their electrochemical energy storage application.

    Science.gov (United States)

    Xia, Xinhui; Zhu, Changrong; Luo, Jingshan; Zeng, Zhiyuan; Guan, Cao; Ng, Chin Fan; Zhang, Hua; Fan, Hong Jin

    2014-02-26

    Metal sulfides are an emerging class of high-performance electrode materials for solar cells and electrochemical energy storage devices. Here, a facile and powerful method based on anion exchange reactions is reported to achieve metal sulfide nanoarrays through a topotactical transformation from their metal oxide and hydroxide preforms. Demonstrations are made to CoS and NiS nanowires, nanowalls, and core-branch nanotrees on carbon cloth and nickel foam substrates. The sulfide nanoarrays exhibit superior redox reactivity for electrochemical energy storage. The self-supported CoS nanowire arrays are tested as the pseudo-capacitor cathode, which demonstrate enhanced high-rate specific capacities and better cycle life as compared to the powder counterparts. The outstanding electrochemical properties of the sulfide nanoarrays are a consequence of the preservation of the nanoarray architecture and rigid connection with the current collector after the anion exchange reactions.

  14. Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis.

    Science.gov (United States)

    Kumar, Manoj; Francisco, Joseph S

    2016-03-18

    The role of metal free dual catalysis in the hydrogen sulfide (H2S)-induced activation of carbon dioxide (CO2) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Electronic structures and water reactivity of mixed metal sulfide cluster anions.

    Science.gov (United States)

    Saha, Arjun; Raghavachari, Krishnan

    2014-08-21

    The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS4(-)) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H2 release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo2S4(-) and W2S4(-)) as well as mixed metal oxides (MoWO4(-)).

  16. Solidification of metallic aluminum on magnesium phosphate cements

    International Nuclear Information System (INIS)

    Lahalle, Hugo

    2016-01-01

    This work deals with the stabilization/solidification of radioactive waste using cement. More particularly, it aims at assessing the chemical compatibility between metallic aluminum and mortars based on magnesium phosphate cement. The physical and chemical processes leading to setting and hardening of the cement are first investigated. X-ray diffraction (XRD), thermogravimetry (TGA) and nuclear magnetic resonance spectroscopy ( 31 P and 11 B MAS-NMR) are first used to characterize the solid phases formed during hydration, while inductively coupled plasma atomic emission spectroscopy analysis (ICP-AES), electrical conductometry and pH measurements provide information on the pore solution composition. Then, the corrosion of metallic aluminum in magnesium phosphate mortars is studied by monitoring the equilibrium potential and by electrochemical impedance spectroscopy (EIS). Magnesium phosphate cement is prepared from a mix of magnesium oxide (MgO) and potassium dihydrogen orthophosphate (KH 2 PO 4 ). In the presence of water, hydration occurs according to a dissolution - precipitation process. The main hydrate is K-struvite (MgKPO 4 .6H 2 O). Its precipitation is preceded by that of two transient phases: phosphorrosslerite (MgHPO 4 .7H 2 O) and Mg 2 KH(PO 4 ) 2 .15H 2 O. Boric acid retards cement hydration by delaying the formation of cement hydrates. Two processes may be involved in this retardation: the initial precipitation of amorphous or poorly crystallized minerals containing boron and phosphorus atoms, and/or the stabilization of cations (Mg 2+ , K + ) in solution. As compared with a Portland cement-based matrix, corrosion of aluminum is strongly limited in magnesium phosphate mortar. The pore solution pH is close to neutrality and falls within the passivation domain of aluminum. Corrosion depends on several parameters: it is promoted by a water-to-cement ratio (w/c) significantly higher than the chemical water demand of cement (w/c = 0.51), and by the

  17. Selectivity of layered double hydroxides and their derivative mixed metal oxides as sorbents of hydrogen sulfide.

    Science.gov (United States)

    Othman, Mohamed A; Zahid, Waleed M; Abasaeed, Ahmed E

    2013-06-15

    In the context of finding high efficient sorbent materials for removing hydrogen sulfide (H2S) from air stream, a screening study was performed to find the best combination of metals for the synthesis of layered double hydroxides (LDHs) and their derivative mixed metal oxides. Based on selectivity of 998 natural mineral species of sulfur-containing compounds, Cu(2+), Ni(2+) and Zn(2+) were selected as divalent metals, and Fe(3+), Al(3+) and Cr(3+) as trivalent metals to synthesis the LDHs sorbents. 10 LDHs materials and their calcined mixed metal oxides, Ni(0.66)Al(0.34), Cu(0.35)Ni(0.32)Al(0.33), Zn(0.66)Al(0.34), Cu(0.36)Zn(0.32)Al(0.32), Ni(0.64)Fe(0.36), Cu(0.35)Ni(0.31)Fe(0.34), Ni(0.66)Cr(0.34), Cu(0.35)Ni(0.31)Cr(0.34), Zn(0.66)Cr(0.34), Cu(0.33)Zn(0.32)Cr(0.35) were synthesized, characterized chemically and physically, and then tested using breakthrough test to determine their sulfur uptake. Ni(0.64)Fe(0.36) mixed metal oxides was found to have the best uptake of hydrogen sulfide (136 mg H₂S/g). Regeneration of spent Ni(0.64)Fe(0.36) mixed metal oxides was studied using two different mixture solutions, NaCl/NaOH and acetate-buffer/NaCl/NaOH. The latter mixture successfully desorbed the sulfur from the Ni0.64Fe0.36 sorbent for 2 cycles of regeneration/sorption. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Assessment of heavy metals and alpha activity in Indian phosphate fertilizer: possible environmental implications

    International Nuclear Information System (INIS)

    Ghosh, Dipak; Deb, Argha; Bera, Sukumar; Sengupta, Rosalima; Patra, Kanchan Kumar; Dutta, Sidhartha

    2007-01-01

    The study of radioactivity and heavy metals in phosphate fertilizers are very important from environmental point of view. Inorganic phosphate fertilizers may contain radionuclides, heavy metals and fluorine. The present work is the continuation of our study on radioactivity of phosphate fertilizers. Here we have determined the concentrations of heavy metals (Cu, Cr, Zn, Pb, and Mn) in phosphate fertilizers by atomic absorption spectrometer (AAS) in order to estimate the effect of the use of phosphate fertilizers on human health. Also we have measured the concentrations of heavy metals in nonphosphate fertilizers and compared with the phosphate fertilizers. An attempt has been made to establish the correlation between radioactivity and heavy metals in phosphate fertilizers. The sampling sites were randomly selected in the cultivated area in Midnapore district, West Bengal, where phosphate fertilizers are widely used for large agricultural production of mainly potato. Measured data indicates that the concentration of Pb is higher than that of other heavy metals present in phosphate and nonphosphate fertilizer samples. These data might help us to calculate the environmental toxicity of heavy metals on human health due to the direct application of phosphate fertilizers. (author)

  19. Lithium/metal sulfide cells and battery development progress at Eagle-Picher Industries

    Science.gov (United States)

    Cupp, E. B.

    A program aimed at the design, development, and fabrication of lithium/metal sulfide secondary batteries with a molten-salt electrolyte that has been under way since 1975 is reviewed. The goals of the program are to develop a long-life, high-power, high-energy-density battery for electric-vehicle applications. The tasks accomplished so far are discussed with particular attention given to the development of current collectors for both FeS and FeS2 cells, separator improvements, sealing techniques, and active-material balances. The present state-of-the-art Li/MS(x) molten-salt batteries are characterized.

  20. Novel Metal Sulfides to Achieve Effective Capture and Durable Consolidation of Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Kanatzidis, Mercouri [Northwestern Univ., Evanston, IL (United States); Riley, Brian [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Chun, Jaehun [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-01-30

    This report documents the work done under NEUP grant to examine the capability of novel chalcogels and some binary metal chalcogenides as a host matrix for the capture of gaseous iodine and the feasibility of their iodine-laden materials to be converted into a permanent waste form. The presented work was conducted over last two years. A number of novel chalcogels Zn2Sn2S6, Sb4Sn4S12, NiMoS4, CoMoS4, antimony sulfide (SbSx) chalcogels, silver functionalized chalcogels and binary metal sulfides (Sb2S3) were developed and studies for their iodine absorption efficacies. A new and simple route was devised for the large scale preparation of antimony sulfide chalcogel. The chalcogel was obtained by treating Sb2S3 with Na2S in the presence of water followed by addition of formamide. The obtained gels have a low-density sponge like network of meso porous nature having BET surface area of 125 m2/g. The chalcogels, silver functionalized chalcogel and the binary metal sulfides were exposed to iodine vapors in a closed container. Silver-functionalized chalcogels and Sb2S3 powders showed iodine uptake up to 100 wt%, the highest iodine uptake of 200 wt% was observed for the SbS-III chalcogel. The PXRD patterns of iodine-laden specimens revealed that iodine shows spontaneous chemisorption to the matrix used. The iodine loaded chalcogels and the binary chalcogenides were sealed under vacuum in fused silica ampoules and heated in a temperature controlled furnace. The consolidated products were analyzed by PXRD, energy dispersive spectroscopy (EDS), UV-Vis and Raman spectroscopy. The final products were found to be amorphous in most of the cases with high amount (~4-35 wt%) of iodine and aapproximately ~60- 90 % of the absorbed iodine could be consolidated into the final waste form. Alginate

  1. Bismuth(III) dialkyldithiophosphates: Facile single source precursors for the preparation of bismuth sulfide nanorods and bismuth phosphate thin films

    International Nuclear Information System (INIS)

    Biswal, Jasmine B.; Garje, Shivram S.; Nuwad, Jitendra; Pillai, C.G.S.

    2013-01-01

    Two different phase pure materials (Bi 2 S 3 and Bi 2 P 4 O 13 ) have been prepared under different conditions using the same single source precursors. Solvothermal decomposition of the complexes, Bi(S 2 P(OR) 2 ) 3 [where, R=Methyl (Me) (1), Ethyl (Et) (2), n-Propyl (Pr n ) (3) and iso-Propyl (Pr i ) (4)] in ethylene glycol gave orthorhombic bismuth sulfide nanorods, whereas aerosol assisted chemical vapor deposition (AACVD) of the same precursors deposited monoclinic bismuth tetraphosphate (Bi 2 P 4 O 13 ) thin films on glass substrates. Surface study of the thin films using SEM illustrated the formation of variety of nanoscale morphologies (spherical-, wire-, pendent-, doughnut- and flower-like) at different temperatures. AFM studies were carried out to evaluate quality of the films in terms of uniformity and roughness. Thin films of average roughness as low as 1.4 nm were deposited using these precursors. Photoluminescence studies of Bi 2 P 4 O 13 thin films were also carried out. - Graphical abstract: Solvothermal decomposition of bismuth(III) dialkyldithiophosphates in ethylene glycol gave Bi 2 S 3 nanoparticles, whereas aerosol assisted chemical vapor deposition of these single source precursors deposited Bi 2 P 4 O 13 thin films. Display Omitted - Highlights: • Preparation of phase pure orthorhombic Bi 2 S 3 nanorods and monoclinic Bi 2 P 4 O 13 thin films. • Use of single source precursors for deposition of bismuth phosphate thin films. • Use of solvothermal decomposition and AACVD methods. • Morphology controlled synthesis of Bi 2 P 4 O 13 thin films. • Bi 2 S 3 nanorods and Bi 2 P 4 O 13 thin films using same single source precursors

  2. Aerobic transformation of cadmium through metal sulfide biosynthesis in photosynthetic microorganisms.

    Science.gov (United States)

    Edwards, Chad D; Beatty, Joseph C; Loiselle, Jacqueline B R; Vlassov, Katya A; Lefebvre, Daniel D

    2013-07-15

    Cadmium is a non-essential metal that is toxic because of its interference with essential metals such as iron, calcium and zinc causing numerous detrimental metabolic and cellular effects. The amount of this metal in the environment has increased dramatically since the advent of the industrial age as a result of mining activities, the use of fertilizers and sewage sludge in farming, and discharges from manufacturing activities. The metal bioremediation utility of phototrophic microbes has been demonstrated through their ability to detoxify Hg(II) into HgS under aerobic conditions. Metal sulfides are generally very insoluble and therefore, biologically unavailable. When Cd(II) was exposed to cells it was bioconverted into CdS by the green alga Chlamydomonas reinhardtii, the red alga Cyanidioschyzon merolae, and the cyanobacterium, Synechoccocus leopoliensis. Supplementation of the two eukaryotic algae with extra sulfate, but not sulfite or cysteine, increased their cadmium tolerances as well as their abilities to produce CdS, indicating an involvement of sulfate assimilation in the detoxification process. However, the combined activities of extracted serine acetyl-transferase (SAT) and O-acetylserine(thiol)lyase (OASTL) used to monitor sulfate assimilation, was not significantly elevated during cell treatments that favored sulfide biosynthesis. It is possible that the prolonged incubation of the experiments occurring over two days could have compensated for the low rates of sulfate assimilation. This was also the case for S. leopoliensis where sulfite and cysteine as well as sulfate supplementation enhanced CdS synthesis. In general, conditions that increased cadmium sulfide production also resulted in elevated cysteine desulfhydrase activities, strongly suggesting that cysteine is the direct source of sulfur for CdS synthesis. Cadmium(II) tolerance and CdS formation were significantly enhanced by sulfate supplementation, thus indicating that algae and cyanobacteria

  3. Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulfidic marine sediments

    Energy Technology Data Exchange (ETDEWEB)

    Glass, DR. Jennifer [California Institute of Technology, Pasadena; Yu, DR. Hang [California Institute of Technology, Pasadena; Steele, Joshua [California Institute of Technology, Pasadena; Dawson, Katherine [California Institute of Technology, Pasadena; Sun, S [University of California, San Diego; Chourey, Karuna [ORNL; Hettich, Robert {Bob} L [ORNL; Orphan, V [California Institute of Technology, Pasadena

    2014-01-01

    Microbes have obligate requirements for trace metals in metalloenzymes that catalyze important biogeochemical reactions. In anoxic methane- and sulfide-rich environments, microbes may have unique adaptations for metal acquisition and utilization due to decreased bioavailability as a result of metal sulfide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulfidic (>1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5-270 nM), cobalt (0.5-6 nM), molybdenum (10-5,600 nM) and tungsten (0.3-8 nM) in Hydrate Ridge sediment porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalyzing anaerobic oxidation of methane utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrotolerant microorganisms. Finally, our data suggest that chemical speciation of metals in highly sulfidic porewaters may exert a stronger influence on microbial bioavailability than total concentration

  4. Metal Nanoparticle-Decorated Two-Dimensional Molybdenum Sulfide for Plasmonic-Enhanced Polymer Photovoltaic Devices

    Directory of Open Access Journals (Sweden)

    Ming-Kai Chuang

    2015-08-01

    Full Text Available Atomically thin two-dimensional (2D transition metal dichalcogenides have also attracted immense interest because they exhibit appealing electronic, optical and mechanical properties. In this work, we prepared gold nanoparticle-decorated molybdenum sulfide (AuNP@MoS2 through a simple spontaneous redox reaction. Transmission electron microscopy, UV-Vis spectroscopy, and Raman spectroscopy were used to characterize the properties of the AuNP@MoS2 nanomaterials. Then we employed such nanocomposites as the cathode buffer layers of organic photovoltaic devices (OPVs to trigger surface plasmonic resonance, leading to noticeable enhancements in overall device efficiencies. We attribute the primary origin of the improvement in device performance to local field enhancement induced by the effects of localized surface plasmonic resonance. Our results suggest that the metal nanoparticle-decorated two-dimensional materials appear to have great potential for use in high-performance OPVs.

  5. Method and apparatus for ion sequestration and a nanostructured metal phosphate

    Science.gov (United States)

    Mattigod, Shas V [Richland, WA; Fryxell, Glen E [Kennewic, WA; Li, Xiaohong [Richland, WA; Parker, Kent E [Kennewick, WA; Wellman, Dawn M [West Richland, WA

    2010-04-06

    A nanostructured substance, a process for sequestration of ionic waste, and an ion-sequestration apparatus are disclosed in the specification. The nanostructured substance can comprise a Lewis acid transition metal bound to a phosphate, wherein the phosphate comprises a primary structural component of the substance and the Lewis acid transition metal is a reducing agent. The nanostructured substance has a Brunner-Emmet-Teller (BET) surface area greater than or equal to approximately 100 m.sup.2/g, and a distribution coefficient for an analyte, K.sub.d, greater than or equal to approximately 5000 ml/g. The process can comprise contacting a fluid and a nanostructured metal phosphate. The apparatus can comprise a vessel and a nanostructured metal phosphate. The vessel defines a volume wherein a fluid contacts the nanostructured metal phosphate.

  6. Damage of Metal Structures Under the Action of Hydrogen Sulfide Containing Environments

    Science.gov (United States)

    Kushnarenko, V. M.; Uzyakov, R. N.; Repyakh, V. S.

    2018-01-01

    The effect of hydrogen sulfide containing environments, stress-strain states, stress concentration and external actions on the hydrogen sulfide cracking of steels is considered. Examples of typical and atypical action of hydrogen sulfide containing environments on carbon and stainless steels are presented. The factors responsible for hydrogen sulfide cracking are determined. Recommendations are given on design and production of equipment contacting hydrogen sulfide environments.

  7. Complex sulfides and thiosalts

    International Nuclear Information System (INIS)

    Uehlls, A.

    1987-01-01

    Different types of the structures of complex sulfides, thiosalts of alkali, alkaline earth, rare earth, transition and actinide metals are considered in the review of the papers published before 1980 and devoted to the crystal structure of complex sulfides

  8. Origin of kamacite, schreibersite, and perryite in metal-sulfide nodules of the enstatite chondrite Sahara 97072 (EH3)

    Science.gov (United States)

    Lehner, Stephen W.; Buseck, Peter R.; McDonough, William F.

    2010-02-01

    Perryite [(Fe,Ni)x(Si,P)y], schreibersite [(Fe,Ni)3P], and kamacite (αFeNi) are constituent minerals of the metal-sulfide nodules in the Sahara 97072 (EH3) enstatite chondrite meteorite. We have measured concentrations of Ni, Cu, Ga, Au, Ir, Ru, and Pd in these minerals with laser ablation, inductively coupled plasma mass spectrometry (ICP-MS). We also measured their Fe, Ni, P, Si, and Co concentrations with electron microprobe. In kamacite, ratios of Ru/Ir, Pd/Ir, and Pd/Ru cluster around their respective CI values and all elements analyzed plot near the intersection of the equilibrium condensation trajectory versus Ni and the respective CI ratios. In schreibersite, the Pd/Ru ratio is near the CI value and perryite contains significant Cu, Ga, and Pd. We propose that schreibersite and perryite formed separately near the condensation temperatures of P and Si in a reduced gas and were incorporated into Fe-Ni alloy. Upon further cooling, sulfidation of Fe in kamacite resulted in the formation of additional perryite at the sulfide interface. Still later, transient heating re-melted this perryite near the Fe-FeS eutectic temperature during partial melting of the metal-sulfide nodules. The metal-sulfide nodules are pre-accretionary objects that retain CI ratios of most siderophile elements, although they have experienced transient heating events.

  9. Na, Rb and Cs partitioning between metal, silicate and sulfide: Implications for volatile depletion in terrestrial planets

    Science.gov (United States)

    Boujibar, A.; Fei, Y.; Du, Z.; Righter, K.; Bullock, E. S.

    2017-12-01

    Inner Solar System materials are known for their depletion in volatile elements, including the moderately volatile alkalis: Na, K, Rb, and Cs. The origin of this depletion is still uncertain, as several processes could have been involved, during the nebular condensation or planetary accretion. Volatile depletion is commonly estimated through comparison of alkali concentrations relatively to those of chondrites, assuming they remain in planetary mantles during core segregation. However, experimental studies show that substantial K can partition into metals that are enriched in sulfur and oxygen. Several models have also suggested that sulfides may have played an important role during episodes of sulfide segregation from a crystallizing magma ocean (sulfide matte) or accretion of S-rich planetary embryos. For Mercury, a sulfide layer could be present between core and mantle, due to immiscibility between Si-rich and S-rich metals. Therefore, here we investigate whether alkali elements (Na, Cs and Rb) could be partly sequestered in planetary cores during their differentiation. We conducted experiments at high pressure and temperature (1 to 5 GPa and up to 1900 °C) to determine partition coefficients of Na, Rb and Cs between metal and silicate. Our results show that pressure, temperature, sulfur and oxygen in metals enhance the partitioning of Na, Rb and Cs into metals, as previously found for K. For all three investigated alkalis (Na, Rb and Cs), we found a maximum partition coefficient of 1 between sulfides containing 13 wt% O and silicate melt. Therefore, S-rich cores or sulfide layers formed due to immiscibility in Fe-S-O systems could have acted as important geochemical reservoirs for alkali elements. Using our experimental data and different assumptions on initial bulk abundances, we evaluate volatile depletion in terrestrial planets, by comparing resulting mantle alkali concentrations after core segregation, with actual concentrations in the Earth's mantle.

  10. Growth and characterization of semiconducting nickel sulfide nanocrystals from air-stable single-source metal organic precursors

    Directory of Open Access Journals (Sweden)

    Sohail Saeed

    2015-12-01

    Full Text Available Three symmetrical and unsymmetrical nickel(II complexes [cis-(C3H72NC(SNC(OC6H3(3,5-NO22]2Ni(II, [cis-(C4H92NC(SNC(OC6H3(3,5-NO22]2Ni(II, and [cis-(Hex(Me2NC(SNC(O C6H3(3,5-NO22]2Ni(II were synthesized and characterized by FTIR spectroscopy, elemental analysis, and mass spectrometry. These metal complexes have been used as single-source precursors for the preparation of semiconducting nickel sulfide nanocrystals. Rapid injection of metal complexes into oleylamine at 230°C, followed by immediate cooling, led to the formation of irregular-shaped 20–170-nm nickel sulfide nanocrystals. The deposited nickel sulfide nanocrystals were characterized by X-ray powder diffraction and transmission electron microscopy.

  11. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    Energy Technology Data Exchange (ETDEWEB)

    Marking, Gregory Allen [Iowa State Univ., Ames, IA (United States)

    1994-01-04

    Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf10Ta3S3 was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported "stuffed" gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co2Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.

  12. Assessing pollution in a Mediterranean lagoon using acid volatile sulfides and estimations of simultaneously extracted metals.

    Science.gov (United States)

    Zaaboub, Noureddine; Helali, Mohamed Amine; Martins, Maria Virgínia Alves; Ennouri, Rym; Béjaoui, Béchir; da Silva, Eduardo Ferreira; El Bour, Monia; Aleya, Lotfi

    2016-11-01

    Bizerte Lagoon is a southern Mediterranean semi-enclosed lagoon with a maximum depth of 12 m. After assessing sediment quality, the authors report on the physicochemical characteristics of the lagoon's surface sediment using SEM (simultaneously extracted metals) and AVS (acid volatile sulfides) as proxies. Biogeochemical tools are used to investigate the environmental disturbance at the water-sediment interface by means of SEM and AVS to seek conclusions concerning the study area's pollution status. Results confirm accumulation of trace elements in sediment. The use of the SEM-AVS model with organic matter in sediment (ƒOC) confirms possible bioavailability of accumulated trace elements, especially Zn, in the southern part of the lagoon, with organic matter playing an important role in SEM excess correction to affirm a nontoxic total metal sediment state. Individual trace element toxicity is dependent on the bioavailable fraction of SEM Metal on sediment, as is the influence of lagoon inflow from southern water sources on element bioavailability. Appropriate management strategies are highly recommended to mitigate any potential harmful effects on health from this heavy-metal-based pollution.

  13. Multiplexed electrochemical immunoassay of biomarkers using metal sulfide quantum dot nanolabels and trifunctionalized magnetic beads.

    Science.gov (United States)

    Tang, Dianping; Hou, Li; Niessner, Reinhard; Xu, Mingdi; Gao, Zhuangqiang; Knopp, Dietmar

    2013-08-15

    A novel multiplexed stripping voltammetric immunoassay protocol was designed for the simultaneous detection of multiple biomarkers (CA 125, CA 15-3, and CA 19-9 used as models) using PAMAM dendrimer-metal sulfide quantum dot (QD) nanolabels as distinguishable signal tags and trifunctionalized magnetic beads as an immunosensing probe. The probe was prepared by means of co-immobilization of primary monoclonal anti-CA 125, anti-CA 15-3 and anti-CA 19-9 antibodies on a single magnetic bead. The PAMAM dendrimer-metal sulfide QD nanolabels containing CdS, ZnS and PbS were synthesized by using in situ synthesis method, which were utilized for the labeling of polyclonal rabbit anti-CA 125, anti-CA 15-3 and anti-CA 19-9 detection antibodies, respectively. A sandwich-type immunoassay format was adopted for the simultaneous determination of target biomarkers in a low-binding microtiter plate. The subsequent anodic stripping voltammetric analysis of cadmium, zinc, and lead components released by acid from the corresponding QD nanolabels was conducted at an in situ prepared mercury film electrode based on the difference of peak potentials. Experimental results indicated that the multiplexed immunoassay enabled the simultaneous detection of three cancer biomarkers in a single run with wide dynamic ranges of 0.01-50 U mL(-1) and detection limits (LODs) of 0.005 U mL(-1). Intra-assay and inter-assay coefficients of variation (CVs) were less than 7.2% and 10.4%, respectively. No significant differences at the 0.05 significance level were encountered in the analysis of 10 clinical serum specimens between the multiplexed immunoassay and a commercially available enzyme-linked immunosorbent assay (ELISA). Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Solvent-Free Synthesis of Quaternary Metal Sulfide Nanoparticles Derived from Thiourea

    KAUST Repository

    Bhunia, Manas Kumar

    2017-08-09

    The synthesis of metal sulfide (MS) materials with sizes in the sub-10 nm regime often requires capping agents with long hydrocarbon chains that affect their structures and properties. Herein, this study presents a molten-state synthesis method for a series of transition-MS nanoparticles using thiourea as a reactive precursor without capping agents. This study also reports the synthesis of MS with single metals (Fe, Co, Ni, Cu, and Zn) and quaternary CuGa2In3S8 using the same synthesis protocol. Thiourea first melts to form a molten-state condition to serve as the reaction medium at a relatively low temperature (<200 °C), followed by its thermal decomposition to induce a reaction with the metal precursor to form different MS. This synthesis protocol, owing to its dynamic characteristics, involves the formation of a variety of organic carbon nitride polymeric complexes around the MS particles. Dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy is effective to identify the polymeric compositions and structures as well as their interactions with the MS. These results provided thorough structural descriptions of the MS nanoparticles surrounded by the carbon nitride species derived from thiourea, which may find various applications, including photocatalytic water splitting.

  15. Na-Fe-Phosphate Globules in Impact Metal-Troilite Associations of Chelyabinsk Meteorite

    Science.gov (United States)

    Sharygin, V. V.; Karmanov, N. S.; Podgornykh, N. M.

    2016-08-01

    Multi- and monophase phosphate globules have been found in the impact metal-troilite aggregates of the Chelyabinsk chondrite. Their phase composition varies and they contain galileiite, sarcopside, graftonite and Na-Fe-phosphate Na2(Fe,Mn)5(PO4)4.

  16. Photocatalytic properties of zinc sulfide nanocrystals biofabricated by metal-reducing bacterium Shewanella oneidensis MR-1

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Xiang [School of The Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China); Ma, Xiao-Bo [School of The Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Yuan, Hang [Key Laboratory of Ion Beam Bioengineering, Institute of Technical Biology & Agriculture Engineering, Chinese Academy of Sciences, Hefei 230031 (China); Liu, Peng-Cheng; Lei, Yu-Bin; Xu, Hui [School of The Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Du, Dao-Lin, E-mail: ddl@ujs.edu.cn [School of The Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China); Sun, Jian-Fan [School of The Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Feng, Yu-Jie, E-mail: yujief@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China)

    2015-05-15

    Highlights: • S. oneidensis MR-1 biofabricated ZnS nanocrystals using artificial wastewater. • ZnS nanocrystals were 5 nm in diameter and aggregated extracellularly. • ZnS had good catalytic activity in the degradation of RHB under UV irradiation. • Photogenerated holes mainly contributed to the degradation of RhB. - Abstract: Accumulation and utilization of heavy metals from wastewater by biological treatment system has aroused great interest. In the present study, a metal-reducing bacterium Shewanella oneidensis MR-1 was used to explore the biofabrication of ZnS nanocrystals from the artificial wastewater. The biogenic H{sub 2}S produced via the reduction of thiosulfate precipitated the Zn(II) as sulfide extracellularly. Characterization by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscope (FESEM) confirmed the precipitates as ZnS nanocrystals. The biogenic ZnS nanocrystals appeared spherical in shape with an average diameter of 5 nm and mainly aggregated in the medium and cell surface of S. oneidensis MR-1. UV–vis DRS spectra showed ZnS nanoparticles appeared a strong absorption below 360 nm. Thus, the photocatalytic activity of ZnS was evaluated by the photodegradation of rhodamine B (RhB) under UV irradiation. The biogenic ZnS nanocrystals showed a high level of photodegradation efficiency to RhB coupled with a significant blue-shift of maximum adsorption peak. A detailed analysis indicated the photogenerated holes, rather than hydroxyl radicals, contributed to the photocatalytic decolorization of RhB. This approach of coupling biosynthesis of nanoparticles with heavy metal removal may offer a potential avenue for efficient bioremediation of heavy metal wastewater.

  17. Photocatalytic properties of zinc sulfide nanocrystals biofabricated by metal-reducing bacterium Shewanella oneidensis MR-1

    International Nuclear Information System (INIS)

    Xiao, Xiang; Ma, Xiao-Bo; Yuan, Hang; Liu, Peng-Cheng; Lei, Yu-Bin; Xu, Hui; Du, Dao-Lin; Sun, Jian-Fan; Feng, Yu-Jie

    2015-01-01

    Highlights: • S. oneidensis MR-1 biofabricated ZnS nanocrystals using artificial wastewater. • ZnS nanocrystals were 5 nm in diameter and aggregated extracellularly. • ZnS had good catalytic activity in the degradation of RHB under UV irradiation. • Photogenerated holes mainly contributed to the degradation of RhB. - Abstract: Accumulation and utilization of heavy metals from wastewater by biological treatment system has aroused great interest. In the present study, a metal-reducing bacterium Shewanella oneidensis MR-1 was used to explore the biofabrication of ZnS nanocrystals from the artificial wastewater. The biogenic H 2 S produced via the reduction of thiosulfate precipitated the Zn(II) as sulfide extracellularly. Characterization by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscope (FESEM) confirmed the precipitates as ZnS nanocrystals. The biogenic ZnS nanocrystals appeared spherical in shape with an average diameter of 5 nm and mainly aggregated in the medium and cell surface of S. oneidensis MR-1. UV–vis DRS spectra showed ZnS nanoparticles appeared a strong absorption below 360 nm. Thus, the photocatalytic activity of ZnS was evaluated by the photodegradation of rhodamine B (RhB) under UV irradiation. The biogenic ZnS nanocrystals showed a high level of photodegradation efficiency to RhB coupled with a significant blue-shift of maximum adsorption peak. A detailed analysis indicated the photogenerated holes, rather than hydroxyl radicals, contributed to the photocatalytic decolorization of RhB. This approach of coupling biosynthesis of nanoparticles with heavy metal removal may offer a potential avenue for efficient bioremediation of heavy metal wastewater

  18. Metal Phosphates as Proton Conducting Materials for Intermediate Temperature Fuel Cell and Electrolyser Applications

    DEFF Research Database (Denmark)

    Anfimova, Tatiana

    of phosphates were systematically reviewed including solid acids or alkali hydrogen phosphates, pyrophosphates, and rare earth metal phosphates. Demonstration of the fuel cell technology based on solid acid proton conductor CsH2PO4 has inspired the active research in the area. Based on the literature survey....... The conductivity and its stability are studied and correlated with the phosphate morphologies. The additional solid state NMR studies have been performed in collaboration with Southern Denmark University (SDU). Chapter 8 presents the result obtained for a novel proton conductor based on cerium ultraphosphate...

  19. Availability of metals in samples of phosphogypsum and phosphate fertilizers used in agriculture

    International Nuclear Information System (INIS)

    Bourlegat, Fernanda Melo le

    2010-01-01

    The Brazilian phosphate fertilizer is obtained by wet reaction of the igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid, and dehydrated calcium sulphate (phosphogypsum) as by-product. Part of this phosphogypsum is stored in stacks at open air and part has been used in agriculture, as soil amendment. To assure a safe utilization of phosphogypsum it is important to determine the levels of impurities, particularly of metals, present in phosphogypsum. In this paper, the concentration of metals (As, Ba, Cd, Cr, Co, Cu, Hg, Ni, Pb, Se, Zn and rare earth elements) present in Brazilian phosphogypsum and also in single super phosphate (SSP), triple super phosphate (TSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP) were determined. The metals Cd, Cu, Ni, Pb and Zn were determined following the procedure 'EPA 3052'. The same elements, As and Se were also determined following the procedure 'EPA 3050B', recommended by Ministerio da Agricultura, Pecuaria e Abastecimento (MAPA). All these metals are controlled by environmental and agriculture regulation institutes in Brazil. The concentrations obtained for the metals analyzed by using the two procedures were different. Ba, Co, Cr and rare earth elements were determined by neutron activation analysis. In order to evaluate the availability of these metals As, Cd, Cr, Co, Cu, Ni, Pb, Se and Zn to the environment, the content of the same elements were determined following a procedure established by the EC (European Community), which includes an initial attack of the samples with EDTA-NH 4 0.05M, at pH 7.0. In all these cases, phosphogypsum presented metals concentration lower than the phosphate fertilizers, and the results are below the limits adopted by MAPA and Companhia Ambiental do Estado de Sao Paulo (CETESB). The results obtained using the methodology with mild attack show that the metals are not available to the environment, giving evidence that the application of

  20. Rh Nanoparticle Anchoring on Metal Phosphates: Fundamental Aspects and Practical Impacts on Catalysis.

    Science.gov (United States)

    Machida, Masato

    2016-10-01

    Metal phosphates stabilize Rh nanoparticles on their surface via Rh-O-P bonds, in contrast to the Rh-O-M bonds formed on metal oxides (MO x ). The local structure, electronic structure, and redox properties of Rh nanoparticles anchored on metal phosphates, and their practical impacts on catalysis, are reviewed based on recent publications from the author's research group. Because of the covalency of the Rh-O-P bond, Rh oxide is readily reduced to metallic Rh having a higher catalytic activity, whereas Rh oxide on metal oxide supports is more difficult to reduce with an increase of the anchoring strength. Furthermore, Rh metal shows a higher tolerance to reoxidation when supported on metal phosphates because the Rh-O-P bond is preserved under reducing atmospheres. The electron deficiency of Rh metal is another feature that affects its catalytic properties, and the extent of the electron deficiency can be tuned by replacing the metal in the metal phosphate with one of higher basicity. Further impacts on practical performance (thermal stability, poisoning stability, and lean NO x purification) in automobile catalyst applications are also described. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part I. the absorption of hydrogen sulfide in metal sulfate solutions

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    The desulfurization of gas streams using aqueous iron(II)sulfate (Fe(II)SO4), zinc sulfate (ZnSO4) and copper sulfate (CuSO4) solutions as washing liquor is studied theoretically and experimentally. The desulfurization is accomplished by a precipitation reaction that occurs when sulfide ions and

  2. Review of Phosphate in soils: Interaction with micronutrients, radionuclides, and heavy metals

    Science.gov (United States)

    Phosphate-phosphorus present in the vadose zone of soil as native, added, or residual fertilizer influences the retention, transport, and bioavailability of heavy metals, metalloids, or metallic radionuclides to aboveground vegetation, soil microorganisms, and fauna that browse that vegetation, or d...

  3. Synthesis and Characterization of Metal Sulfides Nanoparticles/Poly(methyl methacrylate Nanocomposites

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2014-01-01

    Full Text Available Metal sulfides nanoparticles in poly(methyl methacrylate matrices were prepared and characterized by infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, scanning electron microscope (SEM, and transmission electron microscope (TEM. The FTIR confirms the dispersion of the nanoparticles in PMMA matrices with the C=O and C–O–C bonds of the PMMA shifting slightly which may be attributed to the interactions between the nanoparticles and PMMA. The ZnS nanoparticles in PMMA have average crystallite sizes of 4–7 nm while the CdS has particle size of 10 nm and HgS has crystallite sizes of 8–20 nm. The increasing order of particle sizes as calculated from the XRD is ZnS/PMMA

  4. Rapid microwave-assisted preparation of binary and ternary transition metal sulfide compounds

    Energy Technology Data Exchange (ETDEWEB)

    Butala, Megan M.; Perez, Minue A.; Arnon, Shiri; Göbel, Claudia; Preefer, Molleigh B.; Seshadri, Ram

    2017-12-01

    Transition metal chalcogenides are of interest for energy applications, including energy generation in photoelectrochemical cells and as electrodes for next-generation electrochemical energy storage. Synthetic routes for such chalcogenides typically involve extended heating at elevated temperatures for multiple weeks. We demonstrate here the feasibility of rapidly preparing select sulfide compounds in a matter of minutes, rather than weeks, using microwave-assisted heating in domestic microwaves. We report the preparations of phase pure FeS2, CoS2, and solid solutions thereof from the elements with only 40 min of heating. Conventional furnace and rapid microwave preparations of CuTi2S4 both result in a majority of the targeted phase, even with the significantly shorter heating time of 40 min for microwave methods relative to 12 days using a conventional furnace. The preparations we describe for these compounds can be extended to related structures and chemistries and thus enable rapid screening of the properties and performance of various compositions of interest for electronic, optical, and electrochemical applications.

  5. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    Science.gov (United States)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization

  6. PREPARATION AND CHARACTERIZATION THE NON-SULFIDED METAL CATALYST: Ni/USY and NiMo/USY

    Directory of Open Access Journals (Sweden)

    Khoirina Dwi Nugrahaningtyas

    2010-06-01

    Full Text Available The two-new catalysts had been prepared by using the impregnation method according to Nugrahaningtyas [6] and Li [4]. One catalyst is of Nickel (Ni, supported on Ultra Stable Zeolite Y (USY, whereas the other one is NiMo supported on same supporting agent. These new catalysts are expected to be more effective when applied on the hydrotreatment reaction in standpoint of its capabilities on removing the unwanted-heteroatom. Characterization those two types of catalysts then carried out by using the criteria of acidity, porosity and, metal content. The result shows that these non-sulfide catalysts have several good characters that supporting their usefulness in hydrotreatment-catalytic reaction. In addition, catalyst NiMo/USY - 1 performs many ideal criteria as the best functional catalyst.   Keywords: Non-sulfided Catalyst, hydro-treating, preparation, characterization

  7. Diffused vs. Focused Flow - Metaproteogenomic Insights into Effects of Hydrothermal Fluid Flow on Metal-Sulfide Chimney Colonizing Biofilms

    Science.gov (United States)

    Pjevac, P.; Markert, S.; Richter, M.; Gruber-Vodicka, H.; Schweder, T.; Amann, R.; Meyerdierks, A.

    2014-12-01

    At many sites of hydrothermal discharge in the deep-sea, the deposition of metal sulfides from hydrothermal fluids leads to the formation of geological structures known as hydrothermal chimneys. The mixing of reduced hydrothermal fluids with oxygenated seawater leads to the formation of steep redox gradients within the chimney walls. These gradients facilitate the co-existence of metabolically diverse microorganisms in the narrow habitable zone of hydrothermal chimney walls. However, the overall composition of chimney-associated microbial community is usually of low complexity and represents an environment suitable for metaomic-based studies. We used metagenomic and metaproteomic tools to compare microbial communities colonizing two metal-sulfide chimneys from the Manus Basin back-arc spreading center in the Bismarck Sea off Papua New Guinea. These chimneys were supplied by the same source hydrothermal fluids, but exhibited different fluid flow regimes. One chimney (RMR5) had a focused venting edifice, while the other (RMR-D) displayed diffuse fluid efflux on its entire outer surface. Although the microbial diversity of both chimneys is similar and dominated by mesophilic Epsilonproteobacteria, our results indicate a strong structuring effect of hydrothermal fluid flow regime on chimney-associated biofilms. The microbial community composition indicates a homogeneous colonization of the diffuse chimney walls. In contrast, the walls of the focused venting chimney appear to be colonized in layers reflecting different temperature tolerances of the dominant microorganisms. Sulfide-oxidation is likely the key metabolism in both chimneys, which is in line with the high sulfide content of the source hydrothermal fluid. However, preliminary metaproteome analysis indicates high activity of low-abundant methanotrophic Bacteria in the diffuser chimney walls. This finding is particularly interesting in light of the very low methane content of the source hydrothermal fluid

  8. Size Modulation of Zirconium-Based Metal Organic Frameworks for Highly Efficient Phosphate Remediation.

    Science.gov (United States)

    Gu, Yue; Xie, Donghua; Ma, Yue; Qin, Wenxiu; Zhang, Haimin; Wang, Guozhong; Zhang, Yunxia; Zhao, Huijun

    2017-09-20

    Eutrophication of water bodies caused by the excessive phosphate discharge has constituted a serious threat on a global scale. It is imperative to exploit new advanced materials featuring abundant binding sites and high affinity to achieve highly efficient and specific capture of phosphate from polluted waters. Herein, water stable Zr-based metal organic frameworks (MOFs, UiO-66) with rational structural design and size modulation have been successfully synthesized based on a simple solvothermal method for effective phosphate remediation. Impressively, the size of the resulting UiO-66 particles can be effectively adjusted by simply altering reaction time and the amount of acetic acid with the purpose of understanding the crucial effect of structural design on the phosphate capture performance. Representatively, UiO-66 particles with small size demonstrates 415 mg/g of phosphate uptake capacity, outperforming most of the previously reported phosphate adsorbents. Meanwhile, the developed absorbents can rapidly reduce highly concentrated phosphate to below the permitted level in drinking water within a few minutes. More significantly, the current absorbents display remarkable phosphate sorption selectivity against the common interfering ions, which can be attributed to strong affinity between Zr-OH groups in UiO-66 and phosphate species. Furthermore, the spent UiO-66 particles can be readily regenerated and reused for multiple sorption-desorption cycles without obvious decrease in removal performance, rendering them promising sustainable materials. Hence, the developed UiO-66 adsorbents hold significant prospects for phosphate sequestration to mitigate the increasingly eutrophic problems.

  9. CH4 Auto-thermal Reforming over Ni/(Metal phosphate)

    International Nuclear Information System (INIS)

    Katsutoshi Nagaoka; Toshikazu Eiraku; Hiroyasu Nishiguchi; Yusaku Takita

    2006-01-01

    Ni was supported on various types of metal phosphates and their availability in auto-thermal reforming of CH 4 was investigated. It has been found that Ni/(rare earth phosphate), particularly Ni/(Gd, Ce or ErPO 4 ), show high and stable activities. The catalysts also exhibited extremely high resistance against coking. On the other hand, catalysts including Zr, or GaPO 4 or Ca 2 P 2 O 7 were deactivated/inactive and did not show activity eventually. Results of XRD measurements after different treatments revealed that difference of the catalytic behaviour was associated to the stability of metal phosphate during H 2 reduction at high temperature. (authors)

  10. Effect of Zinc Phosphate on the Corrosion Behavior of Waterborne Acrylic Coating/Metal Interface

    Directory of Open Access Journals (Sweden)

    Hongxia Wan

    2017-06-01

    Full Text Available Waterborne coating has recently been paid much attention. However, it cannot be used widely due to its performance limitations. Under the specified conditions of the selected resin, selecting the function pigment is key to improving the anticorrosive properties of the coating. Zinc phosphate is an environmentally protective and efficient anticorrosion pigment. In this work, zinc phosphate was used in modifying waterborne acrylic coatings. Moreover, the disbonding resistance of the coating was studied. Results showed that adding zinc phosphate can effectively inhibit the anode process of metal corrosion and enhance the wet adhesion of the coating, and consequently prevent the horizontal diffusion of the corrosive medium into the coating/metal interface and slow down the disbonding of the coating.

  11. Effect of Zinc Phosphate on the Corrosion Behavior of Waterborne Acrylic Coating/Metal Interface.

    Science.gov (United States)

    Wan, Hongxia; Song, Dongdong; Li, Xiaogang; Zhang, Dawei; Gao, Jin; Du, Cuiwei

    2017-06-14

    Waterborne coating has recently been paid much attention. However, it cannot be used widely due to its performance limitations. Under the specified conditions of the selected resin, selecting the function pigment is key to improving the anticorrosive properties of the coating. Zinc phosphate is an environmentally protective and efficient anticorrosion pigment. In this work, zinc phosphate was used in modifying waterborne acrylic coatings. Moreover, the disbonding resistance of the coating was studied. Results showed that adding zinc phosphate can effectively inhibit the anode process of metal corrosion and enhance the wet adhesion of the coating, and consequently prevent the horizontal diffusion of the corrosive medium into the coating/metal interface and slow down the disbonding of the coating.

  12. Metal-free catalytic oxidation of sulfides to sulfoxides with ammonium nitrate, ammonium hydrogen sulfate and ammonium bromide as catalyst

    OpenAIRE

    Ghorbani-Choghamarani, Arash; Zolfigol, Mohammad Ali; Ayazi-Nasrabadi, Roia

    2010-01-01

    A general and metal-free catalytic oxidation of aliphatic and aromatic sulfides to their corresponding sulfoxides via combination of ammonium nitrate (NH4NO3), supported ammonium hydrogen sulfate on silica gel (NH4HSO4-SiO2) and a catalytic amount of ammonium bromide (NH4Br) in the presence of wet SiO2 (50%, w/w) has been investigated. The reactions were carried out heterogeneously and selectively in short reaction times in CH2Cl2 at room temperature. This protocol is mild and efficient compa...

  13. TRACE ELEMENT CHEMISTRY IN RESIDUAL-TREATED SOIL: KEY CONCEPTS AND METAL BIOAVAILABILITY

    Science.gov (United States)

    Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are importan...

  14. Role of phosphate fertilizers in heavy metal uptake and detoxification of toxic metals.

    Science.gov (United States)

    Gupta, D K; Chatterjee, S; Datta, S; Veer, V; Walther, C

    2014-08-01

    As a nonrenewable resource, phosphorus (P) is the second most important macronutrient for plant growth and nutrition. Demand of phosphorus application in the agricultural production is increasing fast throughout the globe. The bioavailability of phosphorus is distinctively low due to its slow diffusion and high fixation in soils which make phosphorus a key limiting factor for crop production. Applications of phosphorus-based fertilizers improve the soil fertility and agriculture yield but at the same time concerns over a number of factors that lead to environmental damage need to be addressed properly. Phosphate rock mining leads to reallocation and exposure of several heavy metals and radionuclides in crop fields and water bodies throughout the world. Proper management of phosphorus along with its fertilizers is required that may help the maximum utilization by plants and minimum run-off and wastage. Phosphorus solubilizing bacteria along with the root rhizosphere of plant integrated with root morphological and physiological adaptive strategies need to be explored further for utilization of this extremely valuable nonrenewable resource judiciously. The main objective of this review is to assess the role of phosphorus in fertilizers, their uptake along with other elements and signaling during P starvation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Risk assessment of heavy metals in Vembanad Lake sediments (south-west coast of India), based on acid-volatile sulfide (AVS)-simultaneously extracted metal (SEM) approach.

    Science.gov (United States)

    Shyleshchandran, Mohanachandran Nair; Mohan, Mahesh; Ramasamy, Eswara Venkatesaperumal

    2018-03-01

    Contamination of estuarine system due to heavy metals is a severe issue in tropical countries, especially in India. For the evaluation of the risk due to heavy metals, the current study assessed spatial and temporal variation of acid-volatile sulfide (AVS), simultaneously extracted metal (SEM), and total metal concentration as toxicity indicator of aquatic sediments in Vembanad Lake System (VLS), India. Surface sediment samples collected from 12 locations from the northern portion of VLS for 4 years during different seasons. The results suggest, in post-monsoon season, 91% of the sampling locations possessed high bioavailability of metals and results in toxicity to aquatic biota. The average seasonal distribution of SEM during the period of observations was in the order post-monsoon > pre-monsoon > monsoon (1.76 ± 2.00 > 1.35 ± 0.60 > 0.80 ± 0.54 μmol/g). The concentration of individual metals on ∑SEM are in the order SEM Zn > SEM Cu> SEM Cd ≈ SEM Pb > SEM Hg. Considering annual ΣSEM/AVS ratio, 83% of the sites cross the critical value of 'One,' reveals that active sulfide phase of the sediment for fixing the metals is saturated. The molar ratio (differences between SEM and AVS) and its normalized organic carbon ratio reveals that in the post-monsoon season, about 42% of the sites are in the category of adverse effects are possible. The study suggests the toxicity and mobility of the metals largely depend on the available AVS, and the current situation may pose harm to benthic organisms.

  16. Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells

    Science.gov (United States)

    Heo, Jungwoo; Kim, Gi-Hwan; Jeong, Jaeki; Yoon, Yung Jin; Seo, Jung Hwa; Walker, Bright; Kim, Jin Young

    2016-11-01

    We report the preparation of Cu2S, In2S3, CuInS2 and Cu(In,Ga)S2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.

  17. Crystal structure of hydrazine iron(III phosphate, the first transition metal phosphate containing hydrazine

    Directory of Open Access Journals (Sweden)

    Renald David

    2015-12-01

    Full Text Available The title compound, poly[(μ2-hydrazine(μ4-phosphatoiron(III], [Fe(PO4(N2H4]n, was prepared under hydrothermal conditions. Its asymmetric unit contains one FeIII atom located on an inversion centre, one P atom located on a twofold rotation axis, and two O, one N and two H atoms located on general positions. The FeIII atom is bound to four O atoms of symmetry-related PO4 tetrahedra and to two N atoms of two symmetry-related hydrazine ligands, resulting in a slightly distorted FeO4N2 octahedron. The crystal structure consists of a three-dimensional hydrazine/iron phoshate framework whereby each PO4 tetrahedron bridges four FeIII atoms and each hydrazine ligand bridges two FeIII atoms. The H atoms of the hydrazine ligands are also involved in moderate N—H...O hydrogen bonding with phosphate O atoms. The crystal structure is isotypic with the sulfates [Co(SO4(N2H4] and [Mn(SO4(N2H4].

  18. Composition Directed Generation of Reactive Oxygen Species in Irradiated Mixed Metal Sulfides Correlated with Their Photocatalytic Activities.

    Science.gov (United States)

    He, Weiwei; Jia, Huimin; Yang, Dongfang; Xiao, Pin; Fan, Xiaoli; Zheng, Zhi; Kim, Hyun-Kyung; Wamer, Wayne G; Yin, Jun-Jie

    2015-08-05

    The ability of nanostructures to facilitate the generation of reactive oxygen species and charge carriers underlies many of their chemical and biological activities. Elucidating which factors are essential and how these influence the production of various active intermediates is fundamental to understanding potential applications of these nanostructures, as well as potential risks. Using electron spin resonance spectroscopy coupled with spin trapping and spin labeling techniques, we assessed 3 mixed metal sulfides of varying compositions for their abilities to generate reactive oxygen species, photogenerate electrons, and consume oxygen during photoirradiation. We found these irradiated mixed metal sulfides exhibited composition dependent generation of ROS: ZnIn2S4 can generate (•)OH, O2(-•) and (1)O2; CdIn2S4 can produce O2(-•) and (1)O2, while AgInS2 only produces O2(-•). Our characterizations of the reactivity of the photogenerated electrons and consumption of dissolved oxygen, performed using spin labeling, showed the same trend in activity: ZnIn2S4 > CdIn2S4 > AgInS2. These intrinsic abilities to generate ROS and the reactivity of charge carriers correlated closely with the photocatalytic degradation and photoassisted antibacterial activities of these nanomaterials.

  19. Dual Roles of Protein as a Template and a Sulfur Provider: A General Approach to Metal Sulfides for Efficient Photothermal Therapy of Cancer.

    Science.gov (United States)

    Sheng, Jianping; Wang, Liqiang; Han, Yajing; Chen, Wansong; Liu, Hong; Zhang, Min; Deng, Liu; Liu, You-Nian

    2018-01-01

    Fabrication of clinically translatable nanoparticles (NPs) as photothermal therapy (PTT) agents against cancer is becoming increasingly desirable, but still challenging, especially in facile and controllable synthesis of biocompatible NPs with high photothermal efficiency. A new strategy which uses protein as both a template and a sulfur provider is proposed for facile, cost-effective, and large-scale construction of biocompatible metal sulfide NPs with controlled structure and high photothermal efficiency. Upon mixing proteins and metal ions under alkaline conditions, the metal ions can be rapidly coordinated via a biuret-reaction like process. In the presence of alkali, the inert disulfide bonds of S-rich proteins can be activated to react with metal ions and generate metal sulfide NPs under gentle conditions. As a template, the protein can confine and regulate the nucleation and growth of the metal sulfide NPs within the protein formed cavities. Thus, the obtained metal sulfides such as Ag 2 S, Bi 2 S 3 , CdS, and CuS NPs are all with small size and coated with proteins, affording them biocompatible surfaces. As a model material, CuS NPs are evaluated as a PTT agent for cancer treatment. They exhibit high photothermal efficiency, high stability, water solubility, and good biocompatibility, making them an excellent PTT agent against tumors. This work paves a new avenue toward the synthesis of structure-controlled and biocompatible metal sulfide NPs, which can find wide applications in biomedical fields. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Nonaqueous chlorination of uranium metal in tributyl phosphate

    International Nuclear Information System (INIS)

    Buchikhin, E.P.; Kuznetsov, A.Yu.; Shatalov, V.V.; Vidanov, V.L.; Chekmarev, A.M.

    2005-01-01

    Low-temperature (30-50 deg C) chlorination of uranium metal in the TBP-TCE-Cl 2 system (TCE = tetrachloroethylene) was studied. Dissolution of uranium in the dipolar aprotic solvent proceeds with formation of U(IV) compounds. The activation energy of this process is 31.24 kJ mol -1 , and relative reaction order with respect to Cl 2 is 2. The effect of TBP concentration on chlorination was examined. The chlorination rate sharply increases at a water content in the TBP-TCE system of 0.2- 0.6 vol % [ru

  1. Gas-Liquid Precipitation of water dissolved heavy metal ions using hydrogen sulfide gas

    NARCIS (Netherlands)

    Al Tarazi, M.Y.M.

    2004-01-01

    Precipitation of solids promoted by gas-liquid reactions is applied in many industrial processes such as the production of ammonium phosphate, ammonium sulphate, barium carbonate, calcium carbonate, calcium fluoride, ypsum (calcium sulphate), goethite, sodium bicarbonate, strontium carbonate and

  2. Bioavailability assessment of toxic metals using the technique "acid-volatile sulfide (AVS)-simultaneously extracted metals (SEM)" in marine sediments collected in Todos os Santos Bay, Brazil.

    Science.gov (United States)

    Silva, Jucelino B; Nascimento, Rodrigo A; de Oliva, Sergio T; de Oliveira, Olívia M C; Ferreira, Sergio L C

    2015-10-01

    This paper reports the bioavailability of the metals (cadmium, copper, zinc, lead, and nickel) in sediment samples collected in seven stations from the São Paulo Estuary, Todos os Santos Bay, Brazil. The bioavailability was determined by employing the technique "acid-volatile sulfide (AVS) and simultaneously extracted metal (SEM)". The elements cadmium, copper, lead, and zinc were determined using differential pulse anodic stripping voltammetry (DPASV), while nickel was quantified utilizing electrothermal atomic absorption spectrometry (ET AAS). The accuracy of these methods was confirmed using a certified reference material of estuarine sediment (NIST 1646). The sulfide was quantified using potentiometry with selective electrode and the organic matter determination employing an indirect volumetric method using potassium dichromate and iron(II) sulfate solutions. The bioavailability of the metals was estimated by relationship between the concentration of AVS and the sum of the concentrations of the simultaneously extracted metals (ΣSEM), considering a significant toxicity when (ΣSEM)/(AVS) is higher than 1. The bioavailability values in the seven stations studied varied from 0.93 to 1.31 (June, 2014) and from 0.34 to 0.58 (September, 2014). These results demonstrated a critical condition of toxicity (bioavailability >1) in six of the seven sediment samples collected during the rainy season (June, 2014). In the other period (September, 2014), the bioavailability was always lower than 1 for all sediment samples collected in the seven stations. The individual values of the concentrations of the five metals were compared with the parameters PEL (probable effects level) and TEL (threshold effects level), which are commonly employed for characterization of ecological risk in environmental systems. This comparison revealed that all metals have concentrations lower than the PEL and only zinc and lead in some stations have contents higher than the TEL. The

  3. Phosphate chemical conversion coatings on metallic substrates for biomedical application: a review.

    Science.gov (United States)

    Liu, Bing; Zhang, Xian; Xiao, Gui-yong; Lu, Yu-peng

    2015-02-01

    Phosphate chemical conversion (PCC) technology has been investigated for improving the surface performance of metallic implants in the biomedical field over the last decade. The metallic materials, such as magnesium and its alloys, titanium, pure iron and stainless steel are widely used as orthopedic devices for immobilization of bone fractures in clinic. They were previously studied as metal substrates for PCC coating aiming to modify their biocompatibility and osteoconductivity. Zinc, calcium and zinc-calcium PCC coatings are frequently utilized considering their nature and the end-use. Although PCC coating has been confirmed to potentially improve the bio-performance of metallic implants in vitro and in vivo by many researchers, there are no unified standards or regulations to give quantitative appraisal of its quality and property. As such, an overview of several main phosphate phases together with their properties and behaviors in vitro and in vivo was conducted. The mechanism of phosphating was also briefly discussed. Critical qualities of PCC coating used for biomedical application including corrosion resistance, wettability and bonding strength were analyzed separately. Biological response including in vitro cell investigations and in vivo tissue response were discussed in terms of the cytocompatibility and bioactivity of PCC coating. Further investigations are proposed to develop appropriate performance evaluation measurements by combining conventional technologies and biomedical procedures. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Metals concentration in phosphogypsum and phosphate fertilizers produced in Brazil using INAA

    Energy Technology Data Exchange (ETDEWEB)

    Le Bourlegat, Fernanda M.; Saueia, Catia H.R.; Mazzilli, Barbara P.; Favaro, Deborah I.T., E-mail: mazzilli@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2009-07-01

    Phosphogypsum is obtained by wet reaction of the igneous phosphate rock with concentrated sulphuric acid, giving as final product phosphoric acid and dihydrated calcium sulphate (CaSO{sub 4}.2H{sub 2}O) as by-product. It may contain high quantities of P{sub 2}O{sub 5}, trace metals and radionuclides of U and Th series. Phosphogypsum worldwide production on 2006 was estimated in 170 million tons. All the countries that produce phosphate fertilizers by wet process are facing the same problem of finding solutions for the safe application of phosphogypsum, in order to minimize the impact caused by the disposal of large amounts of this by-product. Phosphogypsum can be used in agriculture as a soil amendment; however, for its safe application the concentration of the impurities present and their behaviour in the environment should be better understood. The radiological characterization has been extensively studied in the last decade, but there are few studies about the metals concentration in phosphogypsum. This work intends to determine the concentration of metals (Ba, Co, Cr, Fe, Hf, Na, Sc, Ta, Th, U, Zn e Zr) and rare earth elements (REE) present in phosphogypsum produced in Brazil and to compare the results with those found in the phosphate fertilizers commonly commercialized. The technique used for the determination of the metals was instrumental neutron activation analysis (INAA). (author)

  5. Piezoelectric sensor for sensitive determination of metal ions based on the phosphate-modified dendrimer

    Science.gov (United States)

    Wang, S. H.; Shen, C. Y.; Lin, Y. M.; Du, J. C.

    2016-08-01

    Heavy metal ions arising from human activities are retained strongly in water; therefore public water supplies must be monitored regularly to ensure the timely detection of potential problems. A phosphate-modified dendrimer film was investigated on a quartz crystal microbalance (QCM) for sensing metal ions in water at room temperature in this study. The chemical structures and sensing properties were characterized by Fourier transform infrared spectroscopy and QCM measurement, respectively. This phosphate-modified dendrimer sensor can directly detect metal ions in aqueous solutions. This novel sensor was evaluated for its capacity to sense various metal ions. The sensor exhibited a higher sensitivity level and shorter response time to copper(II) ions than other sensors. The linear detection range of the prepared QCM based on the phosphate-modified dendrimer was 0.0001 ∼ 1 μM Cu(II) ions (R2 = 0.98). The detection properties, including sensitivity, response time, selectivity, reusability, maximum adsorption capacity, and adsorption equilibrium constants, were also investigated.

  6. Alkaline and alkaline earth metal phosphate halides and phosphors

    Science.gov (United States)

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  7. Metal-catalyzed double migratory cascade reactions of propargylic esters and phosphates.

    Science.gov (United States)

    Kazem Shiroodi, Roohollah; Gevorgyan, Vladimir

    2013-06-21

    Propargylic esters and phosphates are easily accessible substrates, which exhibit rich and tunable reactivities in the presence of transition metal catalysts. π-Acidic metals, mostly gold and platinum salts, activate these substrates for an initial 1,2- or 1,3-acyloxy and phosphatyloxy migration process to form reactive intermediates. These intermediates are able to undergo further cascade reactions leading to a variety of diverse structures. This tutorial review systematically introduces the double migratory reactions of propargylic esters and phosphates as a novel synthetic method, in which further cascade reaction of the reactive intermediate is accompanied by a second migration of a different group, thus offering a rapid route to a wide range of functionalized products. The serendipitous observations, as well as designed approaches involving the double migratory cascade reactions, will be discussed with emphasis placed on the mechanistic aspects and the synthetic utilities of the obtained products.

  8. Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction

    Directory of Open Access Journals (Sweden)

    Joel Sanchez

    2017-05-01

    Full Text Available Zirconium phosphate (ZrP, an inorganic layered nanomaterial, is currently being investigated as a catalyst support for transition metal-based electrocatalysts for the oxygen evolution reaction (OER. Two metal-modified ZrP catalyst systems were synthesized: metal-intercalated ZrP and metal-adsorbed ZrP, each involving Fe(II, Fe(III, Co(II, and Ni(II cations. Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the composite materials and confirm the incorporation of the metal cations either between the layers or on the surface of ZrP. Both types of metal-modified systems were examined for their catalytic activity for the OER in 0.1 M KOH solution. All metal-modified ZrP systems were active for the OER. Trends in activity are discussed as a function of the molar ratio in relation to the two types of catalyst systems, resulting in overpotentials for metal-adsorbed ZrP catalysts that were less than, or equal to, their metal-intercalated counterparts.

  9. Integrated process using non-stoichiometric sulfides or oxides of potassium for making less active metals and hydrocarbons

    International Nuclear Information System (INIS)

    Swanson, R.

    1984-01-01

    Disclosed is a combinative integrated chemical process using inorganic reactants and yielding, if desired, organic products. The process involves first the production of elemental potassium by the thermal or thermal-reduced pressure decomposition of potassium oxide or potassium sulfide and distillation of the potassium. This elemental potassium is then used to reduce ores or ore concentrates of copper, zinc, lead, magnesium, cadmium, iron, arsenic, antimony or silver to yield one or more of these less active metals in elemental form. Process potassium can also be used to produce hydrogen by reaction with water or potassium hydroxide. This hydrogen is reacted with potassium to produce potassium hydride. Heating the latter with carbon produces potassium acetylide which forms acetylene when treated with water. Acetylene is hydrogenated to ethene or ethane with process hydrogen. Using Wurtz-Fittig reaction conditions, the ethane can be upgraded to a mixture of hydrocarbons boiling in the fuel range

  10. The dynamics of the laser-induced metal-semiconductor phase transition of samarium sulfide (SmS)

    International Nuclear Information System (INIS)

    Kaempfer, Tino

    2009-01-01

    The present thesis is dedicated to the experimental study of the metal-semiconductor phase transition of samarium sulfide (SmS): Temperature- and time-resolved experiments on the characterization of the phase transition of mixed-valence SmS samples (M-SmS) are presented. The measurement of the dynamics of the laser-induced phase transition pursues via time-resolved ultrashort-time microscopy and by X-ray diffraction with sub-picosecond time resolution. The electronic and structural processes, which follow an excitation of M-SmS with infrared femtosecond laser pulses, are physically interpreted on the base of the results obtained in this thesis and model imaginations. [de

  11. Metallic Iron-Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media.

    Science.gov (United States)

    Long, Xia; Li, Guixia; Wang, Zilong; Zhu, HouYu; Zhang, Teng; Xiao, Shuang; Guo, Wenyue; Yang, Shihe

    2015-09-23

    We report on the synthesis of iron-nickel sulfide (INS) ultrathin nanosheets by topotactic conversion from a hydroxide precursor. The INS nanosheets exhibit excellent activity and stability in strong acidic solutions as a hydrogen evolution reaction (HER) catalyst, lending an attractive alternative to the Pt catalyst. The metallic α-INS nanosheets show an even lower overpotential of 105 mV at 10 mA/cm(2) and a smaller Tafel slope of 40 mV/dec. With the help of DFT calculations, the high specific surface area, facile ion transport and charge transfer, abundant electrochemical active sites, suitable H(+) adsorption, and H2 formation kinetics and energetics are proposed to contribute to the high activity of the INS ultrathin nanosheets toward HER.

  12. METHOD FOR ELECTROCHEMICAL PHOSPHATING OF METAL SURFACES, PARTICULARLY STAINLESS STEEL, AND APPLICATION OF AN AQUEOUS PHOSPHATING SOLUTION FOR SUCH A METHOD

    DEFF Research Database (Denmark)

    1998-01-01

    A method for electrochemical phosphating of metal surfaces, particularly stainless steel, in connection with cold forming of metal workpieces, which method provides the cold formed work-piece with a lubricant after phosphating, involves an electrochemical phosphating through a cathodic process...... applying an aqueous phosphating solution containing: 0.5 to 100 g Ca?2+¿/1, 0.5 to 100 g Zn?2+¿/1, 5 to 100 g PO¿4??3-¿/1, 0 to 100 g NO¿3??-¿/1, 0 to 100 g ClO¿3??-¿/1 and 0 to 50 g F?-¿ or Cl?-¿/1, by which the temperature of the solution is between 0 and 95 °C, the pH-value of the solution is between 0.......5 and 5, and the current density is between 0.1 and 250 mA/cm?2¿. This gives a good lubrication effect, a good adhesion to the metal surface, particularly stainless steel, and a more expedient texture than ordinary phosphating....

  13. Microkinetic interpretation of HDS/HYDO selectivity of the transformation of a model FCC gasoline over transition metal sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Daudin, A. [UMR CNRS 6503, Catalyse en Chimie Organique, Universite de Poitiers, Faculte des Sciences Fondamentales et Appliquees, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France); IFP-Lyon, Direction Catalyse et Separation, BP 3, 69390 Vernaison (France); Lamic, A.F.; Perot, G.; Brunet, S. [UMR CNRS 6503, Catalyse en Chimie Organique, Universite de Poitiers, Faculte des Sciences Fondamentales et Appliquees, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex (France); Raybaud, P. [IFP, Direction Chimie et Physico-Chimie Appliquees, 1-4 Av. de Bois Preau, 92858 Rueil Malmaison (France); IFP-Lyon, Direction Catalyse et Separation, BP 3, 69390 Vernaison (France); Bouchy, C. [IFP-Lyon, Direction Catalyse et Separation, BP 3, 69390 Vernaison (France)

    2008-01-15

    The conversion of a model FCC gasoline (composed of 2-methylthiophene (2MT), 2,3-dimethylbut-2-ene (23DMDB2N) and orthoxylene in n-heptane) under realistic hydrodesulfurization (HDS) conditions was investigated over a series of transition monometallic sulfides (Ni{sub 3}S{sub 2}, PdS, Co{sub 9}S{sub 8}, Rh{sub 2}S{sub 3}, RuS{sub 2}, PtS and MoS{sub 2}) and unsupported transition bimetallic sulfide catalysts (NiMoS and CoMoS). The results reveal for the first time that a volcano curve relationship exists between the ab initio calculated sulfur-metal bond energy, E(MS), descriptor of bulk TMS and their activities in olefin hydrogenation and in alkylthiophene desulfurization measured simultaneously. In particular, Rh{sub 2}S{sub 3} with an intermediate sulfur-metal bond energy of 119 kJ/mol is the most active catalyst in both case hydrogenation of the olefin and in HDS of a sulfur compound. Furthermore, the HDS/HYDO selectivity which is the most important parameter in the deep HDS of gasoline, presents a maximum for the NiMoS catalyst with E(MS) of 128 kJ/mol. A microkinetic model based on Broensted-Evans-Polanyi relationships and the competitive adsorption of the sulfur molecule and alkene on the catalytic site is proposed to give a rational interpretation of the experimental catalytic results. (author)

  14. Formation of carbonated hydroxyapatite films on metallic surfaces using dihexadecyl phosphate-LB film as template.

    Science.gov (United States)

    de Souza, Israel D; Cruz, Marcos A E; de Faria, Amanda N; Zancanela, Daniela C; Simão, Ana M S; Ciancaglini, Pietro; Ramos, Ana P

    2014-06-01

    Hydroxyapatite serves as a bioactive material for biomedical purposes, because it shares similarities with the inorganic part of the bone. However, how this material deposits on metallic surfaces using biomimetic matrices remains unclear. In this study, we deposited dihexadecyl phosphate, a phospholipid that bears a simple chemical structure, on stainless steel and titanium surfaces using the Langmuir-Blodgett (LB) technique; we employed the resulting matrix to grow carbonated hydroxyapatite. We obtained the calcium phosphate coating via a two-step process: we immersed the surfaces modified with the LB films into phosphate buffer, and then, we exposed the metal to a solution that simulated the concentration of ions in the human plasma. The latter step generated carbonated hydroxyapatite, the same mineral existing in the bone. The free energy related to the surface roughness and composition increased after we modified the supports. We investigated the film morphology by scanning electron and atomic force microscopies and determined surface composition by infrared spectroscopy and energy dispersive X-ray. We also studied the role of the surface roughness and the surface chemistry on cell viability. The surface-modified Ti significantly increased osteoblastic cells proliferation, supporting the potential use of these surfaces as osteogenic materials. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Metal immobilization and phosphorus leaching after stabilization of pyrite ash contaminated soil by phosphate amendments.

    Science.gov (United States)

    Zupančič, Marija; Lavrič, Simona; Bukovec, Peter

    2012-02-01

    In this study we would like to show the importance of a holistic approach to evaluation of chemical stabilization using phosphate amendments. An extensive evaluation of metal stabilization in contaminated soil and an evaluation of the leaching of phosphorus induced after treatment were performed. The soil was highly contaminated with Cu (2894 mg kg(-1)), Zn (3884 mg kg(-1)), As (247 mg kg(-1)), Cd (12.6 mg kg(-1)) and Pb (3154 mg kg(-1)). To immobilize the metals, mixtures of soil with phosphate (from H(3)PO(4) and hydroxyapatite (HA) with varying ratios) were prepared with a constant Pb : P molar ratio of 1: 10. The acetic acid extractable concentration of Pb in the mixture with the highest amount of added phosphoric acid (n(H(3)PO(4)) : n(HA) = 3 : 1) was reduced to 1.9% (0.62 mg L(-1)) of the extractable Pb concentration in the untreated soil, but the content of water extractable phosphorus in the samples increased from 0.04 mg L(-1) in the untreated soil sample up to 14.3 mg L(-1) in the same n(H(3)PO(4)) : n(HA) = 3 : 1 mixture. The high increase in arsenic mobility was also observed after phosphate addition. The PBET test showed phosphate induced reduction in Pb bioavailability. In attempting to stabilize Pb in the soil with the minimum treatment-induced leaching of phosphorus, it was found that a mixture of soil with phosphate addition in the molar ratio of H(3)PO(4) : HA of 0.75 : 1 showed the most promising results, with an acetic acid extractable Pb concentration of 1.35 mg L(-1) and a water extractable phosphorus concentration of 1.76 mg L(-1). The time-dependent leaching characteristics of metals and phosphorus for this mixture were evaluated by a column experiment, where irrigation of the soil mixture with the average annual amount of precipitation in Slovenia (1000 mm) was simulated. The phosphorus concentration in the leachates decreased from 2.60 mg L(-1) at the beginning of irrigation to 1.00 mg L(-1) at the end.

  16. Zirconium-based metal organic frameworks: Highly selective adsorbents for removal of phosphate from water and urine

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Kun-Yi Andrew, E-mail: linky@nchu.edu.tw [Department of Environmental Engineering, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung, Taiwan (China); Chen, Shen-Yi [Department of Environmental Engineering, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung, Taiwan (China); Jochems, Andrew P. [New Mexico Bureau of Geology & Mineral Resources and New Mexico Institute of Mining & Technology, Socorro, NM (United States)

    2015-06-15

    Phosphate is one of the most concerning compounds in wastewater streams and a main nutrient that causes eutrophication. To eliminate the phosphate pollution, Metal Organic Frameworks (MOFs) are proposed in this study as adsorbents to remove phosphate from water. The zirconium-based MOF, UiO-66, was selected as representative MOF given its exceptional stability in water. To investigate the effect of an amine functional group, UiO-66-NH2 was also prepared using an amine-substituted ligand. The adsorption kinetics and isotherm reveal that UiO-66-NH2 exhibited higher adsorption capacities than UiO-66 possibly due to the amine group. However, the interaction between phosphate and zirconium sites of UiO MOFs might be the primary factor accounting for the phosphate adsorption to UiO MOFs. UiO MOFs also exhibited a high selectivity towards phosphate over other anions such as bromate, nitrite and nitrate. Furthermore, UiO MOFs were found to adsorb phosphate and to completely remove diluted phosphate in urine. We also found that UiO MOFs could be easily regenerated and re-used for phosphate adsorption. These findings suggest that UiO MOFs can be effective and selective adsorbents to remove phosphate from water as well as urine. - Highlights: • UiO-66 as the first type of MOFs was used to remove phosphate from water and urine. • The amine group in UiO MOFs was found to enhance the phosphate adsorption. • UiO-66 exhibited a high adsorption selectivity towards phosphate over other anions. • UiO-66 could be easily regenerated and re-used with 85% regeneration efficiency.

  17. Magmatic Hydrothermal Fluids: Experimental Constraints on the Role of Magmatic Sulfide Crystallization and Other Early Magmatic Processes in Moderating the Metal Content of Ore-Forming Fluids

    Science.gov (United States)

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

    2006-05-01

    It has been recognized for some time that sulfide phases, although common in intermediate-felsic volcanic rocks, are not as common in their plutonic equivalents. That sulfide crystallization, or the lack thereof, is important in the protracted magmatic history of porphyry Cu and related systems is supported by the work of e.g., Rowins (2000). Candela and Holland (1986) suggested that sulfide crystallization could moderate the ore metal concentrations in porphyry environments. Experiments show clearly that Au and Cu can partition into Cl-bearing vapor and brine. This effect can be enhanced by S (Simon, this session). However, in some instances enhances this effect. That is, the partitioning of Au and Cu into vapor+brine is highly efficient (e.g. Simon et al. 2003; Frank et al 2003). This suggests that if sulfides do not sequester ore metals early during the history of a magma body from the melt, they will partition strongly into the volatile phases. Whether volatile release occurs in the porphyry ore environment, or at deeper levels upon magma rise, is a yet unsolved question. Little is known about deep release of volatiles (during magma transport at lower- to mid-crustal levels). Saturation of melts with a CO2-bearing fluid could happen at levels much deeper than those typical of ore formation. CO2 is released preferentially, so a high CO2 concentration in fluids in the porphyry ore environment argues against deep fluid release. Of course, this depends upon the specific processes of crystallization and fluid release, which may be complex. Our experiments on sulfides have concentrated on pyrrhotite and Iss. Our partitioning data for Po/melt exhibit wide variations from metal to metal: Cu (2600); Co (170); Au (140); Ni (100); Bi, Zn and Mn (2). These results suggest that crystallization of Po can contribute to variable ore metal ratios (e.g. Cu/Au). Other sulfides behave differently. If a melt is Iss (Cpy) saturated, then Cu will be buffered at a high value, and Au

  18. MINE WASTE TECHNOLOGY PROGRAM; PHOSPHATE STABILIZATION OF HEAVY METALS CONTAMINATED MINE WASTE YARD SOILS, JOPLIN, MISSOURI NPL SITE

    Science.gov (United States)

    This document summarizes the results of Mine Waste Technology Project 22-Phosphate Stabilization of Heavy Metals-Contaminated Mine Waste Yard Soils. Mining, milling, and smelting of ores near Joplin, Missouri, have resulted in heavy metal contamination of the area. The Joplin s...

  19. Osseoconductive and Corrosion-Inhibiting Plasma-Sprayed Calcium Phosphate Coatings for Metallic Medical Implants

    Directory of Open Access Journals (Sweden)

    Robert B. Heimann

    2017-11-01

    Full Text Available During the last several decades, research into bioceramic coatings for medical implants has emerged as a hot topic among materials scientists and clinical practitioners alike. In particular, today, calcium phosphate-based bioceramic materials are ubiquitously used in clinical applications to coat the stems of metallic endoprosthetic hips as well as the surfaces of dental root implants. Such implants frequently consist of titanium alloys, CoCrMo alloy, or austenitic surgical stainless steels, and aim at replacing lost body parts or restoring functions to diseased or damaged tissues of the human body. In addition, besides such inherently corrosion-resistant metals, increasingly, biodegradable metals such as magnesium alloys are being researched for osseosynthetic devices and coronary stents both of which are intended to remain in the human body for only a short time. Biocompatible coatings provide not only vital biological functions by supporting osseoconductivity but may serve also to protect the metallic parts of implants from corrosion in the aggressive metabolic environment. Moreover, the essential properties of hydroxylapatite-based bioceramic coatings including their in vitro alteration in contact with simulated body fluids will be addressed in this current review paper. In addition, a paradigmatic shift is suggested towards the development of transition metal-substituted calcium hexa-orthophosphates with the NaSiCON (Na superionic conductor structure to be used for implant coatings with superior degradation resistance in the corrosive body environment and with pronounced ionic conductivity that might be utilized in novel devices for electrical bone growth stimulation.

  20. Nanoparticle-based immunosensor with apoferritin templated metallic phosphate label for quantification of phosphorylated acetylcholinesterase

    Energy Technology Data Exchange (ETDEWEB)

    Du, Dan; Chen, Aiqiong; Xie, Yunying; Zhang, Aidong; Lin, Yuehe

    2011-05-15

    A new sandwich-like electrochemical immunosensor has been developed for quantification of organophosphorylated acetylcholinesterase (OP-AChE), an exposure biomarker of organophosphate pesticides and nerve agents. Zirconia nanoparticles (ZrO2 NPs) were anchored on a screen printed electrode (SPE) to preferably capture OP-AChE adducts by metal chelation with phospho-moieties, which was selectively recognized by lead phosphate-apoferritin labeled anti-AChE antibody (LPA-anti-AChE). The sandwich-like immunoreactions were performed among ZrO2 NPs, OP-AChE and LPA-anti-AChE to form ZrO2/OP-AChE/LPA-anti-AChE complex and the released lead ions were detected on a disposable SPE. The binding affinity was investigated by both square wave voltammetry (SWV) and quartz crystal microbalance (QCM) measurements. The proposed immunosensor yielded a linear response current over a broad OP-AChE concentrations range from 0.05 nM to 10 nM, with detection limit of 0.02 nM, which has enough sensitivity for monitoring of low-dose exposure to OPs. This method avoids the drawback of unavailability of commercial OP-specific antibody as well as amplifies detection signal by using apoferritin encoded metallic phosphate nanoparticle tags. This nanoparticle-based immunosensor offers a new method for rapid, sensitive, selective and inexpensive quantification of phosphorylated adducts for monitoring of OP pesticides and nerve agents exposures.

  1. An alternative approach to recovering valuable metals from zinc phosphating sludge.

    Science.gov (United States)

    Kuo, Yi-Ming

    2012-01-30

    This study used a vitrification process (with good potential for commercialization) to recover valuable metals from Zn phosphating sludge. The involved vitrification process achieves two major goals: it transformed hazardous Zn phosphating sludge into inert slag and it concentrated Fe (83.5%) and Zn (92.8%) into ingot and fine particulate-phase material, respectively. The Fe content in the ingot was 278,000 mg/kg, making the ingot a potential raw material for iron making. The fine particulate-phase material (collected from flue gas) contained abundant Zn (544,000 mg/kg) in the form of ZnO. The content (67.7%) of ZnO was high, so it can be directly sold to refineries. The recovered coarse particulate-phase material, with insufficient amount of ZnO, can be recycled as a feeding material for Zn re-concentration. Therefore, the vitrification process can not only treat hazardous materials but also effectively recover valuable metals. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Nanoparticle-based immunosensor with apoferritin templated metallic phosphate label for quantification of phosphorylated acetylcholinesterase

    International Nuclear Information System (INIS)

    Du, Dan; Chen, Aiqiong; Xie, Yunying; Zhang, Aidong; Lin, Yuehe

    2011-01-01

    A new sandwich-like electrochemical immunosensor has been developed for quantification of organophosphorylated acetylcholinesterase (OP-AChE), an exposure biomarker of organophosphate pesticides and nerve agents. Zirconia nanoparticles (ZrO2 NPs) were anchored on a screen printed electrode (SPE) to preferably capture OP-AChE adducts by metal chelation with phospho-moieties, which was selectively recognized by lead phosphate-apoferritin labeled anti-AChE antibody (LPA-anti-AChE). The sandwich-like immunoreactions were performed among ZrO2 NPs, OP-AChE and LPA-anti-AChE to form ZrO2/OP-AChE/LPA-anti-AChE complex and the released lead ions were detected on a disposable SPE. The binding affinity was investigated by both square wave voltammetry (SWV) and quartz crystal microbalance (QCM) measurements. The proposed immunosensor yielded a linear response current over a broad OP-AChE concentrations range from 0.05 nM to 10 nM, with detection limit of 0.02 nM, which has enough sensitivity for monitoring of low-dose exposure to OPs. This method avoids the drawback of unavailability of commercial OP-specific antibody as well as amplifies detection signal by using apoferritin encoded metallic phosphate nanoparticle tags. This nanoparticle-based immunosensor offers a new method for rapid, sensitive, selective and inexpensive quantification of phosphorylated adducts for monitoring of OP pesticides and nerve agents exposures.

  3. The effect of heavy metals and other environmental conditions on the anaerobic phosphate metabolism of Acinetobacter johnsonii.

    Science.gov (United States)

    Boswell, C D; Dick, R E; Macaskie, L E

    1999-07-01

    A strain of Acinetobacter with potential for bioremediation of heavy metal-contaminated waters was isolated from a wastewater-treatment plant operating an enhanced biological phosphate removal process. NMR and extractive methods showed that polyphosphate accumulated aerobically was degraded under anaerobic conditions both in the presence and absence of cadmium or uranium (0.2-0.5 mM). NMR showed that free phosphate was formed at the expense of polyphosphate, and an extractive technique indicated that this reaction could be stimulated by the presence of UO(2)2+ under these conditions. Energy-dispersive X-ray microanalysis demonstrated that only cadmium could enter the cells, and co-localized with intra-cellular granules containing phosphate and other divalent metals. The effects of other environmental parameters on the anaerobic phosphate metabolism were also investigated. Between pH 5.5 and 8.0, phosphate release increased with increasing pH. Between 4 degrees C and 37 degrees C, phosphate release increased with increasing temperature. The presence of nitrate at concentrations of 10 mM and above inhibited anoxic phosphate release, but supplying tungstate in the growth medium prior to anoxic incubation reduced the production of active nitrate reductase and alleviated this effect.

  4. Electrosprayed Metal Oxide Semiconductor Films for Sensitive and Selective Detection of Hydrogen Sulfide

    NARCIS (Netherlands)

    Ghimbeu, C.M.; Lumbreras, M.; Schoonman, J.; Siadat, M.

    2009-01-01

    Semiconductor metal oxide films of copper-doped tin oxide (Cu-SnO2), tungsten oxide (WO3) and indium oxide (In2O3) were deposited on a platinum coated alumina substrate employing the electrostatic spray deposition technique (ESD). The morphology studied with scanning electron microscopy (SEM) and

  5. Metal recovery by bioleaching of sulfidic mining wastes — Application to a European case study

    Science.gov (United States)

    Guézennec, A. G.; Jacob, J.; Joulian, C.; Dupraz, S.; Menard, Y.; d'Hugues, P.

    The non-energy extractive industry (NEEI) of the EU-25 generated a direct turnover of about €40 billion, and provided employment to about 250000 people in 16629 companies in 2004. The use of primary raw materials in the production of other branches of EU industry means they have a central role in guaranteeing industrial and economic sustainability. Nevertheless current demand exceeds production, and so the EU is heavily dependent on minerals and metals imports. In this context of securing access to metals, turning mining wastes into new resources of currently unexploited valuable metals is an important challenge. The mining wastes can contain base and precious metals, but also metalloids and rare earth elements that are nowadays considered as highly critical for the industrial development of the European Union. Nevertheless, the development of alternative routes to conventional processing is still required in order to decrease the cost associated to the treatment of these unconventional resources which are more complex in composition and with lower grades.

  6. Competitive immobilization of Pb in an aqueous ternary-metals system by soluble phosphates with varying pH.

    Science.gov (United States)

    Zhang, Zhuo; Ren, Jie; Wang, Mei; Song, Xinlai; Zhang, Chao; Chen, Jiayu; Li, Fasheng; Guo, Guanlin

    2016-09-01

    Chemical immobilization by phosphates has been widely and successfully applied to treat Pb in wastewater and contaminated soils. Pb in wastewaters and soils, however, always coexists with other heavy metals and their competitive reactions with phosphates have not been quantitatively and systematically studied. In this approach, immobilization of Pb, Zn, and Cd by mono-, di-, and tripotassium phosphate (KH2PO4, K2HPO4, and K3PO4) was observed in the single- and ternary-metals solutions. The immobilization rates of the three metals were determined by the residual concentration. The mineral composition and structure of the precipitates were characterized by powder X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The results indicated that competitive reaction occurred in Pb-Zn-Cd ternary system, with immobilization rates decrease of system. The reaction of Pb with three phosphates exhibited intense competitiveness and the phosphates had a stronger affinity for Pb when Cl(-) was added. Pb-phosphate minerals formed by KH2PO4 with the better crystalline characteristics and largest size were very stable with a low dissolution rate (system. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Physicochemical characteristics and sorption capacities of heavy metal ions of activated carbons derived by activation with different alkyl phosphate triesters

    Science.gov (United States)

    Wang, Jing; Liu, Hai; Yang, Shaokun; Zhang, Jian; Zhang, Chenglu; Wu, Haiming

    2014-10-01

    Five alkyl phosphate triesters (APTEs), including trimethyl phosphate (TMP), triethyl phosphate (TEP), triisopropyl phosphate (TPP), tributyl phosphate (TBP) and trioctyl phosphate (TOP), were used as activating agents for preparing activated carbons (AC-APTEs) with high surface acidity and metal ion sorption capacity. N2 adsorption/desorption isotherms, surface morphologies, elemental compositions, results of Boehm's titration and sorption capacities of heavy metal ions of the carbons were investigated. AC-APTEs contained much more acidic groups and exhibited much less surface area (phosphoric acid activation. For the AC-APTEs, AC-TOP had the highest surface area (488 m2/g), AC-TMP showed the highest yield (41.1%), and AC-TBP possessed the highest acidic groups (2.695 mmol/g), oxygen content (47.0%) and metal ion sorption capacities (40.1 mg/g for Ni(II) and 53.5 mg/g for Cd(II)). For the carbons, AC-APTEs showed much larger Ni(II) and Cd(II) sorption capacities than AC-PPA, except AC-TPP. The differences of the carbons in the physicochemical and sorption properties suggested surface chemistry of the carbons was the main factor influencing their sorption capacities whereas the pore structure played a secondary role.

  8. Structural study of high temperature metal-rich titanium sulfide phases

    Energy Technology Data Exchange (ETDEWEB)

    Owens, J.P.

    1979-01-01

    Ti/sub 2/S and Ti/sub 8/S/sub 3/ have been prepared by high temperature annealing techniques. The crystal structures of these two phases have been determined from single crystal x-ray diffraction data. Both structures were refined using a full-matrix least-squares treatment of positional parameters and isotropic temperature factor coefficients. Ti/sub 2/S crystallizes with orthorhombic symmetry, space group Pnnm, having unit cell dimensions a = 11.367A, b= 14.060A, and c = 3.326A. Ti/sub 2/S is isostructural with Ta/sub 2/P. Ti/sub 8/S/sub 3/ crystallizes with monoclinic symmetry, space group C2/m, a = 32.69A, b = 3.327A, c = 19.35A, ..beta.. = 139.9/sup 0/ (b - unique). Ti/sub 2/S and Ti/sub 8/S/sub 3/ have structural features similar to the features of a large number of metal-rich transition-metal chalcogenides and pnictides. These various structure types have been characterized in terms of nonmetal trigonal prismatic coordination polyhedra, eight different metal partial coordination polyhedra, a short (approximately equal to 3.4A) crystallographic axis, two unique layers of atoms containing both metal and nonmetal atom positions, and mirror planes coincident with the two layers of atom positions. The existence of a variety of structures with these structural features has led to their consideration as a unique structural class. The structural similarities and differences between the structure types of this class have been discussed in detail. Comparison of different structure types emphasized the importance of the metal bonding contribution in understanding the structural features and suggested limitations on qualitative bonding models used to understand the structural-chemical principles underlying structure stability.

  9. Selective heavy metals removal from waters by amorphous zirconium phosphate: behavior and mechanism.

    Science.gov (United States)

    Pan, Bingcai; Zhang, Qingrui; Du, Wei; Zhang, Weiming; Pan, Bingjun; Zhang, Qingjian; Xu, Zhengwen; Zhang, Quanxing

    2007-07-01

    Selective removal of heavy metals from water has been of considerable concern for several decades. In the present study, the amorphous zirconium phosphate (ZrP) was synthesized and characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron micrography (SEM), thermogravimetric analysis (TGA) as well as pH-titration experiments. Uptake of heavy metals including lead, cadmium, and zinc onto ZrP was studied by using a polystyrene sulfonic-acid exchanger D-001 as a reference sorbent and Ca(2+) as a competing cation due to its ubiquity in natural or industrial waters. The results indicated that the uptake of heavy metals onto ZrP is essentially an ion-exchange process and dependent upon solution pH. In comparison with D-001, ZrP exhibited more favorable sorption of heavy metals particularly in terms of high selectivity, as indicated by the distribution coefficients of ZrP even several orders higher than D-001 towards heavy metals when calcium ion coexisted at a high level in solution. The Fourier transform-infrared (FT-IR) spectroscopic investigation indicated that the uptake of calcium, cadmium, and zinc ions onto ZrP is only driven by the electrostatic interaction, while that of lead ion is possibly dependent upon the inner-sphere complex formation with ZrP. XPS results further elucidated that ZrP displays different sorption affinity towards heavy metals in the same order as selectivity sequence of Pb(2+)>Zn(2+) approximately Cd(2+)>Ca(2+), which can be explained by hard and soft acids and bases (HASB) theory. Moreover, uptake of heavy metals onto ZrP approached to equilibrium quickly and the used ZrP could be readily regenerated for reuse by the dilute HCl solution. Thus, all the results suggest that amorphous ZrP has excellent potential as a sorption material for water treatment.

  10. Comprehensive recovery of gold and base-metal sulfide minerals from a low-grade refractory ore

    Science.gov (United States)

    Li, Wen-juan; Liu, Shuang; Song, Yong-sheng; Wen, Jian-kang; Zhou, Gui-ying; Chen, Yong

    2016-12-01

    The comprehensive recovery of small amounts of valuable minerals such as gold and base-metal sulfide minerals from a low-grade refractory ore was investigated. The following treatment strategy was applied to a sample of this ore: gold flotation-gold concentrate leaching-lead and zinc flotation from the gold concentrate leaching residue. Closed-circuit trials of gold flotation yielded a gold concentrate that assayed at 40.23 g·t-1 Au with a recovery of 86.25%. The gold concentrate leaching rate was 98.76%. Two variants of lead-zinc flotation from the residue—preferential flotation of lead and zinc and bulk flotation of lead and zinc—were tested using the middling processing method. Foam from the reflotation was returned to the lead rougher flotation or lead-zinc bulk flotation, whereas middlings from reflotation were discarded. Sulfur concentrate was a byproduct. The combined strategy of flotation, leaching, and flotation is recommended for the treatment of this kind of ore.

  11. A nanoscale Zr-based fluorescent metal-organic framework for selective and sensitive detection of hydrogen sulfide

    Science.gov (United States)

    Li, Yanping; Zhang, Xin; Zhang, Ling; Jiang, Ke; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2017-11-01

    Hydrogen sulfide (H2S) has been commonly viewed as a gas signaling molecule in various physiological and pathological processes. However, the highly efficient H2S detection still remains challenging. Herein, we designed a new robust nano metal-organic framework (MOF) UiO-66-CH=CH2 as a fluorescent probe for rapid, sensitive and selective detection of biological H2S. UiO-66-CH=CH2 was prepared by heating ZrCl4 and 2-vinylterephthalic acid via a simple method. UiO-66-CH=CH2 displayed fluorescence quenching to H2S and kept excellent selectivity in the presence of biological relevant analytes especially the cysteine and glutathione. This MOF-based probe also exhibited fast response (10 s) and high sensitivity with a detection limit of 6.46 μM which was within the concentration range of biological H2S in living system. Moreover, this constructed MOF featured water-stability, nanoscale (20-30 nm) and low toxicity, which made it a promising candidate for biological H2S sensing.

  12. Optimizing the modification of wood waste biochar via metal oxides to remove and recover phosphate from human urine.

    Science.gov (United States)

    Xu, Kangning; Zhang, Chuke; Dou, Xiaomin; Ma, Weifang; Wang, Chengwen

    2017-05-26

    The recovery of phosphate from human urine has been considered as one of the most attractive benefits of urine source separation because P is an essential but limited macronutrient. This study investigated the approach to modify wood waste biochar via metal oxides aiming to recover phosphate from human urine to produce a value-added biochar. Results showed the phosphate removal ability was enhanced for the modified biochar pre-treated in modification solutions of MgCl 2 , AlCl 3 , CaCl 2 and FeCl 3 , respectively, while natural biochar released phosphate to urine. Among the tested biochar, Mg-biochar presented the best capacity for phosphate removal from the hydrolyzed urine, reaching 118 mg P  g -1 at a MgCl 2 concentration of 2.3 M. However, higher MgCl 2 concentration would not further increase the adsorption capacity. Fitting of the adsorption kinetics and isotherms indicated that the phosphate removal process was probably controlled by multiple mechanisms. Both the experimental and fitting results confirmed that the content of Mg oxides was the key factor determining the adsorption rate and capacity of phosphate on Mg-biochar. pH ranges of 7-9 and the ammonium concentration higher than 108 mg N  L -1 enhanced the phosphate adsorption capacity. As such, the Mg-biochar was more favored for the treatment of hydrolyzed urine rather than fresh urine with acidic pH and lower concentration of ammonium. Further calculations were carried out using the Langmuir model to evaluate the removal of phosphate and the product. Results indicate that it is an effective technique to use Mg-biochar for phosphate removal from hydrolyzed urine and it yields phosphate-enriched biochar products.

  13. Band gap tuning and fluorescence properties of lead sulfide Pb0.9A0.1S (A: Fe, Co, and Ni) nanoparticles by transition metal doping

    Science.gov (United States)

    Parveen, Azra; Agrawal, Shraddha; Azam, Ameer

    2018-02-01

    Transition metal-doped lead sulfide nanoparticles (PbS-NPs) were synthesized by co-precipitation method. The crystallite phase and morphological studies were carried out by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Optical studies were performed by UV-Visible absorption, fluorescence emission spectroscopy and Fourier transforms infrared spectroscopy (FTIR). XRD analysis reveals that the pure and transition metal-doped PbS- NPs have a single crystalline phase with cubic structure devoided of any other secondary phase. The notable effect on optical absorbance and band gap was observed with transition metal doping in lead sulphide. The optical energy band gap values were found to increase with the doping of transition metal. UV-Visible absorption and fluorescence emission spectra display a blue shift with subsequent transition metal doping which may arise due to quantum confinement effect making it worth for having applications in optoelectronic devices.

  14. Fractionation of rhenium from osmium during noble metal alloy formation in association with sulfides: Implications for the interpretation of model ages in alloy-bearing magmatic rocks

    Science.gov (United States)

    Fonseca, Raúl O. C.; Brückel, Karoline; Bragagni, Alessandro; Leitzke, Felipe P.; Speelmanns, Iris M.; Wainwright, Ashlea N.

    2017-11-01

    Although Earth's continental crust is thought to derive from melting of the Earth's mantle, how the crust has formed and the timing of its formation are not well understood. The main difficulty in understanding how the crust was extracted from the Earth's mantle is that most isotope systems recorded in mantle rocks have been disturbed by crustal recycling, metasomatic activity and dilution of the signal by mantle convection. In this regard, important age constraints can be obtained from Re-Os model ages in platinum group minerals (PGM), as Re-poor and Os-rich PGM show evidence of melting events up to 4.1 Ga. To constrain the origin of the Re-Os fractionation and Os isotope systematics of natural PGM, we have investigated the linkage between sulfide and PGM grains of variable composition via a series of high-temperature experiments carried out at 1 bar. We show that with the exception of laurite, all experimentally-produced PGM, in particular Pt3Fe (isoferroplatinum) and Pt-Ir metal grains, are systematically richer in Re than their sulfide precursors and will develop radiogenic 187Os /188Os signatures over time relative to their host base metal sulfides. Cooling of an PGM-saturated sulfide assemblage shows a tendency to amplify the extent of Re-Os fractionation between PGM and the different sulfide phases present during cooling. Conversely, laurite grains (RuS2) are shown to accept little to no Re in them and their Os isotope composition changes little over time as a result. Laurite is therefore the PGM that provides the most robust Re-depletion ages in mantle lithologies. Our results are broadly consistent with observations made on natural PGM, where laurites are systematically less radiogenic than Pt-rich PGM. These experimental results highlight the need for the acquisition of large datasets for both mantle materials and ophiolite-derived detrital grains that include measurements of the Os isotope composition of minerals rich in highly siderophile elements at

  15. Bad-metal-layered sulfide oxide CsV{sub 2}S{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Valldor, Martin; Merz, Patrick; Prots, Yurii; Schnelle, Walter [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)

    2016-01-15

    Through a solid-state reaction between stoichiometric amounts of a mixed cesium oxide Cs{sub 2}O{sub 1.3}, VS, S, and V{sub 2}O{sub 5}, a polycrystalline powder of CsV{sub 2}S{sub 2}O was obtained. Small single crystals could be grown in a CsCl melt by allowing Cs{sub 2}SO{sub 4}, V metal and S powders to react. The crystals have a plate-like morphology, consistent with the tetragonal crystal-structure symmetry [P4/mmm, a = 3.9455(1), c = 7.4785(1) Aa]. Magnetic measurements suggest that CsV{sub 2}S{sub 2}O is a temperature-independent paramagnet, and resistivity data concur with a bad metal. The mixed oxidation state of V on one crystallographic site offers a tentative explanation of the electronic properties of the title compound. (Abstract Copyright, Wiley Periodicals, Inc.)

  16. SHI irradiation of metal doped zinc sulfide polymer nanocomposites synthesized using micro emulsion method

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Satyendra [Department of Applied Physics, School of Physical Sciences, Babasaheb Bhimrao Ambedkar University, Lucknow 226025 (India); Singh, Paramjit [University School of Basics and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110078 (India); Sonkawade, R.G. [Inter University Aceelerator Centre, New Delhi 110067 (India); Awasthi, Kamlendra [Department of Physics, Malaviya National Institute of Technology, Jaipur 302017 (India); Kumar, Rajesh, E-mail: rajeshkumaripu@gmail.com [University School of Basics and Applied Sciences, Guru Gobind Singh Indraprastha University, New Delhi 110078 (India)

    2015-09-01

    The metal doped ZnS nanoparticles dispersed in polystyrene were synthesized using micro emulsion method. The synthesized free standing nanocomposites films of 18 μm thickness were irradiated with 60 MeV nickel ions at two different fluences for the modification of structural, optical and chemical properties. The pristine and irradiated samples were characterized by X-ray diffraction, UV–visible and FTIR spectrophotometer. The SEM and XRD results confirmed the synthesis of nanoparticles. The ion irradiation shifted the optical absorption towards higher wavelength and decreased the band gap energy to significant levels. The infrared band at 465 cm{sup −1} confirmed the Zn–S bonding. The intensity of other absorption bands was modified after ion irradiation.

  17. Effect of Incorporating Nanoporous Metal Phosphate Materials on the Compressive Strength of Portland Cement

    Directory of Open Access Journals (Sweden)

    Glen E. Fryxell

    2008-03-01

    Full Text Available Nanoporous metal phosphate (NP-MPO materials are being developed for removal of contaminant oxyanions (As(OHO32−, CrO42−, and TcO4−, and cations (mercury, cadmium, and lead from water and waste streams. Following sequestration, incorporation of metal laden NP-MPOs as a portion of cement formulation would provide an efficient and low-cost way to immobilize metal laden NP-MPOs in an easily handled waste form suitable for permanent disposal. There are no known investigations regarding the incorporation of NP-MPOs in concrete and the effects imparted on the physical and mechanical properties of concrete. Results of this investigation demonstrated that incorporating of NP-MPO materials requires additional water in the concrete formulation which decreases the compressive strength. Thus, incorporation of NP-MPOs in concrete may not serve as an efficient means for long-term disposal.

  18. Highly selective capture of phosphate ions from water by a water stable metal-organic framework modified with polyethyleneimine.

    Science.gov (United States)

    Qiu, Hui; Yang, Luyang; Liu, Fengling; Zhao, Yunxia; Liu, LeLe; Zhu, Jinhong; Song, Mingxia

    2017-10-01

    In this work, a series of polyethyleneimine (PEI) impregnated metal-organic framework (UiO-66) with varying PEI loadings were prepared and applied as sorbents to capture phosphate ions from water. As indicated by SEM and XRD analysis, PEI was dispersed on the outer surface and the inner pores of UiO-66. At 9.45% PEI loadings (UiO-66-3), the saturated adsorption capacity of phosphate reached 73.15 mg P/g at 298 K, which is superior to most sorbents ever reported. UiO-66-3 could sequestrate phosphate over a wide pH range from 2.0 to 7.0 with high efficiency. The sorption toward phosphate reached equilibrium in 50 min. Unlike commercial anion exchanger IRA-900, UiO-66-3 still exhibited high removal toward phosphate even large amount of coexisted anions were present. Successive sorption assay demonstrated that the removal efficiency of UiO-66-3 toward phosphate remained constant after six cyclic runs. All the above results indicated the great potential of UiO-66-3 as a promising sorbent for the decontamination of water from phosphate.

  19. Effects of sediment resuspension on the oxidation of acid-volatile sulfides and release of metals (iron, manganese, zinc) in Pescadero estuary (CA, USA).

    Science.gov (United States)

    Richards, Chandra M; van Puffelen, Jasper L; Pallud, Céline

    2017-11-23

    Bar-built estuaries are unique ecosystems characterized by the presence of a sandbar barrier, which separates the estuary from the ocean for extended periods and can naturally reopen to the ocean with heavy rainfall and freshwater inflows. The physical effects associated with the transition from closed to open state, specifically water mixing and sediment resuspension, often indirectly worsen water quality conditions and are suspected to drive near-annual fish kills at the Pescadero estuary in northern California. The effects of sediment acid-volatile sulfide (AVS) oxidation, specifically oxygen depletion, acidification, and metal release, are believed to aggravate water conditions for fish but remain poorly understood. We performed slurry incubations containing sediment from 4 sites in the Pescadero estuary, representing a gradient from the Pacific Ocean to freshwater tributaries. We measured near-maximum rates of aqueous hydrogen sulfide oxidation, sediment AVS oxidation, sulfate production, and acidification, as well as near-maximum release rates of iron (Fe), manganese (Mn), and zinc (Zn) to the water column. We estimated AVS oxidation rates of 8 to 21 mmol S kg -1  d -1 , which were 3 orders of magnitude higher than aqueous hydrogen sulfide oxidation rates, 6 to 26 μmol S kg -1  d -1 . We suggest that aqueous hydrogen sulfide cannot be responsible for the observed kills because of low concentrations and minimal oxidative effects on pH and metal concentrations. However, the oxidative effects of AVS are potentially severe, decreasing pH to strongly acidic levels and releasing aqueous Fe, Mn, and Zn concentrations up to 11.2 mM, 0.46 mM, and 88 μM, respectively, indicating a potential role in worsening water conditions for fish in the Pescadero estuary. Environ Toxicol Chem 2018;9999:1-14. © 2017 SETAC. © 2017 SETAC.

  20. Partitioning of U, Th and K Between Metal, Sulfide and Silicate, Insights into the Volatile-Content of Mercury

    Science.gov (United States)

    Habermann, M.; Boujibar, A.; Righter, K.; Danielson, L.; Rapp, J.; Righter, M.; Pando, K.; Ross, D. K.; Andreasen, R.; Chidester, B.

    2016-01-01

    During the early stages of the Solar System formation, especially during the T-Tauri phase, the Sun emitted strong solar winds, which are thought to have expelled a portion of the volatile elements from the inner solar system. It is therefore usually believed that the volatile depletion of a planet is correlated with its proximity to the Sun. This trend was supported by the K/Th and K/U ratios of Venus, the Earth, and Mars. Prior to the MESSENGER mission, it was expected that Mercury is the most volatile-depleted planet. However, the Gamma Ray Spectrometer of MESSENGER spacecraft revealed elevated K/U and K/Th ratios for the surface of Mercury, much higher than previous expectations. It is possible that the K/Th and K/U ratios on the surface are not a reliable gauge of the bulk volatile content of Mercury. Mercury is enriched in sulfur and is the most reduced of the terrestrial planets, with oxygen fugacity (fO2) between IW-6.3 and IW-2.6 log units. At these particular compositions, U, Th and K behave differently and can become more siderophile or chalcophile. If significant amounts of U and Th are sequestered in the core, the apparent K/U and K/Th ratios measured on the surface may not represent the volatile budget of the whole planet. An accurate determination of the partitioning of these elements between silicate, metal, and sulfide phases under Mercurian conditions is therefore essential to better constrain Mercury's volatile content and assess planetary formation models.

  1. Electrosprayed metal oxide semiconductor films for sensitive and selective detection of hydrogen sulfide.

    Science.gov (United States)

    Ghimbeu, Camelia Matei; Lumbreras, Martine; Schoonman, Joop; Siadat, Maryam

    2009-01-01

    Semiconductor metal oxide films of copper-doped tin oxide (Cu-SnO(2)), tungsten oxide (WO(3)) and indium oxide (In(2)O(3)) were deposited on a platinum coated alumina substrate employing the electrostatic spray deposition technique (ESD). The morphology studied with scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows porous homogeneous films comprising uniformly distributed aggregates of nano particles. The X-ray diffraction technique (XRD) proves the formation of crystalline phases with no impurities. Besides, the Raman cartographies provided information about the structural homogeneity. Some of the films are highly sensitive to low concentrations of H(2)S (10 ppm) at low operating temperatures (100 and 200 °C) and the best response in terms of R(air)/R(gas) is given by Cu-SnO(2) films (2500) followed by WO(3) (1200) and In(2)O(3) (75). Moreover, all the films exhibit no cross-sensitivity to other reducing (SO(2)) or oxidizing (NO(2)) gases.

  2. Intermediate sulfidation type base metal mineralization at Aliabad-Khanchy, Tarom-Hashtjin metallogenic belt, NW Iran

    Science.gov (United States)

    Kouhestani, Hossein; Mokhtari, Mir Ali Asghar; Chang, Zhaoshan; Johnson, Craig A.

    2018-01-01

    The Aliabad-Khanchy epithermal base metal deposit is located in the Tarom-Hashtjin metallogenic belt (THMB) of northwest Iran. The mineralization occurs as Cu-bearing brecciated quartz veins hosted by Eocene volcanic and volcaniclastic rocks of the Karaj Formation. Ore formation can be divided into five stages, with most ore minerals, such as pyrite and chalcopyrite being formed in the early stages. The main wall-rock alteration is silicification, and chlorite, argillic and propylitic alteration. Microthermometric measurements of fluid inclusion assemblages show that the ore-forming fluids have eutectic temperatures between −30 and −52 °C, trapping temperatures of 150–290 °C, and salinities of 6.6–12.4 wt% NaCl equiv. These data demonstrate that the ore-forming fluids were medium- to high-temperature, medium- to low-salinity, and low-density H2O–NaCl–CaCl2 fluids. Calculated δ18O values indicate that ore-forming hydrothermal fluids had δ18Owater ranging from +3.6‰ to +0.8‰, confirming that the ore–fluid system evolved from dominantly magmatic to dominantly meteoric. The calculated 34SH2S values range from −8.1‰ to −5.0‰, consistent with derivation of the sulfur from either magma or possibly from local volcanic wall-rock. Combined, the fluid inclusion and stable isotope data indicate that the Aliabad-Khanchy deposit formed from magmatic-hydrothermal fluids. After rising to a depth of between 790 and 500 m, the fluid boiled and subsequent hydraulic fracturing may have led to inflow and/or mixing of early magmatic fluids with circulating groundwater causing deposition of base metals due to dilution and/or cooling. The Aliabad-Khanchy deposit is interpreted as an intermediate-sulfidation style of epithermal mineralization. Our data suggest that the mineralization at Aliabad-Khanchy and other epithermal deposits of the THMB formed by hydrothermal activity related to shallow late Eocene magmatism. The altered Eocene volcanic and

  3. Designable architectures on nanoparticle surfaces: zirconium phosphate nanoplatelets as a platform for tetravalent metal and phosphonic acid assemblies.

    Science.gov (United States)

    Mosby, Brian M; Goloby, Mark; Díaz, Agustín; Bakhmutov, Vladimir; Clearfield, Abraham

    2014-03-11

    Surface-functionalized zirconium phosphate (ZrP) nanoparticles were synthesized using a combination of ion exchange and self-assembly techniques. The surface of ZrP was used as a platform to deposit tetravalent metal ions by direct ion exchange with the protons of the surface phosphate groups. Subsequently, phosphonic acids were attached to the metal ion layer, effectively functionalizing the ZrP nanoparticles. Use of axially oriented bisphosphonic acids led to the ability to build layer-by-layer assemblies from the nanoparticle surface. Varying the metal ion and ligand used allowed designable architectures to be synthesized on the nanoparticle surface. X-ray powder diffraction, XPS, electron microprobe, solid-state NMR, FTIR, and TGA were used to characterize the synthesized materials.

  4. Deposition of very thin uniform indium sulfide layers over metallic nano-rods by the Spray-Ion Layer Gas Reaction method

    Energy Technology Data Exchange (ETDEWEB)

    Genduso, G. [Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Università di Palermo, Viale delle Scienze, 90100 Palermo (Italy); Institut for Heterogeneous Material Systems, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); Inguanta, R.; Sunseri, C.; Piazza, S. [Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Università di Palermo, Viale delle Scienze, 90100 Palermo (Italy); Kelch, C.; Sáez-Araoz, R. [Institut for Heterogeneous Material Systems, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); Zykov, A. [Institut for Heterogeneous Material Systems, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); present address: Institut für Physik, Humboldt-Universität zu Berlin, Newtonstr. 15,12489 Berlin (Germany); Fischer, Ch.-H., E-mail: fischer@helmholtz-berlin.de [Institut for Heterogeneous Material Systems, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, D-14109 Berlin (Germany); second affiliation: Free University Berlin, Chemistry Institute, Takustr. 3, D-14195 Berlin (Germany)

    2013-12-02

    Very thin and uniform layers of indium sulfide were deposited on nickel nano-rods using the sequential and cyclical Spray-ILGAR® (Ion Layer Gas Reaction) technique. Substrates were fabricated by electrodeposition of Ni within the pores of polycarbonate membranes and subsequent chemical dissolution of the template. With respect to the depositions on flat substrates, experimental conditions were modified and optimized for the present geometry. Our results show that nano-rods up to a length of 10 μm were covered uniformly along their full length and with an almost constant film growth rate, thus allowing a good control of the coating thickness; the effect of the deposition temperature was also investigated. However, for high numbers of process steps, i.e. thickness, the films became uneven and crusty, especially at higher temperature, mainly owing to the simultaneous side reaction of the metallic Ni forming nickel sulfide at the surface of the rods. However, such a problem occurs only in the case of reactive nano-rod materials, such as less noble metals. It could be strongly reduced by doubling the spray step duration and thereby sealing the metallic surface before the process step of the sulfurization. Thus, quite smooth, about 100 nm thick coatings could be obtained. - Highlights: • Ni nano-rod substrates were grown within polycarbonate membranes. • We can coat nano-rods uniformly by the Ion Layer Gas Reaction method. • As a model we deposited up to about 100 nm In{sub 2}S{sub 3} on Ni nanorods (250 nm × 10 μm). • Element mapping at insulated rods showed homogenous coating over the full length. • Parameter optimization reduced effectively the Ni sulfide formation.

  5. Potential value of phosphate compounds in enhancing immobilization and reducing bioavailability of mixed heavy metal contaminants in shooting range soil.

    Science.gov (United States)

    Seshadri, B; Bolan, N S; Choppala, G; Kunhikrishnan, A; Sanderson, P; Wang, H; Currie, L D; Tsang, Daniel C W; Ok, Y S; Kim, G

    2017-10-01

    Shooting range soils contain mixed heavy metal contaminants including lead (Pb), cadmium (Cd), and zinc (Zn). Phosphate (P) compounds have been used to immobilize these metals, particularly Pb, thereby reducing their bioavailability. However, research on immobilization of Pb's co-contaminants showed the relative importance of soluble and insoluble P compounds, which is critical in evaluating the overall success of in situ stabilization practice in the sustainable remediation of mixed heavy metal contaminated soils. Soluble synthetic P fertilizer (diammonium phosphate; DAP) and reactive (Sechura; SPR) and unreactive (Christmas Island; CPR) natural phosphate rocks (PR) were tested for Cd, Pb and Zn immobilization and later their mobility and bioavailability in a shooting range soil. The addition of P compounds resulted in the immobilization of Cd, Pb and Zn by 1.56-76.2%, 3.21-83.56%, and 2.31-74.6%, respectively. The reactive SPR significantly reduced Cd, Pb and Zn leaching while soluble DAP increased their leachate concentrations. The SPR reduced the bioaccumulation of Cd, Pb and Zn in earthworms by 7.13-23.4% and 14.3-54.6% in comparison with earthworms in the DAP and control treatment, respectively. Bioaccessible Cd, Pb and Zn concentrations as determined using a simplified bioaccessibility extraction test showed higher long-term stability of P-immobilized Pb and Zn than Cd. The differential effect of P-induced immobilization between P compounds and metals is due to the variation in the solubility characteristics of P compounds and nature of metal phosphate compounds formed. Therefore, Pb and Zn immobilization by P compounds is an effective long-term remediation strategy for mixed heavy metal contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Platinum-group elements and gold in base metal sulfides, platinum-group minerals, and Re-Os isotope compositions of the Uitkomst complex, South Africa

    Czech Academy of Sciences Publication Activity Database

    Trubač, Jakub; Ackerman, Lukáš; Gauert, Ch.; Ďurišová, Jana; Hrstka, Tomáš

    2018-01-01

    Roč. 113, č. 2 (2018), s. 439-461 ISSN 0361-0128 R&D Projects: GA ČR GA13-15390S Institutional support: RVO:67985831 Keywords : binary alloys * copper compounds * economic geology * gold * iridium * isotopes * ore deposits * osmium * palladium * platinum * platinum metals * pyrites * Rhenium * rhenium alloys * ruthenium * solid solutions * sulfur compounds * crustal materials * mass-balance calculations * massive sulfides * mineralized zone * monosulfide solid solutions * platinum group elements * platinum group elements (PGEs) * platinum group minerals Subject RIV: DB - Geology ; Mineralogy; AC - Archeology, Anthropology, Ethnology (ARUB-Q) OBOR OECD: Geology; Archaeology (ARUB-Q) Impact factor: 2.519, year: 2016

  7. Metal endowment reflected in chemical composition of silicates and sulfides of mineralized porphyry copper systems, Urumieh-Dokhtar magmatic arc, Iran

    Science.gov (United States)

    Zarasvandi, Alireza; Rezaei, Mohsen; Raith, Johann G.; Pourkaseb, Houshang; Asadi, Sina; Saed, Madineh; Lentz, David R.

    2018-02-01

    The present work attempts to discriminate between the geochemical features of magmatic-hydrothermal systems involved in the early stages of mineralization in high grade versus low grade porphyry copper systems, using chemical compositions of silicate and sulfide minerals (i.e., plagioclase, biotite, pyrite and chalcopyrite). The data indicate that magmatic plagioclase in all of the porphyry copper systems studied here has high An% and Al content with a significant trend of evolution toward AlAl3SiO8 and □Si4O8 endmembers, providing insight into the high melt water contents of the parental magmas. Comparably, excess Al and An% in the high grade deposits appears to be higher than that of selected low grade deposits, representing a direct link between the amounts of exsolving hydrothermal fluids and the potential of metal endowment in porphyry copper deposits (PCDs). Also, higher Al contents accompanied by elevated An% are linked to the increasing intensity of disruptive alteration (phyllic) in feldspars from the high grade deposits. As calculated from biotite compositions, chloride contents are higher in the exsolving hydrothermal fluids that contributed to the early mineralization stages of highly mineralized porphyry systems. However, as evidenced by scattered and elevated log (fH2O)/(fHF) and log (fH2O)/(fHCl) values, chloride contents recorded in biotite could be influenced by post potassic fluids. Geothermometry of biotite associated with the onset of sulfide mineralization indicates that there is a trend of increasing temperature from high grade to low grade porphyry systems. Significantly, this is coupled with a sharp change in copper content of pyrite assemblages precipitated at the early stages of mineralization such that Cu decreased with increasing temperature. Based on EMPA and detailed WDS elemental mapping, trace elements do not exhibit complex compositional zoning or solid solution in the sulfide structure. Nevertheless, significant amounts of Cu and

  8. Thin oxide-free phosphate films of composition formed on the surface of vanadium metal and characterized by x-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Asunskis, D.J.; Sherwood, P.M.A.

    2006-01-01

    This article reports the preparation of thin (less than 100 A) oxide-free phosphate films of various compositions on vanadium metal. These films are interesting because of their potential for corrosion inhibition, adhesion promotion, and biocompatibility. Valence and core-level x-ray photoelectron spectroscopy (XPS) were used to characterize the films. The valence band spectra obtained were compared with spectra generated from band structure calculations for various vanadium phosphates and from previously reported spectra of vanadium phosphates. Vanadium phosphate coatings were created by the reaction of vanadium metal and different phosphorus-oxygen containing acids: H 3 PO 4 , H 3 PO 3 , H 3 PO 2 , and H 2 P 2 O 7 . This article focuses upon the valence band region which shows significant differences between the four vanadium phosphate films formed as well as clear differences between the these phosphates and vanadium oxides. The valence band spectra are effectively interpreted by band structure calculations

  9. Evaluation of natural radioactivity and heavy metals content in Sudanese phosphate rocks used as low cost fertilizer

    International Nuclear Information System (INIS)

    Elkhangi, F.A.; Aamhed, M.M.O.; Abdalla, I.A.

    1997-01-01

    This study was carried out to determine the level of natural radioactivity and heavy metals content of Sudanese rock phosphate used as low cost fertilizer. Thirty samples collected from two types of local phosphate rocks from the Nuba mountains (Uro and Kurun) were used in this study and the activity concentrations of natural radioactivity determined using gamma spectroscopy were compared to those found in samples of imported phosphorous fertilizers Single Super phosphate (SSP) and Triple Super phosphate (TSP). The results showed that the ' Ra activity concentration was 0.6 - 0.8 Bq/g for Uro and 0.3 - 0.5 Bq/g for Kurun. As for the most commonly used imported fertilizer TSP, the result was found to be greater than that of Uro (around 1.0 Bq/g). The heavy metals content of Uro and Kurun rocks measured using X-ray Fluorescence Technique showed their levels were below the toxic levels reported by Christina (1991). It is evident that the environmental hazard is comparable in the local and imported fertilizers and is acceptable in both cases by international standards. The determine factor therefore in optioning for the use of a local or an imported brand should then be the fertilizing efficiency of the brand used against other economic consideration rather than the fertilizers environmental impact

  10. Ratiometric Fluorescent Detection of Phosphate in Aqueous Solution Based on Near Infrared Fluorescent Silver Nanoclusters/Metal-Organic Shell Composite.

    Science.gov (United States)

    Dai, Cong; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2015-11-17

    Synthesis of near-infrared (NIR) fluorescent AgNCs with high quantum yield and stability is challenging but important for sensing and bioimaging application. Here, we report the fabrication of AgNCs/metal-organic shell composite via the deposition of metal-organic (zinc-nitrogen) coordination shell around AgNCs for ratiometric detection of phosphate. The composite exhibits NIR emission at 720 nm with 30 nm red-shift in comparison to bare AgNCs and a weak emission at 510 nm from the shell. The absolute quantum yield of NIR fluorescence of the composite is 15%, owing to FRET from the shell to the AgNCs core under the excitation at 430 nm. Besides, the composite is stable due to the protection of the shell. On the basis of the composite, a novel ratiometric fluorescence probe for the detection of phosphate in aqueous solution with good sensitivity and selectivity was developed. The limit of detection (3s) is 0.06 μM, and the relative standard deviation for 10 replicate detections of 10 μM phosphate was 0.6%. The recoveries of spiked phosphate in water, human urine, and serum samples ranged from 94.1% to 103.4%.

  11. Effect of alkaline earth metal and magnesium cations on cadmium extraction from chloride solutions by tributyl phosphate

    International Nuclear Information System (INIS)

    Prokuev, V.A.; Belousov, E.A.

    1985-01-01

    At 298 K thermodynamic constants of cadmium (2) extraction from chloride solutions of magnesium, calcium, strontium and barium by tributyl phosphate are calculated. It is established, that logarithm of the thermodynamic extraction constant is in a linear dependence from the change in the cation hydration enthalpy in agqueous solution. It is shown, that activity coefficient of neutral complex CdVCl 2 differs from one, and it is the higher the more stable the complex is in alkaline earth metal chloride solutions

  12. Acid-volatile sulfide and simultaneously extracted metals in surface sediments of the southwestern coastal Laizhou Bay, Bohai Sea: concentrations, spatial distributions and the indication of heavy metal pollution status.

    Science.gov (United States)

    Zhuang, Wen; Gao, Xuelu

    2013-11-15

    Surface sediments were collected from the coastal waters of southwestern Laizhou Bay and the rivers it connects with during summer and autumn 2012. The acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) were measured to assess the sediment quality. The results showed that not all sediments with [SEM]-[AVS]>0 were capable of causing toxicity because the organic carbon is also an important metal-binding phase in sediments. Suppose the sediments had not been disturbed and the criteria of US Environmental Protection Agency had been followed, heavy metals in this area had no adverse biological effects in both seasons except for few riverine samples. The major ingredient of SEM was Zn, whereas the contribution of Cd - the most toxic metal studied - to SEM was marine sediments. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Results of LA-ICP-MS sulfide mapping from Algoma-type BIF gold systems with implications for the nature of mineralizing fluids, metal sources, and deposit models

    Science.gov (United States)

    Gourcerol, B.; Kontak, D. J.; Thurston, P. C.; Petrus, J. A.

    2018-01-01

    Quantitative laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) element distribution maps combined with traverse mode analyses have been acquired on various sulfides (pyrite, pyrrhotite, arsenopyrite) from three Canadian Algoma-type BIF-hosted gold deposits ( 4 Moz Au Meadowbank, ≥ 2.8 Moz Au Meliadine district, 6 Moz Au Musselwhite). These data, in conjunction with detailed petrographic and SEM-EDS observations, provide insight into the nature and relative timing of gold events, the presence and implication of trace element zoning regarding crystallization processes, and elemental associations that fingerprint gold events. Furthermore, the use of an innovative method of processing the LA-ICP-MS data in map and traverse modes, whereby the results are fragmented into time-slice data, to generate various binary plots (Ag versus Ni) provides a means to identify elemental associations (Te, Bi) not otherwise apparent. This integrated means of treating geochemical data, along with petrography, allows multiple gold events and remobilization processes to be recognized and their elemental associations determined. The main gold event in each of these deposits is characterized by the coupling of an As-Se-Te-Ag element association coincident with intense stratabound sulfide-replacement of the Fe-rich host rock. Additionally, the data indicate presence of a later remobilization event, which upgraded the Au tenor, as either non-refractory or refractory type, along fracture networks due to the ingress of subsequent base metal-bearing metamorphic fluids (mainly a Pb-Bi association). Furthermore, the data reveal a stratigraphic influence, as reflected in the elemental associations and the elemental enrichments observed and the nature of the sulfide phase hosting the gold mineralization (arsenopyrite versus pyrite).

  14. First-Row Transition Metal Doping in Calcium Phosphate Bioceramics: A Detailed Crystallographic Study

    Directory of Open Access Journals (Sweden)

    Guillaume Renaudin

    2017-01-01

    Full Text Available Doped calcium phosphate bioceramics are promising materials for bone repair surgery because of their chemical resemblance to the mineral constituent of bone. Among these materials, BCP samples composed of hydroxyapatite (Ca10(PO46(OH2 and β-TCP (Ca3(PO42 present a mineral analogy with the nano-multi-substituted hydroxyapatite bio-mineral part of bones. At the same time, doping can be used to tune the biological properties of these ceramics. This paper presents a general overview of the doping mechanisms of BCP samples using cations from the first-row transition metals (from manganese to zinc, with respect to the applied sintering temperature. The results enable the preparation of doped synthetic BCP that can be used to tailor biological properties, in particular by tuning the release amounts upon interaction with biological fluids. Intermediate sintering temperatures stabilize the doping elements in the more soluble β-TCP phase, which favors quick and easy release upon integration in the biological environment, whereas higher sintering temperatures locate the doping elements in the weakly soluble HAp phase, enabling a slow and continuous supply of the bio-inspired properties. An interstitial doping mechanism in the HAp hexagonal channel is observed for the six investigated cations (Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+ with specific characteristics involving a shift away from the center of the hexagonal channel (Fe3+, Co2+, cationic oxidation (Mn3+, Co3+, and also cationic reduction (Cu+. The complete crystallochemical study highlights a complex HAp doping mechanism, mainly realized by an interstitial process combined with calcium substitution for the larger cations of the series leading to potentially calcium deficient HAp.

  15. Siderophile element distribution in metal-sulfide nodules of EH3 Sahara 97072: A relict condensation signature overprinted by transient melting events

    Science.gov (United States)

    Lehner, S. W.; Buseck, P.; McDonough, W. F.; Ash, R.

    2008-12-01

    Evidence of a condensation signature has been detected in the textures and compositions of metal-sulfide nodules (MSN) from the unequilibrated enstatite chondrite Sahara 97072 (EH3). There are two end-member models, both of which can reproduce the siderophile element relations and distribution among the kamacite (αFeNi), schreibersite (FeNiP3), and perryite [(FeNi)x(SiP)y] observed in the MSN. These minerals may have condensed as a single metal alloy that subsequently decomposed in transient melting events or they could have condensed as separate phases. Most likely the minerals were produced from some combination of both processes. Kamacite, schreibersite, and perryite compositions in MSN can reasonably be recombined to produce a metallic phase with Co/Ni and P/Ni ratios similar to those in primitive CI meteorites. The recombined metal has siderophile element (Ir, Ru, Co, Pd, Au, Ga,) ratios closer to CI values than kamacite alone, suggesting it could have been a condensing metal that remained in equilibrium with a cooling reduced gas of near solar composition until Au and Ga condensed. Alternatively, nearly CI chondritic Pd/Ru ratios in schreibersite suggest it could be an early condensate. Perryite may have initially formed as a condensate, as a product of metal sulfurization, or both, but, if so, it appears to also have re-crystallized from a liquid rich in Ni and Si during partial melting of the MSN. Fe, Ni, and P distributions in kamacite near perryite and schreibersite suggest they are primitive minerals in disequilibrium with the metal, indicating they formed in transient melting events as opposed to slow metamorphic heating. The siderophile element distribution in Sahara 97072 MSN is consistent with early condensing material that was later reprocessed by transient melting events.

  16. The geological record of base metal sulfides in the cratonic mantle: A microscale 187Os/188Os study of peridotite xenoliths from Somerset Island, Rae Craton (Canada)

    Science.gov (United States)

    Bragagni, A.; Luguet, A.; Fonseca, R. O. C.; Pearson, D. G.; Lorand, J.-P.; Nowell, G. M.; Kjarsgaard, B. A.

    2017-11-01

    We report detailed petrographic investigations along with 187Os/188Os data in Base Metal Sulfide (BMS) on four cratonic mantle xenoliths from Somerset Island (Rae Craton, Canada). The results shed light on the processes affecting the Re-Os systematics and provide time constraints on the formation and evolution of the cratonic lithospheric mantle beneath the Rae craton. When devoid of alteration, BMS grains mainly consist of pentlandite + pyrrhotite ± chalcopyrite. The relatively high BMS modal abundance of the four investigated xenoliths cannot be reconciled with the residual nature of these peridotites, but requires addition of metasomatic BMS. This is especially evident in the two peridotites with the highest bulk Pd/Ir and Pd/Pt. Metasomatic BMS likely formed during melt/fluid percolation in the Sub Continental Lithospheric Mantle (SCLM) as well as during infiltration of the host kimberlite magma, when djerfisherite crystallized around older Fe-Ni-sulfides. On the whole-rock scale, kimberlite metasomatism is visible in a subset of bulk xenoliths, which defines a Re-Os errorchron that dates the host magma emplacement. The 187Os/188Os measured in the twenty analysed BMS grains vary from 0.1084 to >0.17 and it shows no systematic variation depending on the sulfide mineralogical assemblage. The largest range in 187Os/188Os is observed in BMS grains from the two xenoliths with the highest Pd/Ir, Pd/Pt, and sulfide modal abundance. The whole-rock TRD ages of these two samples underestimate the melting age obtained from BMS, demonstrating that bulk Re-Os model ages from peridotites with clear evidence of metasomatism should be treated with caution. The TRD ages determined in BMS grains are clustered around 2.8-2.7, ∼2.2 and ∼1.9 Ga. The 2.8-2.7 Ga TRD ages document the main SCLM building event in the Rae craton, which is likely related to the formation of the local greenstone belts in a continental rift setting. The Paleoproterozoic TRD ages can be explained by

  17. Sulfide silver architectonics of rat, cat, and guinea pig spinal cord. A light microscopic study with Timm's method for demonstration of heavy metals

    DEFF Research Database (Denmark)

    Schroder, H D

    1977-01-01

    The distribution of heavy metals in the spinal cord of the cat, rat, and guinea pig has been studied histochemically with Timm's sulfide silver method. There was considerable variation in the degree of staining of the neuropil. The dorsal horn showed a laminar staining pattern corresponding......, characterized by heterogeneous staining, also appeared dark, although less obvious in the guinea pig. In the ventral horn the coarser stained particles in lamina IX contrasted with the surrounding lamina. Cell staining varied between different cell groups, and within single cell populations. In the cat thoracic...... cord the cells in nucleus intermedio-lateralis (IL) and nucleus intercalatus (IC) stained very weakly. In Clarke's column and in the motoneuron area cells, uniform in Nissl preparations, could be seen different after Timm staining. The results are discussed in relation to other histochemical patterns...

  18. Prevention of sulfide oxidation in sulfide-rich waste rock

    Science.gov (United States)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  19. Comparative Analysis of Soluble Phosphate Amendments for the Remediation of Heavy Metal Contaminants: Effect on Sediment Hydraulic Conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Wellman, Dawn M.; Icenhower, Jonathan P.; Owen, Antionette T.

    2006-07-10

    A series of conventional, saturated column experiments were conducted to evaluate the effect of utilizing in situ phosphate amendments, for subsurface, metal remediation, on sediment hydraulic conductivity. Experiments were conducted under mildly alkaline/calcareous conditions representative of conditions commonly encountered at sites across the arid western United States, which have been used in weapons and fuel production and display significant subsurface contamination. Results indicate the displacement of a single pore volume of either sodium monophosphate or phytic acid amendments causes approximately a 30% decrease in the hydraulic conductivity of the sediment. Long-chain polyphosphate amendments afford no measurable reduction in hydraulic conductivity. These results demonstrate (1) the utility of long-chain polyphosphate amendments for subsurface metal sequestration and (2) the necessity of conducting column experiments to completely evaluate the effects of subsurface remediation.

  20. Chemical degradation of trimethyl phosphate as surrogate for organo-phosporus pesticides on nanostructured metal oxides

    Czech Academy of Sciences Publication Activity Database

    Štengl, Václav; Henych, Jiří; Matys Grygar, Tomáš; Pérez, Raul

    2015-01-01

    Roč. 61, JAN (2015), s. 259-269 ISSN 0025-5408 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : Nanostructured oxides * Stoichiometric degradation * Trimethyl phosphate Subject RIV: CA - Inorganic Chemistry Impact factor: 2.435, year: 2015

  1. Phosphonate-Derived Nanoporous Metal Phosphates and Their Superior Energy Storage Application.

    Science.gov (United States)

    Pramanik, Malay; Salunkhe, Rahul R; Imura, Masataka; Yamauchi, Yusuke

    2016-04-20

    Nanoporous nickel, aluminum, and zirconium phosphates (hereafter, abbreviated as NiP, AlP, and ZrP, respectively) with high surface areas and controlled morphology and crystallinity have been synthesized through simple calcination of the corresponding phosphonates. For the preparation of phosphonate materials, nitrilotris(methylene)triphosphonic acid (NMPA) is used as phosphorus source. The organic component in the phosphonate materials is thermally removed to form nanoporous structures in the final phosphate materials. The formation mechanism of nanoporous structures, as well as the effect of applied calcination temperatures on the morphology and crystallinity of the final phosphate materials, is carefully discussed. Especially, nanoporous NiP materials have a spherical morphology with a high surface area and can have great applicability as an electrode material for supercapacitors. It has been found that there is a critical effect of particle sizes, surface areas, and the crystallinities of NiP materials toward electrochemical behavior. Our nanoporous NiP material has superior specific capacitance, as compared to various phosphate nanomaterials reported previously. Excellent retention capacity of 97% is realized even after 1000 cycles, which can be ascribed to its high structural stability.

  2. Use of triphenyl phosphate as risk mitigant for metal amide hydrogen storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2016-04-26

    A process in a resulting product of the process in which a hydrogen storage metal amide is modified by a ball milling process using an additive of TPP. The resulting product provides for a hydrogen storage metal amide having a coating that renders the hydrogen storage metal amide resistant to air, ambient moisture, and liquid water while improving useful hydrogen storage and release kinetics.

  3. Comparison of Hypersensitivity in Metal Ceramic Crowns cemented with Zinc Phosphate and Self-adhesive Resin: A Prospective Study.

    Science.gov (United States)

    Shankar, Thatapudi; Garhnayak, Mirna; Garhnayak, Lokanath; Dhal, Angurbala; Kar, Aswini K

    2017-10-01

    Luting agents used to fix artificial prostheses, such as fixed partial denture (FPD) to tooth are basically viscous in nature and show chemical reaction for fixation. Postcementation hypersensitivity is a frequent complaint of patients. The present study was conducted to compare postcementation hypersensitivity with zinc phosphate and self-adhesive resin in complete coverage crown. This study included 30 patients in which 60 porcelein fused to metal crowns was placed. Two metal crowns were placed in each patient in nonantagonis-tic contralateral quadrants. First crown was cemented with zinc phosphate cement, while the other was cemented with self-adhesive resin. Hypersensitivity was evaluated by visual analog scale (VAS) score and by clinical test. For clinical evaluation of sensitivity, hot and cold water was applied to the cervical margin of restoration for 5 seconds and response was recorded. This study consisted of 30 patients in which 60 crowns were given. There was no statistical difference in VAS score of mastication in zinc phosphate cement recorded at baseline, 1 week, 4 weeks, 6 months, 1 year, and 2 years (p > 0.05). Cold response also did not show a significant difference at six time points. Warm response showed slight decrease in subsequent time points but was nonsignificant (p > 0.05). Similarly, with self-adhesive resin cement, VAS score during mastication, hot and cold response was statistically nonsignificant (p > 0.05). Postcementation hypersensitivity is a frequent complaint that patient may experience. However, we found no statistically significant difference in both cements tested. Postcementation hypersensitivity is an unpleasant sensation experienced by patients. This may affect the success of any prosthesis. Thus, selection of luting agent for cementation plays an important role to eliminate this symptom.

  4. (IV) phosphates

    Indian Academy of Sciences (India)

    M(IV) phosphates of the class of tetravalent metal acid (TMA) salts where M (IV) = Zr, Ti, Sn has been synthesized by the sol-gel method. These materials have been characterized for elemental analysis (ICP-AES), thermal analysis (TGA, DSC), X-ray analysis and FTIR spectroscopy. Chemical resistivity of these materials ...

  5. Membrane for hydrogen recovery from streams containing hydrogen sulfide

    Science.gov (United States)

    Agarwal, Pradeep K.

    2007-01-16

    A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

  6. PHOSPHATE-LIMITED GROWTH OF CHROMATIUM-VINOSUM IN CONTINUOUS CULTURE

    NARCIS (Netherlands)

    MAS, J; VANGEMERDEN, H

    Chromatium vinosum DSM 185 was grown in continuous culture at a constant dilution rate of 0.071 h-1 with sulfide as the only electron donor. The organism was subjected to conditions ranging from phosphate limitation (S(R-phosphate) = 2.7-mu-M and S(R-sulfide) = 1.8 mM) to sulfide limitation

  7. Oxidation and Precipitation of Sulfide in Sewer Networks

    DEFF Research Database (Denmark)

    Nielsen, A. H.

    (Fe(II)) and precipitated subsequently with dissolved sulfide as ferrous sulfide (FeS). The ferrous sulfide precipitation was relatively fast, but not immediate. Despite the very low solubility of ferrous sulfide, initially present iron did not react completely with sulfide. This observation...... were studied in both wastewater and biofilms. Particular emphasis was on the importance of iron in the sulfur cycle. Iron is typically among the dominant metals in wastewater. The experiments showed that, ferric iron (Fe(III)) that was added to anaerobic wastewater was rapidly reduced to ferrous iron...... was probably explained by the presence of ligands in the wastewater, which reacted with the iron. The biofilm experiments showed that sulfide accumulated along with several metals in anaerobic biofilms as the result of metal sulfide precipitation. Particularly, zinc and cupper were important...

  8. Nitrate (chloride) melts as media for crystal growth of complex phosphates of alkali and trivalent metals

    Science.gov (United States)

    Livitska, Oksana; Strutynska, Nataliia; Zatovsky, Igor; Slobodyanik, Nikolai; Odinets, Eugen

    2016-01-01

    The interaction in the molten systems MIPO3-MIII2O3-MINO3 (MICl) (MI - Na, K; MIII - Al, Fe, Y, Bi) was investigated at molar ratios P/MIII=1 or 3 at the temperatures 400 °C (for MINO3) or 810 °C (for MICl). Formation conditions of complex phosphates MI3MIII2(PO4)3 and MI3MIII(PO4)2 (MI - Na, K; MIII - Al, Fe, Bi) were established. It was shown that the crystal size of obtained phosphates can be controlled by using different salt melts. The synthesized compounds were characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, Optical microscopy and Scanning electron microscopy with Energy-dispersive X-ray spectroscopy. Differential thermal data for Na3Bi(PO4)2 and Na3Fe(PO4)2 showed congruent and incongruent melting, respectively.

  9. Thermal expansion of NZP-family alkali-metal (Na, K) zirconium phosphates

    International Nuclear Information System (INIS)

    Orlova, A.I.; Kemenov, D.V.; Pet'kov, V.I.; Samojlov, S.G.; Kazantsev, G.N.

    2000-01-01

    By means of high-temperature X-ray diffraction one investigated into thermal expansion of alkali-zirconium phosphates crystallizing in NaZr 2 (PO 4 ) 3 structure type within 20-700 deg C temperature range. One synthesized phosphates of A x Zr 2.25-0.25x (PO 4 ) 3 type two series where A-Na (x = 0.5; 1.0; 2.0; 3.0; 4.0; 5.0) and K (x = 1.0; 3.0; 5.0). One calculated for them a and c parameters of the elementary cells and α a and α c linear expansion temperature coefficients. Anisotropy of thermal expansion the maximum one for AZr 2 (PO 4 ) 3 and Na 5 Zr(PO 4 ) 3 phosphates was determined. K 5 Zr(PO 4 ) 3 compound was characterized by the minimum thermal expansion at the near-zero anisotropy of Na 5 Zr(PO 4 ) 3 [ru

  10. Availability of metals in samples of phosphogypsum and phosphate fertilizers used in agriculture; Disponibilidade de metais em amostras de fosfogesso e fertilizantes fosfatados utilizados na agricultura

    Energy Technology Data Exchange (ETDEWEB)

    Bourlegat, Fernanda Melo le

    2010-07-01

    The Brazilian phosphate fertilizer is obtained by wet reaction of the igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid, and dehydrated calcium sulphate (phosphogypsum) as by-product. Part of this phosphogypsum is stored in stacks at open air and part has been used in agriculture, as soil amendment. To assure a safe utilization of phosphogypsum it is important to determine the levels of impurities, particularly of metals, present in phosphogypsum. In this paper, the concentration of metals (As, Ba, Cd, Cr, Co, Cu, Hg, Ni, Pb, Se, Zn and rare earth elements) present in Brazilian phosphogypsum and also in single super phosphate (SSP), triple super phosphate (TSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP) were determined. The metals Cd, Cu, Ni, Pb and Zn were determined following the procedure 'EPA 3052'. The same elements, As and Se were also determined following the procedure 'EPA 3050B', recommended by Ministerio da Agricultura, Pecuaria e Abastecimento (MAPA). All these metals are controlled by environmental and agriculture regulation institutes in Brazil. The concentrations obtained for the metals analyzed by using the two procedures were different. Ba, Co, Cr and rare earth elements were determined by neutron activation analysis. In order to evaluate the availability of these metals As, Cd, Cr, Co, Cu, Ni, Pb, Se and Zn to the environment, the content of the same elements were determined following a procedure established by the EC (European Community), which includes an initial attack of the samples with EDTA-NH{sub 4} 0.05M, at pH 7.0. In all these cases, phosphogypsum presented metals concentration lower than the phosphate fertilizers, and the results are below the limits adopted by MAPA and Companhia Ambiental do Estado de Sao Paulo (CETESB). The results obtained using the methodology with mild attack show that the metals are not available to the environment, giving

  11. Zinc phosphate conversion coatings

    Energy Technology Data Exchange (ETDEWEB)

    Sugama, Toshifumi (Wading River, NY)

    1997-01-01

    Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate .alpha.-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal.

  12. Zinc phosphate conversion coatings

    Energy Technology Data Exchange (ETDEWEB)

    Sugama, T.

    1997-02-18

    Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate {alpha}-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal. 33 figs.

  13. Periodic Trends Transition Metal Sulfide Catalysis: Intuition and Theory; Evolution des proprietes catalytiques en hydrodesulfurisation en fonction de la position du metal de transition dans la classification periodique: intuition et theorie

    Energy Technology Data Exchange (ETDEWEB)

    Chianelli, R.R. [Texas at El Paso Univ., Materials Research Technology Institute, TX (United States)

    2006-07-01

    The use of Transition Metal Sulfide (TMS) catalysts came about as the need to hydrogenate coal to liquid fuels became urgent in the 1920's. Sabatier won the Nobel Prize in 1912 for describing the phenomenon of hydrogenation by transition metals. However, when the transition metals were used to hydrogenate coal, the TMS emerged as the stable catalytic states due to high sulfur content in the coal liquids. From 1920-1930 I.G. Farbenindustrie A.G. tested over 6000 catalysts. It was from these origins that modern Co (Ni)/Mo/Al{sub 2}O{sub 3} arose. Since that time scientists have developed an understanding of the fundamental properties that lead to both the activity of the simple binary sulfides and the mechanism by which two metals (Co+Mo) acted together to enhance activity (promotion). Initial efforts focused on supported commercial catalysts with limited success. In the early 1980's the periodic trends of TMS catalysts on unsupported catalysts were discovered and these results formed the foundation for further basic understanding of the key properties that led to catalytic activity. These results have been extended over the years to include supported catalysts and many petroleum based substrates. Early results related catalytic activity to the heats of formation of the sulfides and Pauling % d-character of the transition metals. These correlations both pointed to the importance of the 4d an 5d electrons and also to the well established catalytic principle that the metal sulfur bonds needed to be 'just right', not too strong nor too weak thus allowing facile turnover of the adsorbing and de-sorbing molecules. Averaging of the heat of formation of Co{sub 9}S{sub 8} and MoS{sub 2} suggested that promotion operated through sulfur vacancies formed by atoms that shared both a Co atom and a Mo atom on the surface. Theoretical studies also began in this period that further supported the idea that d-electrons in the frontier orbitals of the catalysts were

  14. New studies on the synthesis and structural chemistry of polynary lithium and silver transition metal phosphates

    International Nuclear Information System (INIS)

    Mosymow, Emma

    2015-01-01

    In the course of this work extensive equilibrium studies were carried out in the four-system systems Li / M / P / O (M: Cr, Mn) in the search for new, powerful cathode materials for lithium ion batteries. The phosphates LiCr II 4 (PO 4 ) 3 , NaCr II 4 (PO 4 ) 3 , Li 5 Cr II 2 Cr III (PO 4 ) 4 , monoclines Li 3 Cr 2 (PO 4 ) 3 , Cr II 5 Cr III 2 (P 2 O 7 ) 4 and LiMn II 2 P 3 O 10 were obtained for the first time. The present work reports on their synthesis, crystallographic characterization and their spectroscopic and magnetic properties. The equilibrium studies in the Li / Cr / P / O system led to the elucidation of numerous phase relationships. For example, the coexistence regions LiCr 4 (PO 4 ) 3 / Li 5 Cr 3 (PO 4 ) 4 / Cr 2 O 3 / CrP and Li 9 Cr 3 (PO 4 ) 3 / LiCrP 2 O 7 / CrP. The coexistence of some equilibrium phases such as lithium orthophosphate and lithium manganese(II) orthophosphate as well as lithium metaphosphate and manganese(III) metaphosphate were also investigated in the Li / Mn / P / O system. Furthermore, the de-intercalation behavior of silver manganese phosphates was investigated with the possibility of demonstrating metastable phosphates with manganese in oxidation states higher than 3+. In this case the four-substance system Ag / Mn / P / O with Mn(II) and Mn(III) was considered. The reaction conditions were adapted to those of the experiments in the corresponding lithium-containing systems. Within the scope of the equilibrium studies two new pyrophosphates AgMnP 2 O 7 and Ag 1,6 Mn 3 (P 2 O 7 ) 2 were found and characterized. [de

  15. The Influence of Electrolytic Concentration on the Electrochemical Deposition of Calcium Phosphate Coating on a Direct Laser Metal Forming Surface

    Directory of Open Access Journals (Sweden)

    Qianyue Sun

    2017-01-01

    Full Text Available A calcium phosphate (CaP coating on titanium surface enhances its biocompatibility, thus facilitating osteoconduction and osteoinduction with the inorganic phase of the human bone. Electrochemical deposition has been suggested as an effective means of fabricating CaP coatings on porous surface. The purpose of this study was to develop CaP coatings on a direct laser metal forming implant using electrochemical deposition and to investigate the effect of electrolytic concentration on the coating’s morphology and structure by X-ray diffraction, scanning electron microscopy, water contact angle analysis, and Fourier transform infrared spectroscopy. In group 10−2, coatings were rich in dicalcium phosphate, characterized to be thick, layered, and disordered plates. In contrast, in groups 10−3 and 10−4, the relatively thin and well-ordered coatings predominantly consisted of granular hydroxyapatite. Further, the hydrophilicity and cell affinity were improved as electrolytic concentration increased. In particular, the cells cultured in group 10−3 appeared to have spindle morphology with thick pseudopodia on CaP coatings; these spindles and pseudopodia strongly adhered to the rough and porous surface. By analyzing and evaluating the surface properties, we provided further knowledge on the electrolytic concentration effect, which will be critical for improving CaP coated Ti implants in the future.

  16. U-Pb age for some base-metal sulfide deposits in Ireland: genetic implications for Mississippi Valley-type mineralization

    International Nuclear Information System (INIS)

    Duane, M.J.; Welke, H.J.; Allsopp, H.L.

    1986-01-01

    Evidence is presented that links the timing of vein-type (Cu-Ag(U)) to stratiform Mississippi Valley-type (MVT, Pb-Zn) ore events in Ireland. The rare occurrence of pitchblende, coffinite(?), and brannerite mineralization, which is regarded as a precursor component to the sulfide mineralization in the Gortdrum deposit (Ireland), provides the first direct radiometric dating tool for these carbonate-hosted deposits. The U-Pb (340 +25/-20 Ma) and Pb-Pb (359 +/- 26 Ma) whole-rock ages constrain the uranium and base-metal mineralizing events to the Early Carboniferous. The data support a model according to which MVT and earlier uranium mineralization stages of some major ore bodies resulted from fracturing coincident with large basin-dewatering events. The Pb-Pb and concordia data are consistent with an Early Carboniferous age for the mineralization at Gortdrum and agree closely with a previously published Rb-Sr age of 359 +/- 22 Ma, obtained for Missouri glauconites. Furthermore, other comparative geologic data from Ireland and from North American MVT mineral provinces support a model of Pb-Zn-Cu(U) mobilization on a regional scale that implicates the later closing stages of the proto-Atlantic. 40 references, 3 figures, 1 table

  17. Gum Arabic Microgels As Template for In Situ Metal-Sulfide Based Quantum Dots Preparation and Their Thermal, Spectroscopic, Optical, and Magnetic Characterization

    Science.gov (United States)

    Farooq, Muhammad; Sagbas, Selin; Yildiz, Mustafa; Meral, Kadem; Siddiq, Mohammad; Aktas, Nahit; Sahiner, Nurettin

    2017-07-01

    Here, gum arabic (GA) microgel in 5-50 μm size range was used as a template for in situ quantum dot (QD) preparation. The in situ synthesis of metal sulfide quantum dots (QDs) such as CdS, PbS, CuS, ZnS, CoS, and MnS was accomplished by the absorption of the corresponding metal ions from aqueous solutions and then in situ precipitation with S2- treatments within GA microgels. Transmission electron microscopy (TEM) confirmed the existence of the evenly distributed QDs within GA microgel matrices for each of the prepared QDs. All the fabricated GA-QD composites have shown excellent semiconducting behaviors with relatively larger band gap values of 4.87 eV, 4.60 eV, 6.71 eV, 4.81 eV, 3.68 eV, 5.2 eV, and 4.0 eV for CdS, PbS, ZnS, CuS, CoS, MoS, and MnS, respectively. The results revealed that CdS and ZnS are found to be the most efficient florescence materials amongst the all QDs with 630 and 70 cd/cm2 fluorescence intensities, respectively. Moreover, the magnetic susceptibility study suggests that Mn(IV), Co(III), and Mo(IV), have mononuclear octahedral geometries whereas Zn(II), Cd(II), and Pb(II) show binuclear geometries.

  18. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

    Science.gov (United States)

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

    2013-01-01

    Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

  19. Laser engineered multilayer coating of biphasic calcium phosphate/titanium nanocomposite on metal substrates.

    Science.gov (United States)

    Zhang, Martin Yi; Ye, Chang; Erasquin, Uriel Joseph; Huynh, Toan; Cai, Chengzhi; Cheng, Gary J

    2011-02-01

    In this work, laser coating of biphasic calcium phosphate/titanium (BCP/Ti) nanocomposite on Ti-6Al-4 V substrates was developed. A continuous wave neodymium-doped yttrium aluminium garnet (Nd:YAG) laser was used to form a robust multilayer of BCP/Ti nanocomposite starting from hydroxyapatite and titanium nanoparticles. In this process, low power coating is realized because of the strong laser-nanoparticle interaction and good sinterability of nanosized titanium. To guide the optimization of laser processing conditions for the coating process, a multiphysics model coupling electromagnetic module with heat transfer module was developed. This model was validated by laser coating experiments. Important features of the coated samples, including microstructures, chemical compositions, and interfacial bonding strength, were characterized. We found that a multilayer of BCP, consisting of 72% hydroxyapatite (HA) and 28% beta-tricalcium phosphate (β-TCP), and titanium nanocomposite was formed on Ti-6Al-4 V substrates. Significantly, the coating/substrate interfacial bonding strength was found to be two times higher than that of the commercial plasma sprayed coatings. Preliminary cell culture studies showed that the resultant BCP/Ti nanocomposite coating supported the adhesion and proliferation of osteoblast-like UMR-106 cells.

  20. Sulfide chemiluminescence detection

    Science.gov (United States)

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  1. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    Science.gov (United States)

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K  Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

  2. Sulfidation behavior of Fe20Cr alloys

    International Nuclear Information System (INIS)

    Pillis, Marina Fuser

    2001-01-01

    Alloys for use in high temperature environments rely on the formation of an oxide layer for their protection. Normally, these protective oxides are Cr 2 O 3 , Al 2 O 3 and, some times, SiO 2 . Many industrial gaseous environments contain sulfur. Sulfides, formed in the presence of sulfur are thermodynamically less stable, have lower melting points and deviate much more stoichiometrically, compared to the corresponding oxides. The mechanism of sulfidation of various metals is as yet not clear, in spite of the concerted efforts during the last decade. To help address this situation, the sulfidation behavior of Fe20Cr has been studied as a function of compositional modifications and surface state of the alloy. The alloys Fe20Cr, Fe20Cr0.7Y, Fe20Cr5Al and Fe20Cr5Al0.6Y were prepared and three sets of sulfidation tests were carried out. In the first set, the alloys were sulfidized at 700 deg C and 800 deg C for 10h. In the second set, the alloys were pre-oxidized at 1000 deg C and then sulfidized at 800 deg C for up to 45h. In the third set of tests, the initial stages of sulfidation of the alloys was studied. All the tests were carried out in a thermobalance, in flowing H 2 /2%H 2 S, and the sulfidation behavior determined as mass change per unit area. Scanning electron microscopy coupled to energy dispersive spectroscopy and X-ray diffraction analysis were used to characterize the reaction products. The addition of Y and Al increased sulfidation resistance of Fe20Cr. The addition of Y altered the species that diffused predominantly during sulfide growth. It changed from predominant cationic diffusion to predominant anionic diffusion. The addition of Al caused an even greater increase in sulfidation resistance of Fe20Cr, with the parabolic rate constant decreasing by three orders of magnitude. Y addition to the FeCrAl alloy did not cause any appreciable alteration in sulfidation resistance. Pre-oxidation of the FeCrAl and FeCrAlY alloys resulted in an extended

  3. Micro-Raman spectroscopy studies of the phase separation mechanisms of transition-metal phosphate glasses

    International Nuclear Information System (INIS)

    Mazali, Italo Odone; Alves, Oswaldo Luiz; Gimenez, Iara de Fatima

    2009-01-01

    Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation. (author)

  4. Petroleum sulfides, sulfoxides, and sulfones used as extragents

    International Nuclear Information System (INIS)

    Nikitin, Yu.E.; Lyapina, N.K.; Murinov, Yu.I.

    1988-01-01

    Possibilities of using petroleum sulfides, sulfoxides and sulfones for extraction and separation of wide range of elements are considered. It is shown that petroleum sulfides appear to be effective and selective extractants in extraction and separation of noble metals (Ru, Au, Pt, etc.). Petroleum sulfoxides are promising for solvent extraction of transition metals, actinides, rare earths etc

  5. Effect of metal sulfide pulp density on gene expression of electron transporters in Acidithiobacillus sp. FJ2.

    Science.gov (United States)

    Fatemi, Faezeh; Miri, Saba; Jahani, Samaneh

    2017-05-01

    In Acidithiobacillus ferrooxidans, one of the most important bioleaching bacterial species, the proteins encoded by the rus operon are involved in the electron transfer from Fe 2+ to O 2 . To obtain further knowledge about the mechanism(s) involved in the adaptive responses of the bacteria to growth on the different uranium ore pulp densities, we analyzed the expression of the four genes from the rus operon by real-time PCR, when Acidithiobacillus sp. FJ2 was grown in the presence of different uranium concentrations. The uranium bioleaching results showed the inhibitory effects of the metal pulp densities on the oxidation activity of the bacteria which can affect Eh, pH, Fe oxidation and uranium extractions. Gene expression analysis indicated that Acidithiobacillus sp. FJ2 tries to survive in the stress with increasing in the expression levels of cyc2, cyc1, rus and coxB, but the metal toxicity has a negative effect on the gene expression in different pulp densities. These results indicated that Acidithiobacillus sp. FJ2 could leach the uranium even in high pulp density (50%) by modulation in rus operon gene responses.

  6. Trace metal speciation and bioavailability in anaerobic digestion: A review.

    Science.gov (United States)

    Thanh, Pham Minh; Ketheesan, Balachandran; Yan, Zhou; Stuckey, David

    2016-01-01

    Trace metals are essential for the growth of anaerobic microorganisms, however, in practice they are often added to anaerobic digesters in excessive amounts, which can lead to inhibition. The concept of bioavailability of metals in anaerobic digestion has been poorly understood in the past, and a lack of deep understanding of the relationship between trace metal speciation and bioavailability can result in ineffective metal dosing strategies for anaerobic digesters. Sequential extraction schemes are useful for fractionating trace metals into their different forms, and metal sulfides can serve as a store and source for trace metals during anaerobic digestion, while natural/synthetic chelating agents (soluble microbial products-SMPs, extracellular polysaccharides-EPS, and EDTA/NTA) are capable of controlling trace metal bioavailability. Nevertheless, more work is needed to: investigate the speciation and bioavailability of Ca, Mg, Mn, W, and Se; compare the bioavailability of different forms of trace metals e.g. carbonates, sulfides, phosphates to different anaerobic trophic groups; determine what factors influence metal sulfide dissolution; investigate whether chelating agents can increase trace metal bioavailability; develop and adapt specialized analytical techniques, and; determine how trace metal dynamics change in an anaerobic membrane bioreactor (AnMBR). Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Leach tests on grouts made with actual and trace metal-spiked synthetic phosphate/sulfate waste

    International Nuclear Information System (INIS)

    Serne, R.J.; Martin, W.J.; LeGore, V.L.; Lindenmeier, C.W.; McLaurine, S.B.; Martin, P.F.C.; Lokken, R.O.

    1989-10-01

    Pacific Northwest Laboratory conducted experiments to produce empirical leach rate data for phosphate-sulfate waste (PSW) grout. Effective diffusivities were measured for various radionuclides ( 90 Sr, 99 Tc, 14 C, 129 I, 137 Cs, 60 Co, 54 Mn, and U), stable major components (NO 3 - , SO 4 2- , H 3 BO 3 , K and Na) and the trace constituents Ag, As, Cd, Hg, Pb, and Se. Two types of leach tests were used on samples of actual PSW grout and synthetic PSW grout: the American Nuclear Society (ANS) 16.1 intermittent replacement leach test and a static leach test. Grout produced from both synthetic and real PSW showed low leach rates for the trace metal constituents and most of the waste radionuclides. Many of the spiked trace metals and radionuclides were not detected in any leachates. None of the effluents contained measurable quantities of 137 Cs, 60 Co, 54 Mn, 109 Cd, 51 Cr, 210 Pb, 203 Hg, or As. For those trace species with detectable leach rates, 125 I appeared to have the greatest leach rate, followed by 99 Tc, 75 Se, and finally U, 14 C, and 110m Ag. Leach rates for nitrate are between those for I and Tc, but there is much scatter in the nitrate data because of the very low nitrate inventory. 32 refs., 6 figs., 15 tabs

  8. Metal-Silicate-Sulfide Partitioning of U, Th, and K: Implications for the Budget of Volatile Elements in Mercury

    Science.gov (United States)

    Habermann, M.; Boujibar, A.; Righter, K.; Danielson, L.; Rapp, J.; Righter, M.; Pando, K.; Ross, D. K.; Andreasen, R.

    2016-01-01

    During formation of the solar system, the Sun produced strong solar winds, which stripped away a portion of the volatile elements from the forming planets. Hence, it was expected that planets closest to the sun, such as Mercury, are more depleted in volatile elements in comparison to other terrestrial planets. However, the MESSENGER mission detected higher than expected K/U and K/Th ratios on Mercury's surface, indicating a volatile content between that of Mars and Earth. Our experiments aim to resolve this discrepancy by experimentally determining the partition coefficients (D(sup met/sil)) of K, U, and Th between metal and silicate at varying pressure (1 to 5 GPa), temperature (1500 to 1900 C), oxygen fugacity (IW-2.5 to IW-6.5) and sulfur-content in the metal (0 to 33 wt%). Our data show that U, Th, and K become more siderophile with decreasing fO2 and increasing sulfur-content, with a stronger effect for U and Th in comparison to K. Using these results, the concentrations of U, Th, and K in the bulk planet were calculated for different scenarios, where the planet equilibrated at a fO2 between IW-4 and IW-7, assuming the existence of a FeS layer, between the core and mantle, with variable thickness. These models show that significant amounts of U and Th are partitioned into Mercury's core. The elevated superficial K/U and K/Th values are therefore only a consequence of the sequestration of U and Th into the core, not evidence of the overall volatile content of Mercury.

  9. The dynamics of the laser-induced metal-semiconductor phase transition of samarium sulfide (SmS); Die Dynamik des laserinduzierten Metall-Halbleiter-Phasenuebergangs von Samariumsulfid (SmS)

    Energy Technology Data Exchange (ETDEWEB)

    Kaempfer, Tino

    2009-12-15

    The present thesis is dedicated to the experimental study of the metal-semiconductor phase transition of samarium sulfide (SmS): Temperature- and time-resolved experiments on the characterization of the phase transition of mixed-valence SmS samples (M-SmS) are presented. The measurement of the dynamics of the laser-induced phase transition pursues via time-resolved ultrashort-time microscopy and by X-ray diffraction with sub-picosecond time resolution. The electronic and structural processes, which follow an excitation of M-SmS with infrared femtosecond laser pulses, are physically interpreted on the base of the results obtained in this thesis and model imaginations. [German] Die vorliegende Arbeit ist der experimentellen Untersuchung des Metall-Halbleiter-Phasenuebergangs von Samariumsulfid (SmS) gewidmet. Es werden temperatur- und zeitaufgeloeste Experimente zur Charakterisierung des Phasenuebergangs gemischt-valenter SmS Proben (M-SmS) vorgestellt. Die Messung der Dynamik des laserinduzierten Phasenuebergangs erfolgt ueber zeitaufgeloeste Ultrakurzzeit-Mikroskopie und durch Roentgenbeugung mit subpikosekunden Zeitaufloesung. Die elektronischen und strukturellen Prozesse, welche einer Anregung von M-SmS mit infraroten Femtosekunden-Laserpulsen folgen, werden auf der Basis der in dieser Arbeit gewonnenen Ergebnisse und Modellvorstellungen physikalisch interpretiert. (orig.)

  10. Biochar- and phosphate-induced immobilization of heavy metals in contaminated soil and water: implication on simultaneous remediation of contaminated soil and groundwater.

    Science.gov (United States)

    Liang, Yuan; Cao, Xinde; Zhao, Ling; Arellano, Eduardo

    2014-03-01

    Long-term wastewater irrigation or solid waste disposal has resulted in the heavy metal contamination in both soil and groundwater. It is often separately implemented for remediation of contaminated soil or groundwater at a specific site. The main objective of this study was to demonstrate the hypothesis of simultaneous remediation of both heavy metal contaminated soil and groundwater by integrating the chemical immobilization and pump-and-treat methods. To accomplish the objective, three experiments were conducted, i.e., an incubation experiment was first conducted to determine how dairy-manure-derived biochar and phosphate rock tailing induced immobilization of Cd in the Cd-contaminated soils; second, a batch sorption experiment was carried out to determine whether the pre-amended contaminated soil still had the ability to retain Pb, Zn and Cd from aqueous solution. BCR sequential extraction as well as XRD and SEM analysis were conducted to explore the possible retention mechanism; and last, a laboratory-scale model test was undertaken by leaching the Pb, Zn, and Cd contaminated groundwater through the pre-amended contaminated soils to demonstrate how the heavy metals in both contaminated soil and groundwater were simultaneously retained and immobilized. The incubation experiment showed that the phosphate biochar were effective in immobilizing soil Cd with Cd concentration in TCLP (toxicity characteristics leaching procedure) extract reduced by 19.6 % and 13.7 %, respectively. The batch sorption experiment revealed that the pre-amended soil still had ability to retain Pb, Zn, and Cd from aqueous solution. The phosphate-induced metal retention was mainly due to the metal-phosphate precipitation, while both sorption and precipitation were responsible for the metal stabilization in the biochar amendment. The laboratory-scale test demonstrated that the soil amended with phosphate removed groundwater Pb, Zn, and Cd by 96.4 %, 44.6 %, and 49.2 %, respectively, and the

  11. Kelvin probe imaging of photo-injected electrons in metal oxide nanosheets from metal sulfide quantum dots under remote photochromic coloration

    Science.gov (United States)

    Kondo, A.; Yin, G.; Srinivasan, N.; Atarashi, D.; Sakai, E.; Miyauchi, M.

    2015-07-01

    Metal oxide and quantum dot (QD) heterostructures have attracted considerable recent attention as materials for developing efficient solar cells, photocatalysts, and display devices, thus nanoscale imaging of trapped electrons in these heterostructures provides important insight for developing efficient devices. In the present study, Kelvin probe force microscopy (KPFM) of CdS quantum dot (QD)-grafted Cs4W11O362- nanosheets was performed before and after visible-light irradiation. After visible-light excitation of the CdS QDs, the Cs4W11O362- nanosheet surface exhibited a decreased work function in the vicinity of the junction with CdS QDs, even though the Cs4W11O362- nanosheet did not absorb visible light. X-ray photoelectron spectroscopy revealed that W5+ species were formed in the nanosheet after visible-light irradiation. These results demonstrated that excited electrons in the CdS QDs were injected and trapped in the Cs4W11O362- nanosheet to form color centers. Further, the CdS QDs and Cs4W11O362- nanosheet composite films exhibited efficient remote photochromic coloration, which was attributed to the quantum nanostructure of the film. Notably, the responsive wavelength of the material is tunable by adjusting the size of QDs, and the decoloration rate is highly efficient, as the required length for trapped electrons to diffuse into the nanosheet surface is very short owing to its nanoscale thickness. The unique properties of this photochromic device make it suitable for display or memory applications. In addition, the methodology described in the present study for nanoscale imaging is expected to aid in the understanding of electron transport and trapping processes in metal oxide and metal chalcogenide heterostructure, which are crucial phenomena in QD-based solar cells and/or photocatalytic water-splitting systems.Metal oxide and quantum dot (QD) heterostructures have attracted considerable recent attention as materials for developing efficient solar cells

  12. Leach tests on grouts made with actual and trace metal-spiked synthetic phosphate/sulfate waste

    Energy Technology Data Exchange (ETDEWEB)

    Serne, R.J.; Martin, W.J.; LeGore, V.L.; Lindenmeier, C.W.; McLaurine, S.B.; Martin, P.F.C.; Lokken, R.O.

    1989-10-01

    Pacific Northwest Laboratory conducted experiments to produce empirical leach rate data for phosphate-sulfate waste (PSW) grout. Effective diffusivities were measured for various radionuclides ({sup 90}Sr, {sup 99}Tc, {sup 14}C, {sup 129}I, {sup 137}Cs, {sup 60}Co, {sup 54}Mn, and U), stable major components (NO{sub 3}{sup {minus}}, SO{sub 4}{sup 2{minus}}, H{sub 3}BO{sub 3}, K and Na) and the trace constituents Ag, As, Cd, Hg, Pb, and Se. Two types of leach tests were used on samples of actual PSW grout and synthetic PSW grout: the American Nuclear Society (ANS) 16.1 intermittent replacement leach test and a static leach test. Grout produced from both synthetic and real PSW showed low leach rates for the trace metal constituents and most of the waste radionuclides. Many of the spiked trace metals and radionuclides were not detected in any leachates. None of the effluents contained measurable quantities of {sup 137}Cs, {sup 60}Co, {sup 54}Mn, {sup 109}Cd, {sup 51}Cr, {sup 210}Pb, {sup 203}Hg, or As. For those trace species with detectable leach rates, {sup 125}I appeared to have the greatest leach rate, followed by {sup 99}Tc, {sup 75}Se, and finally U, {sup 14}C, and {sup 110m}Ag. Leach rates for nitrate are between those for I and Tc, but there is much scatter in the nitrate data because of the very low nitrate inventory. 32 refs., 6 figs., 15 tabs.

  13. Effect of pH and phosphate on trapping capacity of various heavy metal ions with ferritin reactor in flowing seawater.

    Science.gov (United States)

    Kong, Bo; Huang, He-Qing; Lin, Qing-Mei; Cai, Zong-Wei; Chen, Ping

    2005-08-01

    We describe a protein reactor consisting of native liver ferritin of Dasyatis akajei (DALF) and a dialysis bag. Our goal was to study a ferritin reactor for its capacity to trap various heavy metal ions (M2+) in flowing seawater. The reactor is sensitive and inexpensive and can be operated by nonprofessional technicians. A positive relationship between the number of trapped M2+ with the DALF reactor and its concentration in the flowing seawater was observed. Both the pH in the medium and the phosphate content within the ferritin cavity strongly affected trapping capacity. It was found that the ferritin released its phosphate compound directly with a shift in pH without the need for releasing reagent, which differs from the phosphate release characteristics of horse spleen ferritin, as previously described. This behavior evidently makes the trapping capacity with the ferritin reactor weaken, indicating that this trapping capacity is tightly connected to its phosphate compound. Our study shows that a self-regulation ability of the ferritin shell rather than its phosphate compound plays an important role in controlling the rate and capacity of trapping M2+. The ferritin reactor was constructed to monitor the contamination level of M2+ in flowing seawater. Our preliminary data along with fieldwork indicate that the DALF reactor is an analytical means for effectively monitoring the contamination level of M2+ in flowing seawater.

  14. Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

    Science.gov (United States)

    Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

    2017-12-01

    Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a

  15. Perspectives on Li and transition metal fluoride phosphates as cathode materials for a new generation of Li-ion batteries

    Directory of Open Access Journals (Sweden)

    Evgeny V. Antipov

    2015-01-01

    Full Text Available To satisfy the needs of rapidly growing applications, Li-ion batteries require further significant improvements of their key properties: specific energy and power, cyclability, safety and costs. The first generation of cathode materials for Li-ion batteries based on mixed oxides with either spinel or rock-salt derivatives has already been widely commercialized, but the potential to improve the performance of these materials further is almost exhausted. Li and transition metal inorganic compounds containing different polyanions are now considered as the most promising cathode materials for the next generation of Li-ion batteries. Further advances in cathode materials are considered to lie in combining different anions [such as (XO4n− and F−] in the anion sublattice, which is expected to enhance the specific energy and power of these materials. This review focuses on recent advances related to the new class of cathode materials for Li-ion batteries containing phosphate and fluoride anions. Special attention is given to their crystal structures and the relationships between structure and properties, which are important for their possible practical applications.

  16. Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors.

    Science.gov (United States)

    Shakeri Yekta, Sepehr; Gustavsson, Jenny; Svensson, Bo H; Skyllberg, Ulf

    2012-01-30

    The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (≈ 60% of total S) and reduced organic S (≈ 30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Synthesis and Ion-Exchange Properties of Graphene Th(IV) Phosphate Composite Cation Exchanger: Its Applications in the Selective Separation of Lead Metal Ions

    OpenAIRE

    Rangreez, Tauseef Ahmad; Inamuddin,; Asiri, Abdullah M.; Alhogbi, Basma G.; Naushad, Mu.

    2017-01-01

    In this study, graphene Th(IV) phosphate was prepared by sol?gel precipitation method. The ion-exchange behavior of this cation-exchanger was studied by investigating properties like ion-exchange capacity for various metal ions, the effect of eluent concentration, elution behavior, and thermal effect on ion-exchange capacity (IEC). Several physicochemical properties as Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) study, thermal studies, scanning electron microscopy ...

  18. Highly effective removal of heavy metals by polymer-based zirconium phosphate: a case study of lead ion.

    Science.gov (United States)

    Pan, B C; Zhang, Q R; Zhang, W M; Pan, B J; Du, W; Lv, L; Zhang, Q J; Xu, Z W; Zhang, Q X

    2007-06-01

    Zirconium phosphate (ZrP) has recently been demonstrated as an excellent sorbent for heavy metals due to its high selectivity, high thermal stability, and absolute insolubility in water. However, it cannot be readily adopted in fixed beds or any other flowthrough system due to the excessive pressure drop and poor mechanical strength resulting from its fine submicrometer particle sizes. In the present study a hybrid sorbent, i.e., polymer-supported ZrP, was prepared by dispersing ZrP within a strongly acidic cation exchanger D-001 and used for enhanced lead removal from contaminated waters. D-001 was selected as a host material for sorbent preparation mainly because of the Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid group on the exchanger surface, which would enhance permeation of the targeted metal ions. The hybrid sorbent (hereafter denoted ZrP-001) was characterized using a nitrogen adsorption technique, scanning electron microscope (SEM), and X-ray diffraction (XRD). Lead sorption onto ZrP-001 was found to be pH dependent due to the ion-exchange mechanism, and its sorption kinetics onto ZrP-001 followed the pseudo-first-order model. Compared to D-001, ZrP-001 exhibited more favorable lead sorption particularly in terms of high selectivity, as indicated by its substantially larger distribution coefficients when other competing cations Na(+), Ca(2+), and Mg(2+) coexisted at a high level in solution. Fixed-bed column runs showed that lead sorption on ZrP-001 resulted in a conspicuous decrease of this toxic metal from 40 mg/L to below 0.05 mg/L. By comparison with D-001 and ZrP-CP (ZrP dispersion within a neutrally charged polymer CP), enhanced removal efficiency of ZrP-001 resulted from the Donnan membrane effect of the host material D-001. Moreover, its feasible regeneration by diluted acid solution and negligible ZrP loss during operation also helps ZrP-001 to be a potential candidate for lead removal from water. Thus

  19. Effects of pH and phosphate on metal distribution with emphasis on As speciation and mobilization in soils from a lead smelting site

    Energy Technology Data Exchange (ETDEWEB)

    Impellitteri, Christopher A. [United States Environmental Protection Agency, National Risk Management Research Laboratory, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)]. E-mail: Impellitteri.christopher@epa.gov

    2005-06-01

    Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and geochemical speciation were analyzed as a function of depth (two sampling sites) and surface distribution. These results were compared with intensive desorption/dissolution experiments performed in a pH stat reactor for samples from the site with the highest degree of As heterogeneity. The objectives of the study were to investigate the solid-phase geochemical As speciation, assess the speciation of As in solutions equilibrated with the solids under controlled pH (pH=4 or 6) and Eh (using hydrogen or air) environments, observe the effects of phosphate on the release of As into solution, and examine the effects of phosphate on metal mobility in the systems. Arsenic was predominantly found in the As(V) valence state, though there was evidence that As(III) and As(0) were present also. The dominant geochemical phase was scorodite (FeAsO{sub 4}.2H{sub 2}O). The pH was controlled in the pH stat experiments by the addition of equinormal solutions of monoprotic (HNO{sub 3}), diprotic (H{sub 2}SO{sub 4}), or triprotic (H{sub 3}PO{sub 4}) acids. For many of the divalent metal cations, solution concentrations greatly decreased in the presence of phosphate. Solutions were also analyzed for anions. Evidence exists for sulfate release into solution. More As was released into solution at lower pH. A slight increase in solution arsenate occurs with the addition of phosphate, but the risk posed from the increased desorption/dissolution of As must be weighed against the decrease in solution concentrations of many metals especially Pb. If tailings from this site underwent acidification (e.g., acid mine drainage), in situ sequestration of metals by phosphate could be combined with placement of subsurface permeable reactive barriers for capture of As to reduce the risk associated with arsenic and trace metal mobilization. Results

  20. Effects of pH and phosphate on metal distribution with emphasis on As speciation and mobilization in soils from a lead smelting site

    International Nuclear Information System (INIS)

    Impellitteri, Christopher A.

    2005-01-01

    Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and geochemical speciation were analyzed as a function of depth (two sampling sites) and surface distribution. These results were compared with intensive desorption/dissolution experiments performed in a pH stat reactor for samples from the site with the highest degree of As heterogeneity. The objectives of the study were to investigate the solid-phase geochemical As speciation, assess the speciation of As in solutions equilibrated with the solids under controlled pH (pH=4 or 6) and Eh (using hydrogen or air) environments, observe the effects of phosphate on the release of As into solution, and examine the effects of phosphate on metal mobility in the systems. Arsenic was predominantly found in the As(V) valence state, though there was evidence that As(III) and As(0) were present also. The dominant geochemical phase was scorodite (FeAsO 4 .2H 2 O). The pH was controlled in the pH stat experiments by the addition of equinormal solutions of monoprotic (HNO 3 ), diprotic (H 2 SO 4 ), or triprotic (H 3 PO 4 ) acids. For many of the divalent metal cations, solution concentrations greatly decreased in the presence of phosphate. Solutions were also analyzed for anions. Evidence exists for sulfate release into solution. More As was released into solution at lower pH. A slight increase in solution arsenate occurs with the addition of phosphate, but the risk posed from the increased desorption/dissolution of As must be weighed against the decrease in solution concentrations of many metals especially Pb. If tailings from this site underwent acidification (e.g., acid mine drainage), in situ sequestration of metals by phosphate could be combined with placement of subsurface permeable reactive barriers for capture of As to reduce the risk associated with arsenic and trace metal mobilization. Results from this study could be used

  1. Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

    Science.gov (United States)

    Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

    2006-01-01

    Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into

  2. Phosphate Salts

    Science.gov (United States)

    ... many different combinations of the chemical phosphate with salts and minerals. Foods high in phosphate include dairy products, whole grain cereals, nuts, and certain meats. Phosphates found in dairy products ... People use phosphate salts for medicine. Be careful not to confuse phosphate ...

  3. Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3)

    Energy Technology Data Exchange (ETDEWEB)

    Sarma, Debajit; Islam, Saiful M.; Subrahmanyam, K. S.; Kanatzidis, Mercouri G.

    2016-09-16

    Heavy metal ions (Cd2+, Hg2+, As3+ and Pb2+) are an important contributor to the contamination of groundwater and other water bodies in and around industrial areas. Herein, we demonstrate the rapid and efficient capacity of a layered metal sulfide material, K2xSn4-xS8-x (x = 0.65-1, KTS-3) for heavy metal ion removal from water. The effect of concentration, pH, kinetics, and competitive ions such as Na+/Ca2+ on the heavy metal ion removal capacity of KTS-3 was systematically investigated. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder X-ray diffraction studies revealed that the heavy metal ion-exchange of KTS-3 is complete (quantitative replacement of all potassium ions) and topotactic. The heavy metal ion-exchange by using KTS-3 follows the Langmuir-Freundlich model with high exchange capacities, q(m) 205(17) mg g-1 for Cd2+, 372(21) mg g-1 for Hg2+ and 391(89) mg g-1 for Pb2+. KTS-3 retains excellent heavy metal ion-exchange capacity even in very high concentration (1 M) of competing ions (Na+/Ca2+) and also over a broad pH range (2-12). KTS-3 also exhibits very good ion-exchange capacity for precious Ag+ and toxic As3+ ions. The kinetics of heavy metal ion adsorption by KTS-3 are rapid (absorbs all ions within a few minutes). These properties and the environmentally friendly character of KTS-3 make it a promising candidate for sequestration of heavy metal ions from water.

  4. Aerobic sulfide production and cadmium precipitation by Escherichia coli expressing the Treponema denticola cysteine desulfhydrase gene.

    Science.gov (United States)

    Wang, C L; Lum, A M; Ozuna, S C; Clark, D S; Keasling, J D

    2001-08-01

    The cysteine desulfhydrase gene of Treponema denticola was over-expressed in Escherichia coli to produce sulfide under aerobic conditions and to precipitate metal sulfide complexes on the cell wall. When grown in a defined salts medium supplemented with cadmium and cysteine, E. coli producing cysteine desulfhydrase secreted sulfide and removed nearly all of the cadmium from solution after 48 h. A control strain produced significantly less sulfide and removed significantly less cadmium. Measurement of acid-labile sulfide and energy dispersive X-ray spectroscopy indicated that cadmium was precipitated as cadmium sulfide. Without supplemental cysteine, both the E. coli producing cysteine desulfhydrase and the control E. coli demonstrated minimal cadmium removal.

  5. Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Huang, Zhen-Feng; Song, Jiajia; Li, Ke; Tahir, Muhammad; Wang, Yu-Tong; Pan, Lun; Wang, Li; Zhang, Xiangwen; Zou, Ji-Jun

    2016-02-03

    The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion.

  6. Hydrogen sulfide removal in water-based drilling fluid by metal oxide nanoparticle and ZnO/TiO2 nanocomposite

    Science.gov (United States)

    Salehi Morgani, M.; Saboori, R.; Sabbaghi, S.

    2017-07-01

    Advanced approaches to the application of nanomaterials for environmental studies, such as waste-water treatment and pollution removal/adsorption, have been considered in recent decades. In this research, hydrogen sulfide removal from water-based drilling fluid by ZnO and TiO2 nanoparticles and a ZnO/TiO2 nanocomposite was studied experimentally. The ZnO and TiO2 nanoparticles were synthesized by sedimentation and the sol-gel method. A sol-chemical was employed to synthesize the ZnO/TiO2 nanocomposite. X-ray diffraction, scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface analysis, inductively coupled plasma mass spectrometry (ICP), dynamic light scattering (DLS) and Fourier transform infrared spectroscopy were used to characterize the produced ZnO and TiO2 nanoparticles, and the ZnO/TiO2 nanocomposite. The results showed that the concentration of hydrogen sulfide decreased from 800 ppm to about 250 ppm (about 70% removal) and less than 150 ppm (more than 80% removal) using the TiO2 and ZnO nanoparticles with a 0.67 wt% concentration, respectively. Hydrogen sulfide removal using the ZnO/TiO2 nanocomposite with a 0.67 wt% showed the highest value of removal in comparison with the TiO2 and ZnO nanoparticles. The hydrogen sulfide level was lowered from 800 ppm to less than 5 ppm (99% removal) by the nanocomposite.

  7. Osteoclastic differentiation and resorption is modulated by bioactive metal ions Co2+, Cu2+ and Cr3+ incorporated into calcium phosphate bone cements

    Science.gov (United States)

    Bernhardt, Anne; Schamel, Martha; Gbureck, Uwe; Gelinsky, Michael

    2017-01-01

    Biologically active metal ions in low doses have the potential to accelerate bone defect healing. For successful remodelling the interaction of bone graft materials with both bone-forming osteoblasts and bone resorbing osteoclasts is crucial. In the present study brushite forming calcium phosphate cements (CPC) were doped with Co2+, Cu2+ and Cr3+ and the influence of these materials on osteoclast differentiation and activity was examined. Human osteoclasts were differentiated from human peripheral blood mononuclear cells (PBMC) both on the surface and in indirect contact to the materials on dentin discs. Release of calcium, phosphate and bioactive metal ions was determined using ICP-MS both in the presence and absence of the cells. While Co2+ and Cu2+ showed a burst release, Cr3+ was released steadily at very low concentrations (below 1 μM) and both calcium and phosphate release of the cements was considerably changed in the Cr3+ modified samples. Direct cultivation of PBMC/osteoclasts on Co2+ cements showed lower attached cell number compared to the reference but high activity of osteoclast specific enzymes tartrate resistant acid phosphatase (TRAP), carbonic anhydrase II (CAII) and cathepsin K (CTSK) and significantly increased gene expression of vitronectin receptor. Indirect cultivation with diluted Co2+ cement extracts revealed highest resorbed area compared to all other modifications and the reference. Cu2+ cements had cytotoxic effect on PBMC/osteoclasts during direct cultivation, while indirect cultivation with diluted extracts from Cu2+ cements did not provoke cytotoxic effects but a strictly inhibited resorption. Cr3+ doped cements did not show cytotoxic effects at all. Gene expression and enzyme activity of CTSK was significantly increased in direct culture. Indirect cultivation with Cr3+ doped cements revealed significantly higher resorbed area compared to the reference. In conclusion Cr3+ doped calcium phosphate cements are an innovative cement

  8. Metal-organic framework templated synthesis of porous inorganic materials as novel sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L.; Lin, Wenbin; Abney, Carter W.

    2017-03-21

    A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.

  9. Distinct configurations of antisite defects in ordered metal phosphates: comparison between LiMnPO4 and LiFePO4.

    Science.gov (United States)

    Chung, Sung-Yoon; Choi, Si-Young; Lee, Seongsu; Ikuhara, Yuichi

    2012-05-11

    By using a combination of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, ab initio density-functional theory calculations, and neutron powder diffraction techniques, We have found completely different configurations of the antisite exchange defects in LiMnPO4 and LiFePO4, with a random distribution of the exchange pairs without aggregation in the former and with zigzag-type clustering behavior preferred in the latter. Recalling the compositional analogy and identical crystal structure of the two metal phosphates, such unexpectedly distinct arrangement of the same type of point defects is a notable structural aspect.

  10. Low temperature setting iron phosphate ceramics as a stabilization and solidification agent for incinerator ash contaminated with transuranic and RCRA metals

    International Nuclear Information System (INIS)

    Medvedev, P.G.; Hansen, M.; Wood, E.L.; Frank, S.M.; Sidwell, R.W.; Giglio, J.J.; Johnson, S.G.; Macheret, J.

    1997-01-01

    Incineration of combustible Mixed Transuranic Waste yields an ash residue that contains oxides of Resource Conservation and Recovery Act (RCRA) and transuranic metals. In order to dispose of this ash safely, it has to be solidified and stabilized to satisfy appropriate requirements for repository disposal. This paper describes a new method for solidification of incinerator ash, using room temperature setting iron phosphate ceramics, and includes fabrication procedures for these waste forms as well as results of the MCC-1 static leach test, XRD analysis, scanning electron microscopy studies and density measurements of the solidified waste form produced

  11. Phosphate conversion coating reduces the degradation rate and suppresses side effects of metallic magnesium implants in an animal model.

    Science.gov (United States)

    Rahim, Muhammad Imran; Tavares, Ana; Evertz, Florian; Kieke, Marc; Seitz, Jan-Marten; Eifler, Rainer; Weizbauer, Andreas; Willbold, Elmar; Jürgen Maier, Hans; Glasmacher, Birgit; Behrens, Peter; Hauser, Hansjörg; Mueller, Peter P

    2017-08-01

    Magnesium alloys have promising mechanical and biological properties for the development of degradable implants. However, rapid implant corrosion and gas accumulations in tissue impede clinical applications. With time, the implant degradation rate is reduced by a highly biocompatible, phosphate-containing corrosion layer. To circumvent initial side effects after implantation it was attempted to develop a simple in vitro procedure to generate a similarly protective phosphate corrosion layer. To this end magnesium samples were pre-incubated in phosphate solutions. The resulting coating was well adherent during routine handling procedures. It completely suppressed the initial burst of corrosion and it reduced the average in vitro magnesium degradation rate over 56 days almost two-fold. In a small animal model phosphate coatings on magnesium implants were highly biocompatible and abrogated the appearance of gas cavities in the tissue. After implantation, the phosphate coating was replaced by a layer with an elemental composition that was highly similar to the corrosion layer that had formed on plain magnesium implants. The data demonstrate that a simple pre-treatment could improve clinically relevant properties of magnesium-based implants. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1622-1635, 2017. © 2016 Wiley Periodicals, Inc.

  12. Phosphate-induced metal stabilization: Use of apatite and bone char for the removal of soluble radionuclides in authentic and simulated DOE groundwater

    International Nuclear Information System (INIS)

    Bostick, W.D.; Jarabek, R.J.; Conca, J.L.

    1999-01-01

    The apatite group of minerals is a family of calcium phosphate phases. Apatite is the principal component of bone tissue, and it also occurs naturally as mineral deposits in the geosphere. Bone char is calcined (coked) animal bone, containing activated carbon as well as calcium phosphate mineral phases. Apatite IItrademark is a more reactive form of apatite, supplied by UFA Ventures, Inc., at a cost of approximately 1/4 that of commercial bone char. Apatite is shown to be effective for the removal of select heavy metal impurities in groundwater. Previous investigations have demonstrated that apatite is an effective medium for the stabilization of soluble lead, cadmium, and zinc from mine waste leachate by the formation of highly insoluble precipitate phases. The performance of bone char and apatite II are compared with other candidate sorption media (including granular activated carbon and anion exchange resin) for the removal of soluble uranyl ion in synthetic DOE Site groundwater supplemented with varying levels of interfering nitrate ion. Apatite II has a greater affinity for U(VI), especially in the presence of nitrate ion, as evidenced by a larger value for the conditional distribution coefficient (Kd) in batch test experiments. Contact of uranyl nitrate solution with apatite II is shown to produce highly insoluble mineral phases of the autunite group (calcium uranyl phosphate hydrates). Apatite II is also demonstrated to be moderately effective for the removal of soluble radioactive isotopes of strontium, but not cesium, when these ions are supplemented into authentic DOE Site groundwater

  13. Scandium phosphates

    International Nuclear Information System (INIS)

    Mel'nikov, P.P.; Komissarova, L.N.

    1988-01-01

    The review deals with scandium phosphates known by now, including mono- and condensed phosphates (di-, tri-, tetra phosphates and more condensed forms). Phosphates with complex cation and anion parts are also considered. The methods of preparation, structural types, structure peculiarities, physicochemical characteristics are generalized and application fields of the compounds mentioned are indicated

  14. Revegetation of Acid Rock Drainage (ARD) Producing Slope Surface Using Phosphate Microencapsulation and Artificial Soil

    Science.gov (United States)

    Kim, Jae Gon

    2017-04-01

    Oxidation of sulfides produces acid rock drainage (ARD) upon their exposure to oxidation environment by construction and mining activities. The ARD causes the acidification and metal contamination of soil, surface water and groundwater, the damage of plant, the deterioration of landscape and the reduction of slope stability. The revegetation of slope surface is one of commonly adopted strategies to reduce erosion and to increase slope stability. However, the revegetation of the ARD producing slope surface is frequently failed due to its high acidity and toxic metal content. We developed a revegetation method consisting of microencapsualtion and artificial soil in the laboratory. The revegetation method was applied on the ARD producing slope on which the revegetation using soil coverage and seeding was failed and monitored the plant growth for one year. The phosphate solution was applied on sulfide containing rock to form stable Fe-phosphate mineral on the surface of sulfide, which worked as a physical barrier to prevent contacting oxidants such as oxygen and Fe3+ ion to the sulfide surface. After the microencapsulation, two artificial soil layers were constructed. The first layer containing organic matter, dolomite powder and soil was constructed at 2 cm thickness to neutralize the rising acidic capillary water from the subsurface and to remove the dissolved oxygen from the percolating rain water. Finally, the second layer containing seeds, organic matter, nutrients and soil was constructed at 3 cm thickness on the top. After application of the method, the pH of the soil below the artificial soil layer increased and the ARD production from the rock fragments reduced. The plant growth showed an ordinary state while the plant died two month after germination for the previous revegetation trial. No soil erosion occurred from the slope during the one year field test.

  15. Synthesis and Ion-Exchange Properties of Graphene Th(IV) Phosphate Composite Cation Exchanger: Its Applications in the Selective Separation of Lead Metal Ions.

    Science.gov (United States)

    Rangreez, Tauseef Ahmad; Asiri, Abdullah M; Alhogbi, Basma G; Naushad, Mu

    2017-07-24

    In this study, graphene Th(IV) phosphate was prepared by sol-gel precipitation method. The ion-exchange behavior of this cation-exchanger was studied by investigating properties like ion-exchange capacity for various metal ions, the effect of eluent concentration, elution behavior, and thermal effect on ion-exchange capacity (IEC). Several physicochemical properties as Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) study, thermal studies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were also carried out. The material possessed an IEC of 1.56 meq·dry·g -1 of the exchanger and was found to be nano-composite. The selectivity studies showed that the material is selective towards Pb(II) ions. The selectivity of this cation-exchanger was demonstrated in the binary separation of Pb(II) ions from mixture with other metal ions. The recovery was found to be both quantitative and reproducible.

  16. Antitumor Allium Sulfides.

    Science.gov (United States)

    Nohara, Toshihiro; Fujiwara, Yukio; El-Aasr, Mona; Ikeda, Tsuyoshi; Ono, Masateru; Nakano, Daisuke; Kinjo, Junei

    2017-01-01

    We examined the sulfides in onion (Allium cepa L.), Welsh onion (A. fistulosum L.), and garlic (A. sativum L.), and obtained three new thiolane-type sulfides (onionins A 1 -A 3 ) from onion; two new thiabicyclic-type sulfides (welsonins A 1 , A 2 ), together with onionins A 1 -A 3 , from Welsh onion; and six new acyclic-type sulfides (garlicnins L-1-L-4, E, and F), ten new thiolane-type sulfides (garlicnins A, B 1 -B 4 , C 1 -C 3 , K 1 , and K 2 ), and three new atypical cyclic-type sulfides (garlicnins G, I, and J) from garlic. Acetone extracts showed the potential of these sulfides in inhibiting the polarization of M2 activated macrophages that are capable of suppressing tumor-cell proliferation. The effect of the thiolane-type sulfide of a major component, onionin A 1 , on tumor progression and metastasis in both osteosarcoma and ovarian cancer-bearing mouse models was then examined. Tumor proliferation was depressed, and tumor metastasis was controlled by regulating macrophage activation. These results showed that onionin A 1 is an effective agent for controlling tumors in both in vitro and in vivo models, and that the antitumor effects observed in vivo are likely caused by reversing the antitumor immune system. Activation of the antitumor immune system by onionin A 1 might be an effective adjuvant therapy for patients with osteosarcoma, ovarian cancer and other malignant tumors. Based on these findings, pharmacological investigations will be conducted in the future to develop natural and healthy foods and anti-cancer agents that can prevent or combat disease.

  17. Case study: heavy metals and fluoride contents in the materials of Syrian phosphate industry and in the vicinity of phosphogypsum piles.

    Science.gov (United States)

    Al Attar, L; Al-Oudat, M; Shamali, K; Abdul Ghany, B; Kanakri, S

    2012-01-01

    This study focuses on the determination of heavy metals and fluoride concentrations in the Syrian phosphate industry and in the vicinity of the phosphogypsum (PG) piles. Four sampling campaigns were carried out, in which 86 soil, 139 plant, 30 air particulate, 16 water, 12 PG, 6 phosphate ore (raw and treated) and 3 fertilizer samples were collected. Differential pulse anode stripping voltammetry was used for Pb and Cd determination, atomic absorption spectrometry was used for Zn, Cr and Cu determination, and instrumental neutron activation analysis was used for Se, Ni, As and Hg determination. Fluoride concentration was determined via fluoride ion selective electrode. The data revealed that most of the heavy metals were retained in the fertilizer. Fluoride content in PG was 0.47%. The presence of PG piles showed no impact on the run-off and ground and lake waters in the area. However, fluoride concentration was double the permissible airborne threshold in the sites to the east of the PG piles because of the prevailing wind in the region. Similarly, enhanced concentrations of fluoride were recorded for the eastern soil samples. The content of heavy metals in plants was element- and plant-specific and influenced by the element concentration in soil, the soil texture and the pH. The maximal mean of fluoride was found in the plants species of the eastern sites (699 mg kg(-1)), which mainly related to PG erosion and airborne deposition. Thus, the main impact of the PG piles was to increase the concentration of fluoride in the surrounding area. A national action should be taken to regulate PG piles.

  18. Bioresorbable Ca-phosphate-polymer/metal and Fe-Ag nanocomposites for macro-porous scaffolds with tunable degradation and drug release

    Science.gov (United States)

    Gotman, I.; Swain, S. K.; Sharipova, A.; Gutmanas, E. Y.

    2016-11-01

    Bioresorbable implants are increasingly gaining popularity as an attractive alternative to traditional permanent bone healing devices. The advantage of bioresorbable implantable devices is that they slowly degrade over time and disappear once their "mission" is accomplished. Thus, no foreign material is left behind that can cause adverse effects on the host, such as long term local or systemic immune response and stress-shielding related bone atrophy. Resorbable materials considered for surgical implant applications include degradable polymers, Ca phosphate ceramics (CaP) and corrodible metals. Degradable polymers, such as polycaprolactone and lactic acid are weak, lack osteoconductivity and degrade to acidic products that can cause late inflammation. Resorbable CaP ceramics (e.g., β-TCP) are attractive materials for bone regeneration bear close resemblance to the bone mineral, however they are intrinsically brittle and thus unsuitable for use in load-bearing sites. Moreover, introducing high porosity required to encourage better cellular ingrowth into bone regeneration scaffolds is detrimental to the mechanical strength of the material. In present work we review and discuss our results on development of strong bioresorbable Ca-phosphate-polymer/metal nanonocomposites and highly porous scaffolds from them. By introduction of nanoscale ductile polymer or metal phase into CaP ceramic an attempt was made to mimic structure of natural bone, where nanocrystallites of CaP ceramic are bonded by thin collagen layers. Recent results on development of high strength scaffolds from Fe-Ag nanocomposites are also reported. High energy milling of powders followed by cold sintering—high pressure consolidation at ambient temperature in combination with modified porogen leaching method was employed for processing. The developed nanocomposites and scaffolds exhibited high mechanical strength coupled with measurable ductility, gradual lost weight and strength during immersion in

  19. Phosphate sensing

    Science.gov (United States)

    Bergwitz, Clemens; Jüppner, Harald

    2011-01-01

    Human phosphate homeostasis is regulated at the level of intestinal absorption of phosphate from the diet, release of phosphate through bone resorption, and renal phosphate excretion and involves the actions of parathyroid hormone (PTH), 1,25-dihydroxy-vitamin D (1,25-(OH)2-D), and fibroblast growth factor 23 (FGF23) to maintain circulating phosphate levels within a narrow normal range, which is essential for numerous cellular functions, for the growth of tissues and for bone mineralization. Prokaryotic and single cellular eukaryotic organisms such as bacteria and yeast “sense” ambient phosphate with a multi-protein complex located in their plasma membrane, which modulates the expression of genes important for phosphate uptake and metabolism (pho pathway). Database searches based on amino acid sequence conservation alone have been unable to identify metazoan orthologs of the bacterial and yeast phosphate sensors. Thus little is known about how human and other metazoan cells sense inorganic phosphate to regulate the effects of phosphate on cell metabolism (“metabolic” sensing) or to regulate the levels of extracellular phosphate via feedback system(s) (“endocrine” sensing). Whether the “metabolic” and the “endocrine” sensor use the same or different signal transduction cascades is unknown. This chapter will review the bacterial and yeast phosphate sensors, and then discuss what is currently known about the metabolic and endocrine effects of phosphate in multicellular organisms and humans. PMID:21406298

  20. Calcium phosphate coating on titanium induced by phosphating

    Energy Technology Data Exchange (ETDEWEB)

    Feng, B. [Sichuan Univ., Chengdu (China). Engineering Research Center in Biomaterials; Sichuan Inst. of Tech., Chengdu (China). Dept. of Material Science and Engineering; Chen, J.Y.; Zhang, X.D. [Sichuan Univ., Chengdu (China). Engineering Research Center in Biomaterials

    2001-07-01

    The phosphatization has been used in anti-corrosion treatment for metals for many years. In this work, the calcium phosphate ceramic coatings (Ca-P coatings) based on titanium were prepared by phosphating titanium and then soaking in a supersaturated calcium phosphate solution. The effect of phosphatization of titanium on the formation of Ca-P coating was investigated. The analysis with a scanning electron microscopy showed microporous surfaces of titanium after phosphatization. The spectra of X-ray photoelectron spectroscopy indicated that the surfaces contained PO{sub 4}{sup 3-}, HPO{sub 4}{sup 2-} and H{sub 2}PO{sup -}. The induced couple plasma atomic emission spectroscopy suggested that precipitation of P be prior to Ca during immersion in the supersaturated calcium phosphate solution. (orig.)

  1. Sodium Phosphate

    Science.gov (United States)

    Sodium phosphate is used in adults 18 years of age or older to empty the colon (large intestine, bowel) ... view of the walls of the colon. Sodium phosphate is in a class of medications called saline ...

  2. Sulfidation behavior of rhenium and cobalt-rhenium alloys

    International Nuclear Information System (INIS)

    Shiring, R.; Douglass, D.L.

    1999-01-01

    The sulfidation behavior of Re and three Co-Re alloys, 15, 30, and 45 w/o, was studied over the temperature range 700--800 C at sulfur pressures of 10 -4 and 10 -2 atm. The kinetics of sulfidation followed the parabolic rate law and the activation energies for all alloys were similar to that of pure cobalt. A positive rate dependency on sulfur pressure was observed and Pt markers were located at the metal-scale interface, both observations clearly suggesting that outward cation diffusion through a P-type sulfide scale occurred. Two dominant sulfides, Co 9 S 8 and ReS 2 , formed. Weight gains decreased for a given set of conditions with increasing rhenium content. An order of magnitude decrease in the sulfidation rate occurred as the rhenium content increased from 15 to 45 w/o. Preferential sulfidation of cobalt initially occurred, causing a rhenium-enriched zone to form in the substrate beneath the cobalt-sulfide scale. The initial sulfide to form was Co 3 S 4 , but, subsequently, Co 9 S 8 became the dominant sulfide, forming beneath the outer Co 3 S 4 layer. ReS 2 formed at lower cobalt levels. Pure Re was also studied, the sulfidation rate being about 10 4 times slower than that of cobalt. The decreasing rate of sulfidation with increasing Re content is attributed primarily to slower cobalt diffusion outward through the Re-enriched substrate, a phenomenon similar to that observed by C. Wagner for the oxidation of Ni-Pt alloys

  3. Heavy metal accumulation in lizards living near a phosphate treatment plant: possible transfer of contaminants from aquatic to terrestrial food webs.

    Science.gov (United States)

    Nasri, Intissar; Hammouda, Abdessalam; Hamza, Foued; Zrig, Ahlem; Selmi, Slaheddine

    2017-05-01

    We investigated the accumulation of heavy metals in Bosk's fringe-toed lizards (Acanthodactylus boskianus) living in Gabès region (southeastern Tunisia), in relation to habitat, diet, and distance from the Gabès-Ghannouche factory complex of phosphate treatment. More specifically, we compared the concentrations of cadmium, lead, and zinc in the stomach contents and samples of the liver, kidney, and tail from lizards living in four sites corresponding to different combinations of habitat (coastal dunes vs backshore) and distance from the factory complex (heavy metals in lizard tissues were overall positively correlated with those in the preys they ingested. Moreover, there was a general tendency towards increased concentrations of cadmium, lead, and zinc in the samples from lizards living on coastal dunes compared to those from the other sites, although some differences still lacked statistical significance. These results suggest that the highest contamination of lizards living on coastal dunes was probably related to the ingestion of contaminated amphipods. Thus, amphipods and Bosk's fringe-toed lizards seem to provide an important link between the marine and terrestrial food webs, with higher concentrations appearing to accumulate from materials released into the sea rather than the terrestrial environment. With regard to metal distribution among tissues, our results were overall in agreement with previous findings in other reptiles. In particular, cadmium was most concentrated in the liver samples, stressing once more the role of the liver as a storage organ of Cd. Moreover, high concentrations of the three assessed metals were found in the kidney samples, showing the role of the kidney as an active site of heavy metal accumulation.

  4. Sulfide treatment to inhibit mercury adsorption onto activated carbon in carbon-in-pulp gold recovery circuits

    Energy Technology Data Exchange (ETDEWEB)

    Touro, F.J.; Lipps, D.A.

    1988-03-29

    A process for treating a mercury-contaminated, precious metal-containing ore slurry is described comprising: (a) reacting sulfide anions in an aqueous ore slurry of a mercury and precious metal-containing carbonaceous ore, and (b) conducting a simultaneous cyanide leach and carbon-in-pulp adsorption of the precious metal from the carbonaceous ore in the sulfide-containing ore slurry.

  5. Geology of volcanogenic massive sulfide deposit near Meli ...

    African Journals Online (AJOL)

    Bheema

    Chloritization is the dominant alteration among others, and the ore body is associated with mafic to intermediate ... attracted both national and international mineral exploration companies to search for the metallic ... metal sulfides are attracting the attention of many exploration companies like, National Mining. Company ...

  6. Homogeneous liquid-liquid extraction of metal ions with non-fluorinated bis(2-ethylhexyl)phosphate ionic liquids having a lower critical solution temperature in combination with water.

    Science.gov (United States)

    Depuydt, Daphne; Liu, Liwang; Glorieux, Christ; Dehaen, Wim; Binnemans, Koen

    2015-09-28

    Ionic liquids with an ether-functionalised cation and the bis(2-ethylhexyl)phosphate anion show thermomorphic behaviour in water, with a lower critical solution temperature. These ionic liquids are useful for homogeneous liquid-liquid extraction of first-row (3d) transition metals.

  7. Separation of oxidized americium from lanthanides by use of pillared metal(IV) phosphate-phosphonate hybrid materials

    Energy Technology Data Exchange (ETDEWEB)

    Burns, J.D.; Clearfield, A. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemistry; Borkowski, M.; Reed, D.T. [Los Alamos National Laboratory, Carlsbad, NM (United States). Earth and Environmental Sciences Div.

    2012-07-01

    Closing the nuclear fuel cycle in the US poses many challenges, one of which is found in the waste streams, which contain both trivalent lanthanides and actinides. The separation of americium from the raffinate will dramatically reduce the long-term radiotoxicity of the waste. The sorption of americium in both the tri- and pentavalent oxidation states was observed for four M(IV) phosphate-phosphonate ion exchange materials in nitric acid at pH 2. High selectivity was observed for reduced Am(III) with K{sub d} values ca. 6 x 10{sup 5} mL/g, while the K{sub d} values for Am(V) were much lower. A new method of synthesizing and stabilizing AmO{sub 2}{sup +} to yield a lifetime of at least 24 h in acidic media using a combination of sodium persulfate and calcium hypochlorite will be described.

  8. Separation of oxidized americium from lanthanides by use of pillared metal(IV) phosphate-phosphonate hybrid materials

    International Nuclear Information System (INIS)

    Burns, J.D.; Clearfield, A.; Borkowski, M.; Reed, D.T.

    2012-01-01

    Closing the nuclear fuel cycle in the US poses many challenges, one of which is found in the waste streams, which contain both trivalent lanthanides and actinides. The separation of americium from the raffinate will dramatically reduce the long-term radiotoxicity of the waste. The sorption of americium in both the tri- and pentavalent oxidation states was observed for four M(IV) phosphate-phosphonate ion exchange materials in nitric acid at pH 2. High selectivity was observed for reduced Am(III) with K d values ca. 6 x 10 5 mL/g, while the K d values for Am(V) were much lower. A new method of synthesizing and stabilizing AmO 2 + to yield a lifetime of at least 24 h in acidic media using a combination of sodium persulfate and calcium hypochlorite will be described.

  9. Multidisciplinary study of radionuclides and heavy-metal concentrations in wildlife on phosphate-mined and reclaimed lands. Final report

    International Nuclear Information System (INIS)

    Pritchard, P.C.H.; Bloodwell, J.M.

    1986-11-01

    The phosphate-rich mineral deposits of central Florida tend to exhibit background radiation levels that are elevated due to the uranium and its decay products found in association with the ore. The report documents radioactivity levels in two groups of animals that had heretofore not been examined by other investigators -- aquatic reptiles (American alligators, softshell turtles, and Florida cooter turtles) and terrestrial mammals (armadillos), based on the criterion that these species have significant proportions of their mass comprised of bony tissue likely to show elevated concentrations of radium. The alligator bones contained only low concentrations of radium, and there were no significant differences between alligators collected from mined, mineralized-unmined, or unmineralized land. Whether the levels of radium in the bones of the turtles represents a hazard to the health of these long-lived animals or to humans who may consume their flesh is unclear

  10. Electrochemical and morphological investigation of silver and zinc modified calcium phosphate bioceramic coatings on metallic implant materials

    International Nuclear Information System (INIS)

    Furko, M.; Jiang, Y.; Wilkins, T.A.; Balázsi, C.

    2016-01-01

    In our research nanostructured silver and zinc doped calcium-phosphate (CaP) bioceramic coatings were prepared on commonly used orthopaedic implant materials (Ti6Al4V). The deposition process was carried out by the pulse current technique at 70 °C from electrolyte containing the appropriate amount of Ca(NO 3 ) 2 and NH 4 H 2 PO 4 components. During the electrochemical deposition Ag + and Zn 2+ ions were introduced into the solution. The electrochemical behaviour and corrosion rate of the bioceramic coatings were investigated by potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) measurements in conventional Ringer's solution in a three electrode open cell. The coating came into contact with the electrolyte and corrosion occurred during immersion. In order to achieve antimicrobial properties, it is important to maintain a continuous release of silver ions into physiological media, while the bioactive CaP layer enhances the biocompatibility properties of the layer by fostering the bone cell growth. The role of Zn 2+ is to shorten wound healing time. Morphology and composition of coatings were studied by Scanning Electron Microscopy, Transmission Electron Microscopy and Energy-dispersive X-ray spectroscopy. Differential thermal analyses (DTA) were performed to determine the thermal stability of the pure and modified CaP bioceramic coatings while the structure and phases of the layers were characterized by X-ray diffraction (XRD) measurements. - Highlights: • Ag and Zn doped calcium phosphate (CaP) layers were electrochemically deposited. • Layer degradation was studied by EIS and potentiodynamic measurements. • The bioceramic coatings became passive after a period of immersion time. • Ag and Zn modified layer shows higher degradation rate compared to pure CaP coating.

  11. Electrochemical and morphological investigation of silver and zinc modified calcium phosphate bioceramic coatings on metallic implant materials

    Energy Technology Data Exchange (ETDEWEB)

    Furko, M., E-mail: monika.furko@bayzoltan.hu [Bay Zoltán Nonprofit Ltd. for Applied Research, H-1116 Budapest, Fehérvári u. 130 (Hungary); Jiang, Y.; Wilkins, T.A. [Institute of Particle Science and Engineering, University of Leeds, LS2 9JT (United Kingdom); Balázsi, C. [Bay Zoltán Nonprofit Ltd. for Applied Research, H-1116 Budapest, Fehérvári u. 130 (Hungary)

    2016-05-01

    In our research nanostructured silver and zinc doped calcium-phosphate (CaP) bioceramic coatings were prepared on commonly used orthopaedic implant materials (Ti6Al4V). The deposition process was carried out by the pulse current technique at 70 °C from electrolyte containing the appropriate amount of Ca(NO{sub 3}){sub 2} and NH{sub 4}H{sub 2}PO{sub 4} components. During the electrochemical deposition Ag{sup +} and Zn{sup 2+} ions were introduced into the solution. The electrochemical behaviour and corrosion rate of the bioceramic coatings were investigated by potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) measurements in conventional Ringer's solution in a three electrode open cell. The coating came into contact with the electrolyte and corrosion occurred during immersion. In order to achieve antimicrobial properties, it is important to maintain a continuous release of silver ions into physiological media, while the bioactive CaP layer enhances the biocompatibility properties of the layer by fostering the bone cell growth. The role of Zn{sup 2+} is to shorten wound healing time. Morphology and composition of coatings were studied by Scanning Electron Microscopy, Transmission Electron Microscopy and Energy-dispersive X-ray spectroscopy. Differential thermal analyses (DTA) were performed to determine the thermal stability of the pure and modified CaP bioceramic coatings while the structure and phases of the layers were characterized by X-ray diffraction (XRD) measurements. - Highlights: • Ag and Zn doped calcium phosphate (CaP) layers were electrochemically deposited. • Layer degradation was studied by EIS and potentiodynamic measurements. • The bioceramic coatings became passive after a period of immersion time. • Ag and Zn modified layer shows higher degradation rate compared to pure CaP coating.

  12. Titanocene sulfide chemistry

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal

    2016-01-01

    Roč. 314, MAY 2016 (2016), s. 83-102 ISSN 0010-8545 R&D Projects: GA ČR(CZ) GAP207/12/2368 Institutional support: RVO:61388955 Keywords : titanocene sulfide chemistry * photolysis * titanocene hydrosulfides Ti-(SH)n Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.324, year: 2016

  13. Promotion of Mo/Al2O3 Sulfide Catalyst by Noble Metals in Simultaneous Hydrodesulfurization of Thiophene and Hydrodenitrogenation of Pyridine: A Comparative Study

    Czech Academy of Sciences Publication Activity Database

    Vít, Zdeněk; Cinibulk, Josef; Gulková, Daniela

    2004-01-01

    Roč. 272, 1-2 (2004), s. 99-107 ISSN 0926-860X R&D Projects: GA AV ČR IAA4072103 Institutional research plan: CEZ:AV0Z4072921 Keywords : Mo catalyst * noble metal * HDS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor : 2.378, year: 2004

  14. Inositol phosphates from barley low-phytate grain mutants analysed by metal-dye detection HPLC and NMR

    DEFF Research Database (Denmark)

    Hatzack, F.; Hübel, F.; Zhang, W.

    2001-01-01

    Inositolphosphates from barley low-phytate grain mutants and their parent variety were analysed by metal-dye detection HPLC and NMR. Compound assignment was carried out by comparison of retention times using a chemical hydrolysate of phytate [Ins(1,2,3,4,5,6)P(6)] as a reference; Co...

  15. Electrochemical Reduction of Zinc Phosphate

    International Nuclear Information System (INIS)

    Kim, Chang Hwan; Lee, Jung Hyun; Shin, Woon Sup

    2010-01-01

    We demonstrated first that the electrochemical reduction of zinc phosphate in neutral phosphate buffer is possible and potentially applicable to bio-compatible rechargeable battery. The actual redox component is Zn(s)/Zn phosphate(s) and the future research about the control of crystal formation for the better cyclability is required. In lead-acid battery, the electrochemical redox reaction of Pb (s) /PbSO 4(s) is used by reducing Pb(II) and oxidizing Pb(0) in sulfate rich solution. Since both reduced form and oxidized form are insoluble, they cannot diffuse to the opposite electrodes and react. It is a very common strategy to make a stable battery electrode that a metal element is reduced and oxidized in solution containing an abundance of anion readily precipitating with the metal ion. For the application of this strategy to construction of rechargeable battery using bio-compatible electrode materials and electrolytes, the use of phosphate ion can be considered as anion readily precipitating with metal ions. If phosphate buffer with neutral pH is used as electrolyte, the better bio-compatibility will be achieved than most of rechargeable battery using strong acid, strong base or organic solvent as electrolyte solution. There are many metal ions readily precipitating with phos-phate ion, and zinc is one of them

  16. Sulfidation behavior and mechanism of zinc silicate roasted with pyrite

    Science.gov (United States)

    Ke, Yong; Peng, Ning; Xue, Ke; Min, Xiaobo; Chai, Liyuan; Pan, Qinglin; Liang, Yanjie; Xiao, Ruiyang; Wang, Yunyan; Tang, Chongjian; Liu, Hui

    2018-03-01

    Sulfidation roasting followed by flotation is widely known as a possible generic technology for enriching valuable metals in low-grade Zn-Pb oxide ores. Zn2SiO4 is the primary Zn phase in willemite. Zn4Si2O7(OH)2(H2O), the main Zn phase in hemimorphite, transforms into Zn2SiO4 at temperatures above 600 °C. To enrich the Zn in willemite and hemimorphite, the Zn species should first be converted to ZnS. Therefore, a thorough understanding of the sulfidation reaction of Zn2SiO4 during roasting with pyrite is of vital important. In this study, the sulfidation behavior and reaction mechanisms of a Zn2SiO4-pyrite roasting system were determined using HSC 5.0 software, TG-FTIR spectroscopy, XRD, XPS and SEM-EDS. The results indicate that the sulfidation process can be divided into three steps: the decomposition of pyrite and formation of a sulfur-rich environment, the sulfur-induced migration of O2- and transformation of sulfur vapor, and the sulfidation reaction via oxygen-sulfur exchange. During the sulfidation roasting process, pyrite was converted to loose and porous Fe3O4, whereas Zn2SiO4 was transformed into ZnS and SiO2 in situ. These findings provide theoretical support for controlling the sulfidation roasting process of willemite and hemimorphite.

  17. Synthesis and Crystal Structure of the New Mixed-metal Bismuth Indium Sulfide, Bi{sub 0.76}In{sub 1.24}S{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Woojin; Kim, Kyounghee; Yun, Hoseop [Ajou University, Suwon (Korea, Republic of)

    2016-05-15

    In these compounds, In atoms are usually coordinated by six S atoms in distorted octahedral fashions but both octahedral and tetrahedral In atoms are found in Bi{sub 2}In{sub 4}S{sub 9}. Compared with In, Bi atoms adopt much more complicated coordinations. In our laboratory, reactive halide fluxes have been exploited to prepare numerous chalcogenophosphates as single crystals and this synthetic technique should be of general utility in finding new metal chalcogenides. In an attempt to search for new phases in the Bi-n-S system using halide-flux techniques, we have found a new nonstoichiometric ternary sulfide. The tube was evacuated to 0.133 Pa, sealed, and heated gradually (20 K/h) to 923 K, where it was kept for 72 h. The tube was cooled to 473 K at the rate 3 K/h and then was quenched to room temperature. The excess halide was removed with distilled water and black needle-shaped crystals were obtained. The crystals are stable in air and water. A qualitative X-ray fluorescence analysis of the crystal indicated the presence of Bi, In, and S. Optical diffuse reflectance spectra of the powdered sample were measured at room temperature using a Shimadzu UV-2400 PC spectrophotometer (Kyoto, Japan) operating in the range of 200-800 nm. Barium sulfate powder was used as reference material. The absorption data were calculated from the diffuse reflectance data with the use of the Kubelka-Munk relation.

  18. Synthesis and evaluation of novel biochar-based and metal oxide-based catalysts for removal of model tar (toluene), ammonia, and hydrogen sulfide from simulated producer gas

    Science.gov (United States)

    Bhandari, Pushpak

    Gasification is a thermochemical conversion process in which carbonaceous feedstock is gasified in a controlled atmosphere to generate producer gas. The producer gas is used for production of heat, power, fuels and chemicals. Various contaminants such as tars, NH3, and H2S in producer gas possess many problems due to their corrosive nature and their ability to clog and deactivate catalysts. In this study, several catalysts were synthesized, characterized, and tested for removal of three contaminants (toluene (model tar), NH3, and H2S) from the biomass-generated producer gas. Biochar, a catalyst, was generated from gasification of switchgrass. Activated carbon and acidic surface activated carbon were synthesized using ultrasonication method from biochar. Acidic surface was synthesized by coating activated carbon with dilute acid. Mixed metal oxide catalysts were synthesized from hydrotalcite precursors using novel synthesis technique using microwave and ultrasonication. Surface area of activated carbon (˜900 m2/g) was significantly higher than that of its precursor biochar (˜60 m2/g). Surface area of metal oxide catalyst was approximately 180 m2/g after calcination. Biochar, activated carbon, and acidic surface activated carbon showed toluene removal efficiencies of approximately 78, 88, and 88 %, respectively, when the catalysts were tested individually with toluene in the presence of producer gas at 800 °C. The toluene removal efficiencies increased to 86, 91, and 97 % using biochar, activated carbon and acidic surface activated carbon, respectively in the presence of NH3 and H2S in the producer gas. Increase in toluene removal efficiencies in presence of NH3 and H2S indicates that NH3 and H 2S play a role in toluene reforming reactions during simultaneous removal of contaminants. Toluene removal efficiency for mixed metal oxide was approximately 83%. Ammonia adsorption capacities were 0.008 g NH3/g catalyst for biochar and 0.03g NH3/g catalyst for activated

  19. Effects of mutagenesis of aspartic acid residues in the putative phosphoribosyl diphosphate binding site of Escherichia coli phosphoribosyl diphosphate synthetase on metal ion specificity and ribose-5-phosphate binding

    DEFF Research Database (Denmark)

    Willemoës, Martin; Nilsson, Dan; Hove-Jensen, Bjarne

    1996-01-01

    The three conserved aspartic acid residues of the 5-phospho-d-ribosyl a-1-diphosphate binding site (213-GRDCVLVDDMIDTGGT-228) of Escherichia coli phosphoribosyl diphosphate synthetase were studied by analysis of the mutant enzymes D220E, D220F, D221A, D224A, and D224S. The mutant enzymes showed...... enzymes were dependent on the metal ion present, suggesting a function of the investigated aspartic acid residues both in the binding of ribose 5-phosphate, possibly via a divalent metal ion, and in the interaction with a divalent metal ion during catalysis....

  20. Evaluation of metallic brackets adhesion after the use of bleaching gels with and without amorphous calcium phosphate (ACP: in vitro study

    Directory of Open Access Journals (Sweden)

    Sissy Maria Mendes Machado

    2013-06-01

    Full Text Available OBJECTIVE: To evaluate in vitro the effects of tooth whitening using gel with Amorphous Calcium Phosphate (ACP on the bond strength of metal brackets. METHODS: Thirty-six bovine incisors were sectioned at the crown-root interface, and the crowns were then placed in PVC cylinders. The specimens were divided into 3 groups (n = 12 according to whitening treatment and type of gel used, as follows: G1 (control = no whitening; G2 = whitening with gel not containing ACP (Whiteness Perfect - FGM, G3 = whitening with gel containing ACP (Nite White ACP - Discus Dental. Groups G2 and G3 were subjected to 14 cycles of whitening followed by an interval of 15 days before the bonding of metal brackets. Shear bond strength testing was performed on a Kratos universal test machine at a speed of 0.5 mm/min. After the mechanical test, the specimens were assessed to determine the adhesive remnant index (ARI. The results were subjected to ANOVA, Tukey's test and Kruskal-Wallis test (5%. RESULTS: Significant differences were noted between the groups. Control group (G1 = 11.10 MPa showed a statistically higher shear bond strength than the groups that underwent whitening (G2 = 5.40 Mpa, G3 = 3.73 MPa, which did not differ from each other. There were no significant differences between the groups in terms of ARI. CONCLUSION: Tooth whitening reduces the bond strength of metal brackets, whereas the presence of ACP in the whitening gel has no bearing on the results.

  1. Sewage sludge ash to phosphate fertilizer by chlorination and thermal treatment: residence time requirements for heavy metal removal.

    Science.gov (United States)

    Nowak, Benedikt; Wegerer, Harald; Aschenbrenner, Philipp; Rechberger, Helmut; Winter, Franz

    2012-01-01

    Heavy metal removal from sewage sludge ash can be performed by mixing the ash with environmentally compatible chlorides (e.g. CaCl2 or MgCl2) and water, pelletizing the mixture and treating the pellets in a rotary reactor at about 1000 degrees C. Thermogravimetry-mass spectroscopy, muffle oven tests (500-1150 degrees C) and investigations in a laboratory-scale rotary reactor (950-1050 degrees C, residence time 1-25 min) were carried out. In the rotary reactor, up to 97% of Cu, 95% Pb and 95% Zn can be removed at 1050 degrees C. As Cl release starts from 400 degrees C (obtained from thermogravimetry-mass spectrometry experiments), heavy metals are already removed partially within the heating period. This heavy metal removal can be described as being similar to a first-order rate law. To meet the limit values specified in the Austrian and German fertilizer ordinances, residence times of the order of minutes are sufficient at 950 degrees C.

  2. Bacterial formation of phosphatic laminites off Peru.

    Science.gov (United States)

    Arning, E T; Birgel, D; Brunner, B; Peckmann, J

    2009-06-01

    Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10 degrees 01' S and 10 degrees 24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS(2)) and sphalerite (ZnS). Low delta(34)S(pyrite) values (average -28.8 per thousand) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C(15:0), i/ai-C(17:0) and 10MeC(16:0)) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

  3. Suicide with hydrogen sulfide.

    Science.gov (United States)

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas

    2013-06-01

    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  4. Micro-aeration for hydrogen sulfide removal from biogas

    Science.gov (United States)

    Duangmanee, Thanapong

    The presence of sulfur compounds (e.g. protein, sulfate, thiosulfate, sulfite, etc.) in the feed stream generates highly corrosive and odorous hydrogen sulfide during anaerobic digestion. The high sulfide level in the biogas stream is not only poisonous to many novel metal catalysts employed in thermo-catalytic processes but also reduces the quality of methane to produce renewable energy. This study used an innovative, low-maintenance, low-cost biological sulfide removal technology to remove sulfides simultaneously from both gas and liquid phase. ORP (Oxidation-Reduction-Potential) was used as the controlling parameter to precisely regulate air injection to the sulfide oxidizing unit (SOU). The microaeration technique provided just enough oxygen to partially oxidize sulfides to elemental sulfur without inhibiting methanogenesis. The SOU was equipped with a diffuser at the bottom for the dispersion of sulfide-laden biogas and injected air throughout the column. The SOU can be operated as a standalone unit or coupled with an anaerobic digester to simultaneously remove sulfide from the biogas and effluent. The integrated system was capable of reducing hydrogen sulfide in biogas from 2,450 to less than 2 ppmV with minimal sulfate production at the highest available sulfide loading rate of 0.24 kg/m3-day. More than 98% of sulfide removed was recovered as elemental sulfur. However, the standalone SOU was able to operate at high hydrogen sulfide loading of 1.46 kg/m 3-day at inlet sulfide concentration of 3000 ppmV and reduce the off-gas hydrogen sulfide concentrations to less than 10 ppmV. The experiment also revealed that the ORP controlled aeration was sensitive enough to prevent oxygen overdosing (dampening effect) during unexpected surges of aeration. Using generalized linear regression, a model predicting output H2S concentration based on input H2S concentrations, SOU medium heights, and biogas flow rates, was derived. With 95% confidence, output H2S concentration

  5. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Dezhao, Liu; Hansen, Michael Jørgen

    oxidizing bacteria but several fungal families including Trichocomaceae. A positive correlation was found between the presence of mold and sulfide uptake. However there have been no reports on fungi metabolizing hydrogen sulfide. We hypothesize that the mold increases the air exposed surface, enabling...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  6. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Liu, Dezhao; Hansen, Michael Jørgen

    2012-01-01

    oxidizing bacteria but several fungal families including Trichocomaceae. A positive correlation was found between the presence of mold and sulfide uptake. However there have been no reports on fungi metabolizing hydrogen sulfide. We hypothesize that the mold increases the air exposed surface, enabling...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  7. Catalysts for the selective oxidation of hydrogen sulfide to sulfur

    Science.gov (United States)

    Srinivas, Girish; Bai, Chuansheng

    2000-08-08

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

  8. Extraction of Nanosized Cobalt Sulfide from Spent Hydrocracking Catalyst

    Directory of Open Access Journals (Sweden)

    Samia A. Kosa

    2013-01-01

    Full Text Available The processes used for the extraction of metals (Co, Mo, and Al from spent hydrotreating catalysts were investigated in this study. A detailed mechanism of the metal extraction process is described. Additionally, a simulation study was performed to understand the sulfidizing mechanism. The suggested separation procedure was effective and achieved an extraction of approximately 80–90%. In addition, the sulfidization mechanism was identified. This sulfidizing process for Co was found to involve an intermediate, the structure of which was proposed. This proposed intermediate was confirmed through simulations. Moreover, the activities of the spent and the regenerated catalyst were examined in the cracking of toluene. The modification of the spent catalyst through the use of different iron oxide loadings improved the catalytic activity.

  9. Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

    Science.gov (United States)

    Manoochehri, S.; Schmidt, M. W.; Guenther, D.

    2013-12-01

    Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder

  10. Platinum-group elements and gold in sulfide melts from modern arc basalt (Tolbachik volcano, Kamchatka)

    Science.gov (United States)

    Zelenski, M.; Kamenetsky, V. S.; Mavrogenes, J. A.; Danyushevsky, L. V.; Matveev, D.; Gurenko, A. A.

    2017-10-01

    Sulfide melt inclusions entrapped in primitive olivine phenocrysts can be used to understand the compositions of early sulfide melts that may ultimately contribute to magmatic sulfide ore deposits. Sulfide globules hosted in olivine (86-92 mol% Fo) from the Tolbachik basalt (the 1941 eruption) are characterized in terms of their major and trace element abundances using electron microscopy and LA-ICP-MS analysis. Distribution of major elements within individual sulfide globules varies from homogeneous to heterogeneous. Phases include monosulfide solid solution (MSS) and intermediate solid solution (ISS) intergrowths and exsolved low-temperature minerals such as pyrrhotite, pentlandite, chalcopyrite and cubanite. Trace elements (platinum-group elements - PGE, Ag, Te, Au, Pb and Bi) are also present in solid solution in sulfide phases and as micron-sized particles ("nuggets"). Such nuggets of dominantly Au, Pt, Au-Pd and Pd-Te are contained randomly within sulfide matrices or, more commonly, at phase boundaries. Nuggets are also attached to outer surfaces of sulfide globules. Concentrations of PGE in sulfides follow a log normal distribution over four orders of magnitude. The highest measured noble metal concentrations in the analyzed globules (436 ppm Au + PGE) are 13.3 ppm Au, 115 ppm Pt and 299 ppm Pd, whereas 40% of globules have < 15 ppm of noble metals. Gold and PGE concentrations correlate, suggesting these elements were concentrated by the same process(es). We propose that a number of anomalous concentrations of one or several noble metals in the analyzed globules can be best explained by entrapment of Au-PGE-rich particles (solid or liquid) from the silicate melt. Although the individual Tolbachik sulfide globules have variable PGE abundances, their mean composition resembles those of major PGE-sulfide ore deposits (e.g., Norilsk, Sudbury, Platreef and Merensky Reef).

  11. Characterization of tin phosphate coatings by CEMS

    International Nuclear Information System (INIS)

    Nomura, Kiyoshi; Ujihira, Yusuke; Takai, Osamu; Kojima, Ryuji

    1992-01-01

    The structure and chemical state of tin in converted tin phosphate coatings, obtained by a treatment of Zn and Mn phosphate in SnCl 2 solution, were characterized by CEMS. Converted Sn(II) phosphate and adsorbed SnO 2 species were main products in the ∝1/3 top layers of Mn and Zn phosphate coatings, and metallic tin was occasionally recognized in deeper layers. Tin phosphate layers, coated directly on a steel substrate by RF sputtering of Ar ions, were composed of two kinds of Sn(IV) species. (orig.)

  12. Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

    Science.gov (United States)

    Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

    2016-01-01

    CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

  13. Conditions of formation of the Mavrokoryfi high-sulfidation epithermal Cu-Ag-Au-Te mineralization (Petrota Graben, NE Greece)

    Science.gov (United States)

    Voudouris, Panagiotis Christos

    2011-01-01

    The Mavrokoryfi Cu-Ag-Au-Te prospect, northeastern Greece, consists of atypical, high-sulfidation mineralization where precious metals were introduced contemporaneously with advanced argillic alteration from magmatic vapors. It occurs as veins of massive sulfides in zones of silicic and advanced argillic alteration spatially associated with an andesitic lava dome and hyaloclastites. Mineralogical data demonstrate an unusual ore and gangue mineralogy that is compatible with formation under very oxidizing conditions (log fO2 values of >-31.8) at temperatures of 200°C to 250°C. Oxidizing conditions favored the formation of hypogene lead sulfates (anglesite and barian celestite) instead of galena. Selenian acanthite, cadmian freibergite, and argentian goldfieldite are the main carriers of silver in the deposit and are reported in Greece for the first time. They were deposited at log fS2 of -9 to -7 and log fTe2 values of -9 to -12.5 (250°C). Ag-poor goldfieldite at Mavrokoryfi has up to 3.7 apfu Te and is the most Te-rich goldfieldite yet reported. The mineralization is accompanied by aluminum-phosphate-sulfate minerals of magmatic-hydrothermal origin and an unusual Pb-enrichment. Ore-forming components were likely derived from andesite porphyries.

  14. Experimental constraints on gold and silver solubility in iron sulfides

    International Nuclear Information System (INIS)

    Pal'yanova, Galina; Mikhlin, Yuri; Kokh, Konstantin; Karmanov, Nick; Seryotkin, Yurii

    2015-01-01

    Experiments were performed to determine crystallization of Fe,S-melts (pyriti≿ and troilitic with molar ratio S/Fe ratios of 2 and 1, respectively) containing traces of gold and silver at (Ag/Au) wt ratios varying from 10 to 0.1. The solid products were studied by optical microscopy, scanning electron microscopy, X-ray powder diffraction (XRD), microprobe analysis, and X-ray photoelectron spectroscopy (XPS) in order to reveal the concentration limits of “invisible” gold and silver in magmatic iron sulfides, and to determine the influence of sulfur on forms of precious metals in the Fe–S system with different Ag/Au ratios. Au–Ag phases do not form inclusions but instead concentrate on the grain boundaries in the synthetic pyrrhotite and troilite, while pyrite comprises micro- (1–5 μm) and macroinclusions of Au–Ag alloys and Au–Ag sulfides. In “pyriti≿” systems, the fineness of alloys increases from 650 to 970‰ and the composition of sulfides changes from acanthite (Ag 2 S) to uytenbogaardtite (Ag 3 AuS 2 ) and petrovskaite (AgAuS) as the Ag/Au ratio decreases. The concentrations of “invisible” precious metals revealed in troilite were 0.040 ± 0.013 wt.% Au and 0.079 ± 0.016 wt.% Ag. Measured concentrations in pyrite and pyrrhotite were <0.024 wt.% Au and <0.030 wt.% Ag. The surface layers of iron sulfides probed with XPS were enriched in the precious metals, and in silver relative to gold, especially in the systems with Fe/S = 1, probably, due to depletion of the metallic alloy surfaces with gold. Au- and Ag-bearing iron sulfides crystallized primarily from melts may be the source of redeposited phases in hydrothermal and hypergene processes. - Highlights: • The samples of Fe–S–Au–Ag system were synthesized. • Coupled solubility of gold and silver in iron sulfides was specified. • Ag–Au inclusions on surfaces of iron sulfides are likely to be enriched in silver. • Au–Ag sulfides can exist along with native gold in

  15. Spectral induced polarization and electrodic potential monitoring of microbially mediated iron sulfide transformations

    Energy Technology Data Exchange (ETDEWEB)

    Hubbard, Susan; Personna, Y.R.; Ntarlagiannis, D.; Slater, L.; Yee, N.; O' Brien, M.; Hubbard, S.

    2008-02-15

    Stimulated sulfate-reduction is a bioremediation technique utilized for the sequestration of heavy metals in the subsurface.We performed laboratory column experiments to investigate the geoelectrical response of iron sulfide transformations by Desulfo vibriovulgaris. Two geoelectrical methods, (1) spectral induced polarization (SIP), and (2) electrodic potential measurements, were investigated. Aqueous geochemistry (sulfate, lactate, sulfide, and acetate), observations of precipitates (identified from electron microscopy as iron sulfide), and electrodic potentials on bisulfide ion (HS) sensitive silver-silver chloride (Ag-AgCl) electrodes (630 mV) were diagnostic of induced transitions between an aerobic iron sulfide forming conditions and aerobic conditions promoting iron sulfide dissolution. The SIP data showed 10m rad anomalies during iron sulfide mineralization accompanying microbial activity under an anaerobic transition. These anomalies disappeared during iron sulfide dissolution under the subsequent aerobic transition. SIP model parameters based on a Cole-Cole relaxation model of the polarization at the mineral-fluid interface were converted to (1) estimated biomineral surface area to pore volume (Sp), and (2) an equivalent polarizable sphere diameter (d) controlling the relaxation time. The temporal variation in these model parameters is consistent with filling and emptying of pores by iron sulfide biofilms, as the system transitions between anaerobic (pore filling) and aerobic (pore emptying) conditions. The results suggest that combined SIP and electrodic potential measurements might be used to monitor spatiotemporal variability in microbial iron sulfide transformations in the field.

  16. Phototrophic sulfide oxidation: environmental insights and a method for kinetic analysis

    Directory of Open Access Journals (Sweden)

    Thomas E Hanson

    2013-12-01

    Full Text Available Previously, we presented data that indicated microbial sulfide oxidation would out-compete strictly chemical, abiotic sulfide oxidation reactions under nearly all conditions relevant to extant ecosystems (Luther et al., 2011. In particular, we showed how anaerobic microbial sulfide oxidation rates were several orders of magnitude higher than even metal catalyzed aerobic sulfide oxidation processes. The fact that biotic anaerobic sulfide oxidation is kinetically superior to abiotic reactions implies that nearly all anaerobic and sulfidic environments should host microbial populations that oxidize sulfide at appreciable rates. This was likely an important biogeochemical process during long stretches of euxinia in the oceans suggested by the geologic record. In particular, phototrophic sulfide oxidation allows the utilization of carbon dioxide as the electron acceptor suggesting that this process should be particularly widespread rather than relying on the presence of other chemical oxidants. Using the Chesapeake Bay as an example, we argue that phototrophic sulfide oxidation may be more important in many environments than is currently appreciated. Finally, we present methodological considerations to assist other groups that wish to study this process.

  17. Origin of Ni-Cu Sulfide Deposits: Questioning 'High-Flux' Models'

    Science.gov (United States)

    Arndt, N. T.

    2015-12-01

    Magmatic sulfide ore bodies contain large amounts of sulfide with high concentrations of metals such as Ni, Cu and PGE. Their presence in relatively small intrusions commonly is attributed to the segregation and accumulation of sulfide droplets from magmas that flow rapidly through conduits. This 'high-flux' model is at odds with the following observations. Many ores appear to have been emplaced as magmatic breccias (Norilsk-Talnakh, Aguablanca) or crystal mushes (Jinchuan) containing a high proportion of sulfide. Such mixtures are very dense and could not have risen up through the crust from a deeper staging chamber. At Uitkomst and Platreef, screens of sedimentary rock maintaining the same orientation as adjacent sedimentary strata separate layers of ultramafic cumulates, some containing abundant sulfide ore. This geometry suggests that ultramafic mush and ore sulfides oozed into the sedimentary sequence, replacing less resistant strata. A mechanism explaining these observations is as follows: mafic-ultramafic intrusions both large and small do not differentiate in place but grow through the injection of magmas of differing compositions and crystallinity. Highly mafic magmas, particularly those charged with ferromagnesian crystals and sulfide, have high densities and they are injected into the lower parts of growing intrusions while less-dense, more evolved and/or plagioclase-rich magmas are injected at higher levels. Accumulation of sulfides probably occurs higher in the magma conduits and sulfide-rich mushes migrate or slump downwards in the conduit to form the ore bodies.

  18. Micelle Mediated Trace Level Sulfide Quantification through Cloud Point Extraction

    Directory of Open Access Journals (Sweden)

    Samrat Devaramani

    2012-01-01

    Full Text Available A simple cloud point extraction protocol has been proposed for the quantification of sulfide at trace level. The method is based on the reduction of iron (III to iron (II by the sulfide and the subsequent complexation of metal ion with nitroso-R salt in alkaline medium. The resulting green-colored complex was extracted through cloud point formation using cationic surfactant, that is, cetylpyridinium chloride, and the obtained surfactant phase was homogenized by ethanol before its absorbance measurement at 710 nm. The reaction variables like metal ion, ligand, surfactant concentration, and medium pH on the cloud point extraction of the metal-ligand complex have been optimized. The interference effect of the common anions and cations was studied. The proposed method has been successfully applied to quantify the trace level sulfide in the leachate samples of the landfill and water samples from bore wells and ponds. The validity of the proposed method has been studied by spiking the samples with known quantities of sulfide as well as comparing with the results obtained by the standard method.

  19. Influences of species of metals and supports on the hydrogenation activity of carbon-supported metal sulfides catalysts; Tanso biryushi tanji shokubai no suisoka kassei ni taisuru kassei kinzoku oyobi tantaishu no eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Sakanishi, K.; Hasuo, H.; Taniguchi, H.; Nagamatsu, T.; Mochida, I. [Kyushu University, Fukuoka (Japan). Institute of Advanced Material Study

    1996-10-28

    In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supported catalysts were prepared. Catalytic activities of them were investigated for the hydrogenation of 1-methylnaphthalene, to discuss the influences of metals and carbon species on the catalytic activity. Various water soluble and oil soluble Mo and Ni salts were used for NiMo supported catalysts. Among various carbon supports, Ketjen Black (KB) was effective for preparing the catalyst showing the most excellent hydrogenation activity. The KB and Black Pearl 2000 (BP2000) showing high hydrogenation activity were fine particles having high specific surface area more than 1000 m{sup 2}/g and primary particle diameter around 30 nm. This was inferred to contribute to the high dispersion support of active metals. Since such fine particles of carbon exhibited hydrophobic surface, they were suitable for preparing catalysts from the methanol-soluble metals. Although Ni and Mo added iron-based catalysts provided lower aromatic hydrogenation activity, they exhibited liquefaction activity competing with the NiMo/KB catalyst. 3 refs., 1 fig., 3 tabs.

  20. Sulfide intrusion and detoxification in Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2014-01-01

    Sulfide intrusion in seagrasses represents a global threat to seagrasses. In contrast seegrasses grow in hostile sediments, where they are constantly exposed to sulfide intrusion. Little is known about the strategies to survive sulfide intrusion, if there are detoxification mechanisms and sulfur...... indicating a possible role of sulfide in the sulfur nutrition beside the detoxification function. Our results suggest different adaptations of Z. marina to reduced sediments and sulfide intrusion ranging from bacterial and chemical reoxidation of sulfide to sulfate to incorporation of sulfide into organic...

  1. Sulfide persistence in oil field waters amended with nitrate and acetate.

    Science.gov (United States)

    Hulecki, Jordan C; Foght, Julia M; Gray, Murray R; Fedorak, Phillip M

    2009-12-01

    Nitrate amendment is normally an effective method for sulfide control in oil field-produced waters. However, this approach has occasionally failed to prevent sulfide accumulation, despite the presence of active nitrate-reducing bacterial populations. Here, we report our study of bulk chemical transformations in microcosms of oil field waters containing nitrate-reducing, sulfide-oxidizing bacteria, but lacking denitrifying heterotrophs. Amendment with combinations of nitrate, acetate, and phosphate altered the microbial sulfur and nitrogen transformations. Elemental sulfur produced by chemotrophic nitrate-reducing bacteria was re-reduced heterotrophically to sulfide. Ammonification, rather than denitrification, was the predominant pathway for nitrate reduction. The application of nitrite led to transient sulfide depletion, possibly due to higher rates of nitrite reduction. The addition of molybdate suppressed both the accumulation of sulfide and the heterotrophic reduction of nitrate. Therefore, sulfidogenesis was likely due to elemental sulfur-reducing heterotrophic bacteria, and the nitrate-reducing microbial community consisted mainly of facultatively chemotrophic microbes. This study describes one set of conditions for continued sulfidogenesis during nitrate reduction, with important implications for nitrate control of sulfide production in oil fields.

  2. Apparatus for use in sulfide chemiluminescence detection

    Science.gov (United States)

    Spurlin, S.R.; Yeung, E.S.

    1987-01-06

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  3. Mechanochemical reduction of copper sulfide

    DEFF Research Database (Denmark)

    Balaz, P.; Takacs, L.; Jiang, Jianzhong

    2002-01-01

    The mechanochemical reduction of copper sulfide with iron was induced in a Fritsch P-6 planetary mill, using WC vial filled with argon and WC balls. Samples milled for specific intervals were analyzed by XRD and Mossbauer spectroscopy. Most of the reaction takes place during the first 10 min...... of milling and only FeS and Cu are found after 60 min. The main chemical process is accompanied by phase transformations of the sulfide phases as a result of milling. Djurleite partially transformed to chalcocite and a tetragonal copper sulfide phase before reduction. The cubic modification of FeS was formed...... first, transforming to hexagonal during the later stages of the process. The formation of off-stoichiometric phases and the release of some elemental sulfur by copper sulfide are also probable....

  4. Chalcophile element (Ni, Cu, PGE, and Au) variations in the Tamarack magmatic sulfide deposit in the Midcontinent Rift System: implications for dynamic ore-forming processes

    Science.gov (United States)

    Taranovic, Valentina; Ripley, Edward M.; Li, Chusi; Rossell, Dean

    2016-10-01

    The Tamarack magmatic sulfide deposit is hosted by the Tamarack Intrusive Complex (1105.6 ± 1.2 Ma) in the Midcontinent Rift System. The most important sulfide mineralization in the Complex occurs in the northern part, which consists of two separate intrusive units: an early funnel-shaped layered peridotite body containing relatively fine-grained olivine (referred to as the FGO Intrusion) at the top, and a late gabbro-troctolite-peridotite dike-like body containing relatively coarse-grained olivine (referred to as the CGO Intrusion) at the bottom. Disseminated, net-textured, and massive sulfides occur in the base of the FGO Intrusion as well as in the upper part of the CGO Intrusion. The widest part of the CGO Intrusion also hosts a large semi-massive (net-textured) sulfide ore body locally surrounded by disseminated sulfide mineralization. Small massive sulfide veins occur in the footwall of the FGO Intrusion and in the wall rocks of the CGO dike. The sulfide mineralization is predominantly composed of pyrrhotite, pentlandite, and chalcopyrite, plus minor magnetite. Pyrrhotite containing the highest Ni and Co contents occurs in the FGO disseminated sulfides and in the CGO semi-massive sulfide ores, respectively. The most important platinum-group minerals associated with the base metal sulfides are sperrylite (PtAs2), sudburyite (PdSb), and michenerite (PdBiTe). Nickel shows a strong positive correlation with S in all types of sulfide mineralization, and Cu shows a strong positive correlation with S in the disseminated sulfide mineralization. At a given S content, the concentrations of Pt, Pd, and Au in the CGO disseminated sulfides are significantly higher than those in the FGO disseminated sulfides. The semi-massive sulfide ores are characterized by significantly higher IPGE (Ir, Os, Ru, and Rh) concentrations than most of the massive sulfide ores. With few exceptions, all of the various textural types of sulfide mineralization collectively show a good positive

  5. Impact of the Prestige oil spill on marsh soils: Relationship between heavy metal, sulfide and total petroleum hydrocarbon contents at the Villarrube and Lires marshes (Galicia, Spain); Impacto de la marea negra del Prestige en suelos de marisma: relacion entre los contenidos de metales pesados, sulfuros e hidrocarburos en las marismas de Villarrube y Lires (Galicia, Espana)

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, L.; Marcet, P.; Covelo, E.F.; Vega, F.A. [Department of Vegetable Biology and Soil Science, Vigo (Spain); Fernandez-Feal, L.; Fernandez-Feal, C. [Escuela Politecnica Superior, Universidad de la Coruna, Ferrol (Spain)

    2004-09-15

    The objectives of this study were to determine the effect of the Prestige oil spill on the total petroleum hydrocarbons and heavy metal contents of soils in two marshes (Lires and Villarrube, Galicia, Spain) and the relationship between their oxidation-reduction potential and the solubility of heavy metals with sulfide and sulfate contents. Soil samples were taken from polluted and unpolluted areas and their petroleum hydrocarbon contents, heavy metal contents and other chemical characteristics were measured. The soils affected by the oil spill show remarkable contents of Cr, Cu, Ni, Pb and V. The Lires marsh soils are more affected by fuel oil than Villarrube marsh. The effects of the contaminating agents on the soils reach distances of up to 500 m from the coastline. In the first 400 m, there are important spatial variations because the fuel oil penetrated into the soils through tidal action and not directly. The Cr, Cu, Ni, Pb and V contents of polluted soils were between 50 and 200 times higher than those of their unpolluted counterparts and the background concentrations in Galician coastal sediments. In the case of Cr, Cu, Ni, Pb and V, their origin through the fuel oil was corroborated by the high correlation (r > 0.90) between the concentrations of these metals and the total petroleum hydrocarbon content of the polluted soils, which shows the combined addition of these metals through the fuel oil. [Spanish] Los objetivos de este trabajo fueron determinar el efecto de la marea negra del buque tanque Prestige en el contenido total de hidrocarburos y de metales pesados en suelos de dos marismas (Lires y Villarrube, Galicia, Espana) y la relacion entre el potencial de oxidacion-reduccion y la solubilidad de los metales pesados con los contenidos de sulfuros y de sulfatos. Se tomaron muestras de suelos de las zonas contaminadas y no contaminadas y se determinaron diversas caracteristicas quimicas, el contenido total de hidrocarburos y de metales pesados. Los

  6. O papel dos sulfetos volatilizados por acidificação no controle do potencial de biodisponibilidade de metais em sedimentos contaminados de um estuário tropical, no sudeste do Brasil The role of acid volatile sulfide in the control of potential metal bioavailability in contaminated sediments from a tropical estuary, southeast Brazil

    Directory of Open Access Journals (Sweden)

    Érico Casare Nizoli

    2009-01-01

    Full Text Available Measurements of acid volatile sulfide (AVS and simultaneously extracted metals (SEM were combined in order to verify the ecological hazard of contaminated sediments from the Santos-Cubatão Estuarine System (SE Brazil, which is located in one of the most industrialized areas in the Latin America. Intertidal sediments from the Morrão River estuary were collected seasonally in short cores. The redox conditions, organic matter contents and grain-size were the main controlling factors on SEM distribution. However, clear relationships among these variables and AVS were not observed. The molar SEM/AVS ratios were frequently > 1 especially in the summer, suggesting major metal bioavailability hazard in this humid hot season.

  7. Theoretical investigation of the reaction mechanism for the phosphate diester hydrolysis using an asymmetric dinuclear metal complex as a biomimetic model of the purple acid phosphatase enzyme.

    Science.gov (United States)

    Ferreira, Dalva E C; De Almeida, Wagner B; Neves, Ademir; Rocha, Willian R

    2008-12-14

    In this work we have applied quantum mechanical calculations, at the density functional theory level, to investigate the phosphate diester hydrolysis promoted by a cationic heterodinuclear Fe(III)...Zn(II) complex that mimics the structural and functional properties of the purple acid phosphatase (PAP) enzymes. The hydrolysis of the dimethyl phosphate diester was investigated in the gas phase and in solution by means of the continuum PCM model, using the B3LYP hybrid exchange-correlation functional. Our computed results showed that the hydrolysis of the dimethyl phosphate ester takes place in two steps. The first step corresponds to a slow P-O bond formation through nucleophilic attack of the coordinated (Fe(III))-OH group. The second step consists of a proton transfer process followed by the release of a methanol molecule. The first step is rate determining with activation free energy of 12.3 kcal mol(-1), which is about 3 times lower than the activation free energy for the uncatalyzed reaction. We also show that the heterodinuclear site plays an important role favoring an associative mechanism for the phosphate diester hydrolysis, favoring the formation of a high energy intermediate phosphorane, and orienting the phosphate group to the nucleophilic attack.

  8. Mineralogy and geochemical environment of formation of the Perama Hill high-sulfidation epithermal Au-Ag-Te-Se deposit, Petrota Graben, NE Greece

    Science.gov (United States)

    Voudouris, Panagiotis Christos; Melfos, Vasilios; Spry, Paul G.; Moritz, Robert; Papavassiliou, Constantinos; Falalakis, George

    2011-11-01

    The Perama Hill deposit is a high-sulfidation Au-Ag-Te-Se epithermal system hosted in silicic- and argillic altered andesitic rocks and overlying sandstones, which were emplaced on the eastern margin of the Petrota graben, northeastern Greece. The deposit evolved from an early stage silica-pyrite rock and argillic alteration followed by the deposition of sulfide-, sulfosalt- and telluride-bearing quartz-barite veins and stockworks. Early ore formation is characterized by a high-sulfidation-type enargite-galena-bearing ore assemblage (consisting of enargite, watanabeite, Fe-free sphalerite, covellite, kesterite, bismuthinite, selenian bismuthinite, lillianite homologues, kawazulite-tetradymite, goldfieldite, and native gold), followed by the formation of an intermediate-sulfidation-type tennantite-bearing assemblage characterized by ferrian/zincian tennantite, tellurobismuthite, tetradymite, melonite, native tellurium, Au-Ag-tellurides (calaverite, krennerite, sylvanite, hessite, petzite, stützite), altaite and electrum. Quartz, barite, kaolinite, sericite and minor aluminum-phosphate-sulfate minerals are gangue minerals. Fluid inclusion data demonstrate that the ore system evolved from an initial high temperature (up to 330°C) and low salinity (up to 4.9 wt.% NaCl equiv.) fluid towards a cooler (200°C) and very low salinity (0.7 wt.% NaCl equiv.) hydrothermal fluid suggesting progressive cooling and dilution of the ore fluid. The ore minerals at Perama Hill reflect variable fS2 and fTe2 conditions during base and precious metal deposition. Early ore deposition took place at ~300°C, at log fS2 values between ≈-8.2 and -5.5, and log fTe2 from -11.8 and -7.8. Late ore deposition occurred at log fS2 = -11.8 to -9.8 and log fTe2 of ≈-9.2 and -7.8. These data and paragenetic studies indicate a shift towards higher log fTe2 and lower log fS2 and log fSe2 values for the mineralizing fluids with time. The kawazulite/tetradymitess-gold association at Perama Hill

  9. Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

    Science.gov (United States)

    Fremerey, Peter; Jess, Andreas; Moos, Ralf

    2015-10-23

    In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

  10. Infrared spectroscopy of solid hydrogen sulfide and deuterium sulfide.

    Science.gov (United States)

    Fathe, Kristin; Holt, Jennifer S; Oxley, Susan P; Pursell, Christopher J

    2006-09-21

    The infrared spectra of solid hydrogen sulfide (H2S) and deuterium sulfide (D2S) were collected at very low temperatures. Vapor deposition of thin films at the lowest temperature of 10 K produced amorphous solids while deposition at 70 K yielded the crystalline phase III. Infrared interference fringe patterns produced by the films during deposition were used to determine the film thickness. Careful measurement of the integrated absorbance peaks, along with the film thickness, allowed determination of the integrated band intensities. This report represents the first complete presentation of the infrared spectra of the amorphous solids. Observations of peaks near 3.915 and 1.982 microm (ca. 2554 and 5045 cm(-1), respectively) may be helpful in the conclusive identification of solid hydrogen sulfide on the surface of Io, a moon of Jupiter.

  11. Electrical properties of phosphate glasses

    International Nuclear Information System (INIS)

    Mogus-Milankovic, A; Santic, A; Reis, S T; Day, D E

    2009-01-01

    Investigation of the electrical properties of phosphate glasses where transition metal oxide such as iron oxide is the network former and network modifier is presented. Phosphate glasses containing iron are electronically conducting glasses where the polaronic conduction is due to the electron hopping from low to high iron valence state. The identification of structural defects caused by ion/polaron migration, the analysis of dipolar states and electrical conductivity in iron phosphate glasses containing various alkali and mixed alkali ions was performed on the basis of the impedance spectroscopy (IS). The changes in electrical conductivity from as-quenched phosphate glass to fully crystallized glass (glass-ceramics) by IS are analyzed. A change in the characteristic features of IS follows the changes in glass and crystallized glass network. Using IS, the contribution of glass matrix, crystallized grains and grain boundary to the total electrical conductivity for iron phosphate glasses was analyzed. It was shown that decrease in conductivity is caused by discontinuities in the conduction pathways as a result of the disruption of crystalline network where two or more crystalline phases are formed. Also, phosphate-based glasses offer a unique range of biomaterials, as they form direct chemical bonding with hard/soft tissue. The surface charges of bioactive glasses are recognized to be the most important factors in determining biological responses. The improved bioactivity of the bioactive glasses as a result of the effects of the surface charges generated by electrical polarization is discussed.

  12. Simulating pH and hydrogen sulfide in a distributed collection system

    DEFF Research Database (Denmark)

    Vollertsen, Jes; Le Guennec, Anne; Nielsen, Asbjørn Haaning

    2013-01-01

    was calibrated to the conveyance system of Tangier, Morocco, and was able to simulate the observed variation in pH as well as the observed levels of hydrogen sulfide in the network. For the sewer system of Tangier, the most important buffer system was the carbonate system, followed by ammonia and amino groups......, and ventilation. The presented concept includes the major buffer systems, namely carbonate, ammonia, amine groups, hydrogen sulfides, phosphates, acetic acid, and propionic acid. It furthermore includes water-gas mass transfer between phases and ventilation of sewer gas into the urban atmosphere. The model...

  13. Silica-rich Chondrules in ALH 84170 and Sahara 97072 EH3 Meteorites: Evidence for Sulfidation of Silicates

    Science.gov (United States)

    Lehner, S. W.; Buseck, P. R.

    2010-03-01

    Silica-rich chondrules in EH3 meteorites contain tridymite, niningerite, and troilite associated with enstatite and olivine and no Fe-Ni metal. We interpret these assemblages as evidence for the formation of niningerite by sulfidation of silicates.

  14. Oxidation process of cadmium sulfide

    International Nuclear Information System (INIS)

    Hashimoto, Koshiro; Toda, Yoshitomo; Sato, Takayori

    1977-01-01

    Complicated thermogravimetric curve was observed on oxidation process of cadmium sulfide precipitate in air. Phases of various oxidation stage were identified by X-ray diffraction method. Cadmium sulfide was first oxidized to cadmium oxide at 400 0 C, while the successive reaction with sulfur dioxide and oxygen gases gave rise to cadmium sulfate. The phases such as 2 CdS. CdSO 4 , Cd 3 SO 6 and β-CdSO 4 appeared during the oxidation process up to 1100 0 C, at which all the particles were converted into cadmium oxide at 1100 0 C. Cadmium sulfide kept in nitrogen gas above 700 0 C was directly converted into cadmium oxide when oxygen gas was introduced into the furnace. (auth.)

  15. The industrial separation of copper and arsenic as sulfides

    Science.gov (United States)

    Gabb, P. J.; Davies, A. L.

    1999-09-01

    At the Kennecott Utah copper smelter in Magna, Utah, bleed streams from the refinery tankhouse and precious-metals plant are combined with smelter weak acid and electrostatic precipitator dust to produce leach solutions containing copper and impurities. Copper and arsenic are precipitated from the solutions as sulfides in a two-stage continuous process that enables excess arsenic to be removed from the circuit and routed to hazardous waste disposal as a highly concentrated material.

  16. Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery.

    Science.gov (United States)

    Kuchar, D; Fukuta, T; Onyango, M S; Matsuda, H

    2007-04-01

    The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.

  17. Infrared-spectroscopy analysis of zinc phosphate and nickel and manganese modified zinc phosphate coatings on electrogalvanized steel

    International Nuclear Information System (INIS)

    Fernandes, Kirlene Salgado; Alvarenga, Evandro de Azevedo; Lins, Vanessa de Freitas Cunha

    2011-01-01

    Hopeite-type phosphate coatings in which zinc is partially replaced by other metals like manganese and nickel are of great interest for the automotive and home appliance industries. Such industries use phosphate conversion coatings on galvanized steels in association with cataphoretic electro painting. Zinc phosphates modified with manganese and nickel are isomorphic with the hopeite, and the phase identification using X-ray diffraction is difficult. In this paper, the phosphate coatings are identified using the Fourier transform infrared spectroscopy (FTIR). (author)

  18. Hydrothermal synthesis and structure of framework cobalt phosphates

    Indian Academy of Sciences (India)

    Administrator

    Open-framework phosphates investigated in the last few years, specially those of transition metals, are of particular interest because of their potential applications in catalysis, sorption and separation techniques. Amongst the transition metals, cobalt phosphate occupies a prime position because of its interesting magnetic ...

  19. 30 CFR 250.604 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

  20. 30 CFR 250.808 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S...

  1. 30 CFR 250.504 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

  2. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

    Directory of Open Access Journals (Sweden)

    Swamiappan Sasikumar and Rajagopalan Vijayaraghavan

    2008-01-01

    Full Text Available Synthetic calcium hydroxyapatite (HAP, Ca10 (PO46 (OH2 is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye–Scherrer formula, is in the range 20–30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.

  3. Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

    Science.gov (United States)

    Sasikumar, Swamiappan; Vijayaraghavan, Rajagopalan

    2008-07-01

    Synthetic calcium hydroxyapatite (HAP, Ca10 (PO4)6 (OH)2) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye-Scherrer formula, is in the range 20-30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.

  4. Sulfide intrusion and detoxification in seagrasses ecosystems

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    is known about the strategies of seagrasses to survive sulfide intrusion, their potential detoxification mechanisms and sulfur nutrition in general. By a global review of sulfide intrusion, coupled with a series of field studies and in situ experiments we elucidate sulfide intrusion and different...... not present in terrestrial plants at that level. Sulfide is not necessarily toxic but used as sulfur nutrition, presupposing healthy seagrass ecosystems that can support detoxification mechanisms. Presence or absence of those mechanisms determines susceptibility of seagrass ecosystems to sediment sulfide...

  5. The use of indigenous plant species and calcium phosphate for the stabilization of highly metal-polluted sites in southern Poland

    NARCIS (Netherlands)

    Kucharski, R.; Sas-Nowosielska, A.; Malkowski, E.; Japenga, J.; Kuperberg, J.M.; Pogrzeba, M.; Krzyzak, J.

    2005-01-01

    Highly metal-polluted (Pb, Cd, Zn) soil from a non-ferrous mine and smelter site in southern Poland, further referred to as Waryski soil, was used to test indigenous plant species for stabilization effectiveness of heavy metals in soils. Results of pilot investigations with commercially available

  6. Use of bauxite residue (red mud) as a low cost sorbent for sulfide removal in polluted water remediation.

    Science.gov (United States)

    Sheng, Yanqing; Sun, Qiyao; Sun, Ruichuan; Burke, Ian T; Mortimer, Robert J G

    Sulfide is an important pollutant in aqueous systems. Sulfide removal from polluted waters is required prior to discharge. Red mud (RM) is a solid waste of bauxite processing that is rich in reactive iron oxides and consequently has the potential to be used to remove sulfide from aqueous systems. A series of experiments was undertaken using raw and sintered RM to remove sulfide from waters. RM was highly efficient at sulfide removal (average 75% sulfide removal at initial concentration of ∼5 mg L(-1), with 500 mg L(-1) RM addition) due to both physical adsorption (high specific area) and chemical reaction (with amorphous Fe). Sintered RM, which has a lower surface area and lower mineral reactivity, was much less efficient at removing sulfide (∼20% removal under equivalent experimental conditions). Furthermore, concomitant metal release from raw RM was lower than for sintered RM during the sulfide removal process. The results showed that raw RM is a potentially suitable material for sulfide removal from polluted waters and consequently could be used as a low cost alternative treatment in certain engineering applications.

  7. Role of biogenic sulfide in attenuating zinc oxide and copper nanoparticle toxicity to acetoclastic methanogenesis.

    Science.gov (United States)

    Gonzalez-Estrella, Jorge; Puyol, Daniel; Sierra-Alvarez, Reyes; Field, Jim A

    2015-01-01

    Soluble ions released by zinc oxide (ZnO) and copper (Cu(0)) nanoparticles (NPs) have been associated with toxicity to methanogens. This study evaluated the role of biogenic sulfide in attenuating ZnO and Cu(0) NP toxicity to methanogens. Short- and long-term batch experiments were conducted to explore ZnO and Cu(0) NPs toxicity to acetoclastic methanogens in sulfate-containing (0.4mM) and sulfate-free conditions. ZnO and Cu(0) were respectively 14 and 7-fold less toxic in sulfate-containing than in sulfate-free assays as indicated by inhibitory constants (Ki). The Ki with respect to residual soluble metal indicated that soluble metal was well correlated with toxicity irrespective of the metal ion source or presence of biogenic sulfide. Long-term assays indicated that ZnO and Cu(0) NPs caused different effects on methanogens. ZnO NPs without protection of sulfide caused a chronic effect, whereas Cu(0) NPs caused an acute effect and recovered. This study confirms that biogenic sulfide effectively attenuates ZnO and Cu(0) NPs toxicity to methanogens by the formation of metal sulfides. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Mineral induced formation of sugar phosphates

    Science.gov (United States)

    Pitsch, S.; Eschenmoser, A.; Gedulin, B.; Hui, S.; Arrhenius, G.

    1995-01-01

    Glycolaldehyde phosphate, sorbed from highly dilute, weakly alkaline solution into the interlayer of common expanding sheet structure metal hydroxide minerals, condenses extensively to racemic aldotetrose-2, 4-diphophates, and aldohexose-2, 4, 6-triphosphates. The reaction proceeds mainly through racemic erythrose-2, 4-phosphate, and terminates with a large fraction of racemic altrose-2, 4, 6-phosphate. In the absence of an inductive mineral phase, no detectable homogeneous reaction takes place in the concentration- and pH range used. The reactant glycolaldehyde phosphate is practically completely sorbed within an hour from solutions with concentrations as low as 50 micron; the half-time for conversion to hexose phosphates is of the order of two days at room temperature and pH 9.5. Total production of sugar phosphates in the mineral interlayer is largely independent of the glycolaldehyde phosphate concentration in the external solution, but is determined by the total amount of GAP offered for sorption up to the capacity of the mineral. In the presence of equimolar amounts of rac-glyceraldehyde-2-phosphate, but under otherwise similar conditions, aldopentose-2, 4, -diphosphates also form, but only as a small fraction of the hexose-2, 4, 6-phosphates.

  9. Issues of natural radioactivity in phosphates

    International Nuclear Information System (INIS)

    Schnug, E.; Haneklaus, S.; Schnier, C.; Scholten, L.C.

    1996-01-01

    The fertilization of phosphorus (P) fertilizers is essential in agricultural production, but phosphates contain in dependence on their origin different amounts of trace elements. The problem of cadmium (Cd) loads and other heavy metals is well known. However, only a limited number of investigations examined the contamination of phosphates with the two heaviest metals, uranium (U) and thorium (Th), which are radioactive. Also potassium (K) is lightly radioactive. Measurements are done n the radioactivity content of phosphates, P fertilizers and soils. The radiation doses to workers and public as well as possible contamination of soils from phosphate rock or fertilizer caused by these elements or their daughter products is of interest with regard to radiation protection. The use of P fertilizers is necessary for a sustainable agriculture, but it involves radioactive contamination of soils. The consequences of the use of P fertilizers is discussed, also with regard to existing and proposed legislation. 11 refs., 2 figs., 7 tabs

  10. Replacive sulfide formation in anhydrite chimneys from the Pacmanus hydrothermal field, Papua New Guinea

    Science.gov (United States)

    Los, Catharina; Bach, Wolfgang; Plümper, Oliver

    2016-04-01

    Hydrothermal flow within the oceanic crust is an important process for the exchange of energy and mass between the lithosphere, hydrosphere and biosphere. Infiltrated seawater heats up and interacts with wall rock, causing mineral replacement reactions. These play a large role in the formation of ore deposits; at the discharge zone, a hot, acidic and metal-rich potential ore fluid exits the crust. It mixes with seawater and forms chimneys, built up of sulfate minerals such as anhydrite (CaSO4), which are subsequently replaced by sulfide minerals. Sulfide formation is related to fluid pathways, defined by cracks and pores in the sulfate chimney. Over time, these systems might develop into massive sulfide deposits. The big question is then: how is sulfate-sulfide replacement related to the evolution of rock porosity? To address this question, sulfide-bearing anhydrite chimneys from the Pacmanus hydrothermal field (Manus Basin, Papua New Guinea) were studied using X-ray tomography, EMPA, FIB-SEM and -TEM. The apparently massive anhydrite turns out highly porous on the micro scale, with sulfide minerals in anhydrite cleavage planes and along grain boundaries. The size of the sulfide grains relates to the pores they grew into, suggesting a tight coupling between dissolution (porosity generation) and growth of replacive minerals. Some of the sulfide grains are hollow and apparently used the dissolving anhydrite as a substrate to start growth in a pore. Another mode of sulfide development is aggregates of euhedral pyrite cores surrounded by colloform chalcopyrite. This occurrence implies that fluid pathways have remained open for some time to allow several stages of precipitation during fluid evolution. To start the replacement and to keep it going, porosity generation is crucial. Our samples show that dissolution of anhydrite occurred along pathways where fluid could enter, such as cleavage planes and grain boundaries. It appears that fluids ascending within the inner

  11. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

    Science.gov (United States)

    Osuntokun, Jejenija; Ajibade, Peter A.

    2016-09-01

    Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato-κS,S'-bis(N,N-dimethylthiourea-κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33-7.21 nm for ZnS and 4.95-7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.

  12. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

    Energy Technology Data Exchange (ETDEWEB)

    Osuntokun, Jejenija; Ajibade, Peter A., E-mail: pajibade@ufh.ac.za

    2016-09-01

    Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato–κS,S’–bis (N,N-dimethylthiourea–κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33–7.21 nm for ZnS and 4.95–7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.

  13. Amorphous molybdenum sulfides as hydrogen evolution catalysts.

    Science.gov (United States)

    Morales-Guio, Carlos G; Hu, Xile

    2014-08-19

    Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

  14. Effect of the temperature and the porosity of the gettering process on the removal of heavy metals from Tunisian phosphate rock

    Directory of Open Access Journals (Sweden)

    R. Daik

    Full Text Available Gettering is a process by which unwanted impurities are removed by providing an alternative location, this method used by many researchers for the purification of silicon wafers or powder. In this work, this method is used for the first time to remove the impurities from Tunisian phosphate rock (TPR. This method consists in two steps: the rapid thermal processing by infrared furnace followed by a rapid chemical etching. In order to enhance the efficiency of this process, a porous layer on the surface of grains was grown. By this method, we have demonstrated in this present work that the majority of impurities were well extracted from TPR. UV–visible absorption spectra show that the highest intensity of absorbance (∼1 appears for the porous sample treated at 900 °C (P900 °C, which due to the presence of large quantities of impurities in the extracted solution. These results were well confirmed by AAS and ICP-AES which show that the majority of the impurities have been almost removed for the P900 °C sample. Keywords: Gettering process, Porous phosphate rock, Temperature, Impurities

  15. Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

    Science.gov (United States)

    Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

    2012-04-01

    Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to

  16. Regulation of serum phosphate

    Science.gov (United States)

    Lederer, Eleanor

    2014-01-01

    The regulation of serum phosphate, an acknowledged risk factor for chronic kidney disease and cardiovascular mortality, is poorly understood. The discovery of fibroblast growth factor 23 (FGF23) as a key regulator of renal phosphate handling and activation of vitamin D has revolutionized our comprehension of phosphate homeostasis. Through as yet undetermined mechanisms, circulating and dietary phosphate appear to have a direct effect on FGF23 release by bone cells that, in turn, causes renal phosphate excretion and decreases intestinal phosphate absorption through a decrease in vitamin D production. Thus, the two major phosphaturic hormones, PTH and FGF23, have opposing effects on vitamin D production, placing vitamin D at the nexus of phosphate homeostasis. While our understanding of phosphate homeostasis has advanced, the factors determining regulation of serum phosphate level remain enigmatic. Diet, time of day, season, gender, age and genetics have all been identified as significant contributors to serum phosphate level. The effects of these factors on serum phosphate have major implications for what is understood as ‘normal’ and for studies of phosphate homeostasis and metabolism. Moreover, other hormonal mediators such as dopamine, insulin-like growth factor, and angiotensin II also affect renal handling of phosphate. How the major hormone effects on phosphate handling are regulated and how the effect of these other factors are integrated to yield the measurable serum phosphate are only now beginning to be studied. PMID:24973411

  17. Application of SnO2 nanoparticle as sulfide gas sensor using UV/VIS/NIR spectrophotometer

    Science.gov (United States)

    Juliasih, N.; Buchari; Noviandri, I.

    2017-04-01

    Sulfide gas monitoring is required to protect organisms from its toxicity. Nanoparticles of metal oxides have characteristics that applicable as sensors for controlling environmental pollution like sulfide gas. Thin film of SnO2 as one part of the sulfide gas sensor was synthesized with the chemical liquid deposition method, and characterized by UV/VIS/NIR-Spectrophotometer before and after gas application, also using FTIR, SEM and XRD. Characterization studies showed nanoparticle sizes from the diameters range of 38-71 nm. Application of SnO2 thin film to sulfide gas detected by UV/VIS/NIR Spectrophotometer with diffuse reflectance showed chemical reaction by the shifting of maximum % R peak at wavelength of 1428 cm. The benefit of measurement of sulfide gas using this SnO2 nano thin film is that it could be done at the room temperature.

  18. Facile one-pot synthesis of spherical zinc sulfide-carbon nanocomposite powders with superior electrochemical properties as anode materials for Li-ion batteries.

    Science.gov (United States)

    Jang, Yong Seung; Kang, Yun Chan

    2013-10-21

    A novel and simple one-pot method of systematically synthesizing spherical metal sulfide-carbon composite powders is reported for the first time. The zinc sulfide-carbon composite is selected as the first target material. The prepared composite powders show superior electrochemical properties as anode materials for lithium-ion batteries.

  19. Photovoltaic effect in individual asymmetrically contacted lead sulfide nanosheets

    Science.gov (United States)

    Dogan, Sedat; Bielewicz, Thomas; Lebedeva, Vera; Klinke, Christian

    2015-03-01

    Solution-processable, two-dimensional semiconductors are promising optoelectronic materials which could find application in low-cost solar cells. Lead sulfide nanocrystals raised attention since the effective band gap can be adapted over a wide range by electronic confinement and observed multi-exciton generation promises higher efficiencies. We report on the influence of the contact metal work function on the properties of transistors based on individual two-dimensional lead sulfide nanosheets. Using palladium we observed mobilities of up to 31 cm2 V-1 s-1. Furthermore, we demonstrate that asymmetrically contacted nanosheets show photovoltaic effect and that the nanosheets' height has a decisive impact on the device performance. Nanosheets with a thickness of 5.4 nm contacted with platinum and titanium show a power conversion efficiency of up to 0.94% (EQE 75.70%). The results underline the high hopes put on such materials.Solution-processable, two-dimensional semiconductors are promising optoelectronic materials which could find application in low-cost solar cells. Lead sulfide nanocrystals raised attention since the effective band gap can be adapted over a wide range by electronic confinement and observed multi-exciton generation promises higher efficiencies. We report on the influence of the contact metal work function on the properties of transistors based on individual two-dimensional lead sulfide nanosheets. Using palladium we observed mobilities of up to 31 cm2 V-1 s-1. Furthermore, we demonstrate that asymmetrically contacted nanosheets show photovoltaic effect and that the nanosheets' height has a decisive impact on the device performance. Nanosheets with a thickness of 5.4 nm contacted with platinum and titanium show a power conversion efficiency of up to 0.94% (EQE 75.70%). The results underline the high hopes put on such materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06957a

  20. Simple micellar electrokinetic chromatography method for the determination of hydrogen sulfide in hen tissues.

    Science.gov (United States)

    Kubalczyk, Paweł; Borowczyk, Kamila; Chwatko, Grażyna; Głowacki, Rafał

    2015-04-01

    A new method for the determination of hydrogen sulfide in hen tissues has been developed and validated. For estimation of hydrogen sulfide content, a sample (0.1 g) of hen tissue was treated according to the procedure consisted of some essential steps: simultaneous homogenization of a tissue and derivatization of hydrogen sulfide to its S-quinolinium derivative with 2-chloro-1-methylquinolinium tetrafluoroborate, separation of so-formed derivative by micellar electrokinetic chromatography with sweeping, and detection and quantitation with the use of UV detector set to measure analytical signals at 375 nm. Effective electrophoretic separation was achieved using fused silica capillary (effective length 41.5 cm, 75 μm id) and 0.05 mol/L, pH 8 phosphate buffer with the addition of 0.04 mol/L SDS and 26% ACN. The lower limit of quantification was 0.12 μmol hydrogen sulfide in 1 g of tissue. The calibration curve prepared in tissue homogenate for hydrogen sulfide showed linearity in the range from 0.15 to 2.0 μmol/g, with the coefficient of correlation 0.9978. The relative standard deviation of the points of the calibration curve varied from 8.3 to 3.2% RSD. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Phosphate Uptake by Phosphate-Starved Euglena

    Science.gov (United States)

    BLUM, J. J.

    1966-01-01

    Phosphate-deprived Euglena acquire the ability to rapidly in-corporate added phosphate and, also, synthesize an induced acid phosphatase localized in the pellicle. The phosphate uptake system is saturated at low concentrations of phosphate and is inhibited by dinitrophenol, by low temperature, by K+, Li+, and Na+ ions, and competitively by arsenate. The orthophosphate incorporated into the cell is rapidly converted into organic forms but enough remains unesterified to suggest that the uptake is an active transport process. The data do not rule out the possibility that the induced phosphatase is involved in the transport process. PMID:5924104

  2. An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

    Science.gov (United States)

    Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

    2018-03-01

    attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (X_{{{Ni}}}^{{{sulfide}}} 0.4-0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6-0.7) at depths near 80-120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (X_{{{Ni}}}^{{{sulfide}}} 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.

  3. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    Science.gov (United States)

    Anstoetz, Manuela; Rose, Terry J; Clark, Malcolm W; Yee, Lachlan H; Raymond, Carolyn A; Vancov, Tony

    2015-01-01

    A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF) was investigated as a microbially-induced slow-release nitrogen (N) and phosphorus (P) fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate) and N (urea) fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1)). While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils.

  4. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic-Frameworks (OPA-MOFs: Can an Iron-Based OPA-MOF Be Used as Slow-Release Fertilizer?

    Directory of Open Access Journals (Sweden)

    Manuela Anstoetz

    Full Text Available A porous iron-based oxalate-phosphate-amine metal-organic framework material (OPA-MOF was investigated as a microbially-induced slow-release nitrogen (N and phosphorus (P fertilizer. Seedling growth, grain yields, nutrient uptake of wheat plants, and soil dynamics in incubated soil, were investigated using OPA-MOF vs standard P (triple-superphosphate and N (urea fertilizers in an acidic Ferralsol at two application rates (equivalent 120 and 40 kg N ha(-1. While urea hydrolysis in the OPA-MOF treatment was rapid, conversion of ammonium to nitrate was significantly inhibited compared to urea treatment. Reduced wheat growth in OPA-MOF treatments was not caused by N-deficiency, but by limited P-bioavailability. Two likely reasons were slow P-mobilisation from the OPA-MOF or rapid P-binding in the acid soil. P-uptake and yield in OPA-MOF treatments were significantly higher than in nil-P controls, but significantly lower than in conventionally-fertilised plants. OPA-MOF showed potential as enhanced efficiency N fertilizer. However, as P-bioavailability was insufficient to meet plant demands, further work should determine if P-availability may be enhanced in alkaline soils, or whether central ions other than Fe, forming the inorganic metal-P framework in the MOF, may act as a more effective P-source in acid soils.

  5. The effect of polyaniline phosphate on mechanical and corrosive properties of protective organic coatings containing high amounts of zinc metal particles

    Czech Academy of Sciences Publication Activity Database

    Kohl, M.; Kalendová, A.; Stejskal, Jaroslav

    2014-01-01

    Roč. 77, č. 2 (2014), s. 512-517 ISSN 0300-9440 R&D Projects: GA ČR(CZ) GA13-00270S Institutional support: RVO:61389013 Keywords : conductive polymers * zinc metal * organic coating Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.358, year: 2014

  6. Isotopic data from proterozoic sediment-hosted sulfide deposits of Brazil: Implications for their metallogenic evolution and for mineral exploration

    International Nuclear Information System (INIS)

    Misi, Aroldo; Coelho, Carlos E.S.; Franca Rocha, Washington J.S.; Gomez, Adriana S.R.; Cunha, Iona A.; Iyer, Sundaram S.; Tassinari, Colombo C.G.; Kyle, J. Richard

    1998-01-01

    Geological, petrographic, fluid inclusions studies and isotopic data of seven Proterozoic sediment-hosted Pb-Zn-Ag sulfide deposits of Brazil, permit the estimation of the age of the hosting sequence and the mineralization, the nature of the sulfur and metal sources, the temperature range of sulfide formation and the environment of deposition of the mineral deposits. The studies suggest that they were formed during periods of extensional tectonics: Growth faults or reactivated basement faults were responsible for localized circulation of metal-bearing fluids within the sedimentary sequences. In most cases, sulfides were formed by the reduction of sedimentary sulfates. Linear structures are important controls for sulfide concentration in these Proterozoic basins. (author)

  7. Uranium from phosphate ores

    International Nuclear Information System (INIS)

    Hurst, F.J.

    1983-01-01

    The following topics are described briefly: the way phosphate fertilizers are made; how uranium is recovered in the phosphate industry; and how to detect covert uranium recovery operations in a phsophate plant

  8. Glucose-6-phosphate dehydrogenase

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/003671.htm Glucose-6-phosphate dehydrogenase test To use the sharing features on this page, please enable JavaScript. Glucose-6-phosphate dehydrogenase (G6PD) is a protein that ...

  9. Formation of mercury sulfide from Hg(II)−thiolate complexes in natural organic matter

    Science.gov (United States)

    Alain Manceau,; Cyprien Lemouchi,; Mironel Enescu,; Anne-Claire Gaillot,; Martine Lanson,; Valerie Magnin,; Pieter Glatzel,; Poulin, Brett; Ryan, Joseph N.; Aiken, George R.; Isabelle Gautier-Lunea,; Kathryn L. Nagy,

    2015-01-01

    Methylmercury is the environmental form of neurotoxic mercury that is biomagnified in the food chain. Methylation rates are reduced when the metal is sequestered in crystalline mercury sulfides or bound to thiol groups in macromolecular natural organic matter. Mercury sulfide minerals are known to nucleate in anoxic zones, by reaction of the thiol-bound mercury with biogenic sulfide, but not in oxic environments. We present experimental evidence that mercury sulfide forms from thiol-bound mercury alone in aqueous dark systems in contact with air. The maximum amount of nanoparticulate mercury sulfide relative to thiol-bound mercury obtained by reacting dissolved mercury and soil organic matter matches that detected in the organic horizon of a contaminated soil situated downstream from Oak Ridge, TN, in the United States. The nearly identical ratios of the two forms of mercury in field and experimental systems suggest a common reaction mechanism for nucleating the mineral. We identified a chemical reaction mechanism that is thermodynamically favorable in which thiol-bound mercury polymerizes to mercury–sulfur clusters. The clusters form by elimination of sulfur from the thiol complexes via breaking of mercury–sulfur bonds as in an alkylation reaction. Addition of sulfide is not required. This nucleation mechanism provides one explanation for how mercury may be immobilized, and eventually sequestered, in oxygenated surface environments.

  10. Soft chemical control of the crystal and magnetic structure of a layered mixed valent manganite oxide sulfide

    Directory of Open Access Journals (Sweden)

    Jack N. Blandy

    2015-04-01

    Full Text Available Oxidative deintercalation of copper ions from the sulfide layers of the layered mixed-valent manganite oxide sulfide Sr2MnO2Cu1.5S2 results in control of the copper-vacancy modulated superstructure and the ordered arrangement of magnetic moments carried by the manganese ions. This soft chemistry enables control of the structures and properties of these complex materials which complement mixed-valent perovskite and perovskite-related transition metal oxides.

  11. X-ray absorption spectroscopy on phosphoric-salt pellets. Determination of the geometric and electronic structure of metal-oxide doped sodium-phosphate glasses

    International Nuclear Information System (INIS)

    Brendebach, B.

    2004-02-01

    Sodium metaphosphate glasses doped with transition metal oxides show characteristic colors. X-ray absorption spectroscopy (XAS) investigations provide information whether the coloration stems from different electronic transitions or changes in the geometrical structure of the glasses. Even though the violet color of MnO y -doped glasses is considered as an evidence for Mn 3+ -ions, Mn K-XAS reveals that the majority of the manganese ions are in the oxidation state +II and have a mixed coordination of four and six oxygen atoms, respectively. The oxygen coordination around the nickel ions in NiO-doped glasses with different metall oxide concentrations is always six. The change of color from citreous to auburn with increasing nickel oxide content is attributed to a systematic change in the bonding characteristic from mainly ionic-like to a small but significant contribution of covalent-like bonding. Analysis of higher coordination shells provides no indication of the formation of metal oxide clusters. (orig.)

  12. Sulfide mineralization in ultramafic rocks of the Faryab ophiolite complex, southern Kerman

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Rajabzadeh

    2015-10-01

    Full Text Available Introduction Worldwide, Ni-Cu and PGE magmatic sulfide deposits are confined to the lower parts of stratiform mafic and ultramafic complexes. However, ophiolite mafic and ultramafic complexes have been rarely explored for sulfide deposits despite the fact that they have been extensively explored and exploited for chromite. Sulfide saturation during magmatic evolution is necessary for sulfide mineralization, in which sulfide melts scavenge chalcophile metals from the parent magma and concentrate them in specific lithological zones. The lack of exploration for sulfides in this environment suggests that sulfide saturation is rarely attained in ophiolite-related magmas. Some ophiolites, however, contain sulfide deposits, such as at Acoje in Philippines, and Cliffs in Shetland, U.K. (Evans, 2000; Naldrett, 2004. The Faryab ophiolite complex in southern Kerman Province, the most important mining area for chromite deposits in Iran, is located in the southwest part of the Makran Zone. Evidence of sulfide mineralization has been reported there by some authors (e.g. Rajabzadeh and Moosavinasab, 2013. This paper discusses the genesis of sulfides in the Faryab ophiolite using mineral chemistry of the major mineral phases in different rocks of the ophiolite column in order to determine the possible lithological location of sulfide deposits. Materials and methods Seventy three rock samples from cumulate units were collected from surficial occurrences and drill core. The samples were studied using conventional microscopic methods and the mineralogy confirmed by x-ray diffraction. Electron microprobe analysis was carried out on different mineral phases in order to determine the chemistry of the minerals used in the interpretation of magma evolution in the Faryab ophiolite. Lithologically, the Faryab ophiolite complex is divided into two major parts: the northern part includes magmatic rocks and the southern part is comprised of rocks residual after partial

  13. Source and fate of inorganic soil contamination around the abandoned Phillips sulfide mine, hudson Highlands, New York

    Science.gov (United States)

    Gilchrist, S.; Gates, A.; Elzinga, E.; Gorring, M.; Szabo, Z.

    2011-01-01

    The abandoned Phillips sulfide mine in the critical Highlands watershed in New York has been shown to produce strongly acidic mine drainage (AMD) with anomalous metal contaminants in first-order streams that exceeded local water standards by up to several orders of magnitude (Gilchrist et al., 2009). The metal-sulfide-rich tailings also produce contaminated soils with pH meter scale is self-similar to those in the bulk soil samples. Generally metals decreased, with some fluctuations, rapidly downslope through suspension of fines and dissolution in AMD leaving the area of substantial contamination << 0.5 km from the source.

  14. Structural studies of copper sulfide films: effect of ambient atmosphere

    Directory of Open Access Journals (Sweden)

    Manisha Kundu et al

    2008-01-01

    Full Text Available We examined the structural properties of copper sulfide films as a function of the sulfurization time of 70-nm-thick Cu films. Copper sulfide films with various phases such as mixed metallic Cu-chalcocite, chalcocite, roxbyite, and covellite phases were formed with increasing sulfurization time. To evaluate the structural stability of various films, all the films were exposed to the ambient atmosphere for the same amount of time. Although the phase structure and stoichiometry of the films were maintained at a greater depth, the near-surface region of the films was oxidized and covered with overlayers of oxide, hydroxide, and/or sulfate species due to the exposure and reaction with the ambient atmosphere. The oxygen uptake and its reactivity with the copper sulfide film surfaces were enhanced with increasing sulfur content of the films. In addition, the type of divalent state of copper formed on the film surfaces depended on the phase structure, composition, and stoichiometry of the films.

  15. Method for Producing Chemically Bonded Phosphate Ceramics and for Stabilizing Contaminants Encapsulated therein Utilizing Reducing Agents

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Dileep; Wagh, Arun S.; Jeong, Seung-Young

    1999-05-05

    Known phosphate ceramic formulations are improved and the ability to produce iron-based phosphate ceramic systems is enabled by the addition of an oxidizing or reducing step during the acid-base reactions that form the phosphate ceramic products. The additives allow control of the rate of the acid-base reactions and concomitant heat generation. In an alternate embodiment, waste containing metal anions is stabilized in phosphate ceramic products by the addition of a reducing agent to the phosphate ceramic mixture. The reduced metal ions are more stable and/or reactive with the phosphate ions, resulting in the formation of insoluble metal species within the phosphate ceramic matrix, such that the resulting chemically bonded phosphate ceramic product has greater leach resistance.

  16. Nitrogen release from forest soils containing sulfide-bearing sediments

    Science.gov (United States)

    Maileena Nieminen, Tiina; Merilä, Päivi; Ukonmaanaho, Liisa

    2014-05-01

    Soils containing sediments dominated by metal sulfides cause high acidity and release of heavy metals, when excavated or drained, as the aeration of these sediments causes formation of sulfuric acid. Consequent leaching of acidity and heavy metals can kill tree seedlings and animals such as fish, contaminate water, and corrode concrete and steel. These types of soils are called acid sulfate soils. Their metamorphic equivalents, such as sulfide rich black shales, pose a very similar risk of acidity and metal release to the environment. Until today the main focus in treatment of the acid sulfate soils has been to prevent acidification and metal toxicity to agricultural crop plants, and only limited attention has been paid to the environmental threat caused by the release of acidity and heavy metals to the surrounding water courses. Even less attention is paid on release of major nutrients, such as nitrogen, although these sediments are extremely rich in carbon and nitrogen and present a potentially high microbiological activity. In Europe, the largest cover of acid sulfate soils is found in coastal lowlands of Finland. Estimates of acid sulfate soils in agricultural use range from 1 300 to 3 000 km2, but the area in other land use classes, such as managed peatland forests, is presumably larger. In Finland, 49 500 km2 of peatlands have been drained for forestry, and most of these peatland forests will be at the regeneration stage within 10 to 30 years. As ditch network maintenance is often a prerequisite for a successful establishment of the following tree generation, the effects of maintenance operations on the quality of drainage water should be under special control in peatlands underlain by sulfide-bearing sediments. Therefore, identification of risk areas and effective prevention of acidity and metal release during drain maintenance related soil excavating are great challenges for forestry on coastal lowlands of Finland. The organic and inorganic nitrogen

  17. Fabrication and characterization of polyvinyl alcohol/metal (Ca, Mg, Ti) doped zirconium phosphate nanocomposite films for scaffold-guided tissue engineering application

    International Nuclear Information System (INIS)

    Kalita, Himani; Pal, Pallabi; Dhara, Santanu; Pathak, Amita

    2017-01-01

    Nanocomposite films of polyvinyl alcohol (PVA) and zirconium phosphate (ZrP)/doped ZrP (doped with Ca, Mg, Ti) nanoparticles have been developed by solvent casting method to assess their potential as matrix material in scaffold-guided tissue engineering application. The prepared ZrP and doped ZrP nanoparticles as well as the nanocomposite films were characterized by various spectroscopic and microscopic techniques. Nanoindentation studies revealed improved nanomechanical properties in the PVA/doped ZrP nanocomposite films (highest for PVA/Ti doped ZrP: hardness = 262.4 MPa; elastic modulus = 5800 MPa) as compared to the PVA/ZrP and neat PVA films. In-vitro cell culture experiments carried out to access the cellular viability, attachment, proliferation, and migration on the substrates, using mouse fibroblast (3T3) cell lines, inferred enhanced bioactivity in the PVA/doped ZrP nanocomposite films (highest for PVA/Ca doped ZrP) in contrast to PVA/ZrP and neat PVA films. Controlled biodegradability as well as swelling behavior, superior bioactivity and improved mechanical properties of the PVA/doped ZrP nanocomposite films make them promising matrix materials for scaffold-guided tissue engineering application. - Highlights: • PVA/ZrP (undoped/doped with Ca, Mg and Ti) nanocomposite scaffolds were developed. • The nanocomposites were prepared via solvent casting method. • PVA/doped ZrP films exhibited enhanced mechanical properties than PVA/undoped ZrP. • Excellent bioactivity was observed in the PVA/doped ZrP films than PVA/undoped ZrP.

  18. SIP response for volume content of sulfide mineral in artificial specimen

    Science.gov (United States)

    Park, Mi Kyung; Park, Samgyu; Jong Yi, Myeong; Kim, Jung Ho

    2014-05-01

    Spectral Induced Polarization (SIP) method has recently been introduced to enhance mineral resource exploration techniques in metal ore deposit, South Korea. Because the valuable mineral ore contains various sulfide minerals such as pyrite (FeS), chalcopyrite (CuFeS2), and galena (PbS), which show IP (Induced Polarization) effect. The conventional IP method was not adequate to find these various sulfide minerals because of certain restrictions, including limited frequency. In order to solve this problem, the SIP (Spectral Induced Polarization) method was introduced, which measures responses like as amplitude (or resistivity) and phase for a wide frequency band. The application of the SIP method has been increasing as an exploration technology for mineral resources, because it can be used to acquire and analyze high quality IP data according to the spectral frequency. SIP responses are strong in the presence of the sulfide minerals; however, sufficient study on the characteristics of the SIP response for the various sulfide minerals is not available so far. In this study, in order to identify the SIP response characteristics of sulfide minerals, the SIP method was used in the laboratory; on artificial specimens filled with glass beads and sulfide minerals. The experiment was controlled by the changing volume content, and grain size, of three kinds of sulfide minerals (i.e., chalcopyrite, pyrite, and galena). The grain sizes of the sulfide minerals were varied in five steps: under 0.5 mm, 0.5 - 1.0 mm, 1.0 - 2.0 mm, 2.0 - 2.85 mm, and 2.85 - 4.0 mm, while the grain size of the glass beads was in the range of 0.75 - 1.0 mm. Variation of the volume content of the sulfide mineral was divided into eight grades. The sulfide minerals occupied 0.5, 1, 2, 3, 5, 7, 10, and 20 percent of the total volume 250 ml specimens. The volume content was converted from the weight using the density of a standard volume of 100 ml for each grain size. The results show that phase response

  19. Novel vanadium phosphate phases as catalysts for selective oxidation

    Indian Academy of Sciences (India)

    Unknown

    Abstract. In our effort to induce novel modifications in the structure of some important vanadium phosphate phases used as selective oxidation catalysts, it has been observed that metal ions such as Zn2+, Ni2+, Pd2+ can be incorporated into the vanadyl hydrogen phosphate VOHPO4⋅0⋅5H2O phase in very different ways.

  20. Metal uptake by lolium perenne in contaminated soils using a four-steps approach

    NARCIS (Netherlands)

    Kalis, E.J.J.; Temminghoff, E.J.M.; Visser, A.; Riemsdijk, van W.H.

    2007-01-01

    Metal bioavailability and toxicity to aquatic organisms are greatly affected by variables such as pH, hardness, organic matter, and sediment acid-volatile sulfide (AVS). Sediment AVS, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides, has been

  1. Sulfide toxicity kinetics of a uasb reactor

    Directory of Open Access Journals (Sweden)

    D. R. Paula Jr.

    2009-12-01

    Full Text Available The effect of sulfide toxicity on kinetic parameters of anaerobic organic matter removal in a UASB (up-flow anaerobic sludge blanket reactor is presented. Two lab-scale UASB reactors (10.5 L were operated continuously during 12 months. The reactors were fed with synthetic wastes prepared daily using glucose, ammonium acetate, methanol and nutrient solution. One of the reactors also received increasing concentrations of sodium sulfide. For both reactors, the flow rate of 16 L.d-1 was held constant throughout the experiment, corresponding to a hydraulic retention time of 15.6 hours. The classic model for non-competitive sulfide inhibition was applied to the experimental data for determining the overall kinetic parameter of specific substrate utilization (q and the sulfide inhibition coefficient (Ki. The application of the kinetic parameters determined allows prediction of methanogenesis inhibition and thus the adoption of operating parameters to minimize sulfide toxicity in UASB reactors.

  2. Effect of hydraulic retention time on metal precipitation in sulfate reducing inverse fluidized bed reactors

    KAUST Repository

    Villa-Gómez, Denys Kristalia

    2014-02-13

    BACKGROUND: Metal sulfide recovery in sulfate reducing bioreactors is a challenge due to the formation of small precipitates with poor settling properties. The size of the metal sulfide precipitates with the change in operational parameters such as pH, sulfide concentration and reactor configuration has been previously studied. The effect of the hydraulic retention time (HRT) on the metal precipitate characteristics such as particle size for settling has not yet been addressed. RESULTS: The change in size of the metal (Cu, Zn, Pb and Cd) sulfide precipitates as a function of the HRT was studied in two sulfate reducing inversed fluidized bed (IFB) reactors operating at different chemical oxygen demand concentrations to produce high and low sulfide concentrations. The decrease of the HRT from 24 to 9h in both IFB reactors affected the contact time of the precipitates formed, thus making differences in aggregation and particle growth regardless of the differences in sulfide concentration. Further HRT decrease to 4.5h affected the sulfate reducing activity for sulfide production and hence, the supersaturation level and solid phase speciation. Metal sulfide precipitates affected the sulfate reducing activity and community in the biofilm, probably because of the stronger local supersaturation causing metal sulfides accumulation in the biofilm. CONCLUSIONS: This study shows that the HRT is an important factor determining the size and thus the settling rate of the metal sulfides formed in bioreactors.

  3. Feasibility of sulfide control in sewers by reuse of iron rich drinking water treatment sludge.

    Science.gov (United States)

    Sun, Jing; Pikaar, Ilje; Sharma, Keshab Raj; Keller, Jürg; Yuan, Zhiguo

    2015-03-15

    Dosage of iron salt is the most commonly used method for sulfide control in sewer networks but incurs high chemical costs. In this study, we experimentally investigate the feasibility of using iron rich drinking water treatment sludge for sulfide control in sewers. A lab-scale rising main sewer biofilm reactor was used. The sulfide concentration in the effluent decreased from 15.5 to 19.8 mgS/L (without dosing) to below 0.7-2.3 mgS/L at a sludge dosing rate achieving an iron to total dissolved inorganic sulfur molar ratio (Fe:S) of 1:1, with further removal of sulfide possible by prolonging the reaction time. In fact, batch tests revealed an Fe consumption to sulfide removal ratio of 0.5 ± 0.02 (mole:mole), suggesting the possible occurrence of other reactions involving the removal of sulfide. Modelling revealed that the reaction between iron in sludge and sulfide has reaction orders of 0.65 ± 0.01 and 0.77 ± 0.02 with respect to the Fe and sulfide concentrations, respectively. The addition of sludge slightly increased the total chemical oxidation demand (tCOD) concentration (by approximately 12%) as expected, but decreased the soluble chemical oxidation demand (sCOD) concentration and methane formation by 7% and 20%, respectively. Some phosphate removal (13%) was also observed at the sludge dosing rate of 1:1 (Fe:S), which is beneficial to nutrient removal from the wastewater. Overall, this study suggests that dosing iron-rich drinking water sludge to sewers could be an effective strategy for sulfide removal in sewer systems, which would also reduce the sludge disposal costs for drinking water treatment works. However, its potential side-effects on sewer sedimentation and on the wastewater treatment plant effluent remain to be investigated. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

    Science.gov (United States)

    Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

    2017-07-21

    Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Biomimetic calcium phosphate coatings on recombinant spider silk fibres

    NARCIS (Netherlands)

    Yang, Liang; Hedhammar, My; Blom, Tobias; Leifer, Klaus; Johansson, Jan; Habibovic, Pamela; van Blitterswijk, Clemens

    2010-01-01

    Calcium phosphate ceramic coatings, applied on surfaces of metallic and polymeric biomaterials, can improve their performance in bone repair and regeneration. Spider silk is biocompatible, strong and elastic, and hence an attractive biomaterial for applications in connective tissue repair. Recently,

  6. Immobilization of radioactive strontium in contaminated soils by phosphate treatment

    International Nuclear Information System (INIS)

    Kim, K.H.; Ammons, J.T.

    1990-01-01

    The feasibility of in situ phosphate- and metal- (calcium, aluminum, and iron) solution treatment for 90 Sr immobilization was investigated. Batch and column experiments were performed to find optimum conditions for coprecipitation of 90 Sr with Ca-, Al-, and Fe-phosphate compounds in contaminated soils. Separate columns were packed with artificially 85 Sr-contaminated acid soil as well as 90 Sr-contaminated soil from the Oak Ridge Reservation. After metal-phosphate treatment, the columns were then leached successively with either tapwater or 0.001 M CaCl 2 solution. Most of the 85 Sr coprecipitated with the metal phosphate compounds. Immobilization of 85 Sr and 90 Sr was affected by such factors as solution pH, metal and phosphate concentration, metal-to-phosphate ratio, and soil characteristics. Equilibration time after treatments also affected 85 Sr immobilization. Many technology aspects still need to be investigated before field applications are feasible, but these experiments indicate that phosphate-based in situ immobilization should prevent groundwater contamination and will be useful as a treatment technology for 90 Sr-contaminated sites. 15 refs., 3 figs., 1 tab

  7. Cadmium versus phosphate in the world ocean

    NARCIS (Netherlands)

    Baar, Hein J.W. de; Saager, Paul M.; Nolting, Rob F.; Meer, Jaap van der

    1994-01-01

    Cadmium (Cd) is one of the best studied trace metals in seawater and at individual stations exhibits a more or less linear relation with phosphate. The compilation of all data from all oceans taken from over 30 different published sources into one global dataset yields only a broad scatterplot of Cd

  8. Mercury stabilization in chemically bonded phosphate ceramics

    International Nuclear Information System (INIS)

    Wagh, A. S.; Singh, D.; Jeong, S. Y.

    2000-01-01

    Mercury stabilization and solidification is a significant challenge for conventional stabilization technologies. This is because of the stringent regulatory limits on leaching of its stabilized products. In a conventional cement stabilization process, Hg is converted at high pH to its hydroxide, which is not a very insoluble compound; hence the preferred route for Hg sulfidation to convert it into insoluble cinnabar (HgS). Unfortunately, efficient formation of this compound is pH-dependent. At a high pH, one obtains a more soluble Hg sulfate, in a very low pH range, insufficient immobilization occurs because of the escape of hydrogen sulfide, while efficient formation of HgS occurs only in a moderately acidic region. Thus, the pH range of 4 to 8 is where stabilization with Chemically Bonded Phosphate Ceramics (CBPC) is carried out. This paper discusses the authors experience on bench-scale stabilization of various US Department of Energy (DOE) waste streams containing Hg in the CBPC process. This process was developed to treat DOE's mixed waste streams. It is a room-temperature-setting process based on an acid-base reaction between magnesium oxide and monopotassium phosphate solution that forms a dense ceramic within hours. For Hg stabilization, addition of a small amount ( 2 S or K 2 S is sufficient in the binder composition. Here the Toxicity Characteristic Leaching Procedure (TCLP) results on CBPC waste forms of surrogate waste streams representing secondary Hg containing wastes such as combustion residues and Delphi DETOXtrademark residues are presented. The results show that although the current limit on leaching of Hg is 0.2 mg/L, the results from the CBPC waste forms are at least one order lower than this stringent limit. Encouraged by these results on surrogate wastes, they treated actual low-level Hg-containing mixed waste from their facility at Idaho. TCLP results on this waste are presented here. The efficient stabilization in all these cases is

  9. A highly stable and sensitive chemically modified screen-printed electrode for sulfide analysis

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, D.-M. [Department of Chemistry, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung 40217, Taiwan (China); Kumar, Annamalai Senthil [Department of Chemistry, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung 40217, Taiwan (China); Zen, J.-M. [Department of Chemistry, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung 40217, Taiwan (China)]. E-mail: jmzen@dragon.nchu.edu.tw

    2006-01-18

    We report here a highly stable and sensitive chemically modified screen-printed carbon electrode (CMSPE) for sulfide analysis. The CMSPE was prepared by first ion-exchanging ferricyanide into a Tosflex anion-exchange polymer and then sealing with a tetraethyl orthosilicate sol-gel layer. The sol-gel overlayer coating was crucial to stabilize the electron mediator (i.e., Fe(China){sub 6} {sup 3-}) from leaching. The strong interaction between the oxy-hydroxy functional group of sol-gel and the hydrophilic sites of Tosflex makes the composite highly rigid to trap the ferricyanide mediator. An obvious electrocatalytic sulfide oxidation current signal at {approx}0.20 V versus Ag/AgCl in pH 7 phosphate buffer solution was observed at the CMSPE. A linear calibration plot over a wide range of 0.1 {mu}M to 1 mM with a slope of 5.6 nA/{mu}M was obtained by flow injection analysis. The detection limit (S/N = 3) was 8.9 nM (i.e., 25.6 ppt). Practical utility of the system was applied to the determination of sulfide trapped from cigarette smoke and sulfide content in hot spring water.

  10. Effect of polyethyleneimine on phosphate coatings on mild steel

    Energy Technology Data Exchange (ETDEWEB)

    Nair, U.B.; Subbaiyan, M. (Univ. of Madras, Madras (India). Dept. of Analytical Chemistry)

    1993-04-01

    The interposition of a phosphate layer between a metal substrate and its paint finish has become a well known method of improving adhesion between them. This paper describes efforts to improve the protective and paint-base properties of phosphate coatings, through the incorporation of polymeric compounds as additives in phosphating compositions. In the present study, a high molecular weight, water-soluble polymer, polyethyleneimine (PEI), was evaluated as an additive in an optimized Ca-Zn cold phosphating formulation. The incorporation of PEI in the bath resulted in the formation of coatings having desirable properties and good corrosion resistance.

  11. Rational Design of Nanoparticle Platforms for "Cutting-the-Fat": Covalent Immobilization of Lipase, Glycerol Kinase, and Glycerol-3-Phosphate Oxidase on Metal Nanoparticles.

    Science.gov (United States)

    Aggarwal, V; Pundir, C S

    2016-01-01

    The aggregates of nanoparticles (NPs) are considered better supports for the immobilization of enzymes, as these promote enzyme kinetics, due to their unusual but favorable properties such as larger surface area to volume ratio, high catalytic efficiency of certain immobilized enzymes, non-toxicity of some of the nanoparticle matrices, high stability, strong adsorption of the enzyme of interest by a number of different approaches, and faster electron transportability. Co-immobilization of multiple enzymes required for a multistep reaction cascade on a single support is more efficient than separately immobilizing the corresponding enzymes and mixing them physically, since products of one enzyme could serve as reactants for another. These products can diffuse much more easily between enzymes on the same particle than diffusion from one particle to the next, in the reaction medium. Thus, co-immobilization of enzymes onto NP aggregates is expected to produce faster kinetics than their individual immobilizations on separate matrices. Lipase, glycerol kinase, and glycerol-3-phosphate oxidase are required for lipid analysis in a cascade reaction, and we describe the co-immobilization of these three enzymes on nanocomposites of zinc oxide nanoparticles (ZnONPs)-chitosan (CHIT) and gold nanoparticles-polypyrrole-polyindole carboxylic acid (AuPPy-Pin5COOH) which are electrodeposited on Pt and Au electrodes, respectively. The kinetic properties and analytes used for amperometric determination of TG are fully described for others to practice in a trained laboratory. Cyclic voltammetry, scanning electron microscopy, Fourier transform infra-red spectra, and electrochemical impedance spectra confirmed their covalent co-immobilization onto electrode surfaces through glutaraldehyde coupling on CHIT-ZnONPs and amide bonding on AuPPy/Pin5COOH. The combined activities of co-immobilized enzymes was tested amperometrically, and these composite nanobiocatalysts showed optimum activity

  12. Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

    Science.gov (United States)

    Nason, Peter; Johnson, Raymond H.; Neuschutz, Clara; Alakangas, Lena; Ohlander, Bjorn

    2014-01-01

    Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

  13. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2015-01-01

    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field...... as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments....

  14. Magnesium-phosphate-glass cements with ceramic-type properties

    Science.gov (United States)

    Sugama, T.; Kukacka, L.E.

    1982-09-23

    Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate, exhibits rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.

  15. Magnesium phosphate glass cements with ceramic-type properties

    Science.gov (United States)

    Sugama, Toshifumi; Kukacka, Lawrence E.

    1984-03-13

    Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate exhibiting rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.

  16. Discussion about magnesium phosphating

    Directory of Open Access Journals (Sweden)

    P. Pokorny

    2016-07-01

    Full Text Available The paper describes results from recently published research focused on production of non-conventional magnesium phosphate Mg3(PO42・4H2O – bobierrite, or MgHPO4・3H2O – newberyite coating for both magnesium alloys and/or mild steel. This new kind of coating is categorized in the context of current state of phosphating technology and its potential advantages and crystal structure is discussed. At the same time, the suitable comparison techniques for magnesium phosphate coating and conventional zinc phosphate coating are discussed.

  17. Phosphorus, phosphorous, and phosphate.

    Science.gov (United States)

    Iheagwara, O Susan; Ing, Todd S; Kjellstrand, Carl M; Lew, Susie Q

    2013-10-01

    This article distinguishes the terms "phosphorus, phosphorous, and phosphate" which are frequently used interchangeably. We point out the difference between phosphorus and phosphate, with an emphasis on the unit of measure. Expressing a value without the proper name or unit of measure may lead to misunderstanding and erroneous conclusions. We indicate why phosphate must be expressed as milligrams per deciliter or millimoles per liter and not as milliequivalents per liter. Therefore, we elucidate the distinction among the terms "phosphorus, phosphorous, and phosphate" and the importance of saying precisely what one really means. © 2012 The Authors. Hemodialysis International © 2012 International Society for Hemodialysis.

  18. Electrochemical Synthesis and Characterization of Zinc Sulfide Nanoparticles

    OpenAIRE

    M. Rahimi-Nasarabadi

    2014-01-01

    Electrosynthesis process has been used for preparation of zinc sulfide nanoparticles. Zinc sulfide nanoparticles in different size and shapes were electrodeposited by electrolysis of zinc plate as anode in sodium sulfide solution. Effects of several reaction variables, such as electrolysis voltage, sulfide ion concentration as reactant, stirring rate of electrolyte solution and temperature on particle size of prepared zinc sulfide were investigated. The significance of these parameters in tun...

  19. Dissolved organic matter enhances microbial mercury methylation under sulfidic conditions

    Science.gov (United States)

    Graham, Andrew M.; Aiken, George R.; Gilmour, Cynthia

    2012-01-01

    Dissolved organic matter (DOM) is generally thought to lower metal bioavailability in aquatic systems due to the formation of metal–DOM complexes that reduce free metal ion concentrations. However, this model may not be pertinent for metal nanoparticles, which are now understood to be ubiquitous, sometimes dominant, metal species in the environment. The influence of DOM on Hg bioavailability to microorganisms was examined under conditions (0.5–5.0 nM Hg and 2–10 μM sulfide) that favor the formation of β-HgS(s) (metacinnabar) nanoparticles. We used the methylation of stable-isotope enriched 201HgCl2 by Desulfovibrio desulfuricans ND132 in short-term washed cell assays as a sensitive, environmentally significant proxy for Hg uptake. Suwannee River humic acid (SRHA) and Williams Lake hydrophobic acid (WLHPoA) substantially enhanced (2- to 38-fold) the bioavailability of Hg to ND132 over a wide range of Hg/DOM ratios (9.4 pmol/mg DOM to 9.4 nmol/mg DOM), including environmentally relevant ratios. Methylmercury (MeHg) production by ND132 increased linearly with either SRHA or WLHPoA concentration, but SRHA, a terrestrially derived DOM, was far more effective at enhancing Hg-methylation than WLHPoA, an aquatic DOM dominated by autochthonous sources. No DOM-dependent enhancement in Hg methylation was observed in Hg–DOM–sulfide solutions amended with sufficient l-cysteine to prevent β-HgS(s) formation. We hypothesize that small HgS particles, stabilized against aggregation by DOM, are bioavailable to Hg-methylating bacteria. Our laboratory experiments provide a mechanism for the positive correlations between DOC and MeHg production observed in many aquatic sediments and wetland soils.

  20. Crossett Hydrogen Sulfide Air Sampling Report

    Science.gov (United States)

    This report summarizes the results of the EPA’s hydrogen sulfide air monitoring conducted along Georgia Pacific’s wastewater treatment system and in surrounding Crossett, AR, neighborhoods in 2017.

  1. Hydrogen peroxide oxidation of mustard-model sulfides catalyzed by iron and manganese tetraarylporphyrines. Oxygen transfer to sulfides versus H(2)O(2) dismutation and catalyst breakdown.

    Science.gov (United States)

    Marques, A; Marin, M; Ruasse, M F

    2001-11-16

    Fe(III)- and Mn(III)-meso-tetraarylporphyrin catalysis of H(2)O(2) oxidation of dibenzyl and phenyl-2-chloroethyl sulfides, 1, is investigated in ethanol with the aim of designing catalytic systems for mustard decontamination. The sulfide conversion, the sulfoxide and sulfone yields, the oxygen transfer from H(2)O(2) to the sulfide, and the catalyst stability depend markedly on the metal, on the substituents of its ligand, and on the presence or the absence of a cocatalyst, imidazole or ammonium acetate. With Fe, sulfones, the only oxidation products, are readily obtained whatever the ligand (TPP, F(20)TPP, or TDCPP) and the cocatalyst; the oxygen transfer is fairly good, up to 95% when the catalyst concentration is small ([1]/[Cat] = 420); the catalyst breakdown is insignificant only in the absence of any cocatalyst. With Mn, the sulfide conversion is achieved completely when the ligand is TDCPP or TSO(3)PP, but not F(20)TPP or TPP; a mixture of sulfoxide, 2, and sulfone, 3, is always obtained with [2]/[3] = 3.5-0.85 depending on the ligand and the cocatalyst (electron withdrawing substituents favor 3 and NH(4)OAc, 2). The catalyst stability is very good, but the oxygen transfer is poor whatever the ligand and the cocatalyst. These results are discussed in terms of a scheme in which sulfide oxygenation, H(2)O(2) dismutation, and oxidative ligand breaking compete. It is shown that the efficiency of the oxygen transfer is related not only to the rate constant of the dismutation route but also to the concentration of the active metal-oxo intermediate, most likely a perferryl or permanganyl species, i.e., to the rate of its formation.

  2. Electrical properties of seafloor massive sulfides

    Science.gov (United States)

    Spagnoli, Giovanni; Hannington, Mark; Bairlein, Katharina; Hördt, Andreas; Jegen, Marion; Petersen, Sven; Laurila, Tea

    2016-06-01

    Seafloor massive sulfide (SMS) deposits are increasingly seen as important marine metal resources for the future. A growing number of industrialized nations are involved in the surveying and sampling of such deposits by drilling. Drill ships are expensive and their availability can be limited; seabed drill rigs are a cost-effective alternative and more suitable for obtaining cores for resource evaluation. In order to achieve the objectives of resource evaluations, details are required of the geological, mineralogical, and physical properties of the polymetallic deposits and their host rocks. Electrical properties of the deposits and their ore minerals are distinct from their unmineralized host rocks. Therefore, the use of electrical methods to detect SMS while drilling and recovering drill cores could decrease the costs and accelerate offshore operations by limiting the amount of drilling in unmineralized material. This paper presents new data regarding the electrical properties of SMS cores that can be used in that assessment. Frequency-dependent complex electrical resistivity in the frequency range between 0.002 and 100 Hz was examined in order to potentially discriminate between different types of fresh rocks, alteration and mineralization. Forty mini-cores of SMS and unmineralized host rocks were tested in the laboratory, originating from different tectonic settings such as the intermediate-spreading ridges of the Galapagos and Axial Seamount, and the Pacmanus back-arc basin. The results indicate that there is a clear potential to distinguish between mineralized and non-mineralized samples, with some evidence that even different types of mineralization can be discriminated. This could be achieved using resistivity magnitude alone with appropriate rig-mounted electrical sensors. Exploiting the frequency-dependent behavior of resistivity might amplify the differences and further improve the rock characterization.

  3. Sulfide as a soil phytotoxin - A review

    Directory of Open Access Journals (Sweden)

    Leon P M Lamers

    2013-07-01

    Full Text Available In wetland soils and underwater sediments of marine, brackish and freshwater systems, the strong phytotoxin sulfide may accumulate as a result of microbial reduction of sulfate during anaerobiosis, its level depending on prevailing edaphic conditions. In this review, we compare an extensive body of literature on phytotoxic effects of this reduced sulfur compound in different ecosystem types, and review the effects of sulfide at multiple ecosystem levels: the ecophysiological functioning of individual plants, plant-microbe associations, and community effects including competition and facilitation interactions. Recent publications on multi-species interactions in the rhizosphere show even more complex mechanisms explaining sulfide resistance. It is concluded that sulfide is a potent phytotoxin, profoundly affecting plant fitness and ecosystem functioning in the full range of wetland types including coastal systems, and at several levels. Traditional toxicity testing including hydroponic approaches generally neglect rhizospheric effects, which makes it difficult to extrapolate results to real ecosystem processes. To explain the differential effects of sulfide at the different organizational levels, profound knowledge about the biogeochemical, plant physiological and ecological rhizosphere processes is vital. This information is even more important, as anthropogenic inputs of sulfur into freshwater ecosystems and organic loads into freshwater and marine systems are still much higher than natural levels, and are steeply increasing in Asia. In addition, higher temperatures as a result of global climate change may lead to higher sulfide production rates in shallow waters.

  4. Air-water transfer of hydrogen sulfide

    DEFF Research Database (Denmark)

    Yongsiri, C.; Vollertsen, J.; Rasmussen, M. R.

    2004-01-01

    The emissions process of hydrogen sulfide was studied to quantify air–water transfer of hydrogen sulfide in sewer networks. Hydrogen sulfide transfer across the air–water interface was investigated at different turbulence levels (expressed in terms of the Froude number) and pH using batch...... experiments. By means of the overall mass–transfer coefficient (KLa), the transfer coefficient of hydrogen sulfide (KLaH2S), referring to total sulfide, was correlated to that of oxygen (KLaO2) (i.e., the reaeration coefficient). Results demonstrate that both turbulence and pH in the water phase play...... a significant role for KLaH2S. An exponential expression is a suitable representation for the relationship between KLaH2S and the Froude number at all pH values studied (4.5 to 8.0). Because of the dissociation of hydrogen sulfide, KLaH2S increased with decreasing pH at a constant turbulence level. Relative...

  5. Mesostructured Metal Germanium Sulfide and Selenide Materials Based on the Tetrahedral [Ge 4S 10] 4- and [Ge 4Se 10] 4- Units: Surfactant Templated Three-Dimensional Disordered Frameworks Perforated with Worm Holes

    Science.gov (United States)

    Wachhold, Michael; Kasthuri Rangan, K.; Lei, Ming; Thorpe, M. F.; Billinge, Simon J. L.; Petkov, Valeri; Heising, Joy; Kanatzidis, Mercouri G.

    2000-06-01

    The polymerization of [Ge4S10]4- and [Ge4Se10]4- unit clusters with the divalent metal ions Zn2+, Cd2+, Hg2+, Ni2+, and Co2+ in the presence of various surfactant cations leads to novel mesostructured phases. The surfactants are the quaternary ammonium salts C12H25NMe3Br, C14H29NMe3Br, C16H33NMe3Br, and C18H37NMe3Br, which play the role of templates, helping to assemble a three-dimensional mesostructured metal-germanium chalcogenide framework. These materials are stoichiometric in nature and have the formula of (R-NMe3)2[MGe4Q10] (Q=S, Se). The local atomic structure was probed by X-ray diffuse scattering and pair distribution function analysis methods and indicates that the adamantane clusters stay intact while the linking metal atoms possess a tetrahedral coordination environment. A model can be derived, from the comparison of measured and simulated X-ray powder diffraction patterns, describing the structure as an amorphous three-dimensional framework consisting of adamantane [Ge4Q10]4- units that are bridged by tetrahedral coordinated M2+ cations. The network structures used in the simulations were derived from corresponding disordered structures developed for amorphous silicon. The frameworks in (R-NMe3)2[MGe4Q10] are perforated with worm hole-like tunnels, occupied by the surfactant cations, which show no long-range order. This motif is supported by transmission electron microscopy images of these materials. The pore sizes of these channels were estimated to lie in the range of 20-30 Å, depending on the appointed surfactant cation length. The framework wall thickness of ca. 10 Å is thereby independent from the surfactant molecules used. Up to 80% of the surfactant molecules can be removed by thermal degradation under vacuum without loss of mesostructural integrity. Physical, chemical, and spectroscopic properties of these materials are discussed.

  6. Phosphate acquisition efficiency and phosphate starvation tolerance ...

    Indian Academy of Sciences (India)

    2011 Developing rice with high yield under phosphorus deficiency: Pup1 sequence to application. Plant Physiol. 156, 1202–1216. Ciereszko I., Gniazdowska A., Mikulska M. and Rychter A. M.. 1996 Assimilate translocation in bean plants (Phaseolus vulgaris. L.) during phosphate deficiency. J. Plant Physiol. 149, 343–. 348.

  7. Phosphate acquisition efficiency and phosphate starvation tolerance ...

    Indian Academy of Sciences (India)

    Here, we have reported the presence as well as the expression of a previously characterized rice gene, phosphate starvation tolerance ... from a cross between Gobindabhog and Satabdi, also did not show any linkage with P-deficiency tolerance ability. Thus, ... vated in P-limiting conditions which work in a cascade and.

  8. Radioactivity of phosphate mineral products

    OpenAIRE

    Mitrović Branislava; Vitorović Gordana; Stojanović Mirjana; Vitorović Duško

    2011-01-01

    The phosphate industry is one of the biggest polluters of the environment with uranium. Different products are derived after processing phosphoric ore, such as mineral and phosphate fertilizers and phosphate mineral supplements (dicalcium-and monocalcium phosphate) for animal feeding. Phosphate mineral additives used in animal food may contain a high activity of uranium. Research in this study should provide an answer to the extent in which phosphate minera...

  9. Radioactivity of phosphate mineral products

    Directory of Open Access Journals (Sweden)

    Mitrović Branislava

    2011-01-01

    Full Text Available The phosphate industry is one of the biggest polluters of the environment with uranium. Different products are derived after processing phosphoric ore, such as mineral and phosphate fertilizers and phosphate mineral supplements (dicalcium-and monocalcium phosphate for animal feeding. Phosphate mineral additives used in animal food may contain a high activity of uranium. Research in this study should provide an answer to the extent in which phosphate mineral products (phosphate fertilizer and phosphate mineral feed additives contribute to the contamination of soil, plants and animals.

  10. Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors

    NARCIS (Netherlands)

    Villa Gomez, D.K.; Cassidy, J.; Keesman, K.J.; Sampaio, R.M.; Lens, P.N.L.

    2014-01-01

    Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4 2- ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing

  11. Phosphate Management: FY2010 Results Of Phosphate Precipitation Tests

    International Nuclear Information System (INIS)

    Hay, M.; King, W.

    2011-01-01

    The Phosphate Management program seeks to develop treatment options for caustic phosphate solutions resulting from the caustic leaching of the bismuth phosphate sludge. The SRNL subtask investigated the precipitation of phosphate salts from caustic solutions through addition of fluoride and by crystallization. The scoping tests examined the: precipitation of phosphate by the addition of sodium fluoride to form the sodium fluorophosphate double salt, Na 7 F(PO 4 ) 2 · 19H 2 O, crystallization of phosphate by reducing the temperature of saturated phosphate solutions, and combinations of precipitation and crystallization. A simplified leachate simulant was used in the study produced by dissolving sodium phosphate in 1 M to 3.5 M sodium hydroxide solutions. The results show that all three processes; precipitation with sodium fluoride, crystallization, and combined precipitation/crystallization can be effective for removing large amounts of phosphate from solution. The combined process of precipitation/crystallization showed >90% removal of phosphate at all hydroxide concentrations when cooling a non-saturated phosphate solution from 65 C to 25 C. Based on the measured solubility of sodium phosphate, pH adjustment/caustic addition will also remove large amounts of phosphate from solution (>80%). For all three processes, the phosphate concentration in the caustic solution must be managed to keep the phosphate from becoming too concentrated and thereby potentially forming a solid mass of sodium phosphate after an effective phosphate removal process.

  12. Phosphate application to firing range soils for Pb immobilization: The unclear role of phosphate

    International Nuclear Information System (INIS)

    Chrysochoou, Maria; Dermatas, Dimitris; Grubb, Dennis G.

    2007-01-01

    Phosphate treatment has emerged as a widely accepted approach to immobilize Pb in contaminated soils and waste media, relying on the formation of the highly insoluble mineral pyromorphite as solubility-controlling phase for Pb. As such, phosphate treatment has been proposed as a Best Management Practice (BMP) for firing ranges where Pb occurs in its metallic forms and several other phases (carbonates, oxides). While pyromorphite thermodynamically has the potential to control Pb solubility at low levels, its formation is kinetically controlled by pH, the solubility of the phosphate source, and the solubility of Pb species. Treatability studies have shown that excess quantities of soluble and acidic phosphate sources, such as phosphoric acid, are necessary for successful in situ treatment. Even under these conditions, Extended X-ray Absorption Fine Structure (EXAFS), the only reliable method to identify and quantify Pb speciation, showed that Pb conversion to pyromorphite in in situ treated soils was less than 45% after 32 months. Furthermore, the use of lime (CaO) to restore soil pH in acidified soil treatments inhibited further conversion. Additionally, phosphate treatment is known to reduce bioavailability through pyromorphite formation in the intestinal tract, and the phytoaccumulation of Pb; both desirable effects for Pb-impacted areas. Given the costs of phosphate treatment, the use of biogenic phosphate sources, such as bone meal, may be a more environmentally sustainable approach toward this end. In the many studies focusing on phosphate treatment, the attendant P leaching and eutrophication have been largely overlooked, along with other issues such as the enhanced leaching of oxyanionic contaminants, such as Se, As and W. The success and sustainability of applying phosphate as a BMP in firing range soils therefore remain questionable

  13. Discussion about magnesium phosphating

    OpenAIRE

    Pokorny, P.; Tej, P.; Szelag, P.

    2016-01-01

    The paper describes results from recently published research focused on production of non-conventional magnesium phosphate Mg3(PO4)2・4H2O – bobierrite, or MgHPO4・3H2O – newberyite) coating for both magnesium alloys and/or mild steel. This new kind of coating is categorized in the context of current state of phosphating technology and its potential advantages and crystal structure is discussed. At the same time, the suitable comparison techniques for magnesium phosphate coating and convention...

  14. Physio-biochemical basis of iron-sulfide nanoparticle induced growth and seed yield enhancement in B. juncea.

    Science.gov (United States)

    Rawat, Madhu; Nayan, Rajeev; Negi, Bhawana; Zaidi, M G H; Arora, Sandeep

    2017-09-01

    Metal nanoparticles have been reported to influence plant growth and productivity. However, the molecular mechanisms underlying the effects have not been completely understood yet. Current work describes the physio-biochemical basis of iron sulfide nanoparticle induced growth and yield enhancement in Brassica juncea. Iron sulfide nanoparticles (0, 2, 4, 6, 8 and 10 ppm) were used for foliar treatment of B. juncea at 30, 45 and 60 days after sowing, under field conditions. Foliar treatment of 4 ppm iron sulfide nanoparticle solution at 30 days after sowing brought maximal enhancement in agronomic attributes of the treated plants. Results of assays i.e. total chlorophyll, electrolyte leakage, Malondialdehyde (MDA), proline, H 2 O 2 and antioxidant enzyme activities indicated the benign effect of iron sulfide nanoparticles on plants. Consequently, improved redox status of the treated plants, enabled them to assimilate higher photosynthate. The augmentation in growth and seed yield in iron sulfide nanoparticle treated plants was amply supported by activation of RUBISCO small subunit (rubisco S), RUBISCO large subunit (rubisco L), glutamine synthetase (gs) and glutamate synthase (gogat) genes. Thus, iron sulfide nanoparticle induced growth and yield enhancement is proposed to be mediated through activation of carbon and nitrogen assimilatory pathways at specific growth stage. The iron content in the leaves and root tissues of the treated plants was also significantly improved. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  15. Synthesis of Copper Sulfide Nanoparticles Using Biogenic H2S Produced by a Low-pH Sulfidogenic Bioreactor

    Directory of Open Access Journals (Sweden)

    Camila Colipai

    2018-01-01

    Full Text Available The application of acidophilic sulfate-reducing bacteria (SRB for the treatment of acidic mine water has been recently developed to integrate mine water remediation and selective biomineralization. The use of biogenic hydrogen sulfide (H2S produced from the dissimilatory reduction of sulfate to fabricate valuable products such as metallic sulfide nanoparticles has potential applications in green chemistry. Here we report on the operation of a low-pH sulfidogenic bioreactor, inoculated with an anaerobic sediment obtained from an acid river in northern Chile, to recover copper via the production of copper sulfide nanoparticles using biogenic H2S. The laboratory-scale system was operated as a continuous flow mode for up to 100 days and the bioreactor pH was maintained by the automatic addition of a pH 2.2 influent liquor to compensate for protons consumed by biosulfidogenesis. The “clean” copper sulfide nanoparticles, produced in a two-step process using bacterially generated sulfide, were examined using transmission electron microscopy, dynamic light scattering, energy dispersive (X-ray spectroscopy and UV-Vis spectroscopy. The results demonstrated a uniform nanoparticle size distribution with an average diameter of less than 50 nm. Overall, we demonstrated the production of biogenic H2S using a system designed for the treatment of acid mine water that holds potential for large-scale abiotic synthesis of copper sulfide nanoparticles.

  16. Manganese phosphate-coating

    International Nuclear Information System (INIS)

    Peyre, Y.

    1999-01-01

    Manganese phosphate-coating is one of the numerous chemical surface treatment which is used industrially. Its applications are usual for improving the friction properties of a lot of mechanical parts. Used for the treatment of steels and cast steels, baths (containing phosphoric acid, manganese phosphate and different additives) lead to the formation of nonmetal coatings of a few micrometers. These manganese-iron or manganese phosphates crystals reduce the friction coefficient and retain the lubricant film in contact with the moving parts. The running noises, the wear and the seizure risks are then strongly reduced. Pure manganese phosphate-coating is currently developing because the obtained coatings are thinner and more regular. (O.M.)

  17. 31P NMR probes of chemical dynamics: paramagnetic relaxation enhancement of the (1)H and (31)P NMR resonances of methyl phosphite and methylethyl phosphate anions by selected metal complexes.

    Science.gov (United States)

    Summers, J S; Hoogstraten, C G; Britt, R D; Base, K; Shaw, B R; Ribeiro, A A; Crumbliss, A L

    2001-12-17

    Methyl phosphite ((CH(3)O)P(H)(O)(2)(-); MeOPH) and methylethyl phosphate ((CH(3)O)P(OCH(2)CH(3))(O)(2)(-); MEP) are two members of a class of anionic ligands whose (31)P T(2) relaxation rates are remarkably sensitive to paramagnetic metal ions. The temperature dependence of the (31)P NMR line broadenings caused by the Mn(H(2)O)(6)(2+) ion and a water-soluble manganese(III) porphyrin (Mn(III)TMPyP(5+)) indicates that the extent of paramagnetic relaxation enhancement is a measure of the rate at which the anionic probes come into physical contact with the paramagnetic center (i.e., enter the inner coordination shell); that is, piDeltanu(par) = k(assn)[M], where Deltanu(par) is the difference between the line widths of the resonance in paramagnetic and diamagnetic solutions, and k(assn) is the second-order rate constant for association of the phosphorus ligand with the metal, M. Comparison of the (31)P T(1) and T(2) relaxation enhancements shows that rapid T(2) relaxation by the metal ion is caused by scalar interaction with the electronic spin. Relaxation of the phosphorus-bound proton of MeOPH ((1)H-P) by Mn(III)TMPyP(5+) displayed intermediate exchange kinetics over much of the observable temperature range. The field strength dependence of (1)H-P T(2) enhancement and the independence of the (31)P T(2) support these assertions. As in the case of the (31)P T(2), the (1)H-P T(2) relaxation enhancement results from scalar interaction with the electronic spin. The scalar coupling interpretation of the NMR data is supported by a pulsed EPR study of the interactions of Mn(H(2)O)(6)(2+) with the P-deuterated analogue of methyl phosphite, CH(3)OP((2)H)(O)(2)(-). The electron to (31)P and (2)H nuclear scalar coupling constants were found to be 4.6 and 0.10 MHz, respectively. In contrast, the effects of paramagnetic ions on the methoxy and ethoxy (1)H resonances of MeOPH and MEP are weak, and the evidence suggests that relaxation of these nuclei occurs by a dipolar mechanism

  18. Metal removal efficiency and ecotoxicological assessment of field-scale passive treatment biochemical reactors

    Science.gov (United States)

    Anaerobic biochemical reactors (BCRs) are useful for removing metals from mining-impacted water (MIW) at remote sites. Removal processes include sorption and precipitation of metal sulfides, carbonates and hydroxides. A question of interest is whether BCRs remove aquatic toxicit...

  19. Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

    Science.gov (United States)

    Rao, D. B.; Nelson, H. G.

    1977-01-01

    The sulfidation of 310 stainless steel was studied over the temperature range from 910 K to 1285 K. By adjusting the ratio of hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39/sqNm, 0.014/sqNm, and 0.00015/sqNm. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer (OL-I), nearest the subscale, contained FE-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. At a given temperature and sulfur potential, the weight gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39/sqNm did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at sulfur potentials below 0.02/sqNm, however, did show a break at 1145 K, which is termed as the transition temperature. This break was found to be associated with the changes which had occurred in the Fe:Cr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kj/mole. Above the transition temperature the rate of sulfidation decreased with temperature but dependent on the Fe:Cr ratio in the iron-chromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed.

  20. The new ret process for hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, S.; Onishi, H.

    1977-11-01

    It was developed for gas streams from rayon production containing either 4500 ppM hydrogen sulfide and 5 ppM carbon disulfide or 900 ppM hydrogen sulfide and 16 ppM carbon disulfide (average values). The process consists of absorption towers, alkali scrubbers for the recovery of carbon disulfide, and an oxidation reactor. The process is catalyzed by an organic iron complex catalyst. For the removal of 1 kg hydrogen sulfide, the process uses 130 g sodium hydroxide, catalyst (20 yen), 2.5 kw-hr electricity, 15 kg steam (3 kg in winter), 2 cu m cooling water (1 cu m in winter), and 8 l. fresh water. The recovered sulfur (99%) is 99.9% pure. Eight litres of 0.03 kg COD wastewater are also produced. The process equipment is described. Flow diagrams, graph, and tables.

  1. Sulfidogenic biotreatment of synthetic acid mine drainage and sulfide oxidation in anaerobic baffled reactor.

    Science.gov (United States)

    Bekmezci, Ozan K; Ucar, Deniz; Kaksonen, Anna H; Sahinkaya, Erkan

    2011-05-30

    The treatment of synthetic acid mine drainage (AMD) water (pH 3.0-6.5) containing sulfate (3.0-3.5 g L(-1)) and various metals (Co, Cu, Fe, Mn, Ni, and Zn) was studied in an ethanol-fed sulfate-reducing 4-compartment anaerobic baffled reactor (ABR) at 32°C. The reactor was operated for 160 days at different chemical oxygen demand (COD)/sulfate ratios, hydraulic retention times (HRT), pH, and metal concentrations to study the robustness of the process. The last compartment of the reactor was aerated at different rates to study the bio-oxidation of sulfide to elemental sulfur. The highest sulfate reduction efficiency (88%) was obtained with a feed sulfate concentration of 3.5 g L(-1), COD/sulfate mass ratio of 0.737, feed pH of 3.0 and HRT of 2 days without aeration in the 4th compartment. The corresponding COD removal efficiency was about 92%. The alkalinity produced in the sulfidogenic ethanol oxidation neutralized the acidic mine water from pH 3.0-4.5 to pH 7.0-8.0. Effluent soluble and total heavy metal concentrations were substantially reduced with removal efficiencies generally higher than 99%, except for Mn (25-77%). Limited aeration in the 4th compartment of ABR promoted incomplete oxidation of sulfide to elemental sulfur rather than complete oxidation to sulfate. Depending on the aeration rate and HRT, 32-74% of produced sulfide was oxidized to elemental sulfur. This study demonstrates that by optimizing operating conditions, sulfate reduction, metal removal, alkalinity generation, and excess sulfide oxidation can be achieved in a single ABR treating AMD. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Reactivity of non conventional supported mixed sulfides for hydro-treatment reactions; Reactivite de sulfures mixtes supportes non conventionnels pour les reactions d`hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Quartararo, J.

    1996-11-07

    The properties of non conventional NiM sulfides (M: Mn, Fe, Cu,Zn, Re, Ru) was evaluated for two hydro treating reactions: hydro desulfurization (HDS) of dibenzo thiophene and benzo thiophene and hydrogenation (HYD) of cyclohexyl. The reactions were t first studied on Ni, Mo and NiMo sulfide catalysts. The influence of the nature of the molecule on the magnitude of promoting effect was demonstrated. The non conventional mono-metallic and bimetallic catalysts studied in this work were characterized by XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy) and TEM (transmission electron microscopy). Ni exhibits a negative effect on the activity of Mn, Cu, Zn and Re sulfide catalysts. This effect could be related to the formation of two separated sulfide phases: base metal sulfide and nickel sulfide. Nevertheless, a promoting effect was found in NiRu catalyst. In this catalyst, the Ru and the Ni are in a mixed phase. The results of this study demonstrate the importance of the type of metal associated to the nickel for the promoting effect and relate this effect to the formation of a mixed phase. (author)

  3. Speciation and fate of trace metals in estuarine sediments under reduced and oxidized conditions, Seaplane Lagoon, Alameda Naval Air Station (USA

    Directory of Open Access Journals (Sweden)

    Esser Brad

    2002-11-01

    Full Text Available We have identified important chemical reactions that control the fate of metal-contaminated estuarine sediments if they are left undisturbed (in situ or if they are dredged. We combined information on the molecular bonding of metals in solids from X-ray absorption spectroscopy (XAS with thermodynamic and kinetic driving forces obtained from dissolved metal concentrations to deduce the dominant reactions under reduced and oxidized conditions. We evaluated the in situ geochemistry of metals (cadmium, chromium, iron, lead, manganese and zinc as a function of sediment depth (to 100 cm from a 60 year record of contamination at the Alameda Naval Air Station, California. Results from XAS and thermodynamic modeling of porewaters show that cadmium and most of the zinc form stable sulfide phases, and that lead and chromium are associated with stable carbonate, phosphate, phyllosilicate, or oxide minerals. Therefore, there is minimal risk associated with the release of these trace metals from the deeper sediments contaminated prior to the Clean Water Act (1975 as long as reducing conditions are maintained. Increased concentrations of dissolved metals with depth were indicative of the formation of metal HS- complexes. The sediments also contain zinc, chromium, and manganese associated with detrital iron-rich phyllosilicates and/or oxides. These phases are recalcitrant at near-neutral pH and do not undergo reductive dissolution within the 60 year depositional history of sediments at this site. The fate of these metals during dredging was evaluated by comparing in situ geochemistry with that of sediments oxidized by seawater in laboratory experiments. Cadmium and zinc pose the greatest hazard from dredging because their sulfides were highly reactive in seawater. However, their dissolved concentrations under oxic conditions were limited eventually by sorption to or co-precipitation with an iron (oxyhydroxide. About 50% of the reacted CdS and 80% of the reacted

  4. Refractory sulfides as IR window materials

    Science.gov (United States)

    White, William B.

    1990-10-01

    The development of sulfide materials as infrared-transmitting optical ceramics is limited by intrinsic optical properties, thermomechanical properties, and considerations of chemical stability. Screening procedures with respect to band gap, electronic absorption, chemical stability, and refractory character reduced the set of all sulfides to about a dozen structural families. Systematic relationships were developed between crystal chemistry and phonon absorption edge, vibrational modes frequencies, and coefficient of thermal expansion which allow possible ranges of properties to be estimated. It is concluded that improved materials are possible but that radically improved new materials are unlikely.

  5. Iron-sulfide crystals in probe deposits

    DEFF Research Database (Denmark)

    Laursen, Karin; Frandsen, Flemming

    1998-01-01

    Iron-sulfides were observed in deposits collected on a probe inserted at the top of the furnace of a coal-fired power station in Denmark. The chemical composition of the iron-sulfides is equivalent to pyrrhotite (FeS). The pyrrhotites are present as crystals and, based on the shape of the crystals......, it was deduced that they were not deposited but instead grew within the deposit. The presence of unburned char particles within the deposits supports the concept that a reducing environment existed in the deposits. Two processes are proposed for explaining the existence of pyrrhotite crystals within a deposit...

  6. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  7. Recent progress in sulfide-based solid electrolytes for Li-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, D., E-mail: liu.dongqiang@ireq.ca; Zhu, W.; Feng, Z.; Guerfi, A.; Vijh, A.; Zaghib, K.

    2016-11-15

    Graphical abstract: Li{sub 2}S-GeS{sub 2}-P{sub 2}S{sub 5} ternary diagram showing various sulphide compounds as solid electrolytes for Li-ion batteries. - Highlights: • Recent progress of sulfide-based solid electrolytes is described from point of view of structure. • Thio-LISICON type electrolytes exhibited high ionic conductivity due to their bcc sublattice and unique Li{sup +} diffusion pathway. • “Mixed-anion effect” is also an effective way to modify the energy landscape as well as the ionic conductivity. - Abstract: Sulfide-based ionic conductors are one of most attractive solid electrolyte candidates for all-solid-state batteries. In this review, recent progress of sulfide-based solid electrolytes is described from point of view of structure. In particular, lithium thio-phosphates such as Li{sub 7}P{sub 3}S{sub 11}, Li{sub 10}GeP{sub 2}S{sub 12} and Li{sub 11}Si{sub 2}PS{sub 12} etc. exhibit extremely high ionic conductivity of over 10{sup −2} S cm{sup −1} at room temperature, even higher than those of commercial organic carbonate electrolytes. The relationship between structure and unprecedented high ionic conductivity is delineated; some potential drawbacks of these electrolytes are also outlined.

  8. What processes at mid-ocean ridges tell us about volcanogenic massive sulfide deposits

    Science.gov (United States)

    Cathles, Lawrence M.

    2011-07-01

    Episodic seafloor spreading, ridge topography, and fault movement at ridges find (more extreme) analogs in the arc and back-arc setting where the volcanogenic massive sulfide (VMS) deposits that we mine today were formed. The factors affecting sulfide accumulation efficiency and the extent to which sulfides are concentrated spatially are the same in both settings, however. The processes occurring at mid-ocean ridges therefore provide a useful insight into those producing VMS deposits in arcs and back-arcs. The critical observation investigated here is that all the heat introduced by seafloor spreading at mid-ocean ridges is carried out of the crust within a few hundred meters of the ridge axis by ˜350°C hydrothermal fluids. The high-temperature ridge hydrothermal systems are tied to the presence of magma at the ridge axis and greatly reduce the size and control the shape of axial magma intrusions. The amount of heat introduced to each square kilometer of ocean crust during its formation can be calculated, and its removal by high-temperature convection allows calculation of the total base metal endowment of the ocean basins. Using reasonable metal deposition efficiencies, we conclude that the ocean floor is a giant VMS district with metal resources >600 times the total known VMS reserves on land and a copper resource which would last >6,000 years at current production rates.

  9. Use of biogenic sulfide for ZnS precipitation

    NARCIS (Netherlands)

    Esposito, G.; Veeken, A.; Weijma, J.; Lens, P.N.L.

    2006-01-01

    A 600 ml continuously stirred tank reactor was used to assess the performance of a zinc sulfide precipitation process using a biogenic sulfide solution (the effluent of a sulfate-reducing bioreactor) as sulfide source. In all experiments, a proportional-integral (PI) control algorithm was used to

  10. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.M.; Graaff, de C.M.; Bosch, van den P.L.F.; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.H.

    2013-01-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was

  11. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Science.gov (United States)

    2010-07-01

    ... § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration method... ferricyanide titration method for the determination of sulfide in wastewaters discharged by plants operating in... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Sulfide analytical methods and...

  12. Metal recovery via geobiotechnology

    International Nuclear Information System (INIS)

    Hedrich, Sabrina; Schippers, Axel

    2017-01-01

    Specialized acidophilic bacteria and archaea are able to extract valuable metals such as copper, gold, cobalt, nickel, zinc, and uranium from sulfide ores. This process is known as bioleaching and its application in the mining industry as biomining. Laboratory studies also demonstrated bioleaching of oxide ores such as laterites and of mining residues such as mine tailings as well as metal recycling from waste (secondary mining). Metals being leached have to be recovered from acidic polymetallic solutions (mine and process waters) which is possible via biosorption or biomineralisation.

  13. Developing porous carbon with dihydrogen phosphate groups as sulfur host for high performance lithium sulfur batteries

    Science.gov (United States)

    Cui, Yanhui; Zhang, Qi; Wu, Junwei; Liang, Xiao; Baker, Andrew P.; Qu, Deyang; Zhang, Hui; Zhang, Huayu; Zhang, Xinhe

    2018-02-01

    Carbon matrix (CM) derived from biomass is low cost and easily mass produced, showing great potential as sulfur host for lithium sulfur batteries. In this paper we report on a dihydrogen phosphate modified CM (PCM-650) prepared from luffa sponge (luffa acutangula) by phosphoric acid treatment. The phosphoric acid not only increases the surface area of the PCM-650, but also introduces dihydrogen phosphate onto PCM-650 (2.28 at% P). Sulfur impregnated (63.6 wt%) PCM-650/S, in comparison with samples with less dihydrogen phosphate LPCM-650/S, shows a significant performance improvement. XPS analysis is conducted for sulfur at different stages, including sulfur (undischarged), polysulfides (discharge to 2.1 V) and short chain sulfides (discharge to 1.7 V). The results consistently show chemical shifts for S2p in PCM-650, suggesting an enhanced adsorption effect. Furthermore, density functional theory (DFT) calculations is used to clarify the molecular binding: carbon/sulfur (0.86 eV), carbon/Li2S (0.3 eV), CH3-O-PO3H2/sulfur (1.24 eV), and CH3-O-PO3H2/Li2S (1.81 eV). It shows that dihydrogen phosphate group can significantly enhance the binding with sulfur and sulfide, consistent with XPS results. Consequently a CM functionalised with dihydrogen phosphate shows great potential as the sulfur host in a Li-S battery.

  14. Application of phosphating techniques to aluminium and carbon steel surfaces using nitro guanidine as oxidizing agent

    International Nuclear Information System (INIS)

    Briseno M, S.A.

    1995-01-01

    Phosphate coatings are inorganic crystalline deposits laid down uniformly on properly prepared surfaces by a chemical reaction with the treated base metal. The reaction consists in dissolving some surface metal by acid attack and then causing surface neutralization of the phosphate solution with consequent precipitation of the phosphate coating. Phosphate coatings do not provide appreciable corrosion protection in themselves. They are useful mainly as a base for paints, ensuring good adherence of paint to steel and decreasing the tendency for corrosion to under cut the paint film at scratches or other defects. In this work firstly were realized phosphate on standard carbon steel, employing technical of cold phosphate (at 40 Centigrade degrees and with a treatment time of 30 minutes) and hot phosphate (at 88 Centigrade degrees and with a treatment time of 15 minutes), where with this last were obtained the best results. Both methods used phosphate solutions of Zn/Mn and using as catalyst Nitro guanidine. Aluminium surfaces were phosphate used solutions of Cr and as catalyst Sodium bi fluoride. The phosphating on this surface were realized at temperature of 50 Centigrade degrees and with a treatment time of 10 minutes. In this work were obtained a new phosphate coatings on steel surfaces, these coatings were realized with a phosphate solution manufactured with the precipitates gathered during the hot phosphating on carbon steel. These coatings show excellent physical characteristics and of corrosion resistance. Were determined the physical testings of the coatings phosphate obtained on carbon steel and aluminium surfaces. These testing were: roughness, thickness, microhardness and adhesion. The best results were showed in carbon steel phosphate with precipitated solutions. The technical of analysis for activation with thermic neutrons was used to determine the phosphate coatings composition. Finally, corrosion testings were realized by means of two methods

  15. Phosphate control in dialysis

    Directory of Open Access Journals (Sweden)

    Cupisti A

    2013-10-01

    Full Text Available Adamasco Cupisti,1 Maurizio Gallieni,2 Maria Antonietta Rizzo,2 Stefania Caria,3 Mario Meola,4 Piergiorgio Bolasco31Department of Clinical and Experimental Medicine, University of Pisa, Pisa, Italy; 2Nephrology and Dialysis Unit, San Carlo Borromeo Hospital, Milan, Italy; 3Territorial Department of Nephrology and Dialysis, ASL Cagliari, Italy; 4Sant'Anna School of Advanced Studies, University of Pisa, Pisa, ItalyAbstract: Prevention and correction of hyperphosphatemia is a major goal of chronic kidney disease–mineral and bone disorder (CKD–MBD management, achievable through avoidance of a positive phosphate balance. To this aim, optimal dialysis removal, careful use of phosphate binders, and dietary phosphate control are needed to optimize the control of phosphate balance in well-nourished patients on a standard three-times-a-week hemodialysis schedule. Using a mixed diffusive–convective hemodialysis tecniques, and increasing the number and/or the duration of dialysis tecniques are all measures able to enhance phosphorus (P mass removal through dialysis. However, dialytic removal does not equal the high P intake linked to the high dietary protein requirement of dialysis patients; hence, the use of intestinal P binders is mandatory to reduce P net intestinal absorption. Unfortunately, even a large dose of P binders is able to bind approximately 200–300 mg of P on a daily basis, so it is evident that their efficacy is limited in the case of an uncontrolled dietary P load. Hence, limitation of dietary P intake is needed to reach the goal of neutral phosphate balance in dialysis, coupled to an adequate protein intake. To this aim, patients should be informed and educated to avoid foods that are naturally rich in phosphate and also processed food with P-containing preservatives. In addition, patients should preferentially choose food with a low P-to-protein ratio. For example, patients could choose egg white or protein from a vegetable source

  16. Uranium production from phosphates

    International Nuclear Information System (INIS)

    Ketzinel, Z.; Folkman, Y.

    1979-05-01

    According to estimates of the world's uranium consumption, exploitation of most rich sources is expected by the 1980's. Forecasts show that the rate of uranium consumption will increase towards the end of the century. It is therefore desirable to exploit poor sources not yet in use. In the near future, the most reasonable source for developing uranium is phosphate rock. Uranium reserves in phosphates are estimated at a few million tons. Production of uranium from phosphates is as a by-product of phosphate rock processing and phosphoric acid production; it will then be possible to save the costs incurred in crushing and dissolving the rock when calculating uranium production costs. Estimates show that the U.S. wastes about 3,000 tons of uranium per annum in phosphoric acid based fertilisers. Studies have also been carried out in France, Yugoslavia and India. In Israel, during the 1950's, a small plant was operated in Haifa by 'Chemical and Phosphates'. Uranium processes have also been developed by linking with the extraction processes at Arad. Currently there is almost no activity on this subject because there are no large phosphoric acid plants which would enable production to take place on a reasonable scale. Discussions are taking place about the installation of a plant for phosphoric acid production utilising the 'wet process', producing 200 to 250,000 tons P 2 O 5 per annum. It is necessary to combine these facilities with uranium production plant. (author)

  17. Microaeration reduces hydrogen sulfide in biogas

    Science.gov (United States)

    Although there are a variety of biological and chemical treatments for removal of hydrogen sulfide (H2S) from biogas, all require some level of chemical or water inputs and maintenance. In practice, managing biogas H2S remains a significant challenge for agricultural digesters where labor and opera...

  18. REACTION PROCESSES OF ARSENIC IN SULFIDIC SOLUTIONS

    Science.gov (United States)

    The fate of arsenic in the environment is fundamentally linked to its speciation. Arsenic in aerobic environments is predominantly arsenate, however under reducing conditions arsenite species dominate. In anoxic or sulfidic environments thioarsenite ((As(OH)x(SH)yz-) species alon...

  19. Microbial Fuel Cells for Sulfide Removal

    NARCIS (Netherlands)

    Rabaey, K.; Sompel, van de S.; Maignien, L.; Boon, N.; Aelterman, P.; Clauwaert, P.; Schamphelaire, de L.; The Pham, H.; Vermeulen, J.; Verhaege, M.; Lens, P.N.L.; Verstraete, W.

    2006-01-01

    Thus far, microbial fuel cells (MFCs) have been used to convert carbon-based substrates to electricity. However, sulfur compounds are ubiquitously present in organic waste and wastewater. In this study, a MFC with a hexacyanoferrate cathodic electrolyte was used to convert dissolved sulfide to

  20. Support Effect in Hydrodesulfurization over Ruthenium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    2009-01-01

    Roč. 51, č. 2 (2009), s. 146-149 ISSN 1337-7027 R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support effect Subject RIV: CC - Organic Chemistry

  1. Mitochondrial Sulfide Quinone Oxidoreductase Prevents Activation of the Unfolded Protein Response in Hydrogen Sulfide*

    OpenAIRE

    Horsman, Joseph W.; Miller, Dana L.

    2015-01-01

    Hydrogen sulfide (H2S) is an endogenously produced gaseous molecule with important roles in cellular signaling. In mammals, exogenous H2S improves survival of ischemia/reperfusion. We have previously shown that exposure to H2S increases the lifespan and thermotolerance in Caenorhabditis elegans, and improves protein homeostasis in low oxygen. The mitochondrial SQRD-1 (sulfide quinone oxidoreductase) protein is a highly conserved enzyme involved in H2S metabolism. SQRD-1 is generally considere...

  2. A safer disposal of hazardous phosphate coating sludge by formation of an amorphous calcium phosphate matrix.

    Science.gov (United States)

    Navarro-Blasco, I; Duran, A; Pérez-Nicolás, M; Fernández, J M; Sirera, R; Alvarez, J I

    2015-08-15

    Phosphate coating hazardous wastes originated from the automotive industry were efficiently encapsulated by an acid-base reaction between phosphates present in the sludge and calcium aluminate cement, yielding very inert and stable monolithic blocks of amorphous calcium phosphate (ACP). Two different compositions of industrial sludge were characterized and loaded in ratios ranging from 10 to 50 wt.%. Setting times and compressive strengths were recorded to establish the feasibility of this method to achieve a good handling and a safe landfilling of these samples. Short solidification periods were found and leaching tests showed an excellent retention for toxic metals (Zn, Ni, Cu, Cr and Mn) and for organic matter. Retentions over 99.9% for Zn and Mn were observed even for loadings as high as 50 wt.% of the wastes. The formation of ACP phase of low porosity and high stability accounted for the effective immobilization of the hazardous components of the wastes. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Hydrogen Sulfide Corrosion of Weld Regions in API X52 Steel

    Directory of Open Access Journals (Sweden)

    García-Cerecero G.

    2012-10-01

    Full Text Available The corrosion behavior of gas metal arc welding (GMAW regions has been studied using potentiodynamic polarization and polarization resistance (LPR techniques. Experiments were conducted in hydrogen sulfide (H2S-containing brine and in H2S-free brine. Welds were made on API 5L X52 steel. Due to differences in their microstructure, chemical composition and residual stress level, weld regions exhibited different responses under H2S corrosion. Base metal exhibited the highest corrosion rate (CR and the most cathodic corrosion potential.

  4. Electrochemical Synthesis and Characterization of Zinc Sulfide Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Rahimi-Nasarabadi

    2014-04-01

    Full Text Available Electrosynthesis process has been used for preparation of zinc sulfide nanoparticles. Zinc sulfide nanoparticles in different size and shapes were electrodeposited by electrolysis of zinc plate as anode in sodium sulfide solution. Effects of several reaction variables, such as electrolysis voltage, sulfide ion concentration as reactant, stirring rate of electrolyte solution and temperature on particle size of prepared zinc sulfide were investigated. The significance of these parameters in tuning the size of zinc sulfide particles was quantitatively evaluated by analysis of variance (ANOVA. Also, optimum conditions for synthesis of zinc sulfide nanoparticles via electrosynthesis reaction were proposed. The structure and composition of prepared nanoparticles under optimum condition was characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, transmission electron microscopy (TEM, and UV-Vis spectrophotometry techniques.

  5. Quantifying heavy metals sequestration by sulfate-reducing bacteria in an acid mine drainage-contaminated wetland

    Directory of Open Access Journals (Sweden)

    John W Moreau

    2013-03-01

    Full Text Available Bioremediation strategies that depend on bacterial sulfate reduction for heavy metals remediation harness the reactivity of these metals with biogenic aqueous sulfide. Quantitative knowledge of the degree to which specific toxic metals are partitioned into various sulfide, oxide, or other phases is important for predicting the long-term mobility of these metals under environmental conditions. Here we report the quantitative partitioning into sedimentary biogenic sulfides of a suite of metals and metalloids associated with acid mine drainage contamination of a natural estuarine wetland for over a century.

  6. Use of extracting agent for decadmiation of phosphate rock

    Science.gov (United States)

    Benredjem, Z.; Delimi, R.

    2009-11-01

    According to World Bank projections, world population will reach 7 billion in 2020. This impressive population must be accommodated, clothed and most importantly it must be fed. It keep into this challenge an increase in the agricultural production must reach 90% of the already cultivated land. It is clear that mineral fertilizers will continue to play an important role in improving agricultural production. A fertilizer is by definition 'any product containing at least 5% of the three major plant nutrients: N, P2O5, and K2 O. The most common fertilizers are nitrogen, phosphate, potassium, magnesium and sulphur fertilizers. They can be simple, single or complex nutrients. Currently, phosphate fertilizers are by far the most prevalent. However, the fertilizers produced from phosphate ores still contain heavy metals that are harmful to human health. These heavy metals are transferred through processing to phosphoric acid: the main intermediary between the rock and phosphate fertilizers. Among these heavy metals, cadmium seems to be the most harmful and toxic element. The occurrence of such element in the fertilizer products causes a serious danger to both human health and environment. Most of the phosphate-bearing rocks contain large Cd amounts that are often above acceptable levels. Phosphate ore industry usually tends to improve the quality of product by eliminating this toxic element. The aim of this study is to present an accurate and less expensive method by which cadmium in phosphate ore would be reduced to lower rates. The method uses ammonium acetate salt, diamine tetra-acetic and hydrochloric acids as extracting agents of cadmium in phosphate. The influence of some parameters was taken into consideration, such as the volume/mass ratios, the extracting agent concentration and the temperature. The results analyses were based on the amount of cadmium extracted and P2O5 loss, and the efficiencies of extracting agents.

  7. A major problem associated with removing metals sulfides as ...

    African Journals Online (AJOL)

    User

    2013-05-22

    May 22, 2013 ... Laboratory scale bioreactors were used to investigate the treatment of arsenic species deliberately ... reverse osmosis (Geucke et al., 2009) have been used to treat ..... Figure 6 Changes in (a) redox potential and (b) pH as a function of initial percentage of As(III) in a total arsenic concentration of. 0.1 mg/l in ...

  8. Disorder and transport of silver in some layered metal sulfides

    NARCIS (Netherlands)

    Gerards, Anthonius Gijsbertus

    1987-01-01

    The chemical and physical properties of compounds with a layered structure are strongly determined by the two-dimensional nature of the bonding, viz. strong bonding within the layers and much weaker bonds between the layers; graphite is an example of such and anisotropic solid. the layered

  9. Understanding the mechanism of iron sulfide-induced fouling in upgrading

    Energy Technology Data Exchange (ETDEWEB)

    Panchal, C.B. [United States Dept. of Energy, Chicago, IL (United States). Argonne National Laboratory

    2006-07-01

    This presentation investigated the underlying mechanisms of iron sulfide-induced fouling and coking in upgrading processes. Experiments to determine the effects of dissolved metals on the rate of fouling were reviewed. It was noted that the presence of species such as active sulfur and diolefins can enhance the effect of dissolved metals. An investigation of a high temperature fouling unit was then conducted to investigate the effect of iron acetate and theiphenol additions to stable heavy gas oil. The deposition rate became strongly dependent on temperature in the presence of the dissolved metals. Fouling deposit analyses from various parts of the refining process consistently showed high concentrations of iron and sulfur. It was observed that the threshold tube-wall temperature corresponded to the decomposition temperature of iron salts. A review of current literature indicated that there is little information on the interactive effects of the thermal stability of dissolved organo-metallic compounds and the reactivity of organic species in generating fouling precursors. The creation of a predictive model of threshold fouling and coking conditions was recommended. It was suggested that the model should be used during the design phases of furnaces and heat exchangers. Other recommendations included the use of on-line sensors to detect iron sulfide formulation; and the monitoring of coking furnaces. Blending guidelines to minimize the interactive effects of dissolved metals and active sulfur compounds were also presented. refs., tabs., figs.

  10. Microvolume turbidimetry for rapid and sensitive determination of the acid labile sulfide fraction in waters after headspace single-drop microextraction with in situ generation of volatile hydrogen sulfide.

    Science.gov (United States)

    Lavilla, I; Pena-Pereira, F; Gil, S; Costas, M; Bendicho, C

    2009-08-04

    In this work, we demonstrate the feasibility of applying headspace single-drop microextraction with in-drop precipitation for the quantitative determination of the acid labile sulfide fraction (H2S, HS-, and S2- (free sulfide), amorphous FeS and some metal sulfide complexes-clusters as ZnS) in aqueous samples by microvolume turbidimetry. The methodology lies in the in situ hydrogen sulfide generation and subsequent sequestration into an alkaline microdrop containing ZnO(2)(2-) and exposed to the headspace above the stirred aqueous sample. The ZnS formed in the drop was then determined by microvolume turbidimetry. The optimum experimental conditions of the proposed method were: 2 microL of a microdrop containing 750 mg L(-1) Zn(II) in 1 mol L(-1) NaOH exposed to the headspace of a 20-mL aqueous sample stirred at 1600 rpm during 80 s after derivatization with 1 mL of 6 mol L(-1) HCl. An enrichment factor of 1710 was achieved in only 80 s. The calibration graph was linear in the range of 5-100 microg L(-1) with a detection limit of 0.5 microg L(-1). The repeatability, expressed as relative standard deviation, was 5.8% (N = 9). Finally, the proposed methodology was successfully applied to the determination of the acid labile sulfide fraction in different natural water samples.

  11. Formation of Zn- and Fe-sulfides near hydrothermal vents at the Eastern Lau Spreading Center: implications for sulfide bioavailability to chemoautotrophs

    Directory of Open Access Journals (Sweden)

    Yucel Mustafa

    2008-05-01

    Full Text Available Abstract Background The speciation of dissolved sulfide in the water immediately surrounding deep-ocean hydrothermal vents is critical to chemoautotrophic organisms that are the primary producers of these ecosystems. The objective of this research was to identify the role of Zn and Fe for controlling the speciation of sulfide in the hydrothermal vent fields at the Eastern Lau Spreading Center (ELSC in the southern Pacific Ocean. Compared to other well-studied hydrothermal systems in the Pacific, the ELSC is notable for unique ridge characteristics and gradients over short distances along the north-south ridge axis. Results In June 2005, diffuse-flow ( 250°C vent fluids were collected from four field sites along the ELSC ridge axis. Total and filtered Zn and Fe concentrations were quantified in the vent fluid samples using voltammetric and spectrometric analyses. The results indicated north-to-south variability in vent fluid composition. In the high temperature vent fluids, the ratio of total Fe to total Zn varied from 39 at Kilo Moana, the most northern site, to less than 7 at the other three sites. The concentrations of total Zn, Fe, and acid-volatile sulfide indicated that oversaturation and precipitation of sphalerite (ZnS(s and pyrite (FeS2(s were possible during cooling of the vent fluids as they mixed with the surrounding seawater. In contrast, most samples were undersaturated with respect to mackinawite (FeS(s. The reactivity of Zn(II in the filtered samples was tested by adding Cu(II to the samples to induce metal-exchange reactions. In a portion of the samples, the concentration of labile Zn2+ increased after the addition of Cu(II, indicating the presence of strongly-bound Zn(II species such as ZnS clusters and nanoparticles. Conclusion Results of this study suggest that Zn is important to sulfide speciation at ELSC vent habitats, particularly at the southern sites where Zn concentrations increase relative to Fe. As the hydrothermal

  12. Reduction of acid rock drainage using steel slag in cover systems over sulfide rock waste piles.

    Science.gov (United States)

    de Almeida, Rodrigo Pereira; Leite, Adilson do Lago; Borghetti Soares, Anderson

    2015-04-01

    The extraction of gold, coal, nickel, uranium, copper and other earth-moving activities almost always leads to environmental damage. In metal and coal extraction, exposure of sulfide minerals to the atmosphere leads to generation of acid rock drainage (ARD) and in underground mining to acid mine drainage (AMD) due to contamination of infiltrating groundwater. This study proposes to develop a reactive cover system that inhibits infiltration of oxygen and also releases alkalinity to increase the pH of generated ARD and attenuate metal contaminants at the same time. The reactive cover system is constructed using steel slag, a waste product generated from steel industries. This study shows that this type of cover system has the potential to reduce some of the adverse effects of sulfide mine waste disposal on land. Geochemical and geotechnical characterization tests were carried out. Different proportions of sulfide mine waste and steel slag were studied in leachate extraction tests. The best proportion was 33% of steel slag in dry weight. Other tests were conducted as follows: soil consolidation, saturated permeability and soil water characteristic curve. The cover system was numerically modeled through unsaturated flux analysis using Vadose/w. The solution proposed is an oxygen transport barrier that allows rain water percolation to treat the ARD in the waste rock pile. The results showed that the waste pile slope is an important factor and the cover system must have 5 m thickness to achieve an acceptable effectiveness. © The Author(s) 2015.

  13. Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

    Science.gov (United States)

    Deonarine, Amrika; Lau, Boris L.T.; Aiken, George R.; Ryan, Joseph N.; Hsu-Kim, Heileen

    2011-01-01

    Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn−S−NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn−S−NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.

  14. Phosphate removal from aqueous solution using slag and fly ash

    Directory of Open Access Journals (Sweden)

    Safaa M. Ragheb

    2013-12-01

    Full Text Available The application of low cost materials in wastewater treatment has recently attracted great interest; fly ash and slag have improved high performance as a low cost material and have been used as a potential adsorbent for removal of phosphate, heavy metals and organic pollutants in wastewater treatment. Batch adsorption experiments were performed in order to evaluate phosphate removal efficiency of slag and fly ash. The effect of various operating variables, i.e. initial pH, adsorbent dose, initial metal ion concentration, and adsorption time of phosphate using the slag and fly ash, has been studied. The sorption process was relatively fast and equilibrium has been reached at 30 min contact time and the maximum removal percentage was achieved at an adsorbent loading weight of 0.5 gm/100 ml. Phosphate removal ratio using slag and fly ash was 93% and 95%, respectively, under the batch test conditions. The overall uptake for the slag was maximum at pH 5 and at pH 7 for fly ash. The sorption data were represented using Freundlich and Langmuir parameters, where the sorption data were better represented by the Freundlich isotherm than by the Langmuir. The optimized method was applied for phosphate removal from wastewater of Proctor and Gamble (P&G Company for household products. The achieved phosphate removal efficiency was 96.15% and 96.9% using slag and fly ash respectively.

  15. Global transcriptional responses of Acidithiobacillus ferrooxidans Wenelen under different sulfide minerals.

    Science.gov (United States)

    Latorre, Mauricio; Ehrenfeld, Nicole; Cortés, María Paz; Travisany, Dante; Budinich, Marko; Aravena, Andrés; González, Mauricio; Bobadilla-Fazzini, Roberto A; Parada, Pilar; Maass, Alejandro

    2016-01-01

    In order to provide new information about the adaptation of Acidithiobacillus ferrooxidans during the bioleaching process, the current analysis presents the first report of the global transcriptional response of the native copper mine strain Wenelen (DSM 16786) oxidized under different sulfide minerals. Microarrays were used to measure the response of At. ferrooxidans Wenelen to shifts from iron supplemented liquid cultures (reference state) to the addition of solid substrates enriched in pyrite or chalcopyrite. Genes encoding for energy metabolism showed a similar transcriptional profile for the two sulfide minerals. Interestingly, four operons related to sulfur metabolism were over-expressed during growth on a reduced sulfur source. Genes associated with metal tolerance (RND and ATPases type P) were up-regulated in the presence of pyrite or chalcopyrite. These results suggest that At. ferrooxidans Wenelen presents an efficient transcriptional system developed to respond to environmental conditions, namely the ability to withstand high copper concentrations. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

    Science.gov (United States)

    Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

    2018-05-01

    This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

  17. As, Bi, Hg, S, Sb, Sn and Te geochemistry of the J-M Reef, Stillwater Complex, Montana: constraints on the origin of PGE-enriched sulfides in layered intrusions

    Science.gov (United States)

    Zientek, M.L.; Fries, T.L.; Vian, R.W.

    1990-01-01

    The J-M Reef is an interval of disseminated sulfides in the Lower Banded series of the Stillwater Complex that is enriched in the platinum group elements (PGE). Palladium and Pt occur in solid solution in base-metal sulfides and as discrete PGE minerals. PGE minerals include sulfides, tellurides, arsenides, antimonides, bismuthides, and alloys with Fe, Sn, Hg, and Au. Several subpopulations can be delineated based on whole-rock chemical analyses for As, Bi, Cu, Hg, Pd, Pt, S, Sb and Te for samples collected from and adjacent to the J-M Reef. In general, samples from within the reef have higher Pt/Cu, Pd/Cu, Pd/Pt, Te/Bi and S/(Te+Bi) than those collected adjacent to the reef. Vertical compositional profiles through the reef suggest that Pd/Cu and Pt/Cu decrease systematically upsection from mineralized to barren rock. The majority of samples with elevated As, Sb and Hg occur adjacent to the reef, not within it, or in sulfide-poor rocks. Neither magma mixing nor fluid migration models readily explain why the minor quantities of sulfide minerals immediately adjacent to the sulfide-enriched layers that form the J-M Reef have different element ratios than the sulfide minerals that form the reef. If all the sulfides formed by exsolution during a magma mixing event and the modal proportion of sulfide now in the rocks are simply the result of mechanical processes that concentrated the sulfides into some layers and not others, then the composition of the sulfide would not be expected to be different. Models that rely upon ascending liquids or fluids are incompatible with the presence of sulfides that are not enriched in PGE immediately below or interlayered with the PGE-enriched sulfides layers. PGE-enriched postcumulus fluids should have reacted to the same extent with sulfides immediately outside the reef as within the reef. One explanation is that some of the sulfide minerals in the rocks outside the reef have a different origin than those that make up the reef. The

  18. Cadmium zinc sulfide by solution growth

    Science.gov (United States)

    Chen, Wen S.

    1992-05-12

    A process for depositing thin layers of a II-VI compound cadmium zinc sulfide (CdZnS) by an aqueous solution growth technique with quality suitable for high efficiency photovoltaic or other devices which can benefit from the band edge shift resulting from the inclusion of Zn in the sulfide. A first solution comprising CdCl.sub.2 2.5H.sub.2 O, NH.sub.4 Cl, NH.sub.4 OH and ZnCl.sub.2, and a second solution comprising thiourea ((NH.sub.2).sub.2 CS) are combined and placed in a deposition cell, along with a substrate to form a thin i.e. 10 nm film of CdZnS on the substrate. This process can be sequentially repeated with to achieve deposition of independent multiple layers having different Zn concentrations.

  19. Iron-sulfide redox flow batteries

    Science.gov (United States)

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2013-12-17

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  20. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... satisfactorily oxidation of OCS over a wide range of stoichiometric air–fuel ratios (0.5 ≤λ≤7.3), temperatures (450–1700 K), and pressures (0.02–3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled...

  1. Ferrocene sulfonates as electrocatalysts for sulfide detection

    International Nuclear Information System (INIS)

    Lawrence, Nathan S.; Tustin, Gary J.; Faulkner, Michael; Jones, Timothy G.J.

    2006-01-01

    The electrochemical characterization of both the mono- and di-substituted forms of ferrocene sulfonate are given. The results show both species produce voltammograms consistent with quasi-irreversible diffusion controlled redox reactions. The FcSO 3 - species was found to be easier to oxidize than its Fc(SO 3 ) 2 2- counterpart, due to the electron withdrawing affect of the sulfonate group on the Fe centre. In the presence of sulfide, the voltammetric response of FcSO 3 - is shown to be consistent with the occurrence of an electrocatalytic EC' reaction. This analytical response was utilized as a means of determining sulfide and was found to be linear over the concentration 0.02-1 mM with a limit of detection of 14 μM

  2. Various communications concerning sulfigran (sodium sulfide)

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, H.; Montfort, F.; Wickert; Horn; Junkermann; Wissel, K.; Pier, M.

    1943-01-01

    Most of these communications concerned the problems experienced by Poelitz when its regular supplier of Sulfigran (sodium sulfide), the I.G. Farbenindustrie plant at Luverkusen, had to shut down for repairs and Poelitz had to get an impure form of Sulfigran mixture (a crude melt of ore) from other suppliers, including the I.G. Farbenindustrie plant at Wolfen (Bitterfeld). Various problems arose in the transition, including the fact that the mixture supplied was not ground finely enough for the coal-paste-preparing machinery at Poelitz to handle without damage. An analysis of one sample of the raw melt mixture gave 68.8% sodium sulfide, 12.0% carbon, 1.5% hydrogen, 1.6% silicon dioxide, 1.8% iron, 1.0% aluminum, 0.6% calcium, traces of magnesium and sulfate, and 15.4% water-insoluble. An analysis for another sample showed about 1.8% less sodium sulfide, 1.5% more silicon dioxide, 0.7% less iron, 0.5% less aluminum, 0.6% more calcium, etc., than the previous analysis. Finally one of the communications was a letter in which Ludwigshafen responded favorably to Poelitz's question about whether it would be advantageous to add Sulfigran directly to the first oven of a hydrogenation chamber instead of grinding it with the coal paste. Ludwigshafen said that in some experiments it had observed deposits at places where Sulfigran and coal paste encountered each other in preheater tubes. The deposits consisted of sodium sulfide and iron compounds. 3 tables.

  3. Hydrogen sulfide prodrugs—a review

    Directory of Open Access Journals (Sweden)

    Yueqin Zheng

    2015-09-01

    Full Text Available Hydrogen sulfide (H2S is recognized as one of three gasotransmitters together with nitric oxide (NO and carbon monoxide (CO. As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications.

  4. Sulfide Precipitation in Wastewater at Short Timescales

    DEFF Research Database (Denmark)

    Kiilerich, Bruno; van de Ven, Wilbert; Nielsen, Asbjørn Haaning

    2017-01-01

    that this is not the case for sulfide precipitation by ferric iron. Instead, the reaction time was found to be on a timescale where it must be considered when performing end-of-pipe treatment. For real wastewaters at pH 7, a stoichiometric ratio around 14 mol Fe(II) (mol S(−II))−1 was obtained after 1.5 s, while the ratio...

  5. Triphenyl phosphate allergy from spectacle frames

    DEFF Research Database (Denmark)

    Carlsen, Lars; Andersen, Klaus E.; Egsgaard, Helge

    1986-01-01

    A case of triphenyl phosphate allergy from spectacle frames is reported. Patch tests with analytical grade triphenyl phosphate, tri-m-cresyl phosphate, and tri-p-cresyl phosphate in the concentrations 5%, 0.5% and 0.05% pet. showed positive reactions to 0.05% triphenyl phosphate and 0.5% tri...... triphenyl phosphate allergy in our patient....

  6. 21 CFR 184.1434 - Magnesium phosphate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Magnesium phosphate. 184.1434 Section 184.1434 Food... Specific Substances Affirmed as GRAS § 184.1434 Magnesium phosphate. (a) Magnesium phosphate includes both magnesium phosphate, dibasic, and magnesium phosphate, tribasic. Magnesium phosphate, dibasic (MgHPO4·3H2O...

  7. Phosphate bonded ceramics as candidate final-waste-form materials

    International Nuclear Information System (INIS)

    Singh, D.; Wagh, A.S.; Cunnane, J.; Sutaria, M.; Kurokawa, S.; Mayberry, J.

    1994-04-01

    Room-temperature setting phosphate-bonded ceramics were studied as candidate materials for stabilization of DOE low-level problem mixed wastes which cannot be treated by other established stabilization techniques. Phosphates of Mg, Mg-Na, Al and Zr were studied to stabilize ash surrogate waste containing RCRA metals as nitrates and RCRA organics. We show that for a typical loading of 35 wt.% of the ash waste, the phosphate ceramics pass the TCLP test. The waste forms have high compression strength exceeding ASTM recommendations for final waste forms. Detailed X-ray diffraction studies and differential thermal analyses of the waste forms show evidence of chemical reaction of the waste with phosphoric acid and the host matrix. The SEM studies show evidence of physical bonding. The excellent performance in the leaching tests is attributed to a chemical solidification and physical as well as chemical bonding of ash wastes in these phosphate ceramics

  8. Recovering Valuable Phosphates: Chemical Biotechnology as a Problem Solver for the Environment.

    Science.gov (United States)

    Heinzelmann, Elsbeth

    2015-01-01

    Researchers from the HES-SO Valais/Wallis have demonstrated how to extract phosphate from sewage sludge on the laboratory scale using renewable energy sources from a microbial fuel cell. The mobilized phosphate barely contains heavy metals and can be used to produce fertilizer of marketable quality. The necessary energy comes from a sewage treatment plant and causes no additional costs.

  9. Influence de la phosphatation au zinc sur la résistance a la ...

    African Journals Online (AJOL)

    Zinc phosphatation influence on the resistance to corrosion of a carbonbased steel in marine medium. In the frame of the present investigation, we have showed that the profile of the cathodic curves of a non phosphated metal, plead in favour to a kinetic profile essentially monitored by a pure diffusion. The corrosion rate ...

  10. Renal phosphate handling: Physiology

    Directory of Open Access Journals (Sweden)

    Narayan Prasad

    2013-01-01

    Full Text Available Phosphorus is a common anion. It plays an important role in energy generation. Renal phosphate handling is regulated by three organs parathyroid, kidney and bone through feedback loops. These counter regulatory loops also regulate intestinal absorption and thus maintain serum phosphorus concentration in physiologic range. The parathyroid hormone, vitamin D, Fibrogenic growth factor 23 (FGF23 and klotho coreceptor are the key regulators of phosphorus balance in body.

  11. Synthesis and characterization of silver phosphate/calcium phosphate mixed particles capable of silver nanoparticle formation by photoreduction.

    Science.gov (United States)

    Natale, Livia C; Alania, Yvette; Rodrigues, Marcela C; Simões, Alyne; de Souza, Douglas N; de Lima, Erick; Arana-Chavez, Victor E; Hewer, Thiago L R; Hiers, Rochelle; Esteban-Florez, Fernando L; Brito, Giancarlo E S; Khajotia, Sharukh; Braga, Roberto R

    2017-07-01

    Silver phosphate is a semi-conductor sensitive to UV-Vis radiation (phosphate/silver phosphate particles as remineralizing and antibacterial fillers in resin-based dental materials. Mixed phosphate particles were synthesized, characterized and added to a dimethacrylate resin in 20% or 30% mass fractions to investigate their efficacy as ion-releasing fillers for dental remineralization and antibacterial activity. The formation of metallic silver nanoparticles after exposure to visible radiation from a dental curing unit (peak emission: 470nm) was demonstrated by particle X-ray diffraction and scanning electron microscopy analysis of the composite fractured surface. Calcium and phosphate release from materials containing the mixed particles were similar to those containing pure CaP particles, whereas Streptococcus mutans colonies were reduced by three orders of magnitude in relation to the control, which can be attributed to silver release. As expected, the optical properties of the materials containing mixed phosphate particles were compromised by the presence of silver. Nevertheless, materials containing mixed phosphate particles presented higher fracture strength and elastic modulus than those with pure CaP particles. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Microaeration for hydrogen sulfide removal in UASB reactor.

    Science.gov (United States)

    Krayzelova, Lucie; Bartacek, Jan; Kolesarova, Nina; Jenicek, Pavel

    2014-11-01

    The removal of hydrogen sulfide from biogas by microaeration was studied in Up-flow Anaerobic Sludge Blanket (UASB) reactors treating synthetic brewery wastewater. A fully anaerobic UASB reactor served as a control while air was dosed into a microaerobic UASB reactor (UMSB). After a year of operation, sulfur balance was described in both reactors. In UASB, sulfur was mainly presented in the effluent as sulfide (49%) and in biogas as hydrogen sulfide (34%). In UMSB, 74% of sulfur was detected in the effluent (41% being sulfide and 33% being elemental sulfur), 10% accumulated in headspace as elemental sulfur and 9% escaped in biogas as hydrogen sulfide. The efficiency of hydrogen sulfide removal in UMSB was on average 73%. Microaeration did not cause any decrease in COD removal or methanogenic activity in UMSB and the elemental sulfur produced by microaeration did not accumulate in granular sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Platinum-group elements fractionation by selective complexing, the Os, Ir, Ru, Rh-arsenide-sulfide systems above 1020 °C

    Science.gov (United States)

    Helmy, Hassan M.; Bragagni, Alessandro

    2017-11-01

    The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low μg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru) + Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020 °C and show that the prominent mineralogical difference between IPGE (+Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200 °C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE + Rh form metal-metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt- and Pd-ligand associations lead to PGE fractionation.

  14. Synthesis of a 4-membered ring zinc phosphate monomer and its ...

    Indian Academy of Sciences (India)

    Administrator

    framework metal phosphates, with the objective of rendering them porous for potential application in catalysis and sorption processes. These materials are generally prepared hydrothermally in the presence of organic amines. One of the crucial ...

  15. Modeling Sulfides, pH and Hydrogen Sulfide Gas in the Sewers of San Francisco

    DEFF Research Database (Denmark)

    Vollertsen, Jes; Revilla, Nohemy; Hvitved-Jacobsen, Thorkild

    2015-01-01

    An extensive measuring campaign targeted on sewer odor problems was undertaken in San Francisco. It was assessed whether a conceptual sewer process model could reproduce the measured concentrations of total sulfide in the wastewater and H2S gas in the sewer atmosphere, and to which degree...... (WATS) sewer process concept, which never had been calibrated to such an extensive dataset. The study showed that the model was capable of reproducing the general levels of wastewater sulfide, wastewater pH, and sewer H2S gas. It could also reproduce the general variability of these parameters, albeit...

  16. Optical detection of sodium salts of fluoride, acetate and phosphate

    Indian Academy of Sciences (India)

    Optical detection of sodium salts of fluoride, acetate and phosphate by a diacylhydrazine ligand by the formation of a colour alkali metal complex. Purnandhu Bose Ranjan Dutta I ... Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A and 2B Raja S C Mullick Road, Kolkata 700032, India ...

  17. Optical detection of sodium salts of fluoride, acetate and phosphate ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 6. Optical detection of sodium salts of fluoride, acetate and phosphate by a diacylhydrazine ligand by the formation of a colour alkali metal complex. Purnandhu Bose Ranjan Dutta I Ravikumar Pradyut Ghosh. Volume 123 Issue 6 November 2011 pp 869- ...

  18. Synthesis, structure and luminescence properties of phosphates A1 ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 40; Issue 1. Synthesis, structure and luminescence properties of phosphates A 1 − 3 x Eu x Zr 2 (PO 4 ) 3 (A—alkali metal). ANTON KANUNOV BENOIT GLORIEUX ALBINA ORLOVA ELENA BOROVIKOVA GALINA ZAVEDEEVA. Volume 40 Issue 1 February 2017 pp 7- ...

  19. Triphenyl phosphate allergy from spectacle frames

    DEFF Research Database (Denmark)

    Carlsen, L; Andersen, K E; Egsgaard, Helge

    1986-01-01

    A case of triphenyl phosphate allergy from spectacle frames is reported. Patch tests with analytical grade triphenyl phosphate, tri-m-cresyl phosphate, and tri-p-cresyl phosphate in the concentrations 5%, 0.5% and 0.05% pet. showed positive reactions to 0.05% triphenyl phosphate and 0.5% tri......-m-cresyl phosphate, but no reaction to tri-p-cresyl phosphate. Gas chromatography of the tricresyl phosphate 5% pet. patch test material supplied from Trolab showed that it contained a mixture of a wide range of triaryl phosphates, including 0.08% triphenyl phosphate which is above the threshold for detecting...

  20. Recent findings on sinks for sulfide in gravity sewer networks

    DEFF Research Database (Denmark)

    Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2006-01-01

    Sulfide buildup in sewer networks is associated with several problems, including health impacts, corrosion of sewer structures and odor nuisance. In recent years, significant advances in the knowledge of the major processes governing sulfide buildup in sewer networks have been made. This paper...... summarizes this newly obtained knowledge and emphasizes important implications of the findings. Model simulations of the in-sewer processes important for the sulfur cycle showed that sulfide oxidation in the wetted biofilm is typically the most important sink for dissolved sulfide in gravity sewers. However...

  1. Eukaryotic and prokaryotic contributions to colonic hydrogen sulfide synthesis.

    Science.gov (United States)

    Flannigan, Kyle L; McCoy, Kathy D; Wallace, John L

    2011-07-01

    Hydrogen sulfide (H(2)S) is an important modulator of many aspects of digestive function, both in health and disease. Colonic tissue H(2)S synthesis increases markedly during injury and inflammation and appears to contribute to resolution. Some of the bacteria residing in the colon can also produce H(2)S. The extent to which bacterial H(2)S synthesis contributes to what is measured as colonic H(2)S synthesis is not clear. Using conventional and germ-free mice, we have delineated the eukaryotic vs. prokaryotic contributions to colonic H(2)S synthesis, both in healthy and colitic mice. Colonic tissue H(2)S production is entirely dependent on the presence of the cofactor pyridoxal 5'-phosphate (vitamin B(6)), while bacterial H(2)S synthesis appears to occur independent of this cofactor. As expected, approximately one-half of the H(2)S produced by feces is derived from eukaryotic cells. While colonic H(2)S synthesis is markedly increased when the tissue is inflamed, and, in proportion to the extent of inflammation, fecal H(2)S synthesis does not change and tissue granulocytes do not appear to be the source of the elevated H(2)S production. Rats fed a B vitamin-deficient diet for 6 wk exhibited significantly diminished colonic H(2)S synthesis, but fecal H(2)S synthesis was not different from that of rats on the control diet. Our results demonstrate that H(2)S production by colonic bacteria does not contribute significantly to what is measured as colonic tissue H(2)S production, using the acetate trapping assay system employed in this study.

  2. Mechanisms of bacterial metals removal from solids

    International Nuclear Information System (INIS)

    Torma, A.E.; Pryfogle, P.A.

    1990-01-01

    The Great Lakes area sediments are contaminated with varying amounts of heavy metals and polychlorinated organic matter. With respect to the bioremediation of metallic contents of these sediments, it was shown that a number of microorganisms exist which can effectively solubilize heavy metals. The basic reaction mechanisms of bioleaching processes were discussed and the effects of semiconductor character of the sulfide substrate explained. A special emphasis was made to comment on INEL's bioremediation capability. 37 refs

  3. Mechanism of radiation and thermal decomposition of sulphide non-ferrous metals

    International Nuclear Information System (INIS)

    Mazhrenova, N.P.

    1998-01-01

    This paper deals with the non-ferrous metals sulfides in term of their radiative sensitivity, directed chances of their physical-chemical, and hence technological properties by radiation influence both on sulfide materials and on the processes with their participation. (author)

  4. Carbon steel protection in G.S. (Girlder sulfide) plants. Iron sulfide scales formation conditions. Pt. 1

    International Nuclear Information System (INIS)

    Bruzzoni, P.; Burkart, A.L.; Garavaglia, R.N.

    1981-11-01

    An ASTM A 516 degree 60 carbon steel superficial protection technique submitted to a hydrogen-water sulfide corrosive medium at 2 MPa of pressure and 40-125 deg C forming on itself an iron sulfide layer was tested. Studies on pH influence, temperature, passivating mean characteristics and exposure time as well as the mechanical resistance of sulfide layers to erosion are included. (Author) [es

  5. 76 FR 64022 - Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting

    Science.gov (United States)

    2011-10-17

    ... Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting AGENCY: Environmental Protection Agency (EPA). ACTION: Lifting of Administrative Stay for Hydrogen Sulfide. SUMMARY: EPA is announcing... (EPCRA) section 313 toxic chemical release reporting requirements for hydrogen sulfide (Chemical...

  6. Integrated assessment of the phosphate industry

    International Nuclear Information System (INIS)

    Ryan, M.T.; Cotter, S.J.

    1980-05-01

    The phosphate industry in the United States includes three major activities, namely, mining and milling of phosphate rock, phosphate product manufacture, and phosphate product use. Phosphatic materials contain uranium, thorium, and their decay products in greater than background amounts. This assessment of the radiological impacts associated with the redistribution of radioactive components of phosphate materials may provide insight into the effects of uranium extraction from phosphate materials for use in the nuclear fuel cycle

  7. Pyridoxal phosphate-dependent neonatal epileptic encephalopathy

    OpenAIRE

    Bagci, S; Zschocke, J; Hoffmann, G F; Bast, T; Klepper, J; Müller, A; Heep, A; Bartmann, P; Franz, A R

    2009-01-01

    Pyridox(am)ine-5′-phosphate oxidase converts pyridoxine phosphate and pyridoxamine phosphate to pyridoxal phosphate, a cofactor in many metabolic reactions, including neurotransmitter synthesis. A family with a mutation in the pyridox(am)ine-5′-phosphate oxidase gene presenting with neonatal seizures unresponsive to pyridoxine and anticonvulsant treatment but responsive to pyridoxal phosphate is described. Pyridoxal phosphate should be considered in neonatal epileptic encephalopathy unrespons...

  8. Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand.

    Science.gov (United States)

    Hug, Katrin; Maher, William A; Stott, Matthew B; Krikowa, Frank; Foster, Simon; Moreau, John W

    2014-01-01

    Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid) resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand). Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic), and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur concentration reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

  9. Stabilities of thiomolybdate complexes of iron; implications for retention of essential trace elements (Fe, Cu, Mo) in sulfidic waters.

    Science.gov (United States)

    Helz, George R; Erickson, Britt E; Vorlicek, Trent P

    2014-06-01

    In aquatic ecosystems, availabilities of Fe, Mo and Cu potentially limit rates of critical biological processes, including nitrogen fixation, nitrate assimilation and N2O decomposition. During long periods in Earth's history when large parts of the ocean were sulfidic, what prevented these elements' quantitative loss from marine habitats as insoluble sulfide phases? They must have been retained by formation of soluble complexes. Identities of the key ligands are poorly known but probably include thioanions. Here, the first determinations of stability constants for Fe(2+)-[MoS4](2-) complexes in aqueous solution are reported based on measurements of pyrrhotite (hexagonal FeS) solubility under mildly alkaline conditions. Two linear complexes, [FeO(OH)MoS4](3-) and [(Fe2S2)(MoS4)2](4-), best explain the observed solubility variations. Complexes that would be consistent with cuboid cluster structures were less successful, implying that such clusters probably are minor or absent in aqueous solution under the conditions studied. The new data, together with prior data on stabilities of Cu(+)-[MoS4](2-) complexes, are used to explore computationally how competition of Fe(2+) and Cu(+) for [MoS4](2-), as well as competition of [MoS4](2-) and HS(-) for both metals would be resolved in solutions representative of sulfidic natural waters. Thiomolybdate complexes will be most important at sulfide concentrations near the [MoO4](2-)-[MoS4](2-) equivalence point. At lower sulfide concentrations, thiomolybdates are insufficiently stable to be competitive ligands in natural waters and at higher sulfide concentrations HS(-) ligands out-compete thiomolybdates.

  10. The proteins of Fusobacterium spp. involved in hydrogen sulfide production from L-cysteine.

    Science.gov (United States)

    Basic, Amina; Blomqvist, Madeleine; Dahlén, Gunnar; Svensäter, Gunnel

    2017-03-14

    Hydrogen sulfide (H 2 S) is a toxic foul-smelling gas produced by subgingival biofilms in patients with periodontal disease and is suggested to be part of the pathogenesis of the disease. We studied the H 2 S-producing protein expression of bacterial strains associated with periodontal disease. Further, we examined the effect of a cysteine-rich growth environment on the synthesis of intracellular enzymes in F. nucleatum polymorphum ATCC 10953. The proteins were subjected to one-dimensional (1DE) and two-dimensional (2DE) gel electrophoresis An in-gel activity assay was used to detect the H 2 S-producing enzymes; Sulfide from H 2 S, produced by the enzymes in the gel, reacted with bismuth forming bismuth sulfide, illustrated as brown bands (1D) or spots (2D) in the gel. The discovered proteins were identified with liquid chromatography - tandem mass spectrometry (LC-MS/MS). Cysteine synthase and proteins involved in the production of the coenzyme pyridoxal 5'phosphate (that catalyzes the production of H 2 S) were frequently found among the discovered enzymes. Interestingly, a higher expression of H 2 S-producing enzymes was detected from bacteria incubated without cysteine prior to the experiment. Numerous enzymes, identified as cysteine synthase, were involved in the production of H 2 S from cysteine and the expression varied among Fusobacterium spp. and strains. No enzymes were detected with the in-gel activity assay among the other periodontitis-associated bacteria tested. The expression of the H 2 S-producing enzymes was dependent on environmental conditions such as cysteine concentration and pH but less dependent on the presence of serum and hemin.

  11. Inhibition of sulfate reduction by iron, cadmium and sulfide in granular sludge

    International Nuclear Information System (INIS)

    Gonzalez-Silva, Blanca M.; Briones-Gallardo, Roberto; Razo-Flores, Elias; Celis, Lourdes B.

    2009-01-01

    This study investigated the inhibition effect of iron, cadmium and sulfide on the substrate utilization rate of sulfate reducing granular sludge. A series of batch experiments in a UASB reactor were conducted with different concentrations of iron (Fe 2+ , 4.0-8.5 mM), cadmium (Cd 2+ , 0.53-3.0 mM) and sulfide (4.2-10.6 mM), the reactor was fed with ethanol at 1 g chemical oxygen demand (COD)/L and sulfate to yield a COD/SO 4 2- (g/g) ratio of 0.5. The addition of iron, up to a concentration of 8.1 mM, had a positive effect on the substrate utilization rate which increased 40% compared to the rate obtained without metal addition (0.25 g COD/g VSS-d). Nonetheless, iron concentration of 8.5 mM inhibited the specific substrate utilization rate by 57% compared to the substrate utilization rate obtained in the batch amended with 4.0 mM Fe 2+ (0.44 g COD/g VSS-d). Cadmium had a negative effect on the specific substrate utilization rate at the concentrations tested; at 3.0 mM Cd 2+ the substrate utilization rate was inhibited by 44% compared with the substrate utilization rate without metal addition. Cadmium precipitation with sulfide did not decrease the inhibition of cadmium on sulfate reduction. These results could have important practical implications mainly when considering the application of the sulfate reducing process to treat effluents with high concentrations of sulfate and dissolved metals such as iron and cadmium.

  12. Inhibition of sulfate reduction by iron, cadmium and sulfide in granular sludge

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Silva, Blanca M. [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico); Briones-Gallardo, Roberto [Facultad de Ingenieria-Instituto de Metalurgia, Universidad Autonoma de San Luis Potosi, Sierra Leona 550, Lomas 2a. Seccion, 78210, San Luis Potosi, S.L.P. (Mexico); Razo-Flores, Elias [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico); Celis, Lourdes B., E-mail: celis@ipicyt.edu.mx [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico)

    2009-12-15

    This study investigated the inhibition effect of iron, cadmium and sulfide on the substrate utilization rate of sulfate reducing granular sludge. A series of batch experiments in a UASB reactor were conducted with different concentrations of iron (Fe{sup 2+}, 4.0-8.5 mM), cadmium (Cd{sup 2+}, 0.53-3.0 mM) and sulfide (4.2-10.6 mM), the reactor was fed with ethanol at 1 g chemical oxygen demand (COD)/L and sulfate to yield a COD/SO{sub 4}{sup 2-} (g/g) ratio of 0.5. The addition of iron, up to a concentration of 8.1 mM, had a positive effect on the substrate utilization rate which increased 40% compared to the rate obtained without metal addition (0.25 g COD/g VSS-d). Nonetheless, iron concentration of 8.5 mM inhibited the specific substrate utilization rate by 57% compared to the substrate utilization rate obtained in the batch amended with 4.0 mM Fe{sup 2+} (0.44 g COD/g VSS-d). Cadmium had a negative effect on the specific substrate utilization rate at the concentrations tested; at 3.0 mM Cd{sup 2+} the substrate utilization rate was inhibited by 44% compared with the substrate utilization rate without metal addition. Cadmium precipitation with sulfide did not decrease the inhibition of cadmium on sulfate reduction. These results could have important practical implications mainly when considering the application of the sulfate reducing process to treat effluents with high concentrations of sulfate and dissolved metals such as iron and cadmium.

  13. Laser Sintered Calcium Phosphate Bone

    National Research Council Canada - National Science Library

    Vail, Neil

    1999-01-01

    ...) technology selective laser sintering (SLS). BME has successfully implemented a pilot facility to fabricate calcium phosphate implants using anatomical data coupled with the selective laser sintering process...

  14. Biofabrication of morphology improved cadmium sulfide nanoparticles using Shewanella oneidensis bacterial cells and ionic liquid: For toxicity against brain cancer cell lines.

    Science.gov (United States)

    Wang, Li; Chen, Siyuan; Ding, Yiming; Zhu, Qiang; Zhang, Nijia; Yu, Shuqing

    2018-01-01

    The present work determines the anticancer activity of bio-mediated synthesized cadmium sulfide nanoparticles using the ionic liquid and bacterial cells (Shewanella oneidensis). Bacterial cells have been exposed to be important resources that hold huge potential as ecofriendly, cost-effective, evading toxic of dangerous chemicals and the alternative of conventional physiochemical synthesis. The Shewanella oneidensis is an important kind of metal reducing bacterium, known as its special anaerobic respiratory and sulfate reducing capacity. The crystalline nature, phase purity and surface morphology of biosynthesized cadmium sulfide nanoparticles were analyzed by Fourier transform infrared spectroscopy, X-ray diffraction, Field emission scanning electron microscopy, Energy dispersive spectroscopy and Transmission electron microscopy. The use of imidazolium based ionic liquids as soft templating agent for controlling self-assembly and crystal growth direction of metal sulfide nanoparticles has also advanced as an important method. The microscopic techniques showed that the nanoparticles are designed on the nano form and have an excellent spherical morphology, due to the self-assembled mechanism of ionic liquid assistance. The antitumor efficiency of the cadmium sulfide nanoparticles was investigated against brain cancer cell lines using rat glioma cell lines. The effectively improved nano-crystalline and morphological structure of CdS nanoparticles in the presence of IL exhibit excellent cytotoxicity and dispersion ability on the cell shape is completely spread out showing a nice toxic environment against cancer cells. The cytotoxicity effect of cadmium sulfide nanoparticles was discussed with a diagrammatic representation. Copyright © 2017. Published by Elsevier B.V.

  15. Improvement of sulfide corrosion resistance of nickel heat resisting alloys by means alloying

    International Nuclear Information System (INIS)

    Oryshkin, I.V.

    1999-01-01

    Paper describes the effect of the alloying elements (chromium, aluminium, titanium, molybdenum, tungsten, niobium, cobalt) on sulfide corrosion (SC) resistance of nickel base heat-resisting alloys during 30 h in 75% Na 2 SO 4 +25% NaCl molten sat under 900 deg C temperature. The obtained patterns are compared with the effect of the mentioned metals on the long-term strength. SC high resistance and the adequate level of heat resistance are ensured by a certain doping of a nickel base [ru

  16. Technetium behavior in sulfide and ferrous iron solutions

    International Nuclear Information System (INIS)

    Lee, S.Y.; Bondietti, E.A.

    1982-01-01

    Pertechnetate oxyanion ( 99 TcO 4- ), a potentially mobile species in leachate from a breached radioactive waste repository, was removed from a brine solution by precipitation with sulfide, iron, and ferrous sulfide at environmental pH's. Maghemite (ν-Fe 2 O 3 ) and geothite (α-FeOOH) were the dominant minerals in the precipitate obtained from the TcO 4- -ferrous iron reaction. The observation of small particle size and poor crystallinity of the minerals formed in the presence of Tc suggested that the Tc was incorporated into the mineral structure after reduction to a lower valence state. Amorphous ferrous sulfide, an initial phase precipitating in the TcO 4- -ferrous iron-sulfide reaction, was transformed to goethite and hematite (α-Fe 2 O 3 ) on aging. The black precipitate obtained from the TcO 4- -sulfide reaction was poorly crystallized technetium sulfide (Tc 2 S 7 ) which was insoluble in both acid and alkaline solution in the absence of strong oxidents. The results suggested that ferrous- and/or sulfide-bearing groundwaters and minerals in host rocks or backfill barriers could reduce the mobility of Tc through the formation of less-soluble Tc-bearing iron and/or sulfide minerals

  17. Effect of Soluble Sulfide on the Activity of Luminescent Bacteria

    Directory of Open Access Journals (Sweden)

    Feng Wang

    2012-05-01

    Full Text Available Sulfide is an important water pollutant widely found in industrial waste water that has attracted much attention. S2−, as a weak acidic anion, is easy hydrolyzed to HS and H2S in aqueous solution. In this study, biological tests were performed to establish the toxicity of sulfide solutions on luminescent bacteria. Considering the sulfide solution was contained three substances—S2−, HS and H2S—the toxicity test was performed at different pH values to investigate which form of sulfide increased light emission and which reduced light emission. It was shown that the EC50 values were close at pH 7.4, 8.0 and 9.0 which were higher than pH 5 and 10. The light emission and sulfide concentrations displayed an inverse exponential dose-response relationship within a certain concentration range at pH 5, 6.5 and 10. The same phenomenon occurred for the high concentration of sulfide at pH 7.4, 8 and 9, in which the concentration of sulfide was HS >> H2S > S2−. An opposite hormesis-effect appeared at the low concentrations of sulfide.

  18. Sulfidation of zinc plating sludge with Na2S for zinc resource recovery

    International Nuclear Information System (INIS)

    Kuchar, D.; Fukuta, T.; Onyango, M.S.; Matsuda, H.

    2006-01-01

    A high amount of zinc disposed in the landfill sites as a mixed-metal plating sludge represents a valuable zinc source. To recover zinc from the plating sludge, a sulfidation treatment is proposed in this study, while it is assumed that ZnS formed could be separated by flotation. The sulfidation treatment was conducted by contacting simulated zinc plating sludge with Na 2 S solution at S 2- to Zn 2+ molar ratio of 1.5 for a period of 1-48 h, while changing the solid to liquid (S:L) ratio from 0.25:50 to 1.00:50. The conversion of zinc compounds to ZnS was determined based on the consumption of sulfide ions. The reaction products formed by the sulfidation of zinc were identified by X-ray diffraction (XRD). As a result, it was found that the conversion of zinc compounds to ZnS increased with an increase in S:L ratio. A maximum conversion of 0.809 was obtained at an S:L ratio of 1.00:50 after 48 h. However, when the zinc sludge treated at S:L ratio of 1.00:50 for 48 h was subjected to XRD analyses, only ZnS was identified in the treated zinc sludge. The result suggested that the rest of zinc sludge remained unreacted inside the agglomerates of ZnS. The formation behavior of ZnS was predicted by Elovich equation, which was found to describe the system satisfactorily indicating the heterogeneous nature of the sludge

  19. Phosphates in pallasite meteorites as probes of mantle processes in small planetary bodies

    Science.gov (United States)

    Davis, Andrew M.; Olsen, Edward J.

    1991-01-01

    Trace element analyses of the phosphates minerals in stony-iron pallasite meteorites are used here to investigate the magmatic history of the silicate portions of pallasites. In Eagle Station and seven other pallasites, the phosphates have relatively low concentrations of REEs and are strongly enriched in heavy relative to light REE. These patterns are consistent with formation of phosphate by subsolidus reactions between metal and silicate, in which phosphate inherits the REE pattern of olivine. In Springwater and Santa Rosalia, calcium-rich phosphates have higher concentrations of REE, are enriched in light relative to heavy REE, and have negative europium anomalies. These patterns are consistent with crystallization of phosphate from a europium-depleted chondritic liquid. This is unlikely to have happened near the base of the differentiating parent-body mantle; it suggests that some pallasites may come from regions of their parent bodies much nearer the surface than the core-mantle boundary.

  20. Recovery of uranium from the Syrian phosphate by solid-liquid method using alkaline solutions

    International Nuclear Information System (INIS)

    Shlewit, H.; Alibrahim, M.

    2007-01-01

    Uranium concentrations were analyzed in the Syrian phosphate deposits. Mean concentrations were found between 50 and 110 ppm. As a consequence, an average phosphate dressing of 22 kg/ha phosphate would charge the soil with 5-20 g/ha uranium when added as a mineral fertilizer. Fine grinding phosphate produced at the Syrian mines was used for uranium recovery by carbonate leaching. The formation of the soluble uranyl tricarbonate anion UO 2 (CO 3 ) 3 4- permits use of alkali solutions of sodium carbonate and sodium bicarbonate salts for the nearly selective dissolution of uranium from phosphate. Separation of iron, aluminum, titanium, etc., from the uranium during leaching was carried out. Formation of some small amounts of molybdates, vanadates, phosphates, aluminates, and some complexes metal was investigated. This process could be used before the manufacture of TSP fertilizer, and the final products would contain smaller uranium quantities. (author)

  1. Phosphate Recovery From Sewage Sludge Containing Iron Phosphate

    NARCIS (Netherlands)

    Wilfert, P.K.

    2018-01-01

    The scope of this thesis was to lay the basis for a phosphate recovery technology that can be applied on sewage sludge containing iron phosphate. Such a technology should come with minimal changes to the existing sludge treatment configuration while keeping the use of chemicals or energy as small as

  2. The Use of Rock Phosphate and Phosphate Solubilising Fungi ...

    African Journals Online (AJOL)

    User

    Department of Soil Science, University of Ghana, Legon. *Corresponding author; Email: sbrempong@yahoo.com. Abstract. Field experiment was conducted to study the effect of rock phosphate (RP) and phosphate solubilizing fungi application on upland rice yield intercropped with pigeon pea from 2009 to 2011 at the ...

  3. 21 CFR 137.175 - Phosphated flour.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 2 2010-04-01 2010-04-01 false Phosphated flour. 137.175 Section 137.175 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Related Products § 137.175 Phosphated flour. Phosphated flour, phosphated white flour, and phosphated...

  4. Hydrogen sulfide: from brain to gut.

    Science.gov (United States)

    Kimura, Hideo

    2010-05-01

    Three hundred years have passed since the first description of the toxicity of hydrogen sulfide (H(2)S). Three papers in 1989 and 1990 described relatively high concentrations of sulfide in the brain. In 1996 we demonstrated that cystathionine beta-synthase (CBS) is a H(2)S producing enzyme in the brain and that H(2)S enhances the activity of NMDA receptors and facilitates the induction of hippocampal long-term potentiation (LTP), a synaptic model of memory. In the following year, we demonstrated that another H(2)S producing enzyme, cystathionine gamma-lyase is in the thoracic aorta, portal vein, and the ileum, and that H(2)S relaxes these tissues. Based on these observations we proposed H(2)S as a neuromodulator as well as a smooth muscle relaxant. We recently demonstrated that the third H(2)S-producing enzyme, 3-mercaptopyruvate sulfurtransferase (3MST) along with cysteine aminotransferase (CAT) produces H(2)S in the brain as well as in vascular endothelium. Various functions in many tissues have been proposed. H(2)S protects neurons and cardiac muscle from oxidative stress. H(2)S has pro- and anti-inflammatory effects, nociceptive effects, the regulatory function of insulin release, and is even involved in longevity. Recent progress in the studies of physiological functions of H(2)S in neurons and smooth muscle was described.

  5. Sulfurization of Dissolved Organic Matter Increases Hg-Sulfide-Dissolved Organic Matter Bioavailability to a Hg-Methylating Bacterium.

    Science.gov (United States)

    Graham, Andrew M; Cameron-Burr, Keaton T; Hajic, Hayley A; Lee, Connie; Msekela, Deborah; Gilmour, Cynthia C

    2017-08-15

    Reactions of dissolved organic matter (DOM) with aqueous sulfide (termed sulfurization) in anoxic environments can substantially increase DOM's reduced sulfur functional group content. Sulfurization may affect DOM-trace metal interactions, including complexation and metal-containing particle precipitation, aggregation, and dissolution. Using a diverse suite of DOM samples, we found that susceptibility to additional sulfur incorporation via reaction with aqueous sulfide increased with increasing DOM aromatic-, carbonyl-, and carboxyl-C content. The role of DOM sulfurization in enhancing Hg bioavailability for microbial methylation was evaluated under conditions typical of Hg methylation environments (μM sulfide concentrations and low Hg-to-DOM molar ratios). Under the conditions of predicted metacinnabar supersaturation, microbial Hg methylation increased with increasing DOM sulfurization, likely reflecting either effective inhibition of metacinnabar growth and aggregation or the formation of Hg(II)-DOM thiol complexes with high bioavailability. Remarkably, Hg methylation efficiencies with the most sulfurized DOM samples were similar (>85% of total Hg methylated) to that observed in the presence of l-cysteine, a ligand facilitating rapid Hg(II) biouptake and methylation. This suggests that complexes of Hg(II) with DOM thiols have similar bioavailability to Hg(II) complexes with low-molecular-weight thiols. Overall, our results are a demonstration of the importance of DOM sulfurization to trace metal and metalloid (especially mercury) fate in the environment. DOM sulfurization likely represents another link between anthropogenic sulfate enrichment and MeHg production in the environment.

  6. Sulindac Sulfide, but Not Sulindac Sulfone, Inhibits Colorectal Cancer Growth

    Directory of Open Access Journals (Sweden)

    Christopher S. Williams

    1999-06-01

    Full Text Available Sulindac sulfide, a metabolite of the nonsteroidal antiinflammatory drug (NSAID sulindac sulfoxide, is effective at reducing tumor burden in both familial adenomatous polyposis patients and in animals with colorectal cancer. Another sulindac sulfoxide metabolite, sulindac sulfone, has been reported to have antitumor properties without inhibiting cyclooxygenase activity. Here we report the effect of sulindac sulfone treatment on the growth of colorectal carcinoma cells. We observed that sulindac sulfide or sulfone treatment of HCA-7 cells led to inhibition of prostaglandin E2 production. Both sulindac sulfide and sulfone inhibited HCA-7 and HCT-116 cell growth in vitro. Sulindac sulfone had no effect on the growth of either HCA-7 or HCT-116 xenografts, whereas the sulfide derivative inhibited HCA-7 growth in vivo. Both sulindac sulfide and sulfone inhibited colon carcinoma cell growth and prostaglandin production in vitro, but sulindac sulfone had no effect on the growth of colon cancer cell xenografts in nude mice.

  7. Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides

    Science.gov (United States)

    Jood, Priyanka; Ohta, Michihiro

    2015-01-01

    Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS2-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS2 sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor. PMID:28787992

  8. Influence of Water Salinity on Air Purification from Hydrogen Sulfide

    Directory of Open Access Journals (Sweden)

    Leybovych L.I.

    2015-12-01

    Full Text Available Mathematical modeling of «sliding» water drop motion in the air flow was performed in software package FlowVision. The result of mathematical modeling of water motion in a droplet with diameter 100 microns at the «sliding» velocity of 15 m/s is shown. It is established that hydrogen sulfide oxidation occurs at the surface of phases contact. The schematic diagram of the experimental setup for studying air purification from hydrogen sulfide is shown. The results of the experimental research of hydrogen sulfide oxidation by tap and distilled water are presented. The dependence determining the share of hydrogen sulfide oxidized at the surface of phases contact from the dimensionless initial concentration of hydrogen sulfide in the air has been obtained.

  9. The selenium isotopic variations in chondrites are mass-dependent; Implications for sulfide formation in the early solar system

    Science.gov (United States)

    Labidi, J.; König, S.; Kurzawa, T.; Yierpan, A.; Schoenberg, R.

    2018-01-01

    Element transfer from the solar nebular gas to solids occurred either through direct condensation or via heterogeneous reactions between gaseous molecules and previously condensed solid matter. The precursors of altered sulfides observed in chondrites are for example attributed to reactions between gaseous hydrogen sulfide and metallic iron grains. The transfer of selenium to solids likely occurred through a similar pathway, allowing the formation of iron selenides concomitantly with sulfides. The formation rate of sulfide however remains difficult to assess. Here we investigate whether the Se isotopic composition of meteorites contributes to constrain sulfide formation during condensation stages of our solar system. We present high precision Se concentration and δ 82 / 78 Se data for 23 chondrites as well as the first δ 74 / 78 Se , δ 76 / 78 Se and δ 77 / 78 Se data for a sub-set of seven chondrites. We combine our dataset with previously published sulfur isotopic data and discuss aspects of sulfide formation for various types of chondrites. Our Se concentration data are within uncertainty to literature values and are consistent with sulfides being the dominant selenium host in chondrites. Our overall average δ 82 / 78 Se value for chondrites is - 0.21 ± 0.43 ‰ (n = 23, 2 s.d.), or - 0.14 ± 0.21 ‰ after exclusion of three weathered chondrites (n = 20, 2 s.d.). These average values are within uncertainty indistinguishable from a previously published estimate. For the first time however, we resolve distinct δ 82 / 78 Se between ordinary (- 0.14 ± 0.07 ‰, n = 9, 2 s.d.), enstatite (- 0.27 ± 0.05 ‰, n = 3, 2 s.d.) and CI carbonaceous chondrites (- 0.01 ± 0.06 ‰, n = 2, 2 s.d.). We also resolve a Se isotopic variability among CM carbonaceous chondrites. In addition, we report on δ 74 / 78 Se , δ 76 / 78 Se and δ 77 / 78 Se values determined for 7 chondrites. Our data allow evaluating the mass dependency of the δ 82 / 78 Se variations. Mass

  10. Tin-phosphate glass anode for sodium ion batteries

    Directory of Open Access Journals (Sweden)

    Tsuyoshi Honma

    2013-11-01

    Full Text Available The electrochemical property of tin-phosphate (designate as GSPO glass anode for the sodium ion battery was studied. During the first charge process, sodium ion diffused into GSPO glass matrix and due to the reduction of Sn2+ to Sn0 state sodiated tin metal nano-size particles are formed in oxide glass matrix. After the second cycle, we confirmed the steady reversible reaction ∼320 mAh/g at 0–1 V cutoff voltage condition by alloying process in NaxSn4. The tin-phosphate glass is a promising candidate of new anode active material that realizes high energy density sodium ion batteries.

  11. Molecular analysis of phosphate limitation in Geobacteraceae during the bioremediation of a uranium-contaminated aquifer

    Energy Technology Data Exchange (ETDEWEB)

    N' Guessan, L.A.; Elifantz, H.; Nevin, K.P.; Mouser, P.J.; Methe, B.; Woodard, T. L.; Manley, K.; Williams, K. H.; Wilkins, M. J.; Larsen, J.T.; Long, P. E.; Lovley, D. R.

    2009-09-01

    Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphate-limitation were identified via microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU the most up-regulated. Quantitative PCR analysis of pstB and phoU transcript levels in G. sulfurreducens grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve due to the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.

  12. Treatment of metal-contaminated water and vertical distribution of metal precipitates in an upflow anaerobic bioreactor.

    Science.gov (United States)

    Quan, Z X; La, H J; Cho, Y G; Hwang, M H; Kim, L S; Lee, S T

    2003-03-01

    A lab-scale upflow anaerobic bioreactor filled with granular sludge and cow manure was operated for 140 days to determine the mechanism of metal removal and the vertical distribution of metal precipitates. Heavy metal ions were removed in the order of Cu2+, Cd2+, Zn2+, Fe2+ and Mn2+ with respect to the height in the reactor. The solid phase analysis showed that the heavy metals were mostly precipitated in the form of metal sulfides by sulfate reduction The contents of metal precipitates in the reactor were as follows: (i) Cd and Zn were highest in the bottom, (ii) Fe was highest at the low-middle layer, and (iii) Mn was increased with the height in the reactor. The vertical distribution of metal sulfides in the reactor was directly related to the solubility product (Ksp). Results obtained in this study suggest a feasibility of the application to separate precipitation metal-containing wastewater.

  13. Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

    Science.gov (United States)

    Hilsenbeck, S.J.; McCarley, R.E.; Schrader, G.L.; Xie, X.B.

    1999-02-16

    New amorphous molybdenum/tungsten sulfides with the general formula M{sup n+}{sub 2x/n}(L{sub 6}S{sub 8})S{sub x}, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M{sub 6}S{sub 8}){sup 0} cluster units are present. Vacuum thermolysis of the amorphous Na{sub 2x}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH first produces poorly crystalline NaMo{sub 6}S{sub 8} by disproportionation at 800 C and well-crystallized NaMo{sub 6}S{sub 8} at {>=} 900 C. Ion-exchange of the sodium material in methanol with soluble M{sup 2+} and M{sup 3+} salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M{sup n+}{sub 2x/n}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M{sup n+}{sub 2x/n}Mo{sub 6}S{sub 8+x}(MeOH){sub y}[MMOS] (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as ``Chevrel phase-like`` in that both contain Mo{sub 6}S{sub 8} cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst is shown to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS{sub 2} catalysts. 9 figs.

  14. Carbon steel protection in G.S. (Girlder sulfide) plants. Pressure influence on iron sulfide scales formation. Pt. 5

    International Nuclear Information System (INIS)

    Delfino, C.A.; Lires, O.A.; Rojo, E.A.

    1987-01-01

    In order to protect carbon steel towers and piping of Girlder sulfide (G.S.) experimental heavy water plants against corrosion produced by the action of aqueous solutions of hydrogen sulfide, a method, previously published, was developed. Carbon steel, exposed to saturated aqueous solutions of hydrogen sulfide, forms iron sulfide scales. In oxygen free solutions evolution of corrosion follows the sequence: mackinawite → cubic ferrous sulfide → troilite → pyrrotite → pyrite. Scales formed by pyrrotite-pyrite or pyrite are the most protective layers (these are obtained at 130 deg C, 2MPa, for periods of 14 days). Experiments, at 125 deg C and periods of 10-25 days, were performed in two different ways: 1- constant pressure operations at 0.5 and 1.1 MPa. 2- variable pressure operation between 0.3-1 MPa. In all cases pyrrotite-pyrite scales were obtained. (Author) [es

  15. Phosphate glasses, containing nitrogen

    International Nuclear Information System (INIS)

    Lisitsyna, E.A.; Khalilev, V.D.; Koryavin, A.A.; Goncharova, L.N.

    1987-01-01

    Possibilities of nitrogen-containing glass synthesis by the introduction into the charge of ammonium salts, as well as aluminium nitride, are studied. Zinc alumoyttrium phosphate glass (mol. %) Zn(PO 3 ) 2 - 4O, Al(PO 3 ) 3 - 3O, Y(PO 3 ) 3 -3O is suggested as a matrix. It is shown that the effect of amide and imide groups on the properties of the glass is less noticeable than the effect of nitride groups. Direct introduction of nitride constituent was realized using AlN, but aluminium introduction was taken into account so that the oxide was subtracted. The attempt to introduce more than 2.5 mass % of nitrogen into initial matrix by aluminium nitride has failed due to repeated restoration of glass with amorphous phosphorus isolation

  16. Light weight phosphate cements

    Science.gov (United States)

    Wagh, Arun S.; Natarajan, Ramkumar,; Kahn, David

    2010-03-09

    A sealant having a specific gravity in the range of from about 0.7 to about 1.6 for heavy oil and/or coal bed methane fields is disclosed. The sealant has a binder including an oxide or hydroxide of Al or of Fe and a phosphoric acid solution. The binder may have MgO or an oxide of Fe and/or an acid phosphate. The binder is present from about 20 to about 50% by weight of the sealant with a lightweight additive present in the range of from about 1 to about 10% by weight of said sealant, a filler, and water sufficient to provide chemically bound water present in the range of from about 9 to about 36% by weight of the sealant when set. A porous ceramic is also disclosed.

  17. Copper scandium zirconium phosphate

    DEFF Research Database (Denmark)

    Bond, Andrew David; Warner, Terence Edwin

    2013-01-01

    The title compound, with nominal formula Cu(2)ScZr(PO(4))(3), has a beige coloration and displays fast Cu(+) cation conduction at elevated temperatures. It adopts a NASICON-type structure in the space group R3c. The examined crystal was an obverse-reverse twin with approximately equal twin...... components. The [Sc(III)Zr(IV)(PO(4))(3)](2-) framework is composed of corner-sharing Sc/ZrO(6) octahedra and PO(4) tetrahedra. The Sc and Zr atoms are disordered on one atomic site on a crystallographic threefold axis. The P atom of the phosphate group lies on a crystallographic twofold axis. Nonframework...... Cu(+) cations occupy three positions. Two of the Cu(+) positions generate an approximately circular distribution around a site of 3 symmetry, referred to as the M1 site in the NASICON-type structure. The other Cu(+) position is situated close to the twofold symmetric M2 site, displaced...

  18. Sulfide gas effects on the power transmission lines; Efeito do gas sulfidrico nos componentes do sistema de transmissao de energia eletrica

    Energy Technology Data Exchange (ETDEWEB)

    Kajimoto, Zehbour Panossian; Almeida, Neusvaldo Lira de

    1992-12-31

    Copper and its alloys when exposed in atmosphere contaminated with sulphur compounds present stains due to sulfidation. This sulfidation is markedly influenced by temperature and air relative humidity. In this works, results from tests with three years of exposition in atmospheres containing H{sub 2}S and SO{sub 2} are related; such results show that the use of these materials in regions with these contaminants must be done with restriction. Besides the high copper corrosion rates, corrosion products which form on this metal can cause serious problems to the electric contact. (author) 8 refs., 4 figs., 4 tabs.

  19. A new lubricant carrier for metal forming

    DEFF Research Database (Denmark)

    Arentoft, Mogens; Bay, Niels; Tang, Peter Torben

    2009-01-01

    A lubricant carrier for metal forming processes is developed. Surfaces with pores of micrometer size for entrapping lubricant are generated by electrochemical deposition of an alloy, consisting of two immiscible metals, of which one metal subsequently is etched away leaving 5 mu m layers with a s...... extrusion at high reduction and excessive stroke comparing with conventionally lubrication using phosphate coating and soap....

  20. Occupational exposure to hydrogen sulfide: management of hydrogen sulfide exposure victims (Preprint No. SA-5)

    International Nuclear Information System (INIS)

    Srivastava, P.P.

    1989-04-01

    National Institute of Occupational Safety and Health, U.S.A. has listed 73 industries with potential exposure to hydrogen sulphide. Though the toxicity of hydrogen sulfide is known to mankind since the beginning of seventeenth century the exact mode of its toxicity and effective therapeutic regimen remains unclear as yet. This paper presents current thoughts on the toxicity of this substance and a discussion on the role of various antidotes used in H 2 S poisoning. (autho r)

  1. Germanium sulfide-based solid electrolytes for non-volatile memory

    Science.gov (United States)

    Balakrishnan, Muralikrishnan

    Programmable Metallization Cell (PMC) technology involves the storage of data as reduced metal ions in a solid electrolyte. Earlier work on Selenide-based (Ag-Ge-Se) PMC devices requires relatively low back-end-of-line processing (BEOL) since the electrolyte may undergo undesirable changes at process temperatures in excess of 200°C. This dissertation is focused on Sulfide-based (Ag/Cu-Ge-S) solid electrolytes which have better temperature stability and the PMC technology based on these materials is compatible with most BEOL process in CMOS Integrated Circuits. The devices fabricated using Ag-Ge-S and Cu-Ge-S solid electrolytes were tested after annealing at 300°C and 430°C. Extensive material analysis was performed on both the systems in an effort to understand the behavior of the devices at elevated temperatures. Electrical characterization testing involved standard memory characterization techniques such as quasi-static measurements tests, retention tests, speed tests, elevated temperature operation tests and endurance tests. The Ag-Ge-S PMC devices were made with different compositions to find out the optimum composition which would ensure reliable operation even after the high temperature anneal. The Sulfide-based PMC devices were also tested for reconfigurable logic applications with special test structures that would demonstrate the low resistance connections that can be achieved by programming the PMC elements using higher currents. Optimum composition of the starting glass was found from the material and data analysis, to ensure reliable operation of the Sulfide-based PMC devices with no degradation in the electrical characteristics even after the typical BEOL anneal.

  2. Photocatalytic degradation and sorption of methylene blue on the surface of metal oxides in aqueous solutions of the dye

    Science.gov (United States)

    Kiselev, V. M.; Evstrop'ev, S. K.; Starodubtsev, A. M.

    2017-11-01

    The photocatalytic activity of some metal oxides and sulfides, as well of C60 fullerene, is compared using the method of photocatalytic degradation of methylene blue simultaneously with comparison of the efficiency of methylene blue adsorption on solid-phase powders of these oxides, sulfides, and fullerene in aqueous solution of the dye in the absence of irradiation.

  3. Azo dye decolorization assisted by chemical and biogenic sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Prato-Garcia, Dorian [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa de San José 2055, San Luis Potosí 78216 (Mexico); Buitrón, Germán, E-mail: gbuitronm@ii.unam.mx [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico)

    2013-04-15

    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection.

  4. Sulfidic vapor phase catalysts, especially tungsten sulfide, in industrial coal hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M.

    1943-01-01

    The historical development of high-pressure processes of the I. G. Farbenindustrie, from ammonia through methanol and gasoline, and the special case of gasoline production with a fixed-bed catalyst (tungsten sulfide) were discussed. The preparation, properties, and uses of this versatile catalyst were discussed, but it was emphasized that with the sotrmy development of the process, a condition which still existed at the time of this report, and with a great number of practical problems to solve, no extensive study of basic facts had ben possible. This tungsten sulfide catalyst was an especially active vapor-phase catalyst which operated at lower temperatures than the molybdenum catalysts formerly used. It also permitted higher thruputs, even with the oils from bituminous coal that were difficult to split. For certain uses, such as the improvement of the antiknock properties or the saving in tungsten, it was strongly diluted. Studies on using up sulfur in the tungsten sulfide catalyst were in progress at this time and showed there was practically no reduction of it under the conditions of hydrogenation under pressure as long as the raw material contained sulfur.

  5. On the pelletizing of sulfide molybdenite concentrate

    International Nuclear Information System (INIS)

    Palant, A.A.

    2007-01-01

    Investigation results are discussed on the process of pelletizing with the use of various binders (water, syrup, sulfite-alcoholic residue and bentonite) for flotation sulfide molybdenite concentrate (∼84 % MoS 2 ) of the Mongolian deposit. It is established that with the use of syrup rather strong pellets (>300 g/p) of desired size (2-3 mm) can be obtained at a binder flowrate of 1 kg per 100 kg of concentrate. The main advantage of using syrup instead of bentonite lies in the fact that in this instance no depletion of a molybdenum calcine obtained by oxidizing roasting of raw ore takes place due to syrup complete burning out. This affects positively subsequent hydrometallurgical conversion because of decreasing molybdenum losses with waste cakes [ru

  6. Modulated structure calculated for superconducting hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Majumdar, Arnab; Tse, John S.; Yao, Yansun [Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, SK (Canada)

    2017-09-11

    Compression of hydrogen sulfide using first principles metadynamics and molecular dynamics calculations revealed a modulated structure with high proton mobility which exhibits a diffraction pattern matching well with experiment. The structure consists of a sublattice of rectangular meandering SH{sup -} chains and molecular-like H{sub 3}S{sup +} stacked alternately in tetragonal and cubic slabs forming a long-period modulation. The novel structure offers a new perspective on the possible origin of the superconductivity at very high temperatures in which the conducting electrons in the SH chains are perturbed by the fluxional motions of the H{sub 3}S resulting in strong electron-phonon coupling. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. New studies on the synthesis and structural chemistry of polynary lithium and silver transition metal phosphates; Neue Untersuchungen zur Synthese und Strukturchemie von polynaeren Lithium- und Silber-Uebergangsmetallphosphaten

    Energy Technology Data Exchange (ETDEWEB)

    Mosymow, Emma

    2015-09-11

    In the course of this work extensive equilibrium studies were carried out in the four-system systems Li / M / P / O (M: Cr, Mn) in the search for new, powerful cathode materials for lithium ion batteries. The phosphates LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}, NaCr{sup II}{sub 4}(PO{sub 4}){sub 3}, Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}, monoclines Li{sub 3}Cr{sub 2}(PO{sub 4}){sub 3}, Cr{sup II}{sub 5}Cr{sup III}{sub 2}(P{sub 2}O{sub 7}){sub 4} and LiMn{sup II}{sub 2}P{sub 3}O{sub 10} were obtained for the first time. The present work reports on their synthesis, crystallographic characterization and their spectroscopic and magnetic properties. The equilibrium studies in the Li / Cr / P / O system led to the elucidation of numerous phase relationships. For example, the coexistence regions LiCr{sub 4}(PO{sub 4}){sub 3} / Li{sub 5}Cr{sub 3}(PO{sub 4}){sub 4} / Cr{sub 2}O{sub 3} / CrP and Li{sub 9}Cr{sub 3}(PO{sub 4}){sub 3} / LiCrP{sub 2}O{sub 7} / CrP. The coexistence of some equilibrium phases such as lithium orthophosphate and lithium manganese(II) orthophosphate as well as lithium metaphosphate and manganese(III) metaphosphate were also investigated in the Li / Mn / P / O system. Furthermore, the de-intercalation behavior of silver manganese phosphates was investigated with the possibility of demonstrating metastable phosphates with manganese in oxidation states higher than 3+. In this case the four-substance system Ag / Mn / P / O with Mn(II) and Mn(III) was considered. The reaction conditions were adapted to those of the experiments in the corresponding lithium-containing systems. Within the scope of the equilibrium studies two new pyrophosphates AgMnP{sub 2}O{sub 7} and Ag{sub 1,6}Mn{sub 3}(P{sub 2}O{sub 7}){sub 2} were found and characterized. [German] Bei der Suche nach neuen, leistungsfaehigen Kathodenmaterialien fuer Lithiumionenbatterien wurden im Rahmen dieser Arbeit umfangreiche Gleichgewichtsuntersuchungen in den Vierstoffsystemen Li /M

  8. 75 FR 8889 - Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting

    Science.gov (United States)

    2010-02-26

    ... Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting AGENCY: Environmental Protection... for hydrogen sulfide (Chemical Abstracts Service Number (CAS No.) 7783-06-4). Hydrogen sulfide was... requirements for hydrogen sulfide in order to evaluate issues brought to the Agency's attention after...

  9. Phosphate stabilization of flue gas ashes from waste incineration; Fosfatstabilisering av roekgasaska fraan avfallsfoerbraenning

    Energy Technology Data Exchange (ETDEWEB)

    Kullberg, S. [Geodesign AB, Linkoeping (Sweden)

    1995-05-01

    This study deals with the immobilization of heavy metals and other elements in flue gas ashes from household waste incineration by the addition of phosphates to the ash. It also describes the FUDD-technique (FUnction-adapted Design and Deposition) for deposition of the stabilized ash. In this work, phosphates obtained from phosphoric acid have been added to ash in proportions of 2.8% and 3.7% by weight of ash. Phosphates have also been injected into the flue gases, in this case with proportions of 4.7% and 16.3%. The samples have been studied both in the field and in the laboratory in regard to compaction properties, permeability, chemical solid phase content, HCl in the flue gases, leaching of metals via batch tests, availability tests and column tests. In batch tests, the stabilized samples show an immobilization of most metals except cadmium. Lead has been reduced by 97.0-99.9%. Cadmium has been mobilized by a factor of 2-30 in this experiment. The best results are obtained with addition of phosphates to the flue gases. In the availability tests, with addition of phosphates to flue gases, all environmentally destructive metals except arsenic and nickel have been immobilized to varying degree. The reduction is greatest for lead, aluminium, copper, mercury and zinc. With the addition of phosphates to ash, aluminium, copper and lead have been immobilized. In opposite, arsenic, cobalt and nickel were mobilized. The addition of 4-5% phosphates in the flue gas reactor produced only a marginal effect on the HCl concentration in the flue gases. The use of phosphates increases the HF concentration by about 3 mg/Nm{sup 3}. The cost for phosphate stabilization have been estimated at SEK 110-220 per ton of ash including costs for stabilization equipment. 18 refs, 15 figs, 13 tabs

  10. Thermoelectric properties of non-stoichiometric lanthanum sulfides

    International Nuclear Information System (INIS)

    Shapiro, E.; Danielson, L.R.

    1983-01-01

    The lanthanum sulfides are promising candidate materials for high-efficiency thermoelectric applications at temperatures up to 1300 0 C. The nonstoichiometric lanthanum sulfides (LaS /SUB x/ , where 1.33 2 //rho/ can be chosen. The thermal conductivity remains approximately constant with stoichiometry, so a material with an optimum value of α 2 //rho/ should possess the optimum figure-of-merit. Data for the Seebeck coefficient and electrical resistivity of non-stoichiometric lanthanum sulfides is presented, together with structural properties of these materials

  11. Sulfide Oxidation in the Anoxic Black-Sea Chemocline

    DEFF Research Database (Denmark)

    JØRGENSEN, BB; FOSSING, H.; WIRSEN, CO

    1991-01-01

    per day, occurred in anoxic water at the top of the sulfide zone concurrent with the highest rates of dark CO2 assimilation. The main soluble oxidized products of sulfide were thiosulfate (68-82%) and sulfate. Indirect evidence was presented for the formation of elemental sulfur which accumulated...... that the measured H2S oxidation rates were 4-fold higher than could be explained by the downward flux of organic carbon and too high to balance the availability of electron acceptors such as oxidized iron or manganese. A nitrate maximum at the lower boundary of the O2 zone did not extend down to the sulfide zone....

  12. Iron sulfide corrosion in the 700 atm. liquid phase preheater

    Energy Technology Data Exchange (ETDEWEB)

    Donath, E.; Nonnenmacher, H.

    1943-07-28

    Equilibrium calculations gave lower bounds on partial pressure of hydrogen sulfide within a 500 atm. hydrogen gas stream, below which no corrosion of the steel tube walls would occur. AT 450/sup 0/C the lower bound was 0.5 atm., whereas at 500/sup 0/C the lower bound was 0.8 atm. However, in most plants, the hydrogen sulfide partial pressure exceeded values, so corrosion by formation of iron sulfide did usually occur. It was estimated that the corrosion reaction rate at 500/sup 0/C was about twice what it was at 450/sup 0/C.

  13. Conspicuous veils formed by vibrioid bacteria on sulfidic marine sediment

    DEFF Research Database (Denmark)

    Thar, Roland Matthias; Kühl, Michael

    2002-01-01

    We describe the morphology and behavior of a hitherto unknown bacterial species that forms conspicuous veils (typical dimensions, 30 by 30 mm) on sulfidic marine sediment. The new bacteria were enriched on complex sulfidic medium within a benthic gradient chamber in oxygen-sulfide countergradients......, but the bacteria have so far not been isolated in pure culture, and a detailed characterization of their metabolism is still lacking. The bacteria are colorless, gram-negative, and vibrioid-shaped (1.3- to 2.5- by 4- to 10-µm) cells that multiply by binary division and contain several spherical inclusions of poly...

  14. Use of sulfide-containing liquors for removing mercury from flue gases

    Science.gov (United States)

    Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

    2006-05-02

    A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

  15. Source and Fate of Inorganic Soil Contamination Around the Abandoned Phillips Sulfide Mine Hudson Highlands New York

    Energy Technology Data Exchange (ETDEWEB)

    S Gilchrist; A Gates; E Elzinga; M Gorring; z Szabo

    2011-12-31

    The abandoned Phillips sulfide mine in the critical Highlands watershed in New York has been shown to produce strongly acidic mine drainage (AMD) with anomalous metal contaminants in first-order streams that exceeded local water standards by up to several orders of magnitude (Gilchrist et al., 2009). The metal-sulfide-rich tailings also produce contaminated soils with pH < 4, organic matter < 2.5% and trace metals sequestered in soil oxides. A geochemical transect to test worst-case soil contamination showed that Cr, Co and Ni correlated positively with Mn, (r = 0.72, r = 0.89, r = 0.80, respectively), suggesting Mn-oxide sequestration and that Cu and Pb correlated with Fe (r = 0.76, r = 0.83, respectively), suggesting sequestration in goethite. Ubiquitous, yellow coating on the mine wastes, including jarosite and goethite, is a carrier of the metals. Geochemical and {mu}-SXRF analyses determined Cu to be the major soil contaminant, {mu}-SXRF also demonstrated that the heterogeneous nature of the soil chemistry at the micro-meter scale is self-similar to those in the bulk soil samples. Generally metals decreased, with some fluctuations, rapidly downslope through suspension of fines and dissolution in AMD leaving the area of substantial contamination << 0.5 km from the source.

  16. Geochemical features of sulfides from the Deyin-1 hydrothermal field at the southern Mid-Atlantic Ridge near 15°S

    Science.gov (United States)

    Wang, Shujie; Li, Huaiming; Zhai, Shikui; Yu, Zenghui; Cai, Zongwei

    2017-12-01

    In this study, geochemical compositions of elements in sulfide samples collected from the Deyin-1 hydrothermal field near the 15°S southern Mid-Atlantic Ridge (SMAR) were analyzed by the X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) to examine the enrichment regulations of ore-forming elements and hydrothermal mineralization. These sulfide precipitates can be classified macroscopically into three types: Fe-rich sulfide, Fe-Cu-rich sulfide and Fe-Zn-rich sulfide, and are characterized by the enrichment of base metal elements along with a sequence of Fe>Zn>Cu. Compared with sulfides from other hydrothermal fields on MAR, Zn concentrations of sulfides in the research area are significantly high, while Cu concentrations are relatively low. For all major, trace or rare-earth elements (REE), their concentrations and related characteristic parameters exhibit significant variations (up to one or two orders of magnitude), which indicates the sulfides from different hydrothermal vents or even a same station were formed at different stages of hydrothermal mineralization, and suggests the variations of chemical compositions of the hydrothermal fluid with respect to time. The hydrothermal temperatures of sulfides precipitation decreased gradually from station TVG10 (st.TVG10) to st.TVG12, and to st.TVG11, indicating that the precipitation of hydrothermal sulfides is subjected to conditions changed from high temperature to low temperature, and that the hydrothermal activity of study area was at the late stage of a general trend of evolution from strong to weak. The abnormally low concentrations of REE in sulfides and their similar chondrite-normalized REE patterns show that REEs in all sulfides were derived from a same source, but underwent different processes of migration or enrichment, or sulfides were formed at different stages of hydrothermal mineralization. The sulfides collected from the active hydrothermal vent were

  17. A study on the mechanism of stress corrosion cracking of duplex stainless steels in hot alkaline-sulfide solution

    Science.gov (United States)

    Chasse, Kevin Robert

    . Environments having different ionic concentrations of inorganic salts, i.e. sodium hydroxide, sodium sulfide, and sodium chloride, were used to understand the effect of liquor alkalinity, percent sulfidity, and chloride content on the corrosion and SCC behavior. Hydrogen embrittlement of S32205 was studied to understand the electrochemical conditions and fracture features associated with this failure mode. The results showed that there is an appreciable increase in the susceptibility of DSS to SCC in the presence of sulfide and chloride in hot alkaline environments. Sulfide and chloride adsorption at active sites on the metal surface caused unstable passivity and defective film formation. Chloride and sulfide available at the electrolyte/film surface reduced the charge transfer resistance and shifted the response of the films to lower frequencies indicating the films became more defective. The surface films had an outer, discontinuous layer, and an inner, barrier layer. Fe, Mo, and Mn were selectively dissolved in hot alkaline environments. The onset of SCC was related to the extent of selective dissolution and was consistent with a slip-step dissolution mechanism. Selective corrosion of the austenite phase depended on percent sulfidity and liquor alkalinity. Chlorides enhanced crack initiation and coalescence along the austenite/ferrite boundaries. Crack initiation and transgranular growth strongly depended on the phase distribution in the banded microstructure of DSS. These findings will augment understanding of SCC in this alloy-environment combination and facilitate materials selection in hot alkaline-sulfide environments, particularly in the petrochemical, nuclear, chemical processing, and pulp and paper industries.

  18. Improvement to a production process of rare earth hydroxide by treatment of ores containing rare earth phosphates

    International Nuclear Information System (INIS)

    Fabre, F.; Lambert, A.; Tognet, J.P.

    1987-01-01

    Ore is treated by an aqueous solution of alkaline metal hydroxide and solid rare earth hydroxides are separated. For recycling the alkaline hydroxide after concentration the alkaline metal phosphate is crystallized and then alkaline earth metal hydroxide is added to avoid silicates concentration in the recycled solution [fr

  19. Magmatic sulfide-rich nickel-copper deposits related to picrite and (or) tholeiitic basalt dike-sill complexes-A preliminary deposit model

    Science.gov (United States)

    Schulz, Klaus J.; Chandler, Val W.; Nicholson, Suzanne W.; Piatak, Nadine M.; Seal, Robert R.; Woodruff, Laurel G.; Zientek, Michael L.

    2010-01-01

    Magmatic sulfide deposits containing nickel (Ni) and copper (Cu), with or without (?) platinum-group elements (PGEs), account for approximately 60 percent of the world's Ni production and are active exploration targets in the United States and elsewhere. On the basis of their principal metal production, magmatic sulfide deposits in mafic rocks can be divided into two major types: those that are sulfide-rich, typically with 10 to 90 percent sulfide minerals, and have economic value primarily because of their Ni and Cu contents; and those that are sulfide-poor, typically with 0.5 to 5 percent sulfide minerals, and are exploited principally for PGE. Because the purpose of this deposit model is to facilitate the assessment for undiscovered, potentially economic magmatic Ni-Cu?PGE sulfide deposits in the United States, it addresses only those deposits of economic significance that are likely to occur in the United States on the basis of known geology. Thus, this model focuses on deposits hosted by small- to medium-sized mafic and (or) ultramafic dikes and sills that are related to picrite and tholeiitic basalt magmatic systems generally emplaced in continental settings as a component of large igneous provinces (LIPs). World-class examples (those containing greater than 1 million tons Ni) of this deposit type include deposits at Noril'sk-Talnakh (Russia), Jinchuan (China), Pechenga (Russia), Voisey's Bay (Canada), and Kabanga (Tanzania). In the United States, this deposit type is represented by the Eagle deposit in northern Michigan, currently under development by Kennecott Minerals.

  20. Synthesis of sub-micron silver and silver sulfide particles via solvothermal silver azide decomposition

    International Nuclear Information System (INIS)

    Grocholl, Luke; Wang Jianjun; Gillan, Edward G.

    2003-01-01

    Many transition-metal azides are thermodynamically unstable with respect to the elements and thus, may serve as energetic precursor sources in nanoscale metal particle synthesis. This report describes the use of silver azide (AgN 3 ) in nonaqueous, solvothermal decomposition reactions to produce crystalline sub-micron silver particles and interconnected structures. The thermal decomposition of AgN 3 directly produces silver and N 2 and no secondary chemical reducing agent is required. This solvothermal conversion was examined in toluene, tetrahydrofuran (THF), and trioctylamine below 250 deg. C. The coordinating solvents produced the smallest particles (150-500 nm), while the toluene reaction products were near 1 μm in size. The addition of soluble elemental sulfur to the THF reaction results in the growth of silver sulfide particles near 1 μm in size. The silver and Ag 2 S products are crystalline by X-ray diffraction and show some faceting by scanning electron microscopy

  1. Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand

    Directory of Open Access Journals (Sweden)

    Katrin eHug

    2014-11-01

    Full Text Available Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand. Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic, and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

  2. Audio magnetotelluric Investigation of Sulfide Mineralization in ...

    Indian Academy of Sciences (India)

    70

    and Research (AMDER) for concealed uranium and rare-earth metals in SSZ. AMDER also carried out several airborne gamma-ray and radiometric surveys for uranium and rare earth metals over possible carbonatite-alkaline rock complexes (Krishnamurthy et al. 2004). Unfortunately, until today only geophysical survey i.e. ...

  3. Explanation for many of the unusual features of the massive sulfide deposits of the Iberian pyrite belt

    Science.gov (United States)

    Solomon, M.; Tornos, F.; Gaspar, O. C.

    2002-01-01

    Newly published fluid-inclusion data from quartz in stockwork veins beneath seven massive sulfide lenses in the Iberian pyrite belt suggest that the lenses were formed from fluids that on reaching the sea reversed buoyancy and ponded in basins. Sulfides quenched in the resulting brine pool would have settled to form a sulfide mud. This process provides a relatively efficient trapping mechanism for metal in the fluids and effectively excludes ambient seawater, accounting for the deposits tending to have the characteristics of large size, sheet-like form, absence of relict chimney structures, and a mineral content characterized by pyrite-arsenopyrite, and absence or scarcity of barite, marcasite, and Fe oxides. If total S was less than total metals in the stockwork fluids, some or all of the more soluble Zn and Pb could have been swept from the basin at the overflow, accounting for the variable but generally low Zn and Pb contents of the ores. The lack of sedimentary source for the high salinities implicates magmatic intrusions, possibly similar to those related to Sn-W mineralization.

  4. Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

    Science.gov (United States)

    Seal, R.R.; Hammarstrom, J.M.; Johnson, A.N.; Piatak, N.M.; Wandless, G.A.

    2008-01-01

    The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

  5. Alkali-metal hydrogen selenate-phosphates M2H3(SeO4)(PO4) (M = Rb or K) and M4H5(SeO4)3(PO4) (M = K or Na)

    International Nuclear Information System (INIS)

    Troyanov, S.I.; Morozov, I.V.; Rybakov, V.B.; Kemnitz, E.

    2000-01-01

    Crystalline hydrogen selenate-phosphates M 2 H 3 (SeO 4 )(PO 4 ) [M = Rb (I) or K (II)] and M 4 H 5 (SeO 4 ) 3 (PO 4 ) [M = K (III) or Na (IV)] were obtained by reactions of Rb, K, and Na carbonates with mixtures of selenic and phosphoric acid solutions. The X-ray structure study of single crystals revealed that I and II are isostructural (sp. gr. Pn). In these structures, SeO 4 and H 3 PO 4 tetrahedra are linked by hydrogen bonds to form corrugated layers. Structures III and IV (sp. gr. P1-bar) have similar arrangements of non-hydrogen atoms but different hydrogen-bond systems. In III K 4 (HSeO 4 ) 2 {H[H(Se,P)O 4 ] 2 }, the HSeO 4 groups branch from the infinite anionic {H[H(Se,P)O 4 ] 2 } chains. In IV = Na 4 [H(SeO 4 ) 2 ]{H[H 1.5 (Se,P)O 4 ] 2 }, the anionic {H[H 1.5 (Se,P)O 4 ] 2 } chains are crosslinked by hydrogen bonds formed by the [H(SeO 4 ) 2 ] dimers

  6. X-ray absorption spectroscopy on phosphoric-salt pellets. Determination of the geometric and electronic structure of metal-oxide doped sodium-phosphate glasses; Roentgenabsorptionsspektroskopie an Phosphorsalzperlen. Bestimmung der geometrischen und elektronischen Struktur von metalloxid-dotierten Natriumphosphatglaesern

    Energy Technology Data Exchange (ETDEWEB)

    Brendebach, B.

    2004-02-01

    Sodium metaphosphate glasses doped with transition metal oxides show characteristic colors. X-ray absorption spectroscopy (XAS) investigations provide information whether the coloration stems from different electronic transitions or changes in the geometrical structure of the glasses. Even though the violet color of MnO{sub y}-doped glasses is considered as an evidence for Mn{sup 3+}-ions, Mn K-XAS reveals that the majority of the manganese ions are in the oxidation state +II and have a mixed coordination of four and six oxygen atoms, respectively. The oxygen coordination around the nickel ions in NiO-doped glasses with different metall oxide concentrations is always six. The change of color from citreous to auburn with increasing nickel oxide content is attributed to a systematic change in the bonding characteristic from mainly ionic-like to a small but significant contribution of covalent-like bonding. Analysis of higher coordination shells provides no indication of the formation of metal oxide clusters. (orig.)

  7. Hydrogen sulfide and nitric oxide metabolites in the blood of free-ranging brown bears and their potential roles in hibernation

    DEFF Research Database (Denmark)

    Revsbech, Inge G; Shen, Xinggui; Chakravarti, Ritu

    2014-01-01

    During winter hibernation, brown bears (Ursus arctos) lie in dens for half a year without eating while their basal metabolism is largely suppressed. To understand the underlying mechanisms of metabolic depression in hibernation, we measured type and content of blood metabolites of two ubiquitous...... inhibitors of mitochondrial respiration, hydrogen sulfide (H2S) and nitric oxide (NO), in winter-hibernating and summer-active free-ranging Scandinavian brown bears. We found that levels of sulfide metabolites were overall similar in summer-active and hibernating bears but their composition in the plasma...... cells of hibernating bears. In contrast, circulating nitrite and erythrocytic S-nitrosation of glyceraldehyde-3-phosphate dehydrogenase, taken as markers of NO metabolism, did not change appreciably. Our findings reveal that remodeling of H2S metabolism and enhanced intracellular GSH levels...

  8. Heavy metals in the spinal cord of normal rats and of animals treated with chelating agents

    DEFF Research Database (Denmark)

    Schrøder, H D; Fjerdingstad, E; Danscher, G

    1978-01-01

    of various levels along the cranio-caudal axis of the rat spinal cord revealed differences in the heavy metal content. The Timm sulfide silver staining method has demonstrated that metals in the spinal cord have a distinct regional distribution. To obtain a differentiation between the stainable metals...

  9. The effect of waste water treatment on river metal concentrations: removal or enrichment?

    NARCIS (Netherlands)

    Teuchies, J.; Bervoets, L.; Cox, T.J.S.; Meire, P.; de Deckere, E.

    2011-01-01

    Purpose Discharge of untreated domestic and industrial waste in many European rivers resulted in low oxygen concentrations and contamination with trace metals, often concentrated in sediments. Under these anoxic conditions, the formation of insoluble metal sulfides is known to reduce metal

  10. Calcium phosphates for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Canillas, M.; Pena, P.; Aza, A.H. de; Rodriguez, M.A.

    2017-07-01

    The history of calcium phosphates in the medicine field starts in 1769 when the first evidence of its existence in the bone tissue is discovered. Since then, the interest for calcium phosphates has increased among the scientific community. Their study has been developed in parallel with new advances in materials sciences, medicine or tissue engineering areas. Bone tissue engineering is the field where calcium phosphates have had a great importance. While the first bioceramics are selected according to bioinert, biocompatibility and mechanical properties with the aim to replace bone tissue damaged, calcium phosphates open the way to the bone tissue regeneration challenge. Nowadays, they are present in the majority of commercial products directed to repair or regenerate damaged bone tissue. Finally, in the last few decades, they have been suggested and studied as drug delivering devices and as vehicles of DNA and RNA for the future generation therapies. (Author)

  11. Calcium phosphates for biomedical applications

    Directory of Open Access Journals (Sweden)

    Maria Canillas

    2017-05-01

    Full Text Available The history of calcium phosphates in the medicine field starts in 1769 when the first evidence of its existence in the bone tissue is discovered. Since then, the interest for calcium phosphates has increased among the scientific community. Their study has been developed in parallel with new advances in materials sciences, medicine or tissue engineering areas. Bone tissue engineering is the field where calcium phosphates have had a great importance. While the first bioceramics are selected according to bioinert, biocompatibility and mechanical properties with the aim to replace bone tissue damaged, calcium phosphates open the way to the bone tissue regeneration challenge. Nowadays, they are present in the majority of commercial products directed to repair or regenerate damaged bone tissue. Finally, in the last few decades, they have been suggested and studied as drug delivering devices and as vehicles of DNA and RNA for the future generation therapies.

  12. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Southwest Sciences proposes to develop small, low power instrumentation for the real-time direct measurement of carbonyl sulfide (OCS) in the atmosphere, especially...

  13. Desulfurizing Difluorination Reaction of Benzyl Sulfides Using IF5

    OpenAIRE

    Fukuhara, Tadahito; Hara, Shoji

    2009-01-01

    A desulfurizing difluorination reaction of benzyl sulfides having a functional group such as an ester, a ketone, a nitrile, or an amide was performed by a reaction with IF5. Consequently, gem-difluoro compounds could be obtained selectively.

  14. The electrical properties of semiconducting vanadium phosphate glasses

    International Nuclear Information System (INIS)

    Moridi, G.R.; Hogarth, C.A.; Hekmat Shooar, N.H.

    1984-01-01

    Vanadium phosphate glasses are a group of oxide glasses which show the semiconducting behaviour. In contrast to the conventional glasses, the conduction mechanism in these glasses is electronic, rather than being ionic. Since 1954, when the first paper appeared on the semiconducting properties of these glasses, much work has been carried out on transition-metal-oxide glasses in general, and vanadium phosphate glasses in particular. The mechanism of conduction is basicaly due to the transport of electrons between the transition-metal ions in different valency states. In the present paper, we have reviewed the previous works on the electrical characteristics of P 2 O 5 -V 2 O 5 glasses and also discussed the current theoretical ideas relevant for the interpretation of the experimental data

  15. Ambient Volatility of Triethyl Phosphate

    Science.gov (United States)

    2017-08-01

    AMBIENT VOLATILITY OF TRIETHYL PHOSPHATE ECBC-TR-1476 James H. Buchanan John J. Mahle RESEARCH AND...2017 2. REPORT TYPE Final 3. DATES COVERED (From - To) Oct 2016 – Jan 2017 4. TITLE: Ambient Volatility of Triethyl Phosphate 5a. CONTRACT...humidity on TEPO volatility is nearly as predicted by Raoult’s law, that is, vapor pressure suppression is proportional to ambient relative humidity. An

  16. Development of sulfide calibration standards for the laser ablation inductively-coupled plasma mass spectrometry technique

    Science.gov (United States)

    Wilson, S.A.; Ridley, W.I.; Koenig, A.E.

    2002-01-01

    The requirements of standard materials for LA-ICP-MS analysis have been difficult to meet for the determination of trace elements in sulfides. We describe a method for the production of synthetic sulfides by precipitation from solution. The method is detailed by the production of approximately 200 g of a material, PS-1, with a suite of chalcophilic trace elements in an Fe-Zn-Cu-S matrix. Preliminary composition data, together with an evaluation of the homogeneity for individual elements, suggests that this type of material meets the requirements for a sulfide calibration standard that allows for quantitative analysis. Contamination of the standard with Na suggests that H2S gas may prove a better sulfur source for future experiments. We recommend that calibration data be collected in whatever mode is closest to that employed for the analysis of the unknown material, because of variable fractionation effects as a function of analytical mode. For instance, if individual spot analyses are attempted on unknown sample, then a raster of several individual spot analyses, not a continuous scan, should be collected and averaged for the standard. Hg and Au are exceptions to the above and calibration data should always be collected in a scanning mode. Au is more heterogeneously distributed than other trace metals and large-area scans are required to provide an average value for calibration purposes. We emphasize that the values given in Table 1 are preliminary values. Further chemical characterization of this standard, through a round-robin analysis program, will allow the USGS to provide both certified and recommended values for individual elements. The USGS has developed PS-1 as a potential new LA-ICP-MS standard for use by the analytical community, and requests for this material should be addressed to S. Wilson. However, it is stressed that an important aspect of the method described here is the flexibility for individual investigators to produce sulfides with a wide range

  17. Synthesis of Black and Red Mercury Sulfide Nano-Powder by Traditional Indian Method for Biomedical Application

    International Nuclear Information System (INIS)

    Padhi, Payodhar; Sahoo, G.; Das, K.; Ghosh, Sudipto; Panigrahi, S. C.

    2008-01-01

    The use of metals and minerals in the traditional Indian system of medicine known as aired is very common and is practiced since seventh century B.C. Metals were reduced to calcined powder form for medicinal purpose. For detoxification, a further step of purification of the metals and minerals with different vegetable extracts was practiced. The people of East India were using mercury and its sulfide as medicine. Gradually this secret was leaked to Arabic physicians who used mercury in skin ointment. Subsequently Italian Physicians adopted Arabic prescriptions of mercurial ointments for skin diseases. In the olden days, metals and minerals were impregnated with decoction and juice of vegetables and animal products like milk and fat for purification. These were then reduced to fine particles by milling with a pestle and mortar. It was known by then that the fineness of the powder had a significant influence on the color, texture, and medicinal properties as is cited by Charak. Nagarjun studied in detail the processing of metals and minerals, particularly mercury and the influence of the processing parameters on the medicinal values. Mercury is unique in many aspects. Indian alchemy developed a wide variety a chemical processes for the ostensible transmutation of metals and preparation of elixir of life, in which mercury occupied a prime position .The present investigation attempts to use the traditional methods as prescribed in the ancient texts to prepare mercury sulfide in both red and black form for medicinal use. XRD, SEM and HRTEM investigations of the sulfides obtained shows that the ancient Indians were able to produce nano-sized powders. Possibly this may be taken as the earliest application of the production and use of nano powder. The study proves that even in ancient time the knowledge of nano particle synthesis was prevalent and used to enhance effectiveness of medicines. Further mercury in the free form is not acceptable in medicines. The ancient

  18. short communication agronomic effectiveness of novel phosphate

    African Journals Online (AJOL)

    A review of literature shows that work on non-conventional phosphate fertilisers has been done exclusively on sedimentary phosphate rocks. The potential of using novel phosphate fertiliser materials derived from unreactive igneous Dorowa (Zimbabwe) phosphate rock was investigated in a greenhouse experiment.

  19. Phosphate solubilization and multiple plant growth promoting ...

    African Journals Online (AJOL)

    Phosphate solubilizing efficiencies of the strains were analyzed using different insoluble phosphorus sources and the results show that most isolates released a substantial amount of soluble phosphate from tricalcium phosphate, rock phosphate and bone meal. Screening for multiple plant growth promoting attributes ...

  20. 21 CFR 573.320 - Diammonium phosphate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Diammonium phosphate. 573.320 Section 573.320 Food... Additive Listing § 573.320 Diammonium phosphate. The food additive diammonium phosphate may be safely used... crude protein from diammonium phosphate, adequate directions for use and a prominent statement, “Warning...