Conductive copper sulfide thin films on polyimide foils

NASA Astrophysics Data System (ADS)

Cardoso, J.; Gomez Daza, O.; Ixtlilco, L.; Nair, M. T. S.; Nair, P. K.

2001-02-01

Kapton polyimide is known for its high thermal stability, >400 °C. Copper sulfide thin films of 75 and 100 nm thickness were coated on DuPont Kapton HN polyimide foils of 25 µm thickness by floating them on a chemical bath containing copper complexes and thiourea. The coated foils were annealed at 150-400 °C in nitrogen, converting the coating from CuS to Cu1.8S. The sheet resistance of the annealed coatings (100 nm) is 10-50 Ω/□ and electrical conductivity, 2-10×103 Ω-1 cm- 1, which remain nearly constant even after the foils are immersed in 0.1-1 M HCl for 30-120 min. The coated polyimide has a transmittance (25-35%) peak located in the wavelength region 550-600 nm, with transmittance dropping to near zero below 450 nm and below 10% in the near-infrared spectral region. These characteristics are relevant in solar radiation control applications. The coated foils might also be used as conductive substrates for electrolytic deposition of metals and semiconductors and for optoelectronic device structures.

Removal of copper from ferrous scrap

DOEpatents

Blander, M.; Sinha, S.N.

1987-07-30

A process for removing copper from ferrous or other metal scrap in which the scrap is contacted with a polyvalent metal sulfide slag in the presence of an excess of copper-sulfide forming additive to convert the copper to copper sulfide which is extracted into the slag to provide a ratio of copper in the slag to copper in the metal scrap of at least about 10.

Removal of copper from ferrous scrap

DOEpatents

Blander, M.; Sinha, S.N.

1990-05-15

A process for removing copper from ferrous or other metal scrap in which the scrap is contacted with a polyvalent metal sulfide slag in the presence of an excess of copper-sulfide forming additive to convert the copper to copper sulfide which is extracted into the slag to provide a ratio of copper in the slag to copper in the metal scrap of at least about 10.

Removal of copper from ferrous scrap

DOEpatents

Blander, Milton; Sinha, Shome N.

1990-01-01

A process for removing copper from ferrous or other metal scrap in which the scrap is contacted with a polyvalent metal sulfide slag in the presence of an excess of copper-sulfide forming additive to convert the copper to copper sulfide which is extracted into the slag to provide a ratio of copper in the slag to copper in the metal scrap of at least about 10.

Structural, optical and electrical properties of copper antimony sulfide thin films grown by a citrate-assisted single chemical bath deposition

NASA Astrophysics Data System (ADS)

Loranca-Ramos, F. E.; Diliegros-Godines, C. J.; Silva González, R.; Pal, Mou

2018-01-01

Copper antimony sulfide (CAS) has been proposed as low toxicity and earth abundant absorber materials for thin film photovoltaics due to their suitable optical band gap, high absorption coefficient and p-type electrical conductivity. The present work reports the formation of copper antimony sulfide by chemical bath deposition using sodium citrate as a complexing agent. We show that by tuning the annealing condition, one can obtain either chalcostibite or tetrahedrite phase. However, the main challenge was co-deposition of copper and antimony as ternary sulfides from a single chemical bath due to the distinct chemical behavior of these metals. The as-deposited films were subjected to several trials of thermal treatment using different temperatures and time to find the optimized annealing condition. The films were characterized by different techniques including Raman spectroscopy, X-ray diffraction (XRD), profilometer, scanning electron microscopy (SEM), UV-vis spectrophotometer, and Hall Effect measurements. The results show that the formation of chalcostibite and tetrahedrite phases is highly sensitive to annealing conditions. The electrical properties obtained for the chalcostibite films varied as the annealing temperature increases from 280 to 350 °C: hole concentration (n) = 1017-1018 cm-3, resistivity (ρ) = 1.74-2.14 Ωcm and carrier mobility (μ) = 4.7-9.26 cm2/Vseg. While for the tetrahedrite films, the electrical properties were n = 5 × 1019 cm-3, μ = 18.24 cm2/Vseg, and ρ = 5.8 × 10-3 Ωcm. A possible mechanism for the formation of ternary copper antimony sulfide has also been proposed.

A pyrazolyl-based thiolato single-source precursor for the selective synthesis of isotropic copper-deficient copper(I) sulfide nanocrystals: synthesis, optical and photocatalytic activity

NASA Astrophysics Data System (ADS)

Mondal, Gopinath; Santra, Ananyakumari; Bera, Pradip; Acharjya, Moumita; Jana, Sumanta; Chattopadhyay, Dipankar; Mondal, Anup; Seok, Sang Il; Bera, Pulakesh

2016-10-01

Hexagonal copper-deficient copper(I) sulfide (Cu2- x S, x = 0.03, 0.2) nanocrystals (NCs) are synthesized from a newly prepared single-source precursor (SP), [Cu(bdpa)2][CuCl2], where bdpa is benzyl 3,5-dimethyl-pyrazole-1-carbodithioate. The SP is crystallized with space group Pī and possesses a distorted tetrahedron structure with a CuN2S2 chromophore where the central copper is in +1 oxidation state. Distortion in copper(I) structure and the low decomposition temperature of SP make it favorable for the low-temperature solvent-assisted selective growth of high-copper content sulfides. The nucleation and growth of Cu2- x S ( x = 0.03, 0.2) are effectively controlled by the SP and the solvent in the solvothermal decomposition process. During decomposition, fragment benzyl thiol (PhCH2SH) from SP effectively passivates the nucleus leading to spherical nanocrystals. Further, solvent plays an important role in the selective thermochemical transformation of CuI-complex to Cu2- x S ( x = 0.03, 0.2) NCs. The chelating binders (solvent) like ethylene diamine (EN) and ethylene glycol (EG) prefer to form spherical Cu1.97S nanoparticles (djurleite), whereas nonchelating hydrazine hydrate (HH) shows the tendency to furnish hexagonal platelets of copper-deficient Cu1.8S. The optical band gap values (2.25-2.50 eV) show quantum confinement effect in the structure. The synthesized NCs display excellent catalytic activity ( 87 %) toward photodegradation of organic dyes like Congo Red (CR) and Methylene Blue (MB).

A review of the fundamental studies of the copper activation mechanisms for selective flotation of the sulfide minerals, sphalerite and pyrite.

PubMed

Chandra, A P; Gerson, A R

2009-01-30

A review of the considerable, but often contradictory, literature examining the specific surface reactions associated with copper adsorption onto the common metal sulfide minerals sphalerite, (Zn,Fe)S, and pyrite (FeS(2)), and the effect of the co-location of the two minerals is presented. Copper "activation", involving the surface adsorption of copper species from solution onto mineral surfaces to activate the surface for hydrophobic collector attachment, is an important step in the flotation and separation of minerals in an ore. Due to the complexity of metal sulfide mineral containing systems this activation process and the emergence of activation products on the mineral surfaces are not fully understood for most sulfide minerals even after decades of research. Factors such as copper concentration, activation time, pH, surface charge, extent of pre-oxidation, water and surface contaminants, pulp potential and galvanic interactions are important factors affecting copper activation of sphalerite and pyrite. A high pH, the correct reagent concentration and activation time and a short time delay between reagent additions is favourable for separation of sphalerite from pyrite. Sufficient oxidation potential is also needed (through O(2) conditioning) to maintain effective galvanic interactions between sphalerite and pyrite. This ensures pyrite is sufficiently depressed while sphalerite floats. Good water quality with low concentrations of contaminant ions, such as Pb(2+)and Fe(2+), is also needed to limit inadvertent activation and flotation of pyrite into zinc concentrates. Selectivity can further be increased and reagent use minimised by opting for inert grinding and by carefully choosing selective pyrite depressants such as sulfoxy or cyanide reagents. Studies that approximate plant conditions are essential for the development of better separation techniques and methodologies. Improved experimental approaches and surface sensitive techniques with high spatial

Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

PubMed

Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

2012-06-27

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

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

He, Kai; Yao, Zhenpeng; Hwang, Sooyeon

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van dermore » Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.« less

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes

DOE PAGES

He, Kai; Yao, Zhenpeng; Hwang, Sooyeon; ...

2017-08-11

Two-dimensional (2D) transition metal chalcogenides have been widely studied and utilized as electrode materials for lithium ion batteries due to their unique layered structures to accommodate reversible lithium insertion. Real-time observation and mechanistic understanding of the phase transformations during lithiation of these materials are critically important for improving battery performance by controlling structures and reaction pathways. Here, we use in situ transmission electron microscopy methods to study the structural, morphological, and chemical evolutions in individual copper sulfide (CuS) nanoflakes during lithiation. We report a highly kinetically driven phase transformation in which lithium ions rapidly intercalate into the 2D van dermore » Waals-stacked interlayers in the initial stage, and further lithiation induces the Cu extrusion via a displacement reaction mechanism that is different from the typical conversion reactions. Density functional theory calculations have confirmed both the thermodynamically favored and the kinetically driven reaction pathways. Lastly, our findings elucidate the reaction pathways of the Li/CuS system under nonequilibrium conditions and provide valuable insight into the atomistic lithiation mechanisms of transition metal sulfides in general.« less

Growth evolution and phase transition from chalcocite to digenite in nanocrystalline copper sulfide: Morphological, optical and electrical properties

PubMed Central

Quintana-Ramirez, Priscilla Vasthi; Santos-Cruz, José; Vega-González, Marina; Martínez-Alvarez, Omar; Castaño-Meneses, Víctor Manuel; Acosta-Torres, Laura Susana; de la Fuente-Hernández, Javier

2014-01-01

Summary Copper sulfide is a promising p-type inorganic semiconductor for optoelectronic devices such as solar cells, due its small band gap energy and its electrical properties. In this work nanocrystalline copper sulfide (CuxS), with two stoichiometric ratios (x = 2, 1.8) was obtained by one-pot synthesis at 220, 230, 240 and 260 °C in an organic solvent and amorphous CuxS was obtained in aqueous solution. Nanoparticle-like nucleation centers are formed at lower temperatures (220 °C), mixtures of morphologies (nanorods, nanodisks and nanoprisms) are seen at 230 and 240 °C, in which the nanodisks are predominant, while big hexagonal/prismatic crystals are obtained at 260 °C according to TEM results. A mixture of chalcocite and digenite phases was found at 230 and 240 °C, while a clear transition to a pure digenite phase was seen at 260 °C. The evolution of morphology and transition of phases is consistent to the electrical, optical, and morphological properties of the copper sulfide. In fact, digenite Cu1.8S is less resistive (346 Ω/sq) and has a lower energy band gap (1.6 eV) than chalcocite Cu2S (5.72 × 105 Ω/sq, 1.87 eV). Low resistivity was also obtained in CuxS synthesized in aqueous solution, despite its amorphous structure. All CuxS products could be promising for optoelectronic applications. PMID:25247136

Growth evolution and phase transition from chalcocite to digenite in nanocrystalline copper sulfide: Morphological, optical and electrical properties.

PubMed

Quintana-Ramirez, Priscilla Vasthi; Arenas-Arrocena, Ma Concepción; Santos-Cruz, José; Vega-González, Marina; Martínez-Alvarez, Omar; Castaño-Meneses, Víctor Manuel; Acosta-Torres, Laura Susana; de la Fuente-Hernández, Javier

2014-01-01

Copper sulfide is a promising p-type inorganic semiconductor for optoelectronic devices such as solar cells, due its small band gap energy and its electrical properties. In this work nanocrystalline copper sulfide (Cu x S), with two stoichiometric ratios (x = 2, 1.8) was obtained by one-pot synthesis at 220, 230, 240 and 260 °C in an organic solvent and amorphous Cu x S was obtained in aqueous solution. Nanoparticle-like nucleation centers are formed at lower temperatures (220 °C), mixtures of morphologies (nanorods, nanodisks and nanoprisms) are seen at 230 and 240 °C, in which the nanodisks are predominant, while big hexagonal/prismatic crystals are obtained at 260 °C according to TEM results. A mixture of chalcocite and digenite phases was found at 230 and 240 °C, while a clear transition to a pure digenite phase was seen at 260 °C. The evolution of morphology and transition of phases is consistent to the electrical, optical, and morphological properties of the copper sulfide. In fact, digenite Cu1.8S is less resistive (346 Ω/sq) and has a lower energy band gap (1.6 eV) than chalcocite Cu2S (5.72 × 10(5) Ω/sq, 1.87 eV). Low resistivity was also obtained in Cu x S synthesized in aqueous solution, despite its amorphous structure. All Cu x S products could be promising for optoelectronic applications.

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 1: Copper-Catalyzed Oxidation.

PubMed

Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

2016-05-25

Sulfidic off-odors as a result of hydrogen sulfide (H2S) and low-molecular-weight thiols are commonly encountered in wine production. These odors are usually removed by the process of Cu(II) fining, a process that remains poorly understood. The present study aims to elucidate the underlying mechanisms by which Cu(II) interacts with H2S and thiol compounds (RSH) under wine-like conditions. Copper complex formation was monitored along with H2S, thiol, oxygen, and acetaldehyde concentrations after the addition of Cu(II) (50 or 100 μM) to air-saturated model wine solutions containing H2S, cysteine, 6-sulfanylhexan-1-ol, or 3-sulfanylhexan-1-ol (300 μM each). The presence of H2S and thiols in excess to Cu(II) led to the rapid formation of ∼1.4:1 H2S/Cu and ∼2:1 thiol/Cu complexes, resulting in the oxidation of H2S and thiols and reduction of Cu(II) to Cu(I), which reacted with oxygen. H2S was observed to initially oxidize rather than form insoluble copper sulfide. The proposed reaction mechanisms provide insight into the extent to which H2S can be selectively removed in the presence of thiols in wine.

Bioflotation of sulfide minerals with Acidithiobacillus ferrooxidans in relation to copper activation and surface oxidation.

PubMed

Pecina-Treviño, E T; Ramos-Escobedo, G T; Gallegos-Acevedo, P M; López-Saucedo, F J; Orrantia-Borunda, E

2012-09-01

Surface oxidation of sulfides and copper (Cu) activation are 2 of the main processes that determine the efficiency of flotation. The present study was developed with the intention to ascertain the role of the phenomena in the biomodification of sulfides by Acidithiobacillus ferrooxidans culture (cells and growth media) and their impact in bioflotation. Surface characteristics of chalcopyrite, sphalerite, and pyrrhotite, alone and in mixtures, after interaction with A. ferrooxidans were evaluated. Chalcopyrite floatability was increased substantially by biomodification, while bacteria depressed pyrrhotite floatability, favoring separation. The results showed that elemental sulfur concentration increased because of the oxidation generated by bacterial cells, the effect is intensified by the Fe(III) left in the culture and by galvanic contact. Acidithiobacillus ferrooxidans culture affects the Cu activation of sphalerite. The implications of elemental sulfur concentration and Cu activation of sphalerite are key factors that must be considered for the future development of sulfide bioflotation processes, since the depressive effect of cells could be counteracted by elemental sulfur generation.

In situ solvothermal growth of metal-organic framework-5 supported on porous copper foam for noninvasive sampling of plant volatile sulfides.

PubMed

Hu, Yuling; Lian, Haixian; Zhou, Langjun; Li, Gongke

2015-01-06

The present study reported on an in situ solvothermal growth method for immobilization of metal-organic framework MOF-5 on porous copper foam support for enrichment of plant volatile sulfides. The porous copper support impregnated with mother liquor of MOF-5 anchors the nucleation and growth of MOF crystallites at its surface, and its architecture of the three-dimensional channel enables accommodation of the MOF-5 crystallite seed. A continuous and well-intergrown MOF-5 layer, evidenced from scanning electron microscope imaging and X-ray diffraction, was successfully immobilized on the porous metal bar with good adhesion and high stability. Results show that the resultant MOF-5 coating was thermally stable up to 420 °C and robust enough for replicate extraction for at least 200 times. The MOF-5 bar was then applied to the headspace sorptive extraction of the volatile organic sulfur compounds in Chinese chive and garlic sprout in combination with thermal desorption-gas chromatography/mass spectrometry. It showed high extraction sensitivity and good selectivity to these plant volatile sulfides owing to the extraordinary porosity of the metal-organic framework as well as the interaction between the S-donor sites and the surface cations at the crystal edges. Several primary sulfur volatiles containing allyl methyl sulfide, dimethyl disulfide, diallyl sulfide, methyl allyl disulfide, and diallyl disulfide were quantified. Their limits of detection were found to be in the range of 0.2-1.7 μg/L. The organic sulfides were detected in the range of 6.0-23.8 μg/g with recoveries of 76.6-100.2% in Chinese chive and 11.4-54.6 μg/g with recoveries of 77.1-99.8% in garlic sprout. The results indicate the immobilization of MOF-5 on copper foam provides an efficient enrichment formats for noninvasive sampling of plant volatiles.

Synthesis of Copper-Antimony-Sulfide Nanocrystals for Solution-Processed Solar Cells.

PubMed

Suehiro, Satoshi; Horita, Keisuke; Yuasa, Masayoshi; Tanaka, Tooru; Fujita, Katsuhiko; Ishiwata, Yoichi; Shimanoe, Kengo; Kida, Tetsuya

2015-08-17

The p-type nanocrystals (NCs) of copper-based chalcogenides, such as CuInSe2 and Cu2ZnSnS4, have attracted increasing attention in photovoltaic applications due to their potential to produce cheap solution-processed solar cells. Herein, we report the synthesis of copper-antimony-sulfide (CAS) NCs with different crystal phases including CuSbS2, Cu3SbS4, and Cu12Sb4S13. In addition, their morphology, crystal phase, and optical properties were characterized using transmission electron microscopy, X-ray diffractometry, UV-vis-near-IR spectroscopy, and photoemission yield spectroscopy. The morphology, crystal phase, and electronic structure were significantly dependent on the chemical composition in the CAS system. Devices were fabricated using particulate films consisting of CAS NCs prepared by spin coating without a high-temperature treatment. The CAS NC-based devices exhibited a diode-like current-voltage characteristic when coupled with an n-type CdS layer. In particular, the CuSbS2 NC devices exhibited photovoltaic responses under simulated sunlight, demonstrating its applicability for use in solution-processed solar cells.

High-performance reagent modes for flotation recovery of platiniferous copper and nickel sulfides from hard-to-beneficiate ores

NASA Astrophysics Data System (ADS)

Matveeva, T. N.; Chanturiya, V. A.

2017-07-01

The paper presents the results of the recent research performed in IPKON Russian Academy of Sciences that deals with development and substantiation of new selective reagents for effective flotation recovery of non-ferrous and noble metals from refractory ores. The choice and development of new selective reagents PTTC, OPDTC, modified butylxanthate (BXm) and modified diethyl-dithiocarbamate (DEDTCm) to float platiniferous copper and nickel sulfide minerals from hard-to-beneficiate ores is substantiated. The mechanism of reagents adsorption and regulation of minerals floatability is discussed. The study of reagent modes indicates that by combining PTTC with the modified xanthate results in 6 - 7 % increase in the recovery of copper, nickel and PGM in the flotation of the low-sulfide platiniferous Cu-Ni ore from the Fedorovo-Panskoye deposit. The substitution of OPDTC for BX makes it possible to increase recovery of Pt by 13 %, Pd by 9 % and 2 - 4 times the noble metal content in the flotation concentrate.

Weathering of sulfidic shale and copper mine waste: Secondary minerals and metal cycling in Great Smoky Mountains National Park, Tennessee, and North Carolina, USA

USGS Publications Warehouse

Hammarstrom, J.M.; Seal, R.R.; Meier, A.L.; Jackson, J.C.

2003-01-01

Metal cycling via physical and chemical weathering of discrete sources (copper mines) and regional (non-point) sources (sulfide-rich shale) is evaluated by examining the mineralogy and chemistry of weathering products in Great Smoky Mountains National Park, Tennessee, and North Carolina, USA. The elements in copper mine waste, secondary minerals, stream sediments, and waters that are most likely to have negative impacts on aquatic ecosystems are aluminum, copper, zinc, and arsenic because these elements locally exceed toxicity guidelines for surface waters or for stream sediments. Acid-mine drainage has not developed in streams draining inactive copper mines. Acid-rock drainage and chemical weathering processes that accompany debris flows or human disturbances of sulfidic rocks are comparable to processes that develop acid-mine drainage elsewhere. Despite the high rainfall in the mountain range, sheltered areas and intermittent dry spells provide local venues for development of secondary weathering products that can impact aquatic ecosystems.

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

NASA Astrophysics Data System (ADS)

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

Microfluidic Synthesis and Biological Evaluation of Photothermal Biodegradable Copper Sulfide Nanoparticles.

PubMed

Ortiz de Solorzano, Isabel; Prieto, Martín; Mendoza, Gracia; Alejo, Teresa; Irusta, Silvia; Sebastian, Victor; Arruebo, Manuel

2016-08-24

The continuous synthesis of biodegradable photothermal copper sulfide nanoparticles has been carried out with the aid of a microfluidic platform. A comparative physicochemical characterization of the resulting products from the microreactor and from a conventional batch reactor has been performed. The microreactor is able to operate in a continuous manner and with a 4-fold reduction in the synthesis times compared to that of the conventional batch reactor producing nanoparticles with the same physicochemical requirements. Biodegradation subproducts obtained under simulated physiological conditions have been identified, and a complete cytotoxicological analysis on different cell lines was performed. The photothermal effect of those nanomaterials has been demonstrated in vitro as well as their ability to generate reactive oxygen species.

Responses of microbial community to pH stress in bioleaching of low grade copper sulfide.

PubMed

Wang, Yuguang; Li, Kai; Chen, Xinhua; Zhou, Hongbo

2018-02-01

The microbial diversity and dynamics in the leachates and on the ore surfaces of different depth of the column were analyzed during bioleaching of low grade copper sulfide at different pH, after inoculation with the same inoculum containing mesophiles and moderate thermophiles. The results indicate that low pH was beneficial to enhance copper extraction. The highest copper extraction (86%) was obtained when pH was controlled at 1.0-1.5. The microbial structures on the ore surfaces were independent of community structures in the leachate, even at the top portion of column. Microbial richness and evenness increased with decreasing pH during bioleaching. pH had significant effects on microbial community structure in the leachate and on the mineral surface of different depth of the column. Leptospirillum ferriphilum accounted for the highest proportions of the community at most times when pH was operated during bioleaching, especially at the end of run. Copyright © 2017 Elsevier Ltd. All rights reserved.

Novel Microbial Assemblages Dominate Weathered Sulfide-Bearing Rock from Copper-Nickel Deposits in the Duluth Complex, Minnesota, USA

PubMed Central

Lapakko, Kim A.; Wenz, Zachary J.; Olson, Michael C.; Roepke, Elizabeth W.; Novak, Paige J.; Bailey, Jake V.

2017-01-01

ABSTRACT The Duluth Complex in northeastern Minnesota hosts economically significant deposits of copper, nickel, and platinum group elements (PGEs). The primary sulfide mineralogy of these deposits includes the minerals pyrrhotite, chalcopyrite, pentlandite, and cubanite, and weathering experiments show that most sulfide-bearing rock from the Duluth Complex generates moderately acidic leachate (pH 4 to 6). Microorganisms are important catalysts for metal sulfide oxidation and could influence the quality of water from mines in the Duluth Complex. Nevertheless, compared with that of extremely acidic environments, much less is known about the microbial ecology of moderately acidic sulfide-bearing mine waste, and so existing information may have little relevance to those microorganisms catalyzing oxidation reactions in the Duluth Complex. Here, we characterized the microbial communities in decade-long weathering experiments (kinetic tests) conducted on crushed rock and tailings from the Duluth Complex. Analyses of 16S rRNA genes and transcripts showed that differences among microbial communities correspond to pH, rock type, and experimental treatment. Moreover, microbial communities from the weathered Duluth Complex rock were dominated by taxa that are not typically associated with acidic mine waste. The most abundant operational taxonomic units (OTUs) were from the genera Meiothermus and Sulfuriferula, as well as from diverse clades of uncultivated Chloroflexi, Acidobacteria, and Betaproteobacteria. Specific taxa, including putative sulfur-oxidizing Sulfuriferula spp., appeared to be primarily associated with Duluth Complex rock, but not pyrite-bearing rocks subjected to the same experimental treatment. We discuss the implications of these results for the microbial ecology of moderately acidic mine waste with low sulfide content, as well as for kinetic testing of mine waste. IMPORTANCE Economic sulfide mineral deposits in the Duluth Complex may represent the largest

Novel Microbial Assemblages Dominate Weathered Sulfide-Bearing Rock from Copper-Nickel Deposits in the Duluth Complex, Minnesota, USA.

PubMed

Jones, Daniel S; Lapakko, Kim A; Wenz, Zachary J; Olson, Michael C; Roepke, Elizabeth W; Sadowsky, Michael J; Novak, Paige J; Bailey, Jake V

2017-08-15

The Duluth Complex in northeastern Minnesota hosts economically significant deposits of copper, nickel, and platinum group elements (PGEs). The primary sulfide mineralogy of these deposits includes the minerals pyrrhotite, chalcopyrite, pentlandite, and cubanite, and weathering experiments show that most sulfide-bearing rock from the Duluth Complex generates moderately acidic leachate (pH 4 to 6). Microorganisms are important catalysts for metal sulfide oxidation and could influence the quality of water from mines in the Duluth Complex. Nevertheless, compared with that of extremely acidic environments, much less is known about the microbial ecology of moderately acidic sulfide-bearing mine waste, and so existing information may have little relevance to those microorganisms catalyzing oxidation reactions in the Duluth Complex. Here, we characterized the microbial communities in decade-long weathering experiments (kinetic tests) conducted on crushed rock and tailings from the Duluth Complex. Analyses of 16S rRNA genes and transcripts showed that differences among microbial communities correspond to pH, rock type, and experimental treatment. Moreover, microbial communities from the weathered Duluth Complex rock were dominated by taxa that are not typically associated with acidic mine waste. The most abundant operational taxonomic units (OTUs) were from the genera Meiothermus and Sulfuriferula , as well as from diverse clades of uncultivated Chloroflexi , Acidobacteria , and Betaproteobacteria Specific taxa, including putative sulfur-oxidizing Sulfuriferula spp., appeared to be primarily associated with Duluth Complex rock, but not pyrite-bearing rocks subjected to the same experimental treatment. We discuss the implications of these results for the microbial ecology of moderately acidic mine waste with low sulfide content, as well as for kinetic testing of mine waste. IMPORTANCE Economic sulfide mineral deposits in the Duluth Complex may represent the largest

Biological and Environmental Transformations of Copper-Based Nanomaterials

PubMed Central

Wang, Zhongying; Von Dem Bussche, Annette; Kabadi, Pranita K.; Kane, Agnes B.; Hurt, Robert H.

2013-01-01

Copper-based nanoparticles are an important class of materials with applications as catalysts, conductive inks, and antimicrobial agents. Environmental and safety issues are particularly important for copper-based nanomaterials because of their potential large-scale use and their high redox activity and toxicity reported from in vitro studies. Elemental nanocopper oxidizes readily upon atmospheric exposure during storage and use, so copper oxides are highly relevant phases to consider in studies of environmental and health impacts. Here we show that copper oxide nanoparticles undergo profound chemical transformations under conditions relevant to living systems and the natural environment. Copper oxide nanoparticle (CuO-NP) dissolution occurs at lysosomal pH (4-5), but not at neutral pH in pure water. Despite the near-neutral pH of cell culture medium, CuO-NPs undergo significant dissolution in media over time scales relevant to toxicity testing due to ligand-assisted ion release, in which amino acid complexation is an important contributor. Electron paramagnetic resonance (EPR) spectroscopy shows that dissolved copper in association with CuO-NPs are the primary redox-active species. CuO-NPs also undergo sulfidation by a dissolution-reprecipitation mechanism, and the new sulfide surfaces act as catalysts for sulfide oxidation. Copper sulfide NPs are found to be much less cytotoxic than CuO NPs, which is consistent with the very low solubility of CuS. Despite this low solubility of CuS, EPR studies show that sulfidated CuO continues to generate some ROS activity due to the release of free copper by H2O2 oxidation during the Fenton-chemistry-based EPR assay. While sulfidation can serve as a natural detoxification process for nanosilver and other chalcophile metals, our results suggest that sulfidation may not fully and permanently detoxify copper in biological or environmental compartments that contain reactive oxygen species. PMID:24032665

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

PubMed

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.

Enhanced reactive oxygen species through direct copper sulfide nanoparticle-doxorubicin complexation

NASA Astrophysics Data System (ADS)

Li, Yajuan; Cupo, Michela; Guo, Liangran; Scott, Julie; Chen, Yi-Tzai; Yan, Bingfang; Lu, Wei

2017-12-01

CuS-based nanostructures loading the chemotherapeutic agent doxorubicin (DOX) exerted excellent cancer photothermal chemotherapy under multi-external stimuli. The DOX loading was generally designed through electrostatic interaction or chemical linkers. However, the interaction between DOX molecules and CuS nanoparticles has not been investigated. In this work, we use PEGylated hollow copper sulfide nanoparticles (HCuSNPs) to directly load DOX through the DOX/Cu2+ chelation process. Distinctively, the synthesized PEG-HCuSNPs-DOX release the DOX/Cu2+ complexes into surrounding environment, which generate significant reactive oxygen species (ROS) in a controlled manner by near-infrared laser. The CuS nanoparticle-mediated photothermal ablation facilitates the ROS-induced cancer cell killing effect. Our current work reveals a DOX/Cu2+-mediated ROS-enhanced cell-killing effect in addition to conventional photothermal chemotherapy through the direct CuS nanoparticle-DOX complexation.

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and

Flexible polypyrrole/copper sulfide/bacterial cellulose nanofibrous composite membranes as supercapacitor electrodes.

PubMed

Peng, Shuo; Fan, Lingling; Wei, Chengzhuo; Liu, Xiaohong; Zhang, Hongwei; Xu, Weilin; Xu, Jie

2017-02-10

Polypyrrole (PPy) and copper sulfide (CuS) have been successfully deposited on bacterial cellulose (BC) membranes to prepare nanofibrous composite electrodes of PPy/CuS/BC for flexible supercapacitor applications. The introduction of CuS remarkably improves the specific capacitance and cycling stability of BC-based electrodes. The specific capacitance of the supercapacitors based on the PPy/CuS/BC electrodes can reach to about 580Fg -1 at a current density of 0.8mAcm -2 and can retain about 73% of their initial value after 300 cycles, while the PPy/BC-based device could retain only 21.7% after 300 cycles. This work provides a promising approach to fabricate cost-effective and flexible nanofibrous composite membranes for high-performance supercapacitor electrodes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Magmatic sulfide-rich nickel-copper deposits related to picrite and (or) tholeiitic basalt dike-sill complexes-A preliminary deposit model

USGS Publications Warehouse

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.

Optical and electrical stability of viral-templated copper sulfide (Cu1.8S) films

NASA Astrophysics Data System (ADS)

Shahriar Zaman, Mohammed; Bernard Grajeda, Gabriel; Haberer, Elaine D.

2014-04-01

The optical and electrical stabilities of viral-templated non-stoichiometric copper sulfide, digenite (Cu1.8S) films were investigated. The films were composed of large agglomerates of randomly aligned Cu1.8S-coated M13 filamentous phage. Free carrier optical absorption associated with localized surface plasmon resonance (LSPR) was observed in the near infrared spectral region, and the films were electrically active, displaying a linear current-voltage relationship. Under ambient conditions, the magnitude of the LSPR absorption increased, following a power law relationship with time, and the electrical resistance of viral-templated films decreased significantly. In contrast, the resistance of films stored under low oxygen, low humidity conditions experienced a smaller reduction in electrical resistance. Changes in optical and electrical film properties under ambient conditions were associated with an increase in free carrier concentration within the copper chalcogenide material due to oxygen exposure. X-ray photoelectron spectroscopy was used to relate this increase in free carrier concentration to compositional changes on the viral-templated material surface.

Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

Formation of selenide, sulfide or mixed selenide-sulfide films on metal or metal coated substrates

DOEpatents

Eser, Erten; Fields, Shannon

2012-05-01

A process and composition for preventing cracking in composite structures comprising a metal coated substrate and a selenide, sulfide or mixed selenide sulfide film. Specifically, cracking is prevented in the coating of molybdenum coated substrates upon which a copper, indium-gallium diselenide (CIGS) film is deposited. Cracking is inhibited by adding a Se passivating amount of oxygen to the Mo and limiting the amount of Se deposited on the Mo coating.

Nickel-cobalt-iron-copper sulfides and arsenides in solution-collapse breccia pipes, northwestern Arizona

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

Wenrich, K.J.; Hlava, P.F.

An extensive suite of Ni-Co-Fe-Cu sulfides and arsenides lies within the matrix of solution-collapse breccias buried deep within the plateaus of the Grand Canyon region. Ceilings over large caverns in the Redwall collapsed, brecciating the overlying sandstone and forming cylindrical breccia pipes up to 300 ft in diameter that extend vertically as much as 3,000 ft. These highly permeable breccias served as a host for the precipitation of a suite of over 100 minerals, including uraninite, sphalerite, galena and various copper phases, in addition to the Ni-Co-bearing-phase discussed here. Intricately zoned crystals of small (<1 mm), euhedral Ni-Co-Fe-As-S minerals weremore » the first to form during the second major episode of mineralization in these pipes. Several of these phases replace minerals, such as barite and anhydrite, from the first episode. Extensive microprobe work has been done on samples from two breccia pipe mines, the Hack 2 and Orphan, which are about 50 miles apart. Mineral compositions are similar except that no copper is found in the Ni-Co-Fe phases from the Hack 2 mine, while pyrites containing 1 wt % Cu are common from the Orphan, which was mined for copper. In some of these pyrites', Cu is dominant and the mineral is actually villamaninite. Pyrites from both mines characteristically contain 0.5 to 3 wt % As. Metal contents in zones pyrite-bravoite-vaesite (M[sub 1]S[sub 2]) crystals at the Hack 2 mine range from Fe[sub 1] to Fe[sub .12], Ni[sub 0] to Ni[sub .86], and Co[sub 0] to Co[sub .10]. The metal content for polydymite-siegenite-violarite averages about (Ni[sub 2.33]Co[sub .39]Fe[sub .23])(S[sub 3.9]As[sub .1]). Orphan mine pyrite-bravoite-vaesite-villamaninite ranges in composition from pure FeS[sub 2] to (Ni[sub .6]Fe[sub .21]Co[sub .17])S[sub 2], and (Cu[sub .46]Ni[sub .27]Fe[sub .21]Co[sub .13])S[sub 2]. Of all the sulfides or arsenides found in these breccia pipes, only nickeline consistently occurs as the pure end member.« less

Industrial Tests to Modify Molten Copper Slag for Improvement of Copper Recovery

NASA Astrophysics Data System (ADS)

Guo, Zhengqi; Zhu, Deqing; Pan, Jian; Zhang, Feng; Yang, Congcong

2018-04-01

In this article, to improve the recovery of copper from copper slag by flotation process, industrial tests of the modification process involving addition of a composite additive into molten copper slag were conducted, and the modified slag was subjected to the flotation process to confirm the modification effect. The phase evolution of the slag in the modification process was revealed by thermodynamic calculations, x-ray diffraction, optical microscopy and scanning electron microscopy. The results show that more copper was transformed and enriched in copper sulfide phases. The magnetite content in the modified slag decreased, and that of "FeO" increased correspondingly, leading to a better fluidity of the molten slag, which improved the aggregation and growth of fine particles of the copper sulfide minerals. Closed-circuit flotation tests of the original and modified slags were conducted, and the results show that the copper recovery increased obviously from 69.15% to 73.38%, and the copper grade of concentrates was elevated slightly from 20.24% to 21.69%, further confirming that the industrial tests of the modification process were successful. Hence, the modification process has a bright future in industrial applications for enhancing the recovery of copper from the copper slag.

Copper sulfide nanodisk as photoacoustic contrast agent for ovarian tumor detection

NASA Astrophysics Data System (ADS)

Wang, Junxin; Hsu, Su-Wen; Tao, Andrea R.; Jokerst, Jesse V.

2017-03-01

Ultrasound is broadly used in the clinics yet is limited in early cancer detection because of its poor contrast between healthy and diseased tissues. Photoacoustic imaging can improve this limitation and has been extensively studied in pre-clinical models. Contrast agents can help improve the accuracy of diagnosis. We recently reported a novel copper sulfide (CuS) nanodisk with strong directionally-localized surface plasmon resonance in the near infrared region. This plasmonic resonance of nanodisks is tunable by changing the size and aspect ratio of CuS nanodisk. Here, we demonstrate this CuS nanodisk is a strong photoacoustic contrast agent. We prepared CuS nanodisks via a solvent-based synthesis followed by surface modification of poly(ethylene glycol) methyl ether thiol for in vivo applications. These CuS nanodisks can be detected at a concentration as low as 26 pM at 920 nm. Their nanosize and strong photoacoustic response make this novel CuS nanodisk a strong candidate for photoacoustic cancer imaging.

Optical and electrical stability of viral-templated copper sulfide (Cu{sub 1.8}S) films

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

Shahriar Zaman, Mohammed; Bernard Grajeda, Gabriel; Haberer, Elaine D., E-mail: haberer@ucr.edu

The optical and electrical stabilities of viral-templated non-stoichiometric copper sulfide, digenite (Cu{sub 1.8}S) films were investigated. The films were composed of large agglomerates of randomly aligned Cu{sub 1.8}S-coated M13 filamentous phage. Free carrier optical absorption associated with localized surface plasmon resonance (LSPR) was observed in the near infrared spectral region, and the films were electrically active, displaying a linear current-voltage relationship. Under ambient conditions, the magnitude of the LSPR absorption increased, following a power law relationship with time, and the electrical resistance of viral-templated films decreased significantly. In contrast, the resistance of films stored under low oxygen, low humidity conditionsmore » experienced a smaller reduction in electrical resistance. Changes in optical and electrical film properties under ambient conditions were associated with an increase in free carrier concentration within the copper chalcogenide material due to oxygen exposure. X-ray photoelectron spectroscopy was used to relate this increase in free carrier concentration to compositional changes on the viral-templated material surface.« less

Using Plasmonic Copper Sulfide Nanocrystals as Smart Light-Driven Sterilants.

PubMed

Liu, Zhen; Liu, Xianjun; Du, Yingda; Ren, Jinsong; Qu, Xiaogang

2015-10-27

As an efficient route to control pet overpopulation and develop neutered experimental animals, male sterilization via surgical techniques, chemical injections, and antifertility vaccines has brought particular attention recently. However, these traditional ways usually induce long-term adverse reactions, immune suppression, and serious infection and pain. To overcome the above limitations, we developed a platform in the present study by using plasmonic copper sulfide nanocrystals (Cu2-xS NCs) as intelligent light-driven sterilants with ideal outcomes. Upon NIR laser irradiation, these well-prepared Cu2-xS NCs can possess NIR-induced hyperthermia and generate high levels of reactive oxygen species (ROS). Due to the cooperation of photothermal and photodynamic effects, these nanocrystals exhibited NIR-mediated toxicity toward Sertoli cells both in vitro and in vivo in a mild manner. We attribute the potential mechanism of cellular injury to the apoptosis-related death and denaturation of protein in the testicles. Furthermore, the possible metabolism route and long-term toxicity of these nanocrystals after testicular injection indicate their high biocompatibility. Taking together, our study on the NIR-induced toxicity of Cu2-xS NCs provides keen insights for the usage of plasmonic nanomaterials in biomedicine.

Determination of (210)Po in drinking water and urine samples using copper sulfide microprecipitation.

PubMed

Guérin, Nicolas; Dai, Xiongxin

2014-06-17

Polonium-210 ((210)Po) can be rapidly determined in drinking water and urine samples by alpha spectrometry using copper sulfide (CuS) microprecipitation. For drinking water, Po in 10 mL samples was directly coprecipitated onto the filter for alpha counting without any purification. For urine, 10 mL of sample was heated, oxidized with KBrO3 for a short time (∼5 min), and subsequently centrifuged to remove the suspended organic matter. The CuS microprecipitation was then applied to the supernatant. Large batches of samples can be prepared using this technique with high recoveries (∼85%). The figures of merit of the methods were determined, and the developed methods fulfill the requirements for emergency and routine radioassays. The efficiency and reliability of the procedures were confirmed using spiked samples.

Determining Prehistoric Mining Practices in Southeastern Europe Using Copper Isotopes

NASA Astrophysics Data System (ADS)

Powell, Wayne; Mathur, Ryan; Bankoff, H. Arthur; Bulatović, Aleksandar; Filipović, Vojislav

2017-04-01

Copper was first smelted from malachite at 5000 BCE in Serbia. There the Eneolithic (Copper Age) began with the production of small jewelry pieces and progressed to the casting of massive copper tools near its end, approximately 2000 years later. However, copper metallurgy in southeastern Europe ceased or significantly decreased in the later third millennium, several centuries before the Bronze Age began. Whether this metallurgical hiatus was the result a cultural shift or depletion of natural resources remains an ongoing subject of debate. It has been speculated that the marked reduction in metal production at the Eneolithic-Bronze Age transition was due to the exhaustion of surficial weathered oxide ores and the technical inability to smelt the underlying sulfide minerals. The behavior of copper isotopes in near-surface environments allows us to differentiate highly weathered oxide ores that occur at Earth's surface from non-weathered sulfide ores that occur at greater depth. The oxidation of copper generates fluids and associated minerals that are enriched in the 65Cu isotope. Thus, oxidative weathering of sulfide ores leads to the development of three stratified isotopic reservoirs for copper: 1) oxides above the water table that are enriched in 65Cu; 2) residual weathered sulfides minerals at the water table that are depleted in 65Cu; and 3) non-fractionated, non-weathered sulfide ore below the water table. And so, the transformative shift to sulfide-based metallurgy will be delineated by a significant decrease in δ65Cu in copper artifacts corresponding to the first use of 65Cu-depleted residual ore. The degree of variability of primary ore composition from numerable ore deposits would likely result in the overlap of copper isotope composition between populations of artifacts. Therefore, shifts in the mean copper isotope values and associated standard deviations would best reflect changes in ores use. A baseline value of -0.2‰ ±0.5 (1) was determined

Surface modification of malachite with ethanediamine and its effect on sulfidization flotation

NASA Astrophysics Data System (ADS)

Feng, Qicheng; Zhao, Wenjuan; Wen, Shuming

2018-04-01

Ethanediamine was used to modify the mineral surface of malachite to improve its sulfidization and flotation behavior. The activation mechanism was investigated by adsorption experiments, X-ray photoelectron spectroscopy (XPS) analysis, and zeta potential measurements. Microflotation experiments showed that the flotation recovery of malachite was enhanced after the pretreatment of the mineral particles with ethanediamine prior to the addition of Na2S. Adsorption tests revealed that numerous sulfide ion species in the pulp solution were transferred onto the mineral surface through the formation of more copper sulfide species. This finding was confirmed by the results of the XPS measurements. Ethanediamine modification not only increased the contents of copper sulfide species on the malachite surface but also enhanced the reactivity of the sulfidization products. During sulfidization, Cu(II) species on the mineral surface were reduced into Cu(I) species, and the percentages of S22- and Sn2- relative to the total S increased after modification, resulting in increased surface hydrophobicity. The results of zeta potential measurements showed that the ethanediamine-modified mineral surface adsorbed with more sulfide ion species was advantageous to the attachment of xanthate species, thereby improving malachite floatability. The proposed ethanediamine modification followed by sulfidization xanthate flotation exhibits potential for industrial application.

Integrated thin film cadmium sulfide solar cell module

NASA Technical Reports Server (NTRS)

Mickelsen, R. A.; Abbott, D. D.

1971-01-01

The design, development, fabrication and tests of flexible integrated thin-film cadmium sulfide solar cells and modules are discussed. The development of low cost and high production rate methods for interconnecting cells into large solar arrays is described. Chromium thin films were applied extensively in the deposited cell structures as a means to: (1) achieve high adherence between the cadmium sulfide films and the vacuum-metallized copper substrates, (2) obtain an ohmic contact to the cadmium sulfide films, and (3) improve the adherence of gold films as grids or contact areas.

Nanostructured metal sulfides for energy storage

NASA Astrophysics Data System (ADS)

Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

2014-08-01

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.

An assessment of silver copper sulfides for photovoltaic applications: theoretical and experimental insights.

PubMed

Savory, Christopher N; Ganose, Alex M; Travis, Will; Atri, Ria S; Palgrave, Robert G; Scanlon, David O

2016-08-28

As the worldwide demand for energy increases, low-cost solar cells are being looked to as a solution for the future. To attain this, non-toxic earth-abundant materials are crucial, however cell efficiencies for current materials are limited in many cases. In this article, we examine the two silver copper sulfides AgCuS and Ag 3 CuS 2 as possible solar absorbers using hybrid density functional theory, diffuse reflectance spectroscopy, XPS and Hall effect measurements. We show that both compounds demonstrate promising electronic structures and band gaps for high theoretical efficiency solar cells, based on Shockley-Queisser limits. Detailed analysis of their optical properties, however, indicates that only AgCuS should be of interest for PV applications, with a high theoretical efficiency. From this, we also calculate the band alignment of AgCuS against various buffer layers to aid in future device construction.

Metallic sulfide additives for positive electrode material within a secondary electrochemical cell

DOEpatents

Walsh, William J.; McPheeters, Charles C.; Yao, Neng-ping; Koura, Kobuyuki

1976-01-01

An improved active material for use within the positive electrode of a secondary electrochemical cell includes a mixture of iron disulfide and a sulfide of a polyvalent metal. Various metal sulfides, particularly sulfides of cobalt, nickel, copper, cerium and manganese, are added in minor weight proportion in respect to iron disulfide for improving the electrode performance and reducing current collector requirements.

Characterization and recovery of copper values from discarded slag.

PubMed

Das, Bisweswar; Mishra, Barada Kanta; Angadi, Shivakumar; Pradhan, Siddharth Kumar; Prakash, Sandur; Mohanty, Jayakrushna

2010-06-01

In any copper smelter large quantities of copper slag are discarded as waste material causing space and environmental problems. This discarded slag contains important amounts of metallic values such as copper and iron. The recovery of copper values from an Indian smelter slag that contains 1.53% Cu, 39.8% Fe and 34.65% SiO(2) was the focus of the present study. A complete investigation of the different phases present in the slag has been carried out by means of optical microscopy, Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) techniques. It is observed that iron and silica are mostly associated with the fayalite phase whereas copper is present in both oxide and sulfide phases. These oxide and sulfide phases of copper are mostly present within the slag phase and to some extent the slag is also embedded inside the oxide and sulfide phases. The recovery of copper values from the discarded slag has been explored by applying a flotation technique using conventional sodium isopropyl xanthate (SIX) as the collector. The effects of flotation parameters such as pH and collector concentration are investigated. Under optimum flotation conditions, it is possible to achieve 21% Cu with more than 80% recovery.

Crystal and electronic structure of copper sulfides

NASA Astrophysics Data System (ADS)

Lukashev, Pavel

Copper sulfides with different copper concentration exist in mineral form ranging from CuS to Cu2S. Among these, chalcosite Cu 2S, and digenite Cu1.8S were the subject of extensive research for decades mainly because of their use as the absorber in photovoltaic cells. Yet; their electronic structure is poorly understood because their crystal structure is complex. Most of the results published so far report the semiconducting nature of these compounds with the energy band gap being in the range of 0.84 to 1.9 eV. The crystal structure consists of a close-packed lattice of S with mobile Cu occupying various types of interstitial sites with a statistical distribution depending on temperature. In this thesis we present the first computational study of their electronic band structure. Initially, we investigated the simpler antifluorite structure. Both local density approximation (LDA) and self-consistent quasiparticle GW calculations with the full-potential linearized muffin-tin orbital method give a semimetallic band structure. Inspection of the nature of the bands shows that the lowest conduction band is mainly Cu-s-like except right near the center of the Brillouin zone where a Cu-s-like state lies about 1 eV below the valence band maximum. Significantly, in GW calculations, this state shifts up by several 0.1 eV but not sufficiently to open a gap. A random distortion of the Cu atoms from the perfect antifluorite positions is found to break the degeneracy of the d state at the Gamma-point and thus opens up a small gap of about 0.1 eV in LDA. As our next step we constructed supercell models for the cubic and hexagonal phases with the Cu positions determined by a weighted random number generator. The low temperature monoclinic phase was also studied. The computed total energies of these structures follow the same order as the reported phases with increasing temperatures. All these models gave similar small band gaps of order 0.1-0.2 eV. However, their conduction band

The Copper Sulfide Coating on Polyacrylonitrile with Chelating Agents by an Electroless Deposition Method and its EMI Shielding Effectiveness

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

Roan, M.-L.; Chen, Y.-H.; Huang, C.-Y.

2008-08-28

In this study, a variety of concentrations of chelating agents were added to obtain the anchoring effect and chelating effect in the electroless plating bath. The mechanism of the Cu{sub x(x=1,2)}S growth and the electromagnetic interference shielding effectiveness (EMI SE) of the composite were studied. It was found that the vinyl acetate residued in PAN substrate would be purged due to the swelling effect by chelating agents solution. And then, the anchoring effect occurred due to the hydrogen bonding between the pits of PAN substrate and the chelating agent. Consequently, the copper sulfide layer deposited by the electroless plating reactionmore » with EDTA and TEA. The swelling degree (S{sub d}) was proposed and evaluated from the FT-IR spectra. The relationship between swelling degree of the PAN films and EDTA (C) is expressed as: S{sub d} = 0.13+0.90xe and (-15.15C). And TEA series is expressed as: S{sub d} = 0.07+1.00xe and (-15.15C). On the other hand, the FESEM micrograph showed that the average thickness of copper sulfide increased from 76 nm to 383 nm when the concentration of EDTA increased from 0.00M to 0.20M. Consequently, the EMI SE of the composites increased from 10{approx}12 dB to 25{approx}27 dB. The GIA-XRD analyze indicated that the deposited layer consisted of CuS and Cu{sub 2}S.« less

Platinum metals in magmatic sulfide ores

USGS Publications Warehouse

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

1980-01-01

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. Copyright ?? 1980 AAAS.

Mineralogy of Copper-Gold Deposit, Masjid Daghi Area, Jolfa, IRAN

NASA Astrophysics Data System (ADS)

Zenoozi, Roya

2010-05-01

The Copper-Gold deposit of Masjid Daghi area is located in the Jolfa quadrangle (scale 1:100,000), East Azerbaijan Province, north-west Iran. The deposit, hosting by sub-volcanic bodies comprise of quartz monzonite composition whose intruded the Tertiary volcanic and volcanic-sedimentary rocks and turbidities. The Tertiary volcanic rocks consist of andesite, trachy andesite and quartz andesite. These mineral-bearing bodies related to Late Eocene sub-volcanic activities which intrudded the Eocene volcanic rocks. Mineralography, XRD and SEM studies showed that the variations in mineralization of the area. The main agent of mineralization is the intrusion of Late Eocene sub volcanic bodies inside the Tertiary volcanic units. The mineralography studies revealed two main groups of mineralization as oxides and sulfides. The sulfide minerals formed as veins, vein lets and stock work.The economic minerals comprise of native gold, copper sulfides. The native gold occurring in siliceous veins and almost as inclusions inside the sulfides minerals such as chalcopyrite. The copper sulfides, contain pyrite, chalcopyrite and chalco-pyrrhoyite. Pyrite is main sulfide in the area and formed as disseminations, cavity filling and colloform. The amount of pyrite, chalcopyrite and chalco-pyrrhoyite increases with depth. Supergene alteration produced digenite, covellite, bornite, and malachite. The alteration occurred as potassic, phyllic, argillic and propylitic minerals. Furthermore, selective sercitic, sericitic-chloritic and alunitic alterations are seen around the mineralized veins. The mineralography studies indicate that pyrite is main mineral phase and native gold occurred in silicious vein almost as inclusions inside the sulfide mineral. Most of economic mineral formed as veins, vein lets, disseminated, cavity filling and colloform which related to intrusions of Late Eocene quartz monzonite bodies into the Eocene volcanic rocks and turbiditse. Some types of alterations such as

Synthesis and Biomedical Applications of Copper Sulfide Nanoparticles: From Sensors to Theranostics

PubMed Central

Goel, Shreya; Chen, Feng; Cai, Weibo

2013-01-01

Copper sulfide (CuS) nanoparticles have attracted increasing attention from biomedical researchers across the globe, because of their intriguing properties which have been mainly explored for energy- and catalysis-related applications to date. This focused review article aims to summarize the recent progress made in the synthesis and biomedical applications of various CuS nanoparticles. After a brief introduction to CuS nanoparticles in the first section, we will provide a concise outline of the various synthetic routes to obtain different morphologies of CuS nanoparticles, which can influence their properties and potential applications. CuS nanoparticles have found broad applications in vitro, especially in the detection of biomolecules, chemicals, and pathogens which will be illustrated in detail. The in vivo uses of CuS nanoparticles have also been investigated in preclinical studies, including molecular imaging with various techniques, cancer therapy based on the photothermal properties of CuS, as well as drug delivery and theranostic applications. Research on CuS nanoparticles will continue to thrive over the next decade, and tremendous opportunities lie ahead for potential biomedical/clinical applications of CuS nanoparticles. PMID:24106015

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

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

Elimelech, Orian; Liu, Jing; Plonka, Anna M.

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sizedmore » NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.« less

Influence of Copper on the Hot Ductility of 20CrMnTi Steel

NASA Astrophysics Data System (ADS)

Peng, Hong-bing; Chen, Wei-qing; Chen, Lie; Guo, Dong

2015-02-01

The hot ductility of 20CrMnTi steel with x% copper (x = 0, 0.34) was investigated. Results show that copper can reduce its hot ductility, but there is no significant copper-segregation at the boundary tested by EPMA. The average copper content at grain boundaries and substrate is 0.352% and 0.318% respectively in steel containing 0.34% copper tensile-tested at 950 °C. The fracture morphology was examined with SEM and many small and shallow dimples were found on the fracture of steel with copper, and fine copper sulfide was found from carbon extraction replicas using TEM. Additionally, adding 0.34% copper caused an increase in the dynamic recrystallization temperature from 950 °C to 1000 °C, which indicates that copper can retard the dynamic recrystallization (DRX) of austenite. The detrimental influence of copper on hot ductility of 20CrMnTi steel is due mainly to the fine copper sulfide in the steel and its retarding the DRX.

Ore microscopy of the Paoli silver-copper deposit, Oklahoma

USGS Publications Warehouse

Thomas, C.A.; Hagni, R.D.; Berendsen, P.

1991-01-01

The Paoli silver-copper deposit is located in south-central Oklahoma, 56 km south-southeast from Norman, Oklahoma. It was mined for high-grade silver-copper near the beginning of this century, and intensive exploratory drilling during the early 1970's delineated unmined portions of the deposit. A collaborative study between the U.S.G.S., the Kansas Geological Survey, and the University of Missouri-Rolla was undertaken to provide new information on the character of red bed copper deposits of the Midcontinent region. The Paoli deposit has been interpreted to occur as a roll-front type of deposit. The silver and copper mineralization occurs within paleochannels in the Permian Wellington Formation. The silver-copper interfaces appear to be controlled by oxidation-reduction interfaces that are marked by grey to red color changes in the host sandstone. Ore microscopic examinations of polished thin sections show that unoxidized ore consists of chalcocite, digenite, chalcopyrite, covellite and pyrite; and oxidized ores are characterized by covellite, bornite, hematite and goethite. In sandstone-hosted ores, chalcocite and digenite replace dolomite and border clastic quartz grains. In siltstone-hosted ores, the copper sulfide grains have varied shapes; most are irregular in shape and 5-25 ??m across, others have euhedral shapes suggestive of pyrite crystal replacements, and some are crudely spherical and are 120-200 ??m across. Chalcopyrite is the predominant copper sulfide at depth. Covellite and malachite replace chalcocite and digenite near the surface. Silver only occurs as native silver; most as irregularly shaped grains 40-80 ??m across, but some as cruciform crystals that are up to 3.5 mm across. The native silver has been deposited after copper sulfides, and locally replaces chalcocite. Surficial nodules of pyrite, malachite and hematite locally are present in outcrops at the oxidation-reduction fronts. Polished sections of the nodules show that malachite forms a

Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator.

PubMed

Wu, Dandan; Ma, Wenhui; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-05-18

In this study, ammonium ion was used to enhance the sulfidation flotation of malachite. The effect of ammonium ion on the sulfidation flotation of malachite was investigated using microflotation test, inductively coupled plasma (ICP) analysis, zeta potential measurements, and scanning electron microscope analysis (SEM). The results of microflotation test show that the addition of sodium sulfide and ammonium sulfate resulted in better sulfidation than the addition of sodium sulfide alone. The results of ICP analysis indicate that the dissolution of enhanced sulfurized malachite surface is significantly decreased. Zeta potential measurements indicate that a smaller isoelectric point value and a large number of copper-sulfide films formed on the malachite surface by enhancing sulfidation resulted in a large amount of sodium butyl xanthate absorbed onto the enhanced sulfurized malachite surface. EDS semi-quantitative analysis and XPS analysis show that malachite was easily sulfurized by sodium sulfide with ammonium ion. These results show that the addition of ammonium ion plays a significant role in the sulfidation of malachite and results in improved flotation performance.

Optoelectronic Properties of Strontium and Barium Copper Sulfides Prepared by Combinatorial Sputtering

DOE PAGES

Han, Yanbing; Siol, Sebastian; Zhang, Qun; ...

2017-09-27

Optically transparent materials with p-type electrical conductivity can facilitate the development of transparent electronics and improve the efficiency of photovoltaic solar cells. Sulfide materials represent an interesting alternative to oxides for these applications due to better hole transport properties. We prepare transparent and conductive Ba-Cu-S thin films by combinatorial cosputtering and characterized for their composition, structure, and optoelectronic properties. The conductivity and transparency of these films are found to be strongly dependent on their chemical composition and the substrate temperature during growth. The conductivity of BaCu 2S 2 and BaCu 4S 3 can reach 53 S/cm (at 250 °C) andmore » 74 S/cm (at 200 degrees C), respectively, which is higher than their solution processed/bulk counterparts. The 90% reflectance corrected transmittance is achieved in the wavelength range 600-1000 nm for BaCu 2S 2 and 650-1000 nm for BaCu 4S 3 (at 250 °C). These electrical and optical properties are comparable with other recently presented transparent p-type conductors, while the 200-350 degrees C processing temperature is low enough to be used in semiconductor devices with limited thermal budgets. Some attempts have been made to synthesize the related Sr-Cu-S materials, following the theoretical suggestion of their potential as transparent p-type conductors, but these attempts resulted only in phase-separated SrS and CuxS phases. Alloying BaCu 2S 2 with Sr on the Ba site on the other hand increases the conductivity to >100 S/cm while only slightly compromising the transparency of the material. To explain the difference between the Ba and the Sr containing copper sulfides, the lower bounds on the SrCu 2S 2 and SrCu 4S 3 formation enthalpies are estimated. While the doping of the Ba-Cu-S materials presented here is too large for application in transparent electronics, it is promising for potential use as p-type contact layers in thin film solar cells.« less

Optoelectronic Properties of Strontium and Barium Copper Sulfides Prepared by Combinatorial Sputtering

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

Han, Yanbing; Siol, Sebastian; Zhang, Qun

Optically transparent materials with p-type electrical conductivity can facilitate the development of transparent electronics and improve the efficiency of photovoltaic solar cells. Sulfide materials represent an interesting alternative to oxides for these applications due to better hole transport properties. We prepare transparent and conductive Ba-Cu-S thin films by combinatorial cosputtering and characterized for their composition, structure, and optoelectronic properties. The conductivity and transparency of these films are found to be strongly dependent on their chemical composition and the substrate temperature during growth. The conductivity of BaCu 2S 2 and BaCu 4S 3 can reach 53 S/cm (at 250 °C) andmore » 74 S/cm (at 200 degrees C), respectively, which is higher than their solution processed/bulk counterparts. The 90% reflectance corrected transmittance is achieved in the wavelength range 600-1000 nm for BaCu 2S 2 and 650-1000 nm for BaCu 4S 3 (at 250 °C). These electrical and optical properties are comparable with other recently presented transparent p-type conductors, while the 200-350 degrees C processing temperature is low enough to be used in semiconductor devices with limited thermal budgets. Some attempts have been made to synthesize the related Sr-Cu-S materials, following the theoretical suggestion of their potential as transparent p-type conductors, but these attempts resulted only in phase-separated SrS and CuxS phases. Alloying BaCu 2S 2 with Sr on the Ba site on the other hand increases the conductivity to >100 S/cm while only slightly compromising the transparency of the material. To explain the difference between the Ba and the Sr containing copper sulfides, the lower bounds on the SrCu 2S 2 and SrCu 4S 3 formation enthalpies are estimated. While the doping of the Ba-Cu-S materials presented here is too large for application in transparent electronics, it is promising for potential use as p-type contact layers in thin film solar cells.« less

Anaerobic Digestion Alters Copper and Zinc Speciation.

PubMed

Legros, Samuel; Levard, Clément; Marcato-Romain, Claire-Emmanuelle; Guiresse, Maritxu; Doelsch, Emmanuel

2017-09-19

Anaerobic digestion is a widely used organic waste treatment process. However, little is known on how it could alter the speciation of contaminants in organic waste. This study was focused on determining the influence of anaerobic digestion on the speciation of copper and zinc, two metals that generally occur at high concentration in organic waste. Copper and zinc speciation was investigated by X-ray absorption spectroscopy in four different raw organic wastes (predigestion) and their digested counterparts (postdigestion, i.e., digestates). The results highlighted an increase in the digestates of the proportion of amorphous or nanostructured copper sulfides as well as amorphous or nanostructured zinc sulfides and zinc phosphate as compared to raw waste. We therefore suggest that the environmental fate of these elements would be different when spreading either digestates or raw waste on cropland.

New influence factor inducing difficulty in selective flotation separation of Cu-Zn mixed sulfide minerals

NASA Astrophysics Data System (ADS)

Deng, Jiu-shuai; Mao, Ying-bo; Wen, Shu-ming; Liu, Jian; Xian, Yong-jun; Feng, Qi-cheng

2015-02-01

Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satisfactory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mechanisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions released from the ancient fluids reached 1.02 × 10-6 mol/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 × 10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.

Synthesis, Deposition, and Microstructure Development of Thin Films Formed by Sulfidation and Selenization of Copper Zinc Tin Sulfide Nanocrystals

NASA Astrophysics Data System (ADS)

Chernomordik, Boris David

Significant reduction in greenhouse gas emission and pollution associated with the global power demand can be accomplished by supplying tens-of-terawatts of power with solar cell technologies. No one solar cell material currently on the market is poised to meet this challenge due to issues such as manufacturing cost, material shortage, or material toxicity. For this reason, there is increasing interest in efficient light-absorbing materials that are comprised of abundant and non-toxic elements for thin film solar cell. Among these materials are copper zinc tin sulfide (Cu2ZnSnS4, or CZTS), copper zinc tin selenide (Cu2ZnSnSe4, or CZTSe), and copper zinc tin sulfoselenide alloys [Cu2ZnSn(SxSe1-x )4, or CZTSSe]. Laboratory power conversion efficiencies of CZTSSe-based solar cells have risen to almost 13% in less than three decades of research. Meeting the terawatt challenge will also require low cost fabrication. CZTSSe thin films from annealed colloidal nanocrystal coatings is an example of solution-based methods that can reduce manufacturing costs through advantages such as high throughput, high material utilization, and low capital expenses. The film microstructure and grain size affects the solar cell performance. To realize low cost commercial production and high efficiencies of CZTSSe-based solar cells, it is necessary to understand the fundamental factors that affect crystal growth and microstructure evolution during CZTSSe annealing. Cu2ZnSnS4 (CZTS) nanocrystals were synthesized via thermolysis of single-source cation and sulfur precursors copper, zinc and tin diethyldithiocarbamates. The average nanocrystal size could be tuned between 2 nm and 40 nm, by varying the synthesis temperature between 150 °C and 340 °C. The synthesis is rapid and is completed in less than 10 minutes. Characterization by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy confirm that the nanocrystals are nominally

Carbon-dot-based fluorescent turn-on sensor for selectively detecting sulfide anions in totally aqueous media and imaging inside live cells.

PubMed

Hou, Xianfeng; Zeng, Fang; Du, Fangkai; Wu, Shuizhu

2013-08-23

Sulfide anions are generated not only as a byproduct from industrial processes but also in biosystems. Hence, robust fluorescent sensors for detecting sulfide anions which are fast-responding, water soluble and biocompatible are highly desirable. Herein, we report a carbon-dot-based fluorescent sensor, which features excellent water solubility, low cytotoxicity and a short response time. This sensor is based on the ligand/Cu(II) approach so as to achieve fast sensing of sulfide anions. The carbon dot (CD) serves as the fluorophore as well as the anchoring site for the ligands which bind with copper ions. For this CD-based system, as copper ions bind with the ligands which reside on the surface of the CD, the paramagnetic copper ions efficiently quench the fluorescence of the CD, affording the system a turn-off sensor for copper ions. More importantly, the subsequently added sulfide anions can extract Cu(2+) from the system and form very stable CuS with Cu(2+), resulting in fluorescence enhancement and affording the system a turn-on sensor for sulfide anions. This fast-responding and selective sensor can operate in totally aqueous solution or in physiological milieu with a low detection limit of 0.78 μM. It displays good biocompatibility, and excellent cell membrane permeability, and can be used to monitor S(2-) levels in running water and living cells.

Metal sulfide for battery applications

NASA Astrophysics Data System (ADS)

Guidotti, Ronald A.

1988-08-01

A number of metal sulfides can be used in batteries as a cathode (reducible) material as part of an electrochemical couple to provide energy. There are a number of physical and chemical characteristics that can be evaluated for screening potential candidates for use in batteries. These include: cell potential vs. Li, thermal and chemical stability, electrical conductivity, allotropic form (phase), reaction kinetics during discharge, type of discharge mechanism, and material rechargeability. These are reviewed in general, with emphasis on sulfides of copper, iron, and molybdenum which are currently being used as cathodes in Li and Li-alloy batteries. The presence of impurities can adversely impact performance when naturally occurring sulfide minerals are used for battery applications. Sandia National Laboratories uses natural pyrite (FeS2) for its high-temperature, thermally activated Li(Si)/FeS2 batteries. The purification and processing procedures for the FeS2 involves both chemical and physical methods. Flotation was found to yield comparable results as HF leaching for removal of silica, but without the negative health and environmental concerns associated with this technique.

The Sanfengshan copper deposit and early Carboniferous volcanogenic massive sulfide mineralization in the Beishan orogenic belt, Northwestern China

NASA Astrophysics Data System (ADS)

Wang, Jialin; Gu, Xuexiang; Zhang, Yongmei; Zhou, Chao; He, Ge; Liu, Ruiping

2018-03-01

The Sanfengshan copper deposit, located in the Beishan orogenic belt, Northwestern China, is hosted in the lower member of the Hongliuyuan Formation, an early Carboniferous metavolcanic-sedimentary sequence. Mineralization occurs as stratiform, stratiform-like and lenticular orebodies, and comprises of laminated, brecciated, banded, massive, and disseminated ores. The mineralogy is dominated by pyrite, chalcopyrite and sphalerite. Fe-Mn chert is widely distributed and generally occurs as massive, laminated, bands or lenses, which are consistent with the orebody. Alteration at Sanfengshan displays a clear concentric zoning pattern and the footwall alteration is more intense and somewhat thicker than the hanging-wall alteration. Systematic geochemical investigation on the volcanic rocks in this area shows that the basalts of the Hongliuyuan Formation (HLY) are predominantly tholeiites with nearly flat rare earth element (REE) pattern, insignificant negative anomalies of high field strength elements (HFSEs), and low Ti/V and Th/Nb ratios. They were most likely derived from partial melting of depleted asthenospheric mantle and formed in a fore-arc setting during initiation of the southward subduction of the Paleo-Asian Ocean. The basalts of the Maotoushan Formation (MTS) display a calc-alkaline nature and are enriched in large ion lithophile elements (LILEs) and depleted in HFSEs, suggesting an active continental margin setting. Sulfur isotope (δ34S) values of the sulfide and sulfate minerals vary between 0‰ and 5.4‰, which are consistent with sulfur derivation from leaching of the host volcanic rocks, although a direct magmatic contribution cannot be ruled out. The Re-Os isotope data of pyrite yield an isochron age of 353 ± 35 Ma, consistent with the age of the host HLY basalts. Thus, a syngenetic (volcanogenic massive sulfide) model is proposed and it is concluded that the Sanfengshan copper deposit is a typical Cyprus-type VMS deposit that formed in an early

Controllable Electrochemical Synthesis of Copper Sulfides as Sodium-Ion Battery Anodes with Superior Rate Capability and Ultralong Cycle Life.

PubMed

Li, Haomiao; Wang, Kangli; Cheng, Shijie; Jiang, Kai

2018-03-07

Sodium-ion batteries (SIBs) are prospective alternative to lithium-ion batteries for large-scale energy-storage applications, owing to the abundant resources of sodium. Metal sulfides are deemed to be promising anode materials for SIBs due to their low-cost and eco-friendliness. Herein, for the first time, series of copper sulfides (Cu 2 S, Cu 7 S 4 , and Cu 7 KS 4 ) are controllably synthesized via a facile electrochemical route in KCl-NaCl-Na 2 S molten salts. The as-prepared Cu 2 S with micron-sized flakes structure is first investigated as anode of SIBs, which delivers a capacity of 430 mAh g -1 with a high initial Coulombic efficiency of 84.9% at a current density of 100 mA g -1 . Moreover, the Cu 2 S anode demonstrates superior capability (337 mAh g -1 at 20 A g -1 , corresponding to 50 C) and ultralong cycle performance (88.2% of capacity retention after 5000 cycles at 5 A g -1 , corresponding to 0.0024% of fade rate per cycle). Meanwhile, the pseudocapacitance contribution and robust porous structure in situ formed during cycling endow the Cu 2 S anodes with outstanding rate capability and enhanced cyclic performance, which are revealed by kinetics analysis and ex situ characterization.

Highly sensitive photodetectors based on hybrid 2D-0D SnS{sub 2}-copper indium sulfide quantum dots

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

Huang, Yun; Zhan, Xueying; Xu, Kai

2016-01-04

Both high speed and efficiency of photoelectric conversion are essential for photodetectors. As an emerging layered metal dichalcogenide (LMD), tin disulfide owns intrinsic faster photodetection ability than most other LMDs but poor light absorption and low photoelectric conversion efficiency. We develop an efficient method to enhance its performance by constructing a SnS{sub 2}-copper indium sulfide hybrid structure. As a result, the responsivity reaches 630 A/W, six times stronger than pristine SnS{sub 2} and much higher than most other LMDs photodetectors. Additionally, the photocurrents are enhanced by more than 1 order of magnitude. Our work may open up a pathway to improvemore » the performance of photodetectors based on LMDs.« less

Evidence for extreme partitioning of copper into a magmatic vapor phase.

PubMed

Lowenstern, J B; Mahood, G A; Rivers, M L; Sutton, S R

1991-06-07

The discovery of copper sulfides in carbon dioxide- and chlorine-bearing bubbles in phenocryst-hosted melt inclusions shows that copper resides in a vapor phase in some shallow magma chambers. Copper is several hundred times more concentrated in magmatic vapor than in coexisting pantellerite melt. The volatile behavior of copper should be considered when modeling the volcanogenic contribution of metals to the atmosphere and may be important in the formation of copper porphyry ore deposits.

Elevated corrosion rates and hydrogen sulfide in homes with 'Chinese Drywall'.

PubMed

Allen, Joseph G; MacIntosh, David L; Saltzman, Lori E; Baker, Brian J; Matheson, Joanna M; Recht, Joel R; Minegishi, Taeko; Fragala, Matt A; Myatt, Theodore A; Spengler, John D; Stewart, James H; McCarthy, John F

2012-06-01

In December 2008, the U.S. Consumer Product Safety Commission (CPSC) began receiving reports about odors, corrosion, and health concerns related to drywall originating from China. In response, a detailed environmental health and engineering evaluation was conducted of 41 complaint and 10 non-complaint homes in the Southeast U.S. Each home investigation included characterization of: 1) drywall composition; 2) indoor and outdoor air quality; 3) temperature, moisture, and building ventilation; and 4) copper and silver corrosion rates. Complaint homes had significantly higher hydrogen sulfide concentrations (mean 0.82 vs. copper sulfide and silver sulfide corrosion compared to non-complaint homes (Cu(2)S: 476 vs. <32 Å/30 d, p<0.01; Ag(2)S: 1472 vs. 389 Å/30 d, p<0.01). The abundance of carbonate and strontium in drywall was also elevated in complaint homes, and appears to be useful objective marker of problematic drywall in homes that meet other screening criteria (e.g., constructed or renovated in 2006-2007, reports of malodor and accelerated corrosion). This research provides empirical evidence of the direct association between homes constructed with 'Chinese Drywall' in 2006-2007 and elevated corrosion rates and hydrogen sulfide concentrations in indoor air. Copyright © 2012. Published by Elsevier B.V.

Copper Recovery from Yulong Complex Copper Oxide Ore by Flotation and Magnetic Separation

NASA Astrophysics Data System (ADS)

Han, Junwei; Xiao, Jun; Qin, Wenqing; Chen, Daixiong; Liu, Wei

2017-09-01

A combined process of flotation and high-gradient magnetic separation was proposed to utilize Yulong complex copper oxide ore. The effects of particle size, activators, Na2S dosage, LA (a mixture of ammonium sulfate and ethylenediamine) dosage, activating time, collectors, COC (a combination collector of modified hydroxyl oxime acid and xanthate) dosage, and magnetic intensity on the copper recovery were investigated. The results showed that 74.08% Cu was recovered by flotation, while the average grade of the copper concentrates was 21.68%. Another 17.34% Cu was further recovered from the flotation tailing by magnetic separation at 0.8 T. The cumulative recovery of copper reached 91.42%. The modifier LA played a positive role in facilitating the sulfidation of copper oxide with Na2S, and the combined collector COC was better than other collectors for the copper flotation. This technology has been successfully applied to industrial production, and the results are consistent with the laboratory data.

Uranium-bearing copper deposits in the Coyote district, Mora County, New Mexico

USGS Publications Warehouse

Zeller, H.D.; Baltz, Elmer Harold

1954-01-01

Uranium-bearing copper deposits occur in steeply dipping beds of the Sangre de Cristo formation of Pennsylvanian and Permian(?) age south of Coyote, Mora County, N. Mex. Mapping and sampling of these deposits indicate that they are found in lenticular carbonaceous zones in shales and arkosic sandstones. Samples from these zones contain as much as 0.067 percent uranium and average 3 percent copper. Metatyuyamunite is dissemihatedin some of the arkosic sandstone beds, and uraninite is present in some of the copper sulfide nodules occurring in the shale. These sulfide nodules are composed principally of chalcocite but include some bornite, covellite, pyrite, and malachite. Most of the samples were collected near the surface from the weathered zone. The copper and uranium were probably deposited with the sediments and concentrated into zones during compaction and lithification. Carbonaceous material in the Sangre de Cristo formation provided the environment that precipitated uranium and copper from mineral-charged connate waters forced from the clayey sediments.

Iron sulfide deposits at Wadi Wassat, Kingdom of Saudi Arabia

USGS Publications Warehouse

Roberts, R.J.; Rossman, D.L.; Bagdady, A.Y.; Conway, C.M.; Helaby, A.M.

1981-01-01

Massive and disseminated iron sulfide deposits in Wadi Wassat form lenticular, stratabound deposits in cherty Precambrian sedimentary rocks interlayered with Precambrian calcareous sedimentary rocks, pyroclastic rocks, and andesitic flow rocks. These rocks have been cut by a wide variety of plutonic and dike rocks including gabbro, diorite, granodiorite, diabase, rhyolite, and granite. The zone containing the sulfide lenses is nearly 16 km long and is cut off by granitic rocks at both the northern and southern ends. The lenses are as much as 200 m thick; one can be traced along strike for more than 4 km. The lenses consist mostly of iron sulfides. Pyrite is the principal sulfide mineral; near intrusive bodies the pyrite has been partially converted to pyrrhotite and locally mobilized into fractures. The sulfides have been oxidized to a depth of about 25 m. Preliminary calculations indicate that about 107,500,000 tons of sulfides, averaging 40 percent iron and 35 percent sulfur, are available to a depth of i00 m. Small amounts of nickel, cobalt, zinc, and copper are also present, but at metal prices prevailing in early 1981, these do not constitute significant resources.

Selenium content in sulfide ores from the Chalkidiki peninsula, Greece.

PubMed

Nicolaidou, A E

1998-01-01

Selenium (Se) was assessed in galena, sphalerite, and pyrite samples. These are components of mixed sulfide ores from the Olympias and Madem Lakkos-Mavres Petres deposits and the Skouries porphyry-copper deposit. We used atomic absorption spectroscopy (AAS) with a hydride generator system. The highest concentration of Se (516 ppm) was found in the fine-grained galena at the -135 level of the Olympias deposits. In the Madem Lakkos-Mavres Petres deposit, the highest concentration of Se (33 ppm) was found in the pyrites of the level 30. The concentration of Se in the arsenopyrites and chalcopyrites is lower than the detection limit of the analytical method (< 100 ppb). The concentrated chalcopyrite from the porphyry copper deposit at Skouries exhibits a significant Se content (average 200 ppm) in contrast to the chalcopyrite from the Olympias and the Madem Lakkos-Mavres Petres. Variations in the Se content of the sulfide minerals studied could be caused by redox-pH and/or temperature conditions, as well as by the difference in crystal structure. The Se found in the areas studied may positively affect the environment. Sulfide minerals are oxidized by microorganisms, infiltrate in the soil-water in the form of selenate or selenite ion, and directly or indirectly influence the human organism.

Copper speciation in variably toxic sediments at the Ely Copper Mine, Vermont, United States

USGS Publications Warehouse

Kimball, Bryn E.; Foster, Andrea L.; Seal, Robert R.; Piatak, Nadine M.; Webb, Samuel M.; Hammarstrom, Jane M.

2016-01-01

At the Ely Copper Mine Superfund site, Cu concentrations exceed background values in both streamwater (160–1200 times) and sediments (15–79 times). Previously, these sediment samples were incubated with laboratory test organisms, and they exhibited variable toxicity for different stream sites. In this study we combined bulk- and microscale techniques to determine Cu speciation and distribution in these contaminated sediments on the basis of evidence from previous work that Cu was the most important stressor in this environment and that variable observed toxicity could have resulted from differences in Cu speciation. Copper speciation results were similar at microscopic and bulk scales. The major Cu species in the more toxic samples were sorbed or coprecipitated with secondary Mn (birnessite) and Fe minerals (jarosite and goethite), which together accounted for nearly 80% of the total Cu. The major Cu species in the less toxic samples were Cu sulfides (chalcopyrite and a covellite-like phase), making up about 80–95% of the total Cu, with minor amounts of Cu associated with jarosite or goethite. These Cu speciation results are consistent with the toxicity results, considering that Cu sorbed or coprecipitated with secondary phases at near-neutral pH is relatively less stable than Cu bound to sulfide at lower pH. The more toxic stream sediment sites were those that contained fewer detrital sulfides and were upstream of the major mine waste pile, suggesting that removal and consolidation of sulfide-bearing waste piles on site may not eliminate all sources of bioaccessible Cu.

Super-hydrophilic copper sulfide films as light absorbers for efficient solar steam generation under one sun illumination

NASA Astrophysics Data System (ADS)

Guo, Zhenzhen; Ming, Xin; Wang, Gang; Hou, Baofei; Liu, Xinghang; Mei, Tao; Li, Jinhua; Wang, Jianying; Wang, Xianbao

2018-02-01

Solar steam technology is one of the simplest, most direct and effective ways to harness solar energy through water evaporation. Here, we report the development using super-hydrophilic copper sulfide (CuS) films with double-layer structures as light absorbers for solar steam generation. In the double-layer structure system, a porous mixed cellulose ester (MCE) membrane is used as a supporting layer, which enables water to get into the CuS light absorbers through a capillary action to provide continuous water during solar steam generation. The super-hydrophilic property of the double-layer system (CuS/MCE) leads to a thinner water film close to the air-water interface where the surface temperature is sufficiently high, leading to more efficient evaporation (˜80 ± 2.5%) under one sun illumination. Furthermore, the evaporation efficiencies still keep a steady value after 15 cycles of testing. The super-hydrophilic CuS film is promising for practical application in water purification and evaporation as a light absorption material.

Copper sulfide nanoparticle-decorated graphene as a catalytic amplification platform for electrochemical detection of alkaline phosphatase activity.

PubMed

Peng, Juan; Han, Xiao-Xia; Zhang, Qing-Chun; Yao, Hui-Qin; Gao, Zuo-Ning

2015-06-09

Copper sulfide nanoparticle-decorated graphene sheet (CuS/GR) was successfully synthesized and used as a signal amplification platform for electrochemical detection of alkaline phosphatase activity. First, CuS/GR was prepared through a microwave-assisted hydrothermal approach. The CuS/GR nanocomposites exhibited excellent electrocatalytic activity toward the oxidation of ALP hydrolyzed products such as 1-naphthol, which produced a current response. Thus, a catalytic amplification platform based on CuS/GR nanocomposite for electrochemical detection of ALP activity was designed using 1-naphthyl phosphate as a model substrate. The current response increased linearly with ALP concentration from 0.1 to 100 U L(-1) with a detection limit of 0.02 U L(-1). The assay was applied to estimate ALP activity in human serum samples with satisfactory results. This strategy may find widespread and promising applications in other sensing systems that involves ALP. Copyright © 2015 Elsevier B.V. All rights reserved.

Formation of Hydrogen Sulfide in Wine: Interactions between Copper and Sulfur Dioxide.

PubMed

Bekker, Marlize Z; Smith, Mark E; Smith, Paul A; Wilkes, Eric N

2016-09-10

The combined synergistic effects of copper (Cu(2+)) and sulfur dioxide (SO₂) on the formation of hydrogen sulfide (H₂S) in Verdelho and Shiraz wine samples post-bottling was studied over a 12-month period. The combined treatment of Cu(2+) and SO₂ significantly increased H₂S formation in Verdelho wines samples that were not previously treated with either Cu(2+) or SO₂. The formation of H₂S produced through Cu(2+) mediated reactions was likely either: (a) directly through the interaction of SO₂ with either Cu(2+) or H₂S; or (b) indirectly through the interaction of SO₂ with other wine matrix compounds. To gain better understanding of the mechanisms responsible for the significant increases in H₂S concentration in the Verdelho samples, the interaction between Cu(2+) and SO₂ was studied in a model wine matrix with and without the presence of a representative thiol quenching compound (4-methylbenzoquinone, 4MBQ). In these model studies, the importance of naturally occurring wine compounds and wine additives, such as quinones, SO₂, and metal ions, in modulating the formation of H₂S post-bottling was demonstrated. When present in equimolar concentrations a 1:1 ratio of H₂S- and SO₂-catechol adducts were produced. At wine relevant concentrations, however, only SO₂-adducts were produced, reinforcing that the competition reactions of sulfur nucleophiles, such as H₂S and SO₂, with wine matrix compounds play a critical role in modulating final H₂S concentrations in wines.

Gold paragenesis and chemistry at Batu Hijau, Indoneisa: implications for gold-rich porphyry copper deposits

NASA Astrophysics Data System (ADS)

Arif, J.; Baker, T.

2004-10-01

Gold is an important by-product in many porphyry-type deposits but the distribution and chemistry of gold in such systems remains poorly understood. Here we report the results of petrographic, electron microprobe, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and flotation test studies of gold and associated copper sulfides within a paragenetic framework from the world-class Batu Hijau (914 mt @ 0.53% Cu, 0.40 g/t Au) porphyry copper gold deposit, Indonesia. Unlike many other porphyry copper gold deposits, early copper minerals (bornite digenite chalcocite) are well preserved at Batu Hijau and the chalcopyrite pyrite overprint is less developed. Hence, it provides an excellent opportunity to study the entire gold paragenesis of the porphyry system. In 105 polished thin sections, 699 native gold grains were identified. Almost all of the native gold grains occurred either within quartz veins, attached to sulfide, or as free gold along quartz or silicate grain boundaries. The native gold grains are dominantly round in shape and mostly 1 12 μm in size. The majority of gold was deposited during the formation of early ‘A’ veins and is dominantly associated with bornite rather than chalcopyrite. The petrographic and LA-ICP-MS study results indicate that in bornite-rich ores gold mostly occurs within copper sulfide grains as invisible gold (i.e., within the sulfide structure) or as native gold grains. In chalcopyrite-rich ores gold mostly occurs as native gold grains with lesser invisible gold. Petrographic observations also indicate a higher proportion of free gold (native gold not attached to any sulfide) in chalcopyrite-rich ores compared to bornite rich ores. The pattern of free gold distribution appears to correlate with the flotation test data, where the average gold recovery value from chalcopyrite-rich ores is consistently lower than bornite-rich ores. Our data suggest that porphyry copper-gold deposits with chalcopyrite-rich ores

Photo-thermal and cytotoxic properties of inkjet-printed copper sulfide films on biocompatible latex coated substrates

NASA Astrophysics Data System (ADS)

Sarfraz, Jawad; Borzenkov, Mykola; Niemelä, Erik; Weinberger, Christian; Törngren, Björn; Rosqvist, Emil; Collini, Maddalena; Pallavicini, Piersandro; Eriksson, John; Peltonen, Jouko; Ihalainen, Petri; Chirico, Giuseppe

2018-03-01

Inkjet-printing of metal nanoparticles is a particularly promising technique for the fabrication and modification of surfaces with a multifunctional nature. Recently copper sulfide nanoparticles (CuS NPs) have attracted wide interest due to a range of valuable properties including long term stability, photo-thermal activity, ease of synthesis and low cost. In the present study, printed CuS patterns were successfully fabricated on latex coated paper substrates and characterized by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), UV-Vis-NIR spectroscopy, and grazing incidence X-ray diffraction (GID). The resulted patterns displayed pronounced photo-thermal effect under Near Infrared Irradiation (NIR) even with relatively low laser power. Finally, by utilizing an automated real-time imaging platform it was possible to verify that the CuS printed film was not cytotoxic to human dermal fibroblast cells (HDF). The pronounced photo-thermal properties and nontoxic nature of these printed low-cost flexible CuS films make them promising candidates for fabrication of devices with localized photo-thermal effect suitable for biomedical applications.

Copper(II)-Mediated Hydrogen Sulfide and Thiol Oxidation to Disulfides and Organic Polysulfanes and Their Reductive Cleavage in Wine: Mechanistic Elucidation and Potential Applications.

PubMed

Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

2017-03-29

Fermentation-derived volatile sulfur compounds (VSCs) are undesirable in wine and are often remediated in a process known as copper fining. In the present study, the addition of Cu(II) to model and real wine systems containing hydrogen sulfide (H 2 S) and thiols provided evidence for the generation of disulfides (disulfanes) and organic polysulfanes. Cu(II) fining of a white wine spiked with glutathione, H 2 S, and methanethiol (MeSH) resulted in the generation of MeSH-glutathione disulfide and trisulfane. In the present study, the mechanisms underlying the interaction of H 2 S and thiols with Cu(II) is discussed, and a prospective diagnostic test for releasing volatile sulfur compounds from their nonvolatile forms in wine is investigated. This test utilized a combination of reducing agents, metal chelators, and low-oxygen conditions to promote the release of H 2 S and MeSH, at levels above their reported sensory thresholds, from red and white wines that were otherwise free of sulfidic off-odors at the time of addition.

Facile room-temperature synthesis of carboxylated graphene oxide-copper sulfide nanocomposite with high photodegradation and disinfection activities under solar light irradiation

PubMed Central

Yu, Shuyan; Liu, Jincheng; Zhu, Wenyu; Hu, Zhong-Ting; Lim, Teik-Thye; Yan, Xiaoli

2015-01-01

Carboxylic acid functionalized graphene oxide-copper (II) sulfide nanoparticle composite (GO-COOH-CuS) was prepared from carboxylated graphene oxide and copper precursor in dimethyl sulfoxide (DMSO) by a facile synthesis process at room temperature. The high-effective combination, the interaction between GO-COOH sheets and CuS nanoparticles, and the enhanced visible light absorption were confirmed by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (DRS) and Photoluminescence (PL) spectra. The as-synthesized GO-COOH-CuS nanocomposite exhibited excellent photocatalytic degradation performance of phenol and rhodamine B, high antibacterial activity toward E. coli and B. subtilis, and good recovery and reusability. The influence of CuS content, the synergistic reaction between CuS and GO-COOH, and the charge-transfer mechanism were systematically investigated. The facile and low-energy synthesis process combined with the excellent degradation and antibacterial performance signify that the GO-COOH-CuS has a great potential for water treatment application. PMID:26553709

Mechanism of Selenium Loss in Copper Slag

NASA Astrophysics Data System (ADS)

Desai, Bhavin; Tathavadkar, Vilas; Basu, Somnath

2018-03-01

During smelting of copper sulfide concentrate, selenium is distributed between silica-saturated iron-silicate slag and copper-iron sulfide matte. The recovery coefficients of selenium between slag and matte were determined as a function of the initial concentration of selenium at 1523 K (1250 °C) under an inert atmosphere in a vertical tubular furnace. The initial concentration of selenium was varied by the addition of metallic selenium as well as selenium dioxide to the mixture of slag and matte. Analysis of the results indicated high affinity of selenium for matte. The apparent loss of selenium with the slag was attributed to the presence of selenium-enriched matte particles entrapped in the slag, rather than dissolved SeO2. The mechanisms proposed by previous investigators were discussed and also compared with the results of the present investigation.

Mechanism of Selenium Loss in Copper Slag

NASA Astrophysics Data System (ADS)

Desai, Bhavin; Tathavadkar, Vilas; Basu, Somnath

2018-06-01

During smelting of copper sulfide concentrate, selenium is distributed between silica-saturated iron-silicate slag and copper-iron sulfide matte. The recovery coefficients of selenium between slag and matte were determined as a function of the initial concentration of selenium at 1523 K (1250 °C) under an inert atmosphere in a vertical tubular furnace. The initial concentration of selenium was varied by the addition of metallic selenium as well as selenium dioxide to the mixture of slag and matte. Analysis of the results indicated high affinity of selenium for matte. The apparent loss of selenium with the slag was attributed to the presence of selenium-enriched matte particles entrapped in the slag, rather than dissolved SeO2. The mechanisms proposed by previous investigators were discussed and also compared with the results of the present investigation.

The Potential for Prophyry Copper-Molybdenum Deposits in the Eastern United States

USGS Publications Warehouse

Schmidt, Robert Gordon

1978-01-01

Several significant porphyry-type deposits of Paleozoic age are known in New England and eastern Canada. Disseminated copper-molybdenum deposits of Paleozoic age are in the Southeastern United States, and copper is produced from porphyry-type deposits of both Precambrian and Paleozoic age in eastern Canada. Although these old deposits are surely less abundant than those in Cenozoic and Tertiary porphyry belts, the known Precrambrian and Paleozoic deposits in Eastern North America appear to be valid exploration targets. The difficult of 'prospecting in drift-covered and saprolite-mantled terrains suggests that all such deposits probably have not been discovered. Although such deposits are more costly to discover in this region than a massive sulfide deposit, the total amount of copper in even a medium-sized porphyry copper deposit is much greater than in most massive sulfide deposits. This report summarizes current knowledge of porphyry copper-molybdenum-type deposits in the Eastern United States and suggests more favorable areas for mineral exploration. Selected Canadian deposits are discussed because of their bearing on planning exploration in this country.

Global transcriptional responses of Acidithiobacillus ferrooxidans Wenelen under different sulfide minerals.

PubMed

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.

Lead-Sulfide-Selenide Quantum Dots and Gold-Copper Alloy Nanoparticles Augment the Light-Harvesting Ability of Solar Cells.

PubMed

Das, Aparajita; Deepa, Melepurath; Ghosal, Partha

2017-04-05

Lead-sulfide-selenide (PbSSe) quantum dots (QDs) and gold-copper (AuCu) alloy nanoparticles (NPs) were incorporated into a cadmium sulfide (CdS)/titanium oxide (TiO 2 ) photoanode for the first time to achieve enhanced conversion of solar energy into electricity. PbSSe QDs with a band gap of 1.02 eV extend the light-harvesting range of the photoanode from the visible region to the near-infrared region. The conduction band (CB) edge of the PbSSe QDs is wedged between the CBs of TiO 2 and CdS; this additional level coupled with the good electrical conductivity of the dots facilitate charge transport and collection, and a high power conversion efficiency (PCE) of 4.44 % is achieved for the champion cell with the TiO 2 /PbSSe/CdS electrode. Upon including AuCu alloy NPs in the QD-sensitized electrodes, light absorption is enhance by plasmonic and light-scattering effects and also by the injection of hot electrons to the CBs of the QDs. Comparison of the incident photon-to-current conversion efficiency enhancement factors in addition to fluorescence decay and impedance studies reveal that the PbSSe QDs and AuCu alloy NPs promote charge injection to the current collector and increase the photogenerated charges produced, which thus enables the TiO 2 /PbSSe/CdS/AuCu cell to deliver the highest PCE of 5.26 % among all the various photoanode compositions used. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid Volatile Sulfides and Simultaneously Extracted Copper, Lead, and Zinc in Sediments of Sinclair Inlet, Washington

DTIC Science & Technology

1993-09-01

to Doug Vaught, J. Towell, and Eric Schlierman of Puget Sound Naval Shipyard for providing laboratory space, equipment, and logistical support for the...availability and mobility of toxic metal contamination in the sediments of Sinclair Inlet, Puget Sound , Washington, acid volatile sulfide (AVS) and... Puget Sound , Washington ........ 1 2. Apparatus used for measuring acid volatile sulfides ........................... 5 3. Sulfide electrode

Iron Sulfide Attenuates the Methanogenic Toxicity of Elemental Copper and Zinc Oxide Nanoparticles and their Soluble Metal Ion Analogs

PubMed Central

Gonzalez-Estrella, Jorge; Gallagher, Sara; Sierra-Alvarez, Reyes; Field, Jim A.

2016-01-01

Elemental copper (Cu0) and zinc oxide (ZnO) nanoparticle (NP) toxicity to methanogens has been attributed to the release of soluble metal ions. Iron sulfide (FeS) partially controls the soluble concentration of heavy metals and their toxicity in aquatic environments. Heavy metals displace the Fe from FeS forming poorly soluble metal sulfides in the FeS matrix. Therefore, FeS may be expected to attenuate the NP toxicity. This work assessed FeS as an attenuator of the methanogenic toxicity of Cu0 and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25–75 µm) and coarse (500 to 1200 µm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu0 and ZnO NPs. FeS-f attenuated methanogenic toxicity better than FeS-c. The results revealed that 2.5× less FeS-f than FeS-c was required to recover the methanogenic activity to 50% (activity normalized to uninhibited controls). The results also indicated that a molar FeS-f/Cu0 NP, FeS-f/ZnO NP, FeS-f/ZnCl2, and FeS-f/CuCl2 ratio of 2.14, 2.14, 4.28, and 8.56 respectively, was necessary to recover the methanogenic activity to >75%. Displacement experiments demonstrated that CuCl2 and ZnCl2 partially displaced Fe from FeS. As a whole, the results indicate that not all the sulfide in FeS was readily available to react with the soluble Cu and Zn ions which may explain the need for a large stoichiometric excesses of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu0 and ZnO NPs and their soluble ion analogs to methanogens. PMID:26803736

Solubility product constants of covellite and a poorly crystalline copper sulfide precipitate at 298 K

NASA Astrophysics Data System (ADS)

Shea, Damian; Helz, George R.

1989-02-01

The equilibrium constant at 25°C for the following reaction has been measured in NaCl media by an indirect method: CuS(cov) + H +(aq) ⇄ Cu 2+(aq) + HS -(qa), Ksp = MCu 2+MHS -(10 +pH) where CuS(cov) designates synthetic covellite. Values of pKsp are 21.39, 21.04 and 20.95 at NaCl = 0.2, 0.7 and 1.0 M, respectively; the uncertainty in these Ksp values is ±0.15. The free energy of formation of covellite, for which published values are discordant, is calculated to be -11.83±0.4 kcal/mole at 298 K (-49.50 ± 1.7 kJ/mole). This value is obtained by extrapolating the meaured pKsp values to infinite dilution with corrections for Cl - complexing. Applying similar Cl - complexing corrections, based on recent measurements by Seward, to previously published solubility data for galena yields a revised pKsp0 for galena of 12.78. A poorly crystalline precipitate, obtained by mixing Cu 2+ and HS - solutions, yielded a reversible solubility product 3 orders of magnitude greater than that of covellite but about 3 orders of magnitude less than that of a truly amorphous phase, super-cooled liquid CuS. The poorly crystalline phase has not been studied previously. Its bulk composition was Cu 1.18S, but microprobe analysis revealed that it was a partially exsolved mixture of roughly Cu 1.11S and Cu 1.32S (similar to known blaubleibender covellites). It was kinetically unstable, and converted to covellite when thermally annealed or when exposed to polysulfide solutions. Because of its instability, a material of this nature is unlikely to account for the amorphous copper sulfide alleged to occur in the Red Sea Brine deposits. However, it is possible that on short time scales dissolved Cu in sulfidic waters is controlled by metastable, rather than stable phases, as is known to be the case with dissolved Fe.

Measurement of labile copper in wine by medium exchange stripping potentiometry utilising screen printed carbon electrodes.

PubMed

Clark, Andrew C; Kontoudakis, Nikolaos; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R

2016-07-01

The presence of copper in wine is known to impact the reductive, oxidative and colloidal stability of wine, and techniques enabling measurement of different forms of copper in wine are of particular interest in understanding these spoilage processes. Electrochemical stripping techniques developed to date require significant pretreatment of wine, potentially disturbing the copper binding equilibria. A thin mercury film on a screen printed carbon electrode was utilised in a flow system for the direct analysis of labile copper in red and white wine by constant current stripping potentiometry with medium exchange. Under the optimised conditions, including an enrichment time of 500s and constant current of 1.0μA, the response range was linear from 0.015 to 0.200mg/L. The analysis of 52 red and white wines showed that this technique generally provided lower labile copper concentrations than reported for batch measurement by related techniques. Studies in a model system and in finished wines showed that the copper sulfide was not measured as labile copper, and that loss of hydrogen sulfide via volatilisation induced an increase in labile copper within the model wine system. Copyright © 2016 Elsevier B.V. All rights reserved.

On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

Structural, optical and electronic properties of indium sulfide compositions under influence of copper impurity produced by chemical method

NASA Astrophysics Data System (ADS)

Esmaili, Parisa; Kangarlou, Haleh; Savaloni, Hadi; Ghorannevis, Mahmood

Aqueous solutions with 70 °C and pH = 2.5 constant values were prepared from convenient chemical compounds to produce In2S3: Cu crystals and thin films. Crystal compositions were grown in this solution under special conditions. Micrographs showed amorphous In2S3 orange powder and transparent vitreous pieces of CuInS2 crystals. Indium sulfide films were produced using the same solution in CBD method, on the glass substrates at different [Cu/In] molar ratio concentrations. Cu+ ions by different concentration doped from copper chloride source into In2S3 films. The produced films were post-annealed at 400 °C for about 1 h. Their crystallography, phase transitions, element analysis and nanostructures were investigated by X-ray diffraction, SEM, EDAX and AFM analyses. β-In2S3 phase was dominant and by doping copper impurity, XRD results suggested the formation of CuInS2 compositions. Morphology of the films, nano-structures, grain shapes and hardness was changed. Optical reflectance was measured in the UV-VIS wavelength range by a spectrophotometer. Other optical properties and optical band gaps were calculated using Kramers-Kronig relations on reflectivity curves. Electronic properties were calculated by full potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). In this approach, generalized gradient approximation (GGA) was used for the exchange-correlation potential calculation. Band gap structures, density of states and imaginary parts of dielectric function were calculated for In2S3: Cu compositions.

Seasonal and spatial patterns of metals at a restored copper mine site. I. Stream copper and zinc

USGS Publications Warehouse

Bambic, D.G.; Alpers, Charles N.; Green, P.G.; Fanelli, E.; Silk, W.K.

2006-01-01

Seasonal and spatial variations in metal concentrations and pH were found in a stream at a restored copper mine site located near a massive sulfide deposit in the Foothill copper-zinc belt of the Sierra Nevada, California. At the mouth of the stream, copper concentrations increased and pH decreased with increased streamflow after the onset of winter rain and, unexpectedly, reached extreme values 1 or 2 months after peaks in the seasonal hydrographs. In contrast, aqueous zinc and sulfate concentrations were highest during low-flow periods. Spatial variation was assessed in 400 m of reach encompassing an acidic, metal-laden seep. At this seep, pH remained low (2-3) throughout the year, and copper concentrations were highest. In contrast, the zinc concentrations increased with downstream distance. These spatial patterns were caused by immobilization of copper by hydrous ferric oxides in benthic sediments, coupled with increasing downstream supply of zinc from groundwater seepage.

The cytochrome bd oxidase of Escherichia coli prevents respiratory inhibition by endogenous and exogenous hydrogen sulfide

PubMed Central

Korshunov, Sergey; Imlay, Karin R. C.; Imlay, James A.

2016-01-01

Summary When sulfur compounds are scarce or difficult to process, E. coli adapts by inducing the high-level expression of sulfur-compound importers. If cystine then becomes available, the cystine is rapidly overimported and reduced, leading to a burgeoning pool of intracellular cysteine. Most of the excess cysteine is exported, but some is adventitiously degraded, with the consequent release of sulfide. Sulfide is a potent ligand of copper and heme moieties, raising the prospect that it interferes with enzymes. We observed that when cystine was provided and sulfide levels rose, E. coli became strictly dependent upon cytochrome bd oxidase for continued respiration. Inspection revealed that low-micromolar levels of sulfide inhibited the proton-pumping cytochrome bo oxidase that is regarded as the primary respiratory oxidase. In the absence of the back-up cytochrome bd oxidase, growth failed. Exogenous sulfide elicited the same effect. The potency of sulfide was enhanced when oxygen concentrations were low. Natural oxic-anoxic interfaces are often sulfidic, including the intestinal environment where E. coli dwells. We propose that the sulfide resistance of the cytochrome bd oxidase is a key trait that permits respiration in such habitats. PMID:26991114

BIOLOGICAL RESPONSE TO VARIATION OF ACID-VOLATILE SULFIDES AND METALS IN FIELD-EXPOSED SPIKED SEDIMENTS

EPA Science Inventory

Vertical and temporal variations of acid-volatile sulfides (AVS) and simultaneously extracted metals (SEM) in sediment can control biological impacts of metals. To assess the significance of these variations in field sediments, sediments spiked with cadmium, copper, lead, nickel ...

Oxidation Potentials in Matte Smelting of Copper and Nickel

NASA Astrophysics Data System (ADS)

Matousek, Jan W.

2014-09-01

The oxidation potential, given as the base-ten logarithm of the oxygen partial pressure in bars and the temperature [log pO2/ T, °C], defines the state of oxidation of pyrometallurgical extraction and refining processes. This property varies from copper making, [-6/1150]; to lead/zinc smelting, [-10/1200]; to iron smelting, [-13/1600]. The current article extends the analysis to the smelting of copper and nickel/copper sulfide concentrates to produce mattes of the type Cu(Ni)FeS(O) and iron silicate slags, FeOxSiO2—with oxidation potentials of [-7.5/1250].

[Biohydrometallurgical technology of a complex copper concentrate process].

PubMed

Murav'ev, M I; Fomchenko, N V; Kondrat'eva, T F

2011-01-01

Leaching of sulfide-oxidized copper concentrate of the Udokan deposit ore with a copper content of 37.4% was studied. In the course of treatment in a sulfuric acid solution with pH 1.2, a copper leaching rate was 6.9 g/kg h for 22 h, which allowed extraction of 40.6% of copper. As a result of subsequent chemical leaching at 80 degrees C during 7 h with a solution of sulphate ferric iron obtained after bio-oxidation by an association of microorganisms, the rate of copper recovery was 52.7 g/kg h. The total copper recovery was 94.5% (over 29 h). Regeneration of the Fe3+ ions was carried out by an association of moderately thermophilic microorganisms, including bacteria of genus Sulfobacillus and archaea of genus Ferroplasma acidiphilum, at 1.0 g/l h at 40 degrees C in the presence of 3% solids obtained by chemical leaching of copper concentrate. A technological scheme of a complex copper concentrate process with the use of bacterial-chemical leaching is proposed.

Size-tunable copper nanocluster aggregates and their application in hydrogen sulfide sensing on paper-based devices

NASA Astrophysics Data System (ADS)

Chen, Po-Cheng; Li, Yu-Chi; Ma, Jia-Yin; Huang, Jia-Yu; Chen, Chien-Fu; Chang, Huan-Tsung

2016-04-01

Polystyrene sulfonate (PSS), a strong polyelectrolyte, was used to prepare red photoluminescent PSS-penicillamine (PA) copper (Cu) nanoclusters (NC) aggregates, which displayed high selectivity and sensitivity to the detection of hydrogen sulfide (H2S). The size of the PSS-PA-Cu NC aggregates could be readily controlled from 5.5 μm to 173 nm using different concentrations of PSS, which enabled better dispersity and higher sensitivity towards H2S. PSS-PA-Cu NC aggregates provided rapid H2S detection by using the strong Cu-S interaction to quench NC photoluminescence as a sensing mechanism. As a result, a detection limit of 650 nM, which is lower than the maximum level permitted in drinking water by the World Health Organization, was achieved for the analysis of H2S in spring-water samples. Moreover, highly dispersed PSS-PA-Cu NC aggregates could be incorporated into a plate-format paper-based analytical device which enables ultra-low sample volumes (5 μL) and feature shorter analysis times (30 min) compared to conventional solution-based methods. The advantages of low reagent consumption, rapid result readout, limited equipment, and long-term storage make this platform sensitive and simple enough to use without specialized training in resource constrained settings.

Coper Isotope Fractionation in Porphyry Copper Deposits: A Controlled Experiment

NASA Astrophysics Data System (ADS)

Ruiz, J.; Mathur, R.; Uhrie, J. L.; Hiskey, B.

2001-12-01

Previous studies have shown that copper is fractionated in the environment. However, the mechanisms for isotope fractionation and the role of organic and inorganic processes in the fractionation are not well understood. Here we used the well controlled experiments used by Phelps Dodge Corporation aimed at leaching copper from their ore deposits to constrain the mechanism of copper isotope fractionation in natural systems. The isotope data were collected on a Micromass Isoprobe. High temperature copper sulfides from ore deposits in Chile and Arizona yield delta 65Cu near 0 permil. The reproducibility of the data is better that 0.1 permil. Controlled experiments consisting of large columns of rocks were fed solutions containing bacteria such as Thiobacillus ferroxidans and Leptospirrilium ferroxidan. Solutions fom the columns were sampled for sixty days and analyzed for copper concentrations, oxidation potential, ferrous/ferric ratios and pH. The results indicate that the bacterially aided dissolution of copper fractionated copper. Preliminary experiments of copper dissolution not using bacteria show no isotope fractionation The original rock in the experiment has a delta 65Cu of -2.1. The first solutions that were collected from the columns had a delta 65Cu of -5.0 per mil. The liquid changed its isotopic composition from -50 to -10 during the sixty days of sampling. The greatest shift in the isotope ratios occurred the first 30 days when the copper recovered was less than 40% and the ferrous/ferric ratios were somewhat constant. At approximately 35 days after the start of the experiments, the copper recovery increases the ferrousferric ratio decreased and the copper isotope ratio of the fluids remained fairly constant. The data suggest that the bacteria are required to effectively fractionate copper isotopes in natural systems and that the mechanisms of bacterial aided copper dissolution may include a direct dissolution of the sulfides by the bacteria. Experiments

The effect of iron and copper impurities on the wettability of sphalerite (110) surface.

PubMed

Simpson, Darren J; Bredow, Thomas; Chandra, Anand P; Cavallaro, Giuseppe P; Gerson, Andrea R

2011-07-15

The effect of impurities in the zinc sulfide mineral sphalerite on surface wettability has been investigated theoretically to shed light on previously reported conflicting results on sphalerite flotation. The effect of iron and copper impurities on the sphalerite (110) surface energy and on the water adsorption energy was calculated with the semi-empirical method modified symmetrically orthogonalized intermediate neglect of differential overlap (MSINDO) using the cyclic cluster model. The effect of impurities or dopants on surface energies is small but significant. The surface energy increases with increasing surface iron concentration while the opposite effect is reported for increasing copper concentration. The effect on adsorption energies is much more pronounced with water clearly preferring to adsorb on an iron site followed by a zinc site, and copper site least favorable. The theoretical results indicate that a sphalerite (110) surface containing iron is more hydrophilic than the undoped zinc sulfide surface. In agreement with the literature, the surface containing copper (either naturally or by activation) is more hydrophobic than the undoped surface. Copyright © 2011 Wiley Periodicals, Inc.

Case Study: Microbial Ecology and Forensics of Chinese Drywall-Elemental Sulfur Disproportionation as Primary Generator of Hydrogen Sulfide.

PubMed

Tomei Torres, Francisco A

2017-06-21

Drywall manufactured in China released foul odors attributed to volatile sulfur compounds. These included hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Given that calcium sulfate is the main component of drywall, one would suspect bacterial reduction of sulfate to sulfide as the primary culprit. However, when the forensics, i.e., the microbial and chemical signatures left in the drywall, are studied, the evidence suggests that, rather than dissimilatory sulfate reduction, disproportionation of elemental sulfur to hydrogen sulfide and sulfate was actually the primary cause of the malodors. Forensic evidence suggests that the transformation of elemental sulfur went through several abiological and microbial stages: (1) partial volatilization of elemental sulfur during the manufacture of plaster of Paris, (2) partial abiotic disproportionation of elemental sulfur to sulfide and thiosulfate during the manufacture of drywall, (3) microbial disproportionation of elemental sulfur to sulfide and sulfate resulting in neutralization of all alkalinity, and acidification below pH 4, (4) acidophilic microbial disproportionation of elemental sulfur to sulfide and sulfuric acid, and (5) hydrogen sulfide volatilization, coating of copper fixtures resulting in corrosion, and oxidation to sulfur dioxide.

Microbiological Leaching of Metallic Sulfides

PubMed Central

Razzell, W. E.; Trussell, P. C.

1963-01-01

The percentage of chalcopyrite leached in percolators by Thiobacillus ferrooxidans was dependent on the surface area of the ore but not on the amount. Typical examples of ore leaching, which demonstrate the role of the bacteria, are presented. In stationary fermentations, changes in KH2PO4 concentration above or below 0.1% decreased copper leaching as did reduction in the MgSO4·7H2O and increase in the (NH4)2SO4 concentration. Bacterial leaching of chalcopyrite was more effective than nonbiological leaching with ferric sulfate; ferric sulfate appeared to retard biological leaching, but this effect was likely caused by formation of an insoluble copper-iron complex. Ferrous sulfate and sodium chloride singly accentuated both bacterial and nonbiological leaching of chalcocite but jointly depressed bacterial action. Sodium chloride appeared to block bacterial iron oxidation without interfering with sulfide oxidation. Bacterial leaching of millerite, bornite, and chalcocite was greatest at pH 2.5. The economics of leaching a number of British Columbia ore bodies was discussed. PMID:16349627

Geology of the Copper King Mine area, Prairie Divide, Larimer County, Colorado (Part 1)

USGS Publications Warehouse

Sims, Paul Kibler; Phair, George

1952-01-01

The Copper King mine, in Larimer County, Colo., in the northern part of the Front Range of Colorado, was operated for a short time prior to World War II for copper and zino, but since 1949, when pitchblende was discovered on the mine dump, it has been worked for uranium. The bedrock in the mine area consists predominantly of pre-Cambrian (Silver Plums) granite with minor migmatite and metasediments--biotite-quartz-plagioclase gneiss, biotite schist, quartzite, amphibolite, amphibole skarn, and biotite skols. The metasediments occur as inclusions that trend northeast in the granite. This trend is essentially parallel to the prevailing foliation in the granite. At places the metasediments are crosscut sharply by the granite to form angular, partly discordant, steep-walled bodies in the granite. Faults, confined to a narrow zone that extends through the mine, cut both the pre-Cambrian rocks and the contained sulfide deposits. The Copper King fault, a breccia zone, contains a deposit of pitchblende; the other faults are believed to be later than the ore. The two types of mineral deposits--massive sulfide and pitchblende deposits--in the mine area, are of widely different mineralogy, age, and origin. The massive sulfide deposits are small and consist of pyrite, sphalerite, chalcopyrite, pyrrhotite, and in places magnetite in amphibole skarn, mice skols, and quartzite. The deposit at the Copper King mine has yielded small quantities of high-grade sphalerite ore. The massive sulfides are pyrometasomatic deposits of pre-Cambrian age. The pitchblende at the Copper King mine is principally in the Copper King vein, a tight, hard breccia zone that cuts through both granite and the massive sulfide deposit. A small part of the pitchblende is in small fractures near the vein and in boxwork pyrite adjacent to the vein; the post-ore faults, close to their intersection with the Copper King vein, contain some radioactive material, but elsewhere, so far as is known, they are barren

In vitro and in vivo corrosion evaluation of nickel-chromium- and copper-aluminum-based alloys.

PubMed

Benatti, O F; Miranda, W G; Muench, A

2000-09-01

The low resistance to corrosion is the major problem related to the use of copper-aluminum alloys. This in vitro and in vivo study evaluated the corrosion of 2 copper-aluminum alloys (Cu-Al and Cu-Al-Zn) compared with a nickel-chromium alloy. For the in vitro test, specimens were immersed in the following 3 corrosion solutions: artificial saliva, 0.9% sodium chloride, and 1.0% sodium sulfide. For the in vivo test, specimens were embedded in complete dentures, so that one surface was left exposed. The 3 testing sites were (1) close to the oral mucosa (partial self-cleaning site), (2) surface exposed to the oral cavity (self-cleaning site), and (3) specimen bottom surface exposed to the saliva by means of a tunnel-shaped perforation (non-self-cleaning site). Almost no corrosion occurred with the nickel-chromium alloy, for either the in vitro or in vivo test. On the other hand, the 2 copper-aluminum-based alloys exhibited high corrosion in the sulfide solution. These same alloys also underwent high corrosion in non-self-cleaning sites for the in vivo test, although minimal attack was observed in self-cleaning sites. The nickel-chromium alloy presented high resistance to corrosion. Both copper-aluminum alloys showed considerable corrosion in the sulfide solution and clinically in the non-self-cleaning site. However, in self-cleaning sites these 2 alloys did not show substantial corrosion.

A novel peptide-based fluorescence chemosensor for selective imaging of hydrogen sulfide both in living cells and zebrafish.

PubMed

Wang, Peng; Wu, Jiang; Di, Cuixia; Zhou, Rong; Zhang, Hong; Su, Pingru; Xu, Cong; Zhou, Panpan; Ge, Yushu; Liu, Dan; Liu, Weisheng; Tang, Yu

2017-06-15

Hydrogen sulfide (H 2 S) plays an important role as a signaling compound (gasotransmitter) in living systems. However, the development of an efficient imaging chemosensor of H 2 S in live animals is a challenging field for chemists. Herein, a novel peptide-based fluorescence chemosensor L-Cu was designed and synthesized on the basis of the copper chelating with the peptide ligand (FITC-Ahx-Ser-Pro-Gly-His-NH 2 , L), and its H 2 S sensing ability has been evaluated both in living cells and zebrafish. The peptide backbone and Cu 2+ -removal sensing mechanism are used to deliver rapid response time, high sensitivity, and good biocompatibility. After a fast fluorescence quench by Cu 2+ coordinated with L, the fluorescence of L is recovered by adding S 2- to form insoluble copper sulfide in aqueous solution with a detection limit for hydrogen sulfide measured to be 31nM. Furthermore, the fluorescence chemosensor L-Cu showed excellent cell permeation and low biotoxicity to realize the intracellular biosensing, L-Cu has also been applied to image hydrogen sulfide in live zebrafish larvae. We expect that this peptide-based fluorescence chemosensor L-Cu can be used to study H 2 S-related chemical biology in physiological and pathological events. Copyright © 2016 Elsevier B.V. All rights reserved.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Metal sulfide thin films by chemical spray pyrolysis

NASA Astrophysics Data System (ADS)

Krunks, Malle; Mellikov, Enn

2001-04-01

CdS, ZnS and CuS thin films were prepared by spray pyrolysis method using metal chlorides and thiourea (tu) as starting materials. Metal sulfide films form as products of thermal decomposition of complexes Cd(tu)2Cl2, Zn(tu)2Cl2 and Cu(tu)Cl(DOT)1/2H2O, originally formed in aqueous solution at precursors molar ratio 1:2. The metal-ligand bonding is thermally stable up to 220 degrees Celsius, followed by multistep degradation process of complexes. The TG/DTA analysis show similar thermal behavior of complexes up to 300 degrees Celsius with the formation of metal sulfides in this decomposition step. In air intensive oxidation processes are detected close to 400, 600 and 720 degrees Celsius for Cu, Cd and Zn complexes, respectively. The results of thermoanalytical study and XRD of sprayed films show that CdS and ZnS films could be grown at 450 degrees Celsius even in air while deposition of copper sulfide films should be performed in an inert atmosphere. High total impurities content of 10 wt% in CdS films prepared at 240 degrees Celsius is originated from the precursor and reduced to 2 wt% by increasing the growth temperature up to 400 degrees Celsius.

Size-tunable copper nanocluster aggregates and their application in hydrogen sulfide sensing on paper-based devices

PubMed Central

Chen, Po-Cheng; Li, Yu-Chi; Ma, Jia-Yin; Huang, Jia-Yu; Chen, Chien-Fu; Chang, Huan-Tsung

2016-01-01

Polystyrene sulfonate (PSS), a strong polyelectrolyte, was used to prepare red photoluminescent PSS-penicillamine (PA) copper (Cu) nanoclusters (NC) aggregates, which displayed high selectivity and sensitivity to the detection of hydrogen sulfide (H2S). The size of the PSS-PA-Cu NC aggregates could be readily controlled from 5.5 μm to 173 nm using different concentrations of PSS, which enabled better dispersity and higher sensitivity towards H2S. PSS-PA-Cu NC aggregates provided rapid H2S detection by using the strong Cu-S interaction to quench NC photoluminescence as a sensing mechanism. As a result, a detection limit of 650 nM, which is lower than the maximum level permitted in drinking water by the World Health Organization, was achieved for the analysis of H2S in spring-water samples. Moreover, highly dispersed PSS-PA-Cu NC aggregates could be incorporated into a plate-format paper-based analytical device which enables ultra-low sample volumes (5 μL) and feature shorter analysis times (30 min) compared to conventional solution-based methods. The advantages of low reagent consumption, rapid result readout, limited equipment, and long-term storage make this platform sensitive and simple enough to use without specialized training in resource constrained settings. PMID:27113330

Cyanide and Copper Recovery from Barren Solution of the Merrill Crowe Process

NASA Astrophysics Data System (ADS)

Parga, José R.; Valenzuela, Jesús L.; Díaz, J. A.

This paper is a brief overview of the role of inducing the nucleated precipitation of copper and cyanide in a flashtube serpentine reactor, using sodium sulfide as the precipitate and sulfuric acid as pH control. The results showed that pH had a great effect on copper cyanide removal efficiency and the optimum pH was about 3 to 3.5. At this pH value copper cyanide removal efficiency could be achieved above 97 and 99 %, when influent copper concentration ions were 650 and 900 ppm respectively. In this process the cyanide associated with the copper, zinc, iron cyanide complexes are released as HCN gas under strong acidic conditions, allowing it to be recycled back to the cyanidation process as free cyanide.

Mechanisms of Corrosion of Copper-Nickel Alloys in Sulfide-Polluted Seawater

DTIC Science & Technology

1981-02-01

anaerobic bacteria, which convert the natural sulfate content of the seawater into sulfides. Also, the putrefaction of organic compounds containing...corrosion rate bozause the Cu2 0 growth3 292 probably follows a parabolic rate law. The corrosion behavior at high oxygen concentrations (> 7.0 g/m ) is...determined using the rotating ring disk electrode method or SRI’s recently developed rotating cylinder- collector electrode.3 In these methods, the

The arsenic removal from arsenopyrite in sulfide mineral by physicochemical extraction

NASA Astrophysics Data System (ADS)

Jo, Jiyu; Cho, Kanghee; Choi, Nagchoul; Park*, Cheonyoung

2015-04-01

The most abundant As ore mineral is arsenopyrite (FeAsS). Arsenopyrite is present in sulfide ores associated with sediment-hosted Au deposits, it tends to be the earliest-formed mineral, derived from hydrothermal solutions and formed at temperatures typically of 100(degree Celsius) or more. The aim of this study was to investigate the mineralogical phase change and arsenic removal from arsenopyrite as a penalty element in sulfide mineral contained Au by physical extraction (high frequency) and chemical leaching (thiocyanate). Arsenic removal experiments for were performed under various conditions of high frequency exposure(1~35 min), thiocyanate concentration (0.1~1.0M), HCl concentration (0.1~2.0M), copper(2) sulfate concentration (0.1~1.0M), temperature (30~60 degree Celsius). Increasing the high frequency exposure produced a positive effect on arsenic removal in arsenopyrite. The highest percentage arsenic removal of 96.67% was obtained under the following conditions by thiocyanate leaching: thiocyanate concentration = 1.0M ; HCl concentration = 2.0M ; copper(2) sulfate concentration = 1.0M ; temperature = 60(degree Celsius) This study demonstrates the adequate performance of physical extraction (high frequency) and chemical leaching (thiocyanate) for the arsenic removal from arsenopyrite as a penalty element.

Structural and electronic properties of copper-doped chalcogenide glasses

NASA Astrophysics Data System (ADS)

Guzman, David M.; Strachan, Alejandro

2017-10-01

Using ab initio molecular dynamics based on density functional theory, we study the atomic and electronic structure, and transport properties of copper-doped germanium-based chalcogenide glasses. These mixed ionic-electronic conductor materials exhibit resistance or threshold switching under external electric field depending on slight variations of chemical composition. Understanding the origin of the transport character is essential for the functionalization of glassy chalcogenides for nanoelectronics applications. To this end, we generated atomic structures for GeX3 and GeX6 (X = S, Se, Te) at different copper concentrations and characterized the atomic origin of electronic states responsible for transport and the tendency of copper clustering as a function of metal concentration. Our results show that copper dissolution energies explain the tendency of copper to agglomerate in telluride glasses, consistent with filamentary conduction. In contrast, copper is less prone to cluster in sulfides and selenides leading to hysteresisless threshold switching where the nature of transport is dominated by electronic midgap defects derived from polar chalcogen bonds and copper atoms. Simulated I -V curves show that at least 35% by weight of copper is required to achieve the current demands of threshold-based devices for memory applications.

Facile Synthesis of Flower-Like Copper-Cobalt Sulfide as Binder-Free Faradaic Electrodes for Supercapacitors with Improved Electrochemical Properties

PubMed Central

Wang, Tianlei; Liu, Meitang; Ma, Hongwen

2017-01-01

Supercapacitors have been one of the highest potential candidates for energy storage because of their significant advantages beyond rechargeable batteries in terms of large power density, short recharging time, and long cycle lifespan. In this work, Cu–Co sulfides with uniform flower-like structure have been successfully obtained via a traditional two-step hydrothermal method. The as-fabricated Cu–Co sulfide vulcanized from precursor (P–Cu–Co sulfide) is able to deliver superior specific capacitance of 592 F g−1 at 1 A g−1 and 518 F g−1 at 10 A g−1 which are surprisingly about 1.44 times and 2.39 times higher than those of Cu–Co oxide electrode, respectively. At the same time, excellent cycling stability of P–Cu–Co sulfide is indicated by 90.4% capacitance retention at high current density of 10 A g−1 after 3000 cycles. Because of the introduction of sulfur during the vulcanization process, these new developed sulfides can get more flexible structure and larger reaction surface area, and will own richer redox reaction sites between the interfaces of active material/electrolyte. The uniform flower-like P–Cu–Co sulfide electrode materials will have more potential alternatives for oxides electrode materials in the future. PMID:28590417

Facile Synthesis of Flower-Like Copper-Cobalt Sulfide as Binder-Free Faradaic Electrodes for Supercapacitors with Improved Electrochemical Properties.

PubMed

Wang, Tianlei; Liu, Meitang; Ma, Hongwen

2017-06-07

Supercapacitors have been one of the highest potential candidates for energy storage because of their significant advantages beyond rechargeable batteries in terms of large power density, short recharging time, and long cycle lifespan. In this work, Cu-Co sulfides with uniform flower-like structure have been successfully obtained via a traditional two-step hydrothermal method. The as-fabricated Cu-Co sulfide vulcanized from precursor (P-Cu-Co sulfide) is able to deliver superior specific capacitance of 592 F g -1 at 1 A g -1 and 518 F g -1 at 10 A g -1 which are surprisingly about 1.44 times and 2.39 times higher than those of Cu-Co oxide electrode, respectively. At the same time, excellent cycling stability of P-Cu-Co sulfide is indicated by 90.4% capacitance retention at high current density of 10 A g -1 after 3000 cycles. Because of the introduction of sulfur during the vulcanization process, these new developed sulfides can get more flexible structure and larger reaction surface area, and will own richer redox reaction sites between the interfaces of active material/electrolyte. The uniform flower-like P-Cu-Co sulfide electrode materials will have more potential alternatives for oxides electrode materials in the future.

Improved ohmic contact of Ga-Doped ZnO to p-GaN by using copper sulfide intermediate layers

NASA Astrophysics Data System (ADS)

Gu, Wen; Xu, Tao; Zhang, Jianhua

2013-11-01

Copper sulfide (CuS) was used as the intermediate layer to build ohmic contact of Ga-Doped ZnO (GZO) transparent conduction layer (TCL) to p-GaN. The CuS and GZO layers were prepared by thermal evaporation and RF magnetron sputtering, respectively. Although the GZO-only contacts to p-GaN exhibit nonlinear behavior, ohmic contact with a specific contact resistance of 1.6 × 10-2 Ω cm2 has been realized by inserting 3 nm CuS layer between GZO and p-GaN. The optical transmittance of CuS/GZO film was measured to be higher than 80% in the range of 450-600 nm wavelength. The possible mechanism for the ohmic contact behavior can be attributed to the increased hole concentration of p-GaN surface induced by CuS films after annealing. The forward voltage of LEDs with CuS/GZO TCL has been reduced by 1.7 V at 20 mA and the output power has been increased by 29.6% at 100 mA compared with LEDs without CuS interlayer. These results indicated that using CuS intermediate layer could be a potential ohmic contact method to realize high-efficiency LEDs.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

A method of 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.

Sulfide chemiluminescence detection

DOEpatents

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.

Influence of various surface pretreatments on adherence of sputtered molybdenum disulfide to silver, gold, copper, and bronze

NASA Technical Reports Server (NTRS)

Spalvins, T.

1973-01-01

Solid film lubricants of radio frequency sputtered molybdenum disulfide (MoS2) were applied to silver, gold, copper, and bronze surfaces that had various pretreatments (mechanical polishing, sputter etching, oxidation, and sulfurization). Optical and electron transmission micrographs and electron diffraction patterns were used to interpret the film formation characteristics and to evaluate the sputtering conditions in regard to the film and substrate compatibility. Sputtered MoS2 films flaked and peeled on silver, copper, and bronze surfaces except when the surfaces had been specially oxidized. The flaking and peeling was a result of sulfide compound formation and the corresponding grain growth of the sulfide film. Sputtered MoS2 films showed no peeling and flaking on gold surfaces regardless of surface pretreatment.

Intense pulsed light annealing of copper zinc tin sulfide nanocrystal coatings

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

Williams, Bryce A.; Smeaton, Michelle A.; Holgate, Collin S.

2016-09-15

A promising method for forming the absorber layer in copper zinc tin sulfide [Cu{sub 2}ZnSnS{sub 4} (CZTS)] thin film solar cells is thermal annealing of coatings cast from dispersions of CZTS nanocrystals. Intense pulsed light (IPL) annealing utilizing xenon flash lamps is a potential high-throughput, low-cost, roll-to-roll manufacturing compatible alternative to thermal annealing in conventional furnaces. The authors studied the effects of flash energy density (3.9–11.6 J/cm{sup 2}) and number of flashes (1–400) during IPL annealing on the microstructure of CZTS nanocrystal coatings cast on molybdenum-coated soda lime glass substrates (Mo-coated SLG). The annealed coatings exhibited cracks with two distinct linearmore » crack densities, 0.01 and 0.2 μm{sup −1}, depending on the flash intensity and total number of flashes. Low density cracking (0.01 μm{sup −1}, ∼1 crack per 100 μm) is caused by decomposition of CZTS at the Mo-coating interface. Vapor decomposition products at the interface cause blisters as they escape the coating. Residual decomposition products within the blisters were imaged using confocal Raman spectroscopy. In support of this hypothesis, replacing the Mo-coated SLG substrate with quartz eliminated blistering and low-density cracking. High density cracking is caused by rapid thermal expansion and contraction of the coating constricted on the substrate as it is heated and cooled during IPL annealing. Finite element modeling showed that CZTS coatings on low thermal diffusivity materials (i.e., SLG) underwent significant differential heating with respect to the substrate with rapid rises and falls of the coating temperature as the flash is turned on and off, possibly causing a build-up of tensile stress within the coating prompting cracking. Use of a high thermal diffusivity substrate, such as a molybdenum foil (Mo foil), reduces this differential heating and eliminates the high-density cracking. IPL annealing in presence

Processing of Copper Zinc Tin Sulfide Nanocrystal Dispersions for Thin Film Solar Cells

NASA Astrophysics Data System (ADS)

Williams, Bryce Arthur

A scalable and inexpensive renewable energy source is needed to meet the expected increase in electricity demand throughout the developed and developing world in the next 15 years without contributing further to global warming through CO2 emissions. Photovoltaics may meet this need but current technologies are less than ideal requiring complex manufacturing processes and/or use of toxic, rare-earth materials. Copper zinc tin sulfide (Cu 2ZnSnS4, CZTS) solar cells offer a true "green" alternative based upon non-toxic and abundant elements. Solution-based processes utilizing CZTS nanocrystal dispersions followed by high temperature annealing have received significant research attention due to their compatibility with traditional roll-to-roll coating processes. In this work, CZTS nanocrystal (5-35 nm diameters) dispersions were utilized as a production pathway to form solar absorber layers. Aerosol-based coating methods (aerosol jet printing and ultrasonic spray coating) were optimized for formation of dense, crack-free CZTS nanocrystal coatings. The primary variables underlying determination of coating morphology within the aerosol-coating parameter space were investigated. It was found that the liquid content of the aerosol droplets at the time of substrate impingement play a critical role. Evaporation of the liquid from the aerosol droplets during coating was altered through changes to coating parameters as well as to the CZTS nanocrystal dispersions. In addition, factors influencing conversion of CZTS nanocrystal coatings into dense, large-grained polycrystalline films suitable for solar cell development during thermal annealing were studied. The roles nanocrystal size, carbon content, sodium uptake, and sulfur pressure were found to have pivotal roles in film microstructure evolution. The effects of these parameters on film morphology, grain growth rates, and chemical makeup were analyzed from electron microscopy images as well as compositional analysis

Temperature, Crystalline Phase and Influence of Substrate Properties in Intense Pulsed Light Sintering of Copper Sulfide Nanoparticle Thin Films.

PubMed

Dexter, Michael; Gao, Zhongwei; Bansal, Shalu; Chang, Chih-Hung; Malhotra, Rajiv

2018-02-02

Intense Pulsed Light sintering (IPL) uses pulsed, visible light to sinter nanoparticles (NPs) into films used in functional devices. While IPL of chalcogenide NPs is demonstrated, there is limited work on prediction of crystalline phase of the film and the impact of optical properties of the substrate. Here we characterize and model the evolution of film temperature and crystalline phase during IPL of chalcogenide copper sulfide NP films on glass. Recrystallization of the film to crystalline covellite and digenite phases occurs at 126 °C and 155 °C respectively within 2-7 seconds. Post-IPL films exhibit p-type behavior, lower resistivity (~10 -3 -10 -4  Ω-cm), similar visible transmission and lower near-infrared transmission as compared to the as-deposited film. A thermal model is experimentally validated, and extended by combining it with a thermodynamic approach for crystal phase prediction and via incorporating the influence of film transmittivity and optical properties of the substrate on heating during IPL. The model is used to show the need to a-priori control IPL parameters to concurrently account for both the thermal and optical properties of the film and substrate in order to obtain a desired crystalline phase during IPL of such thin films on paper and polycarbonate substrates.

Multi-phase structures of boron-doped copper tin sulfide nanoparticles synthesized by chemical bath deposition for optoelectronic devices

NASA Astrophysics Data System (ADS)

Rakspun, Jariya; Kantip, Nathakan; Vailikhit, Veeramol; Choopun, Supab; Tubtimtae, Auttasit

2018-04-01

We investigated the influence of boron doping on the structural, optical, and electrical properties of copper tin sulfide (CTS) nanoparticles coated on a WO3 surface and synthesized using chemical bath deposition. Boron doping at concentrations of 0.5, 1.0, 1.5, and 2.0 wt% was investigated. The X-ray diffraction pattern of CTS showed the presence of monoclinic Cu2Sn3S7, cubic Cu2SnS3, and orthorhombic Cu4SnS4. Boron doping influenced the preferred orientation of the nanoparticles for all phase structures and produced a lattice strain effect and changes in the dislocation density. Increasing the concentration of boron in CTS from 0.5 wt% to 2.0 wt% reduced the band gap for all phases of CTS from 1.46 to 1.29 eV and reduced the optical transmittance. Optical constants, such as the refractive index, extinction coefficient, and dissipation factor, were also obtained for B-doped CTS. The dispersion behavior of the refractive index was investigated in terms of a single oscillator model and the physical parameters were determined. Fourier transform infrared spectroscopy confirmed the successful synthesis of CTS nanoparticles. Cyclic voltammetry indicated that optimum boron doping (<1.5 wt% for all phases) resulted in desirable p-n junction behavior for optoelectronic applications.

Effect of Tin, Copper and Boron on the Hot Ductility of 20CrMnTi Steel between 650 °C and 1100 °C

NASA Astrophysics Data System (ADS)

Peng, Hong-bing; Chen, Wei-qing; Chen, Lie; Guo, Dong

2015-02-01

The hot ductility of 20CrMnTi steel with x% tin, y% copper and z ppm boron (x = 0, 0.02; y = 0, 0.2; z = 0, 60) was investigated. The results show that tin and copper in 20CrMnTi steel are detrimental to its hot ductility while adding boron can eliminate the adverse effect and enhance hot ductility greatly. Tin is found to segregate to the boundaries tested by EPMA in 20CrMnTi steel containing tin and copper and tin-segregation is suppressed by adding boron, moreover, copper was found not to segregate to boundaries, however, fine copper sulfide was found from carbon extraction replicas using TEM. The adverse effect of tin and copper on the hot ductility was due mainly to tin segregation and fine copper sulfide in the steel. The proeutectoid ferrite film precipitating along the austenite grain boundary causes the ductility trough of the three examined steels. Tin and copper in 20CrMnTi steel can retard the occurrence of dynamic recrystallization (DRX) while boron-addition can compensate for that change. The beneficial effect of boron on 20CrMnTi steel containing tin and copper might be ascribed to the fact that boron segregates to grain boundaries, accelerates onset of DRX, retards austenite/ferrite transformation and promotes intragranular nucleation of ferrite.

Ultra-deep oxidation and exotic copper formation at the late pliocene boyongan and bayugo porphyry copper-gold deposits, surigao, philippines: Geology, mineralogy, paleoaltimetry, and their implications for Geologic, physiographic, and tectonic controls

USGS Publications Warehouse

Braxton, D.P.; Cooke, D.R.; Ignacio, A.M.; Rye, R.O.; Waters, P.J.

2009-01-01

The Boyongan and Bayugo porphyry copper-gold deposits are part of an emerging belt of intrusion-centered gold-rich deposits in the Surigao district of northeast Mindanao, Philippines. Exhumation and weathering of these Late Pliocene-age deposits has led to the development of the world's deepest known porphyry oxidation profile at Boyongan (600 m), and yet only a modest (30-70 m) oxidation profile at adjacent Bayugo. Debris flows, volcanic rocks, and fluviolacustrine sediments accumulating in the actively extending Mainit graben subsequently covered the deposits and preserved the supergene profiles. At Boyongan and Bayugo, there is a vertical transition from shallower supergene copper oxide minerals (malachite + azurite + cuprite) to deeper sulfide-stable assemblages (chalcocite ?? hypogene sulfides). This transition provides a time-integrated proxy for the position of the water table at the base of the saturated zone during supergene oxidation. Contours of the elevation of the paleopotentiometric surface based on this min- eralogical transition show that the thickest portions of the unsaturated zone coincided with a silt-sand matrix diatreme breccia complex at Boyongan. Within the breccia complex, the thickness of the unsaturated zone approached 600 in, whereas outside the breccia complex (e.g., at Bayugo), the thickness averaged 50 m. Contours of the paleopotentiometric surface suggest that during weathering, groundwater flowed into the breccia complex from the north, south, and east, and exited along a high permeability zone to the west. The high relief (>550 m) on the elevation of the paleopotentiometric surface is consistent with an environment of high topographic relief, and the outflow zone to the west of the breccia complex probably reflects proximity to a steep scarp intersecting the western breccia complex margin. Stable isotope paleoaltimetry has enabled estimation of the elevation of the land surface, which further constrains the physiographic setting

Effect of particle-particle shearing on the bioleaching of sulfide minerals.

PubMed

Chong, N; Karamanev, D G; Margaritis, A

2002-11-05

The biological leaching of sulfide minerals, used for the production of gold, copper, zinc, cobalt, and other metals, is very often carried out in slurry bioreactors, where the shearing between sulfide particles is intensive. In order to be able to improve the efficiency of the bioleaching, it is of significant importance to know the effect of particle shearing on the rate of leaching. The recently proposed concept of ore immobilization allowed us to study the effect of particle shearing on the rate of sulfide (pyrite) leaching by Thiobacillus ferrooxidans. Using this concept, we designed two very similar bioreactors, the main difference between which was the presence and absence of particle-particle shearing. It was shown that when the oxygen mass transfer was not the rate-limiting step, the rate of bioleaching in the frictionless bioreactor was 2.5 times higher than that in a bioreactor with particle friction (shearing). The concentration of free suspended cells in the frictionless bioreactor was by orders of magnitude lower than that in the frictional bioreactor, which showed that particle friction strongly reduces the microbial attachment to sulfide surface, which, in turn, reduces the rate of bioleaching. Surprisingly, it was found that formation of a layer of insoluble iron salts on the surface of sulfide particles is much slower under shearless conditions than in the presence of particle-particle shearing. This was explained by the effect of particle friction on liquid-solid mass transfer rate. The results of this study show that reduction of the particle friction during bioleaching of sulfide minerals can bring important advantages not only by increasing significantly the bioleaching rate, but also by increasing the rate of gas-liquid oxygen mass transfer, reducing the formation of iron precipitates and reducing the energy consumption. One of the efficient methods for reduction of particle friction is ore immobilization in a porous matrix. Copyright 2002

Selenium Sulfide

MedlinePlus

... minutes.Do not leave selenium sulfide on your hair, scalp, or skin for long periods (e.g., ... jewelry; selenium sulfide may damage it. Wash your hair with ordinary shampoo and rinse it well. Shake ...

Electrochemical hydrogen sulfide biosensors.

PubMed

Xu, Tailin; Scafa, Nikki; Xu, Li-Ping; Zhou, Shufeng; Abdullah Al-Ghanem, Khalid; Mahboob, Shahid; Fugetsu, Bunshi; Zhang, Xueji

2016-02-21

The measurement of sulfide, especially hydrogen sulfide, has held the attention of the analytical community due to its unique physiological and pathophysiological roles in biological systems. Electrochemical detection offers a rapid, highly sensitive, affordable, simple, and real-time technique to measure hydrogen sulfide concentration, which has been a well-documented and reliable method. This review details up-to-date research on the electrochemical detection of hydrogen sulfide (ion selective electrodes, polarographic hydrogen sulfide sensors, etc.) in biological samples for potential therapeutic use.

Cross-Comparison of Leaching Strains Isolated from Two Different Regions: Chambishi and Dexing Copper Mines

PubMed Central

Ngom, Baba; Liang, Yili; Liu, Xueduan

2014-01-01

A cross-comparison of six strains isolated from two different regions, Chambishi copper mine (Zambia, Africa) and Dexing copper mine (China, Asia), was conducted to study the leaching efficiency of low grade copper ores. The strains belong to the three major species often encountered in bioleaching of copper sulfide ores under mesophilic conditions: Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, and Leptospirillum ferriphilum. Prior to their study in bioleaching, the different strains were characterized and compared at physiological level. The results revealed that, except for copper tolerance, strains within species presented almost similar physiological traits with slight advantages of Chambishi strains. However, in terms of leaching efficiency, native strains always achieved higher cell density and greater iron and copper extraction rates than the foreign microorganisms. In addition, microbial community analysis revealed that the different mixed cultures shared almost the same profile, and At. ferrooxidans strains always outcompeted the other strains. PMID:25478575

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents by X-ray photoelectron spectroscopy and scanning electron microscopy

NASA Astrophysics Data System (ADS)

Siriwardane, Ranjani V.; Poston, James A.

1993-05-01

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents was performed by X-ray photoelectron spectroscopy and scanning electron microscopy/energy-dispersive spectroscopy at temperatures of 298 to 823 K. Analysis of copper oxides indicated that the satellite structure of the Cu22p region was absent in the Cu(I) state but was present in the Cu(II) state. Reduction of CuO at room temperature was observed when the ion gauge was placed close to the sample. The satellite structure was absent in all the copper oxides at 823 K in vacuum. Differentiation of the oxidation state of copper utilizing both Cu(L 3M 4,5M 4,5) X-ray-induced Auger lines and Cu2p satellite structure, indicated that the copper in zinc copper ferrite was in the + 1 oxidation state at 823 K. This + 1 state of copper was not significantly changed after exposure to H 2, CO, and H 2O. There was an increase in Cu/Zn ratio and a decrease in Fe/Zn ratio on the surface of zinc copper ferrite at 823 K compared to that at room temperature. These conditions of copper offered the best sulfidation equilibrium for the zinc copper ferrite desulfurization sorbent. Analysis of iron oxides indicated that there was some reduction of both Fe 2O 3 and FeO at 823K. The iron in zinc copper ferrite was similar to that of Fe 2O 3 at room temperature but there was some reduction of this Fe(III) state to Fe(II) at 823 K. This reduction was more enhanced in the presence of H 2 and CO. Reduction to Fe(II) may not be desirable for the lifetime of the sorbent.

Prevention of sulfide oxidation in sulfide-rich waste rock

NASA Astrophysics Data System (ADS)

Nyström, Elsa; Alakangas, Lena

2015-04-01

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

One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media

NASA Astrophysics Data System (ADS)

Lv, Kun; Chen, Jian; Wang, Hong; Zhang, Peisheng; Yu, Maolin; Long, Yunfei; Yi, Pinggui

2017-04-01

The design of effective tools for detecting copper ion (Cu2 +) and sulfide anion (S2 -) is of great importance due to the abnormal level of Cu2 + and S2 - has been associated with an increase in risk of many diseases. Herein, we report on the fabrication of fluorescence resonance energy transfer (FRET) based fluorescent probe PF (PEI-FITC) for detecting Cu2 + and S2 - in 100% aqueous media via a facile one-pot method by covalent linking fluorescein isothiocyanate (FITC) with branched-polyethylenimine (b-PEI). PF could selectively coordinate with Cu2 + among 10 metal ions to form PF-Cu2 + complex, resulting in fluorescence quenching through FRET mechanism. Furthermore, the in situ generated PF-Cu2 + complex can be used to selectively detect S2 - based on the displacement approach, resulting in an off-on type sensing. There is no obvious interference from other anions, such as Cl-, NO3-, ClO4-, SO42 -, HCO3-, CO32 -, Br-, HPO42 -, F- and S2O32 -. In addition, PF was successfully used to determine Cu2 + and S2 - in human serum and tap water samples. Therefore, the FRET-based probe PF may provide a new method for selective detection of multifarious analysts in biological and environmental applications, and even hold promise for application in more complicated systems.

Copper(II) mediated facile and ultra fast peptide synthesis in methanol.

PubMed

Mali, Sachitanand M; Jadhav, Sandip V; Gopi, Hosahudya N

2012-07-18

A novel, ultrafast, mild and scalable amide bond formation strategy in methanol using simple thioacids and amines is described. The mechanism suggests that the coupling reactions are initially mediated by CuSO(4)·5H(2)O and subsequently catalyzed by in situ generated copper sulfide. The pure peptides were isolated in satisfactory yields in less than 5 minutes.

Cadmium sulfide membranes

DOEpatents

Spanhel, Lubomir; Anderson, Marc A.

1992-07-07

A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

Cadmium sulfide membranes

DOEpatents

Spanhel, Lubomir; Anderson, Marc A.

1991-10-22

A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

Integration of Semiconducting Sulfides for Full-Spectrum Solar Energy Absorption and Efficient Charge Separation.

PubMed

Zhuang, Tao-Tao; Liu, Yan; Li, Yi; Zhao, Yuan; Wu, Liang; Jiang, Jun; Yu, Shu-Hong

2016-05-23

The full harvest of solar energy by semiconductors requires a material that simultaneously absorbs across the whole solar spectrum and collects photogenerated electrons and holes separately. The stepwise integration of three semiconducting sulfides, namely ZnS, CdS, and Cu2-x S, into a single nanocrystal, led to a unique ternary multi-node sheath ZnS-CdS-Cu2-x S heteronanorod for full-spectrum solar energy absorption. Localized surface plasmon resonance (LSPR) in the nonstoichiometric copper sulfide nanostructures enables effective NIR absorption. More significantly, the construction of pn heterojunctions between Cu2-x S and CdS leads to staggered gaps, as confirmed by first-principles simulations. This band alignment causes effective electron-hole separation in the ternary system and hence enables efficient solar energy conversion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase*

PubMed Central

Mishanina, Tatiana V.; Yadav, Pramod K.; Ballou, David P.; Banerjee, Ruma

2015-01-01

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be −123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

PubMed

Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

2015-10-09

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.

2004-01-01

Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

SULFIDE MINERALS IN SEDIMENTS

EPA Science Inventory

The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.

PubMed

Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

2016-05-25

Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

DOE PAGES

Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis; ...

2017-02-01

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effectsmore » of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

Soft X-ray absorption spectroscopy investigation of the surface chemistry and treatments of copper indium gallium diselenide (CIGS)

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

Schwartz, Craig; Nordlund, Dennis; Sokaras, Dimosthenis

The surface and near surface structure of copper-indium-gallium-selenide (CIGS) absorber layers is integral to the producing a high-quality photovoltaic junction. By using X-ray absorption spectroscopy (XAS) and monitoring multiple elemental absorption edges with both theory and experiment, we are able to identify several features of the surface of CIGS as a function of composition and surface treatments. The XAS data shows trends in the near surface region of oxygen, copper, indium and gallium species as the copper content is varied in the films. The oxygen surface species are also monitored through a series of experiments that systematically investigates the effectsmore » of water and various solutions of: ammonium hydroxide, cadmium sulfate, and thiourea. These being components of cadmium sulfide chemical bath deposition (CBD). Characteristics of the CBD are correlated with a restorative effect that produces as normalized, uniform surface chemistry as measured by XAS. This surface chemistry is found in CIGS solar cells with excellent power conversion efficiency (<19%). The results provide new insight for CIGS processing strategies that seek to replace CBD and/or cadmium sulfide.« less

Sulfides from Martian and Lunar Basalts: Comparative Chemistry for Ni Co Cu and Se

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

J Papike; P Burger; C Shearer

2011-12-31

Here Mars and Moon are used as 'natural laboratories' with Moon displaying lower oxygen fugacities ({approx}IW-1) than Mars ({approx}IW to FMQ). Moon has lower concentrations of Ni and Co in basaltic melts than does Mars. The major sulfides are troilite (FeS) in lunar basalts and pyrrhotite (Fe{sub 1-x}S) in martian basalts. This study focuses on the concentrations of Ni, Co, Cu, and Se. We chose these elements because of their geochemical importance and the feasibility of analyzing them with a combination of synchrotron X-ray fluorescence (SXRF) and electron microprobe (EPMA) techniques. The selenium concentrations could only be analyzed, at highmore » precision, with SXRF techniques as they are <150 ppm, similar to concentrations seen in carbonaceous chondrites and interplanetary dust particles (IDPs). Nickel and Co are in higher concentrations in martian sulfides than lunar and are higher in martian olivine-bearing lithologies than olivine-free varieties. The sulfides in individual samples show very large ranges in concentration (e.g., Ni ranges from 50 000 ppm to <5 ppm). These large ranges are mainly due to compositional heterogeneities within individual grains due to diffusion and phase separation. Electron microprobe wavelength-dispersive (WDS) mapping of Ni, Co, and Cu show the diffusion trajectories. Nickel and Co have almost identical diffusion trajectories leading to the likely nucleation of pentlandite (Ni,Co,Fe){sub 9}S{sub 8}, and copper diffuses along separate pathways likely toward chalcopyrite nucleation sites (CuFeS{sub 2}). The systematics of Ni and Co in lunar and martian sulfides clearly distinguish the two parent bodies, with martian sulfides displaced to higher Ni and Co values.« less

Production of sulfur gases and carbon dioxide by synthetic weathering of crushed drill cores from the Santa Cruz porphyry copper deposit near Casa Grande, Pinal County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Ryder, J.L.; Sutley, S.J.; Botinelly, T.

1990-01-01

Samples of ground drill cores from the southern part of the Santa Cruz porphyry copper deposit, Casa Grande, Arizona, were oxidized in simulated weathering experiments. The samples were also separated into various mineral fractions and analyzed for contents of metals and sulfide minerals. The principal sulfide mineral present was pyrite. Gases produced in the weathering experiments were measured by gas chromatography. Carbon dioxide, oxygen, carbonyl sulfide, sulfur dioxide and carbon disulfide were found in the gases; no hydrogen sulfide, organic sulfides, or mercaptans were detected. Oxygen concentration was very important for production of the volatiles measured; in general, oxygen concentration was more important to gas production than were metallic element content, sulfide mineral content, or mineral fraction (oxide or sulfide) of the sample. The various volatile species also appeared to be interactive; some of the volatiles measured may have been formed through gas reactions. ?? 1990.

Orogenic-type copper-gold-arsenic-(bismuth) mineralization at Flatschach (Eastern Alps), Austria

NASA Astrophysics Data System (ADS)

Raith, Johann G.; Leitner, Thomas; Paar, Werner H.

2015-10-01

Structurally controlled Cu-Au mineralization in the historic Flatschach mining district (Styria, Austria) occurs in a NE-SW to NNE-WSW oriented vein system as multiple steep-dipping calcite-(dolomite)-quartz veins in amphibolite facies metamorphic rocks (banded gneisses/amphibolites, orthogneisses, metagranitoids) of the poly-metamorphosed Austroalpine Silvretta-Seckau nappe. Vein formation postdated ductile deformation events and Eoalpine (Late Cretaceous) peak metamorphism but predated Early to Middle Miocene sediment deposition in the Fohnsdorf pull-apart basin; coal-bearing sediments cover the metamorphic basement plus the mineralized veins at the northern edge of the basin. Three gold-bearing ore stages consist of a stage 1 primary hydrothermal (mesothermal?) ore assemblage dominated by chalcopyrite, pyrite and arsenopyrite. Associated minor minerals include alloclasite, enargite, bornite, sphalerite, galena, bismuth and matildite. Gold in this stage is spatially associated with chalcopyrite occurring as inclusions, along re-healed micro-fractures or along grain boundaries of chalcopyrite with pyrite or arsenopyrite. Sericite-carbonate alteration is developed around the veins. Stage 2 ore minerals formed by the replacement of stage 1 sulfides and include digenite, anilite, "blue-remaining covellite" (spionkopite, yarrowite), bismuth, and the rare copper arsenides domeykite and koutekite. Gold in stage 2 is angular to rounded in shape and occurs primarily in the carbonate (calcite, Fe-dolomite) gangue and less commonly together with digenite, domeykite/koutekite and bismuth. Stage 3 is a strongly oxidized assemblage that includes hematite, cuprite, and various secondary Cu- and Fe-hydroxides and -carbonates. It formed during supergene weathering. Stage 1 and 2 gold consists mostly of electrum (gold fineness 640-860; mean = 725; n = 46), and rare near pure gold (fineness 930-940; n = 6). Gold in stage 3 is Ag-rich electrum (fineness 350-490, n = 12), and has a

Sulfide-responsive transcriptional repressor SqrR functions as a master regulator of sulfide-dependent photosynthesis.

PubMed

Shimizu, Takayuki; Shen, Jiangchuan; Fang, Mingxu; Zhang, Yixiang; Hori, Koichi; Trinidad, Jonathan C; Bauer, Carl E; Giedroc, David P; Masuda, Shinji

2017-02-28

Sulfide was used as an electron donor early in the evolution of photosynthesis, with many extant photosynthetic bacteria still capable of using sulfur compounds such as hydrogen sulfide (H 2 S) as a photosynthetic electron donor. Although enzymes involved in H 2 S oxidation have been characterized, mechanisms of regulation of sulfide-dependent photosynthesis have not been elucidated. In this study, we have identified a sulfide-responsive transcriptional repressor, SqrR, that functions as a master regulator of sulfide-dependent gene expression in the purple photosynthetic bacterium Rhodobacter capsulatus SqrR has three cysteine residues, two of which, C41 and C107, are conserved in SqrR homologs from other bacteria. Analysis with liquid chromatography coupled with an electrospray-interface tandem-mass spectrometer reveals that SqrR forms an intramolecular tetrasulfide bond between C41 and C107 when incubated with the sulfur donor glutathione persulfide. SqrR is oxidized in sulfide-stressed cells, and tetrasulfide-cross-linked SqrR binds more weakly to a target promoter relative to unmodified SqrR. C41S and C107S R. capsulatus SqrRs lack the ability to respond to sulfide, and constitutively repress target gene expression in cells. These results establish that SqrR is a sensor of H 2 S-derived reactive sulfur species that maintain sulfide homeostasis in this photosynthetic bacterium and reveal the mechanism of sulfide-dependent transcriptional derepression of genes involved in sulfide metabolism.

High strength copper nickel -- Optimization of mechanical strength and marine corrosion resistance for use in naval architecture and offshore oil and gas

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

Tuck, C.D.S.; Bendall, K.C.; Radford, G.W.J.

1996-08-01

Copper nickel alloys which are able to harden by precipitation reactions involving aluminum are described. The main precipitation species is Ni{sub 3}Al present as 10 mn--15 nm size particles, and strengths above 750 N/mm{sup 2} proof stress have been achieved. Two such alloys have been commercialized and they demonstrate higher corrosion resistance to marine environments than standard cupronickels, most probably due to the passivating influence of aluminum. The reaction of one of these alloys with sodium chloride both with and without the presence of sulfides has been studied, using weight loss, Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM)more » and these techniques indicate a greater degree of passivity for this alloy than for copper or standard cupronickels in sulfide environments. The age-hardenable cupronickels also display complete freedom from hydrogen embrittlement and resistance to biofouling. Service experience with these high strength copper-nickel alloys for highly loaded critical components in naval shipbuilding and offshore oil and gas application is discussed.« less

The mineralogical transformation of a polymetallic sulfide ore during partial roasting

NASA Astrophysics Data System (ADS)

Evrard, Louis

2001-12-01

A partial desulfurization roasting process has been tested on a typical copper-zinc sulfide concentrate in a Nichols Herreshoff monohearth pilot furnace. In this process, the sulfur is partially removed and iron, to a certain degree, is preferentially oxidized. The mineralogical characterizations of the reaction products at different residence times enable the recognition of a sequence of reactions and various textural relationships during the roasting. The testing showed that a controlled desulfurization at a temperature as low as 650°C can lead to the decomposition of chalcopyrite, resulting in the formation of discrete particles of Cu2S having a size ranging from five to 20 micrometers or more.

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

USGS Publications Warehouse

Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.

2008-01-01

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4

A field investigation of the relationship between zinc and acid volatile sulfide concentrations in freshwater sediments

USGS Publications Warehouse

Ankley, Gerald T.; Liber, Karsten; Call, Daniel J.; Markee, Thomas P.; Canfield, Timothy J.; Ingersoll, Christopher G.

1996-01-01

Understanding relationships between cationic metals such as cadmium, copper, nickel, lead and zinc, and amorphous iron sulfides, measured as acid volatile sulfide (AVS), is key to predicting metal bioavailability and toxicity insediments. The objective of the present study was to assess seasonal and spatial variations of AVS in freshwater sediments contaminated with zinc. Sediments were sampled from three streams with varying levels of zinc contamination at two different times, March and June of 1995, representing cold- and warm-weather situations. Interstitial (pore) water concentrations of zinc, and solid phase concentrations of AVS and zinc were measured in surficial and deep sediment horizons. Toxicity tests (10-d) with the amphipodHyalella azteca were conducted using intact cores. Sediment zinc concentrations from six sites within the primary test stream differed by about five-fold, and also varied seasonally. Acid volatile sulfide concentrations were generally lower than those of zinc, and pore water zinc concentrations typically were elevated. There was a positive correlation between solid-phase AVS and zinc concentrations, suggesting that the system was dominated by zinc, as opposed to iron sulfides. In contrast to expectations arising from some studies of seasonal variations of AVS in iron-dominated systems, AVS concentrations were smaller in June than in March. However, this was likely due to a major storm event and associated sediment scouring before the June sampling, rather than to seasonal processes related to variations in temperature and dissolved oxygen. Based upon an indirect analysis of depth variations in AVS, there was some indication that zinc sulfide might be less prone to oxidation than iron sulfide. There was a strong correlation between toxicity of the sediment samples toH. azteca and interstitial water concentrations of zinc; however, the possible contribution of other contaminants to sediment toxicity cannot be dismissed.

Synthesis and Characterization of Phase-pure Copper Zinc Tin Sulfide (Cu2ZnSnS4) Nanoparticles

NASA Astrophysics Data System (ADS)

Monahan, Bradley Michael

Semiconductor nanoparticles have been an important area of research in many different disciplines. A substantial amount of this work has been put toward advancing the field of photovoltaics. However, current p-type photovoltaic materials can not sustain the large scale production needed for future energy demands due to their low elemental abundance. Therefore, Earth abundant semiconductor materials have become of great interest to the photovoltaic community especially, the material copper zinc tin sulfide (CZTS), also known by its mineral name kesterite. CZTS exhibits desirable properties for photovoltaics, such as elemental abundance, high absorption coefficient (~104 cm-1 ), high carrier concentration, and optimum direct band gap (1.5 eV). To date, solution based approaches for making CZTS have yielded the most promising conversion efficiencies in solar cells. To that end, the motivation of nanoparticle based inks that can be used in high throughput production are an attractive route for large scale deployment. This has driven the need to make high quality CZTS nanoparticles that possess the properties of the pure kesterite phase with high monodispersity that can be deposited into dense thin films. The inherent challenge of making a quaternary compound of a single phase has made this a difficult task; however, some of those fundamental problems are addressed in this thesis. This had resulted in the synthesis of phase-pure k-CZTS confirmed by powder X-ray diffraction, Raman spectroscopy, UV-visible absorption spectroscopy and energy dispersive x-ray spectroscopy. Furthermore, ultra-fast laser spectroscopy was done on CZTS thin films made from phase-pure kesterite nanoparticles synthesized in this work. This thesis provides new data that directly probes the lifetime of photogenerated free carriers in kesterite CZTS (k-CZTS) thin films.

Potential for Sulfide Mineral Deposits in Australian Waters

NASA Astrophysics Data System (ADS)

McConachy, Timothy F.

The world is witnessing a paradigm shift in relation to marine mineral resources. High-value seafloor massive sulfides at active convergent plate boundaries are attracting serious commercial attention. Under the United Nations Convention on the Law of the Sea, maritime jurisdictional zones will increase by extending over continental margins and ocean basins. For Australia, this means a possible additional 3.37 million km2 of seabed. Australia's sovereign responsibility includes, amongst other roles, the management of the exploitation of nonliving resources and sea-bed mining. What, therefore, is the potential in Australia's marine jurisdiction for similar deposits to those currently attracting commercial attention in neighboring nations and for other types/styles of sulfide deposits? A preliminary review of opportunities suggests the following: (i) volcanogenic copper—lead—zinc—silver—gold mineralization in fossil arcs and back arcs in eastern waters Norfolk Ridge and the Three Kings Ridge; (ii) Mississippi Valley-type lead—zinc—silver mineralization in the NW Shelf area; (iii) ophiolite-hosted copper mineralization in the Macquarie Ridge Complex in the Southern Ocean; and (iv) submerged extensions of prospective land-based terranes, one example being offshore Gawler Craton for iron oxide—copper—gold deposits. These areas would benefit from pre-competitive surveys of detailed swath bathymetry mapping, geophysical surveys, and sampling to help build a strategic inventory of future seafloor mineral resources for Australia.

Mercury mobilization in a flooded soil by incorporation into metallic copper and metal sulfide nanoparticles.

PubMed

Hofacker, Anke F; Voegelin, Andreas; Kaegi, Ralf; Kretzschmar, Ruben

2013-07-16

Mercury is a highly toxic priority pollutant that can be released from wetlands as a result of biogeochemical redox processes. To investigate the temperature-dependent release of colloidal and dissolved Hg induced by flooding of a contaminated riparian soil, we performed laboratory microcosm experiments at 5, 14, and 23 °C. Our results demonstrate substantial colloidal Hg mobilization concomitant with Cu prior to the main period of sulfate reduction. For Cu, we previously showed that this mobilization was due to biomineralization of metallic Cu nanoparticles associated with suspended bacteria. X-ray absorption spectroscopy at the Hg LIII-edge showed that colloidal Hg corresponded to Hg substituting for Cu in the metallic Cu nanoparticles. Over the course of microbial sulfate reduction, colloidal Hg concentrations decreased but continued to dominate total Hg in the pore water for up to 5 weeks of flooding at all temperatures. Transmission electron microscopy (TEM) suggested that Hg became associated with Cu-rich mixed metal sulfide nanoparticles. The formation of Hg-containing metallic Cu and metal sulfide nanoparticles in contaminated riparian soils may influence the availability of Hg for methylation or volatilization processes and has substantial potential to drive Hg release into adjacent water bodies.

Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

PubMed

Villa-Gomez, D K; Cassidy, J; Keesman, K J; Sampaio, R; Lens, P N L

2014-03-01

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 bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L). Copyright © 2013 Elsevier Ltd. All rights reserved.

Cupriavidus necator H16 Uses Flavocytochrome c Sulfide Dehydrogenase To Oxidize Self-Produced and Added Sulfide

PubMed Central

Lü, Chuanjuan; Xia, Yongzhen; Liu, Daixi; Zhao, Rui; Gao, Rui

2017-01-01

ABSTRACT Production of sulfide (H2S, HS−, and S2−) by heterotrophic bacteria during aerobic growth is a common phenomenon. Some bacteria with sulfide:quinone oxidoreductase (SQR) and persulfide dioxygenase (PDO) can oxidize self-produced sulfide to sulfite and thiosulfate, but other bacteria without these enzymes release sulfide into the medium, from which H2S can volatilize into the gas phase. Here, we report that Cupriavidus necator H16, with the fccA and fccB genes encoding flavocytochrome c sulfide dehydrogenases (FCSDs), also oxidized self-produced H2S. A mutant in which fccA and fccB were deleted accumulated and released H2S. When fccA and fccB were expressed in Pseudomonas aeruginosa strain Pa3K with deletions of its sqr and pdo genes, the recombinant rapidly oxidized sulfide to sulfane sulfur. When PDO was also cloned into the recombinant, the recombinant with both FCSD and PDO oxidized sulfide to sulfite and thiosulfate. Thus, the proposed pathway is similar to the pathway catalyzed by SQR and PDO, in which FCSD oxidizes sulfide to polysulfide, polysulfide spontaneously reacts with reduced glutathione (GSH) to produce glutathione persulfide (GSSH), and PDO oxidizes GSSH to sulfite, which chemically reacts with polysulfide to produce thiosulfate. About 20.6% of sequenced bacterial genomes contain SQR, and only 3.9% contain FCSD. This is not a surprise, since SQR is more efficient in conserving energy because it passes electrons from sulfide oxidation into the electron transport chain at the quinone level, while FCSD passes electrons to cytochrome c. The transport of electrons from the latter to O2 conserves less energy. FCSDs are grouped into three subgroups, well conserved at the taxonomic level. Thus, our data show the diversity in sulfide oxidation by heterotrophic bacteria. IMPORTANCE Heterotrophic bacteria with SQR and PDO can oxidize self-produced sulfide and do not release H2S into the gas phase. C. necator H16 has FCSD but not SQR, and it does

Oceanic Pb-isotopic sources of proterozoic and paleozoic volcanogenic massive sulfide deposits on Prince of Wales Island and vicinity, southeastern Alaska

USGS Publications Warehouse

Ayuso, Robert A.; Karl, Susan M.; Slack, John F.; Haeussler, Peter J.; Bittenbender, Peter E.; Wandless, Gregory A.; Colvin, Anna

2005-01-01

Volcanogenic massive sulfide (VMS) deposits on Prince of Wales Island and vicinity in southeastern Alaska are associated with Late Proterozoic through Cambrian volcanosedimentary rocks of the Wales Group and with Ordovician through Early Silurian felsic volcanic rocks of the Moira Sound unit (new informal name). The massive sulfide deposits in the Wales Group include the Big Harbor, Copper City, Corbin, Keete Inlet, Khayyam, Ruby Tuesday, and Stumble-On deposits, and those in the Moira Sound unit include the Barrier Islands, Moira Copper, Niblack, and Nichols Bay deposits. Pb-isotopic signatures were determined on sulfide minerals (galena, pyrite, chalcopyrite, pyrrhotite, and sphalerite) to constrain metal sources of the massive sulfides and for comparison with data for other deposits in the region. Except for the Ruby Tuesday deposit, galena is relatively rare in most of these deposits. Pb-isotopic signatures distinguish the mainly Cu+Zn±Ag±Au massive sulfide deposits in the Wales Group from the Zn+Cu±Ag±Au massive sulfide deposits in the Moira Sound unit. Among the older group of deposits, the Khayyam deposit has the widest variation in Pb-isotopic ratios (206Pb/204Pb=17.169–18.021, 207Pb/204Pb=15.341–15.499, 208Pb/204Pb=36.546–37.817); data for the other massive sulfide deposits in the Wales Group overlap the isotopic variations in the Khayyam deposit. Pb-isotopic ratios for both groups of deposits are lower than those on the average crustal Pbevolution curve (µ=9.74), attesting to a large mantle influence in the Pb source. All the deposits show no evidence for Pb evolution primarily in the upper or lower continental crust. Samples from the younger group of deposits have scattered Pb-isotopic compositions and plot as a broad band on uranogenic and thorogenic Pb diagrams. Data for these deposits overlap the trend for massive sulfide deposits in the Wales Group but extend to significantly more radiogenic Pb-isotopic values. Pb-isotopic ratios of

A novel method for improving cerussite sulfidization

NASA Astrophysics Data System (ADS)

Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

2016-06-01

Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

2017-03-01

The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

Copper-containing ceramic precursor synthesis: Solid-state transformations and materials technology

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Eckles, William E.; Duraj, Stan A.; Andras, Maria T.; Fanwick, Phillip E.; Richman, Robert M.; Sabat, Michael L.; Power, Michael B.; Gordon, Edward M.; Barron, Andrew

1994-01-01

Three copper systems with relevance to materials technology are discussed. In the first, a CuS precursor, Cu4S1O (4-methylpyridine)(sub 4)- (4-MePy), was prepared by three routes: reaction of Cu2S, reaction of CuBr-SMe2, and oxidation of copper powder with excess sulfur in 4-methylpyridine by sulfur. In the second, copper powder was found to react with excess thiourea (H2NC(S)NH2) in 4-methylpyridine to produce thiocyanate (NCS(-)) complexes. Three isolated and characterized compounds are: Cu(NCS)(4-MePy)(sub 2), a polymer, (4-MePy-H)(Cu(NCS)(sub 3)(4-MePy)(sub 2)), a salt, and t-Cu(NCS)(sub 2)(4-MePy)(sub 4). Finally, an attempt to produce a mixed-metal sulfide precursor of Cu and Ga in N-methylimidazole (N-MeIm) resulted in the synthesis of a Cu-containing polymer, Cu(SO4)(N-MeIm). The structures are presented; the chemistry will be briefly discussed in the context of preparation and processing of copper-containing materials for aerospace applications.

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Sulfide oxidation under chemolithoautotrophic denitrifying conditions.

PubMed

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

2006-12-20

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

Microbial control of hydrogen sulfide production

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

Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.

1995-12-31

A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of coresmore » and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.« less

Hydrogen sulfide measurement using sulfide dibimane: critical evaluation with electrospray ion trap mass spectrometry

PubMed Central

Shen, Xinggui; Chakraborty, Sourav; Dugas, Tammy R; Kevil, Christopher G

2015-01-01

Accurate measurement of hydrogen sulfide bioavailability remains a technical challenge due to numerous issues involving sample processing, detection methods used, and actual biochemical products measured. Our group and others have reported that reverse phase HPLC detection of sulfide dibimane (SDB) product from the reaction of H2S/HS− with monobromobimane allows for analytical detection of hydrogen sulfide bioavailability in free and other biochemical forms. However, it remains unclear whether possible interfering contaminants may contribute to HPLC SDB peak readings that may result in inaccurate measurements of bioavailable sulfide. In this study, we critically compared hydrogen sulfide dependent SDB detection using reverse phase HPLC (RP-HPLC) versus quantitative SRM electrospray ionization mass spectrometry (ESI/MS) to obtain greater clarity into the validity of the reverse phase HPLC method for analytical measurement of hydrogen sulfide. Using an LCQ-deca ion-trap mass spectrometer, SDB was identified by ESI/MS positive ion mode, and quantified by selected reaction monitoring (SRM) using hydrocortisone as an internal standard. Collision induced dissociation (CID) parameters were optimized at MS2 level for SDB and hydrocortisone. ESI/MS detection of SDB standard was found to be a log order more sensitive than RP-HPLC with a lower limit of 0.25 nM. Direct comparison of tissue and plasma SDB levels using RP-HPLC and ESI/MS methods revealed comparable sulfide levels in plasma, aorta, heart, lung and brain. Together, these data confirm the use of SDB as valid indicator of H2S bioavailability and highlights differences between analytical detection methods. PMID:24932544

Efficient removal of copper from wastewater by using mechanically activated calcium carbonate.

PubMed

Hu, Huimin; Li, Xuewei; Huang, Pengwu; Zhang, Qiwu; Yuan, Wenyi

2017-12-01

Copper removal from aqueous solution is necessary from the stances of both environmental protection and copper resource recycling. It is important to develop a new chemical precipitation method suitable for removing copper particularly at low concentration as the case of waste mine water, with regards to the various problems related to the current precipitation methods by using strong alkalis or soluble sulfides. In this research, we studied a possible chemical precipitation of copper ions at concentration around 60 mg/L or lower by cogrinding copper sulfate in water with calcium carbonate (CaCO 3 ) using wet stirred ball milling. With the aid of ball milling, copper precipitation as a basic sulfate (posnjakite: Cu 4 (SO 4 ) (OH) 6 ·H 2 O) occurred at a very high copper removal rate of 99.76%, to reduce the residual copper concentration in the solution less than 0.5 mg/L, reaching the discharge limit, even with the addition amount of CaCO 3 as a stoichiometric ratio of CaCO 3 /Cu 2+ at 1:1. It is more interesting to notice that, at the same conditions, other heavy metals such as Ni, Mn, Zn and Cd do not precipitate obviously just with CaCO 3 addition at CaCO 3 /M 2+ at 1:1 so that the precipitate without the impurities can be processed as good source to recover copper. This newly proposed concept can be further developed to treat wastewaters with other metals to serve both purposes of environmental purification and resource recovery in a similar way. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfide binding properties of truncated hemoglobins.

PubMed

Nicoletti, Francesco P; Comandini, Alessandra; Bonamore, Alessandra; Boechi, Leonardo; Boubeta, Fernando Martin; Feis, Alessandro; Smulevich, Giulietta; Boffi, Alberto

2010-03-16

The truncated hemoglobins from Bacillus subtilis (Bs-trHb) and Thermobifida fusca (Tf-trHb) have been shown to form high-affinity complexes with hydrogen sulfide in their ferric state. The recombinant proteins, as extracted from Escherichia coli cells after overexpression, are indeed partially saturated with sulfide, and even highly purified samples still contain a small but significant amount of iron-bound sulfide. Thus, a complete thermodynamic and kinetic study has been undertaken by means of equilibrium and kinetic displacement experiments to assess the relevant sulfide binding parameters. The body of experimental data indicates that both proteins possess a high affinity for hydrogen sulfide (K = 5.0 x 10(6) and 2.8 x 10(6) M(-1) for Bs-trHb and Tf-trHb, respectively, at pH 7.0), though lower with respect to that reported previously for the sulfide avid Lucina pectinata I hemoglobins (2.9 x 10(8) M(-1)). From the kinetic point of view, the overall high affinity resides in the slow rate of sulfide release, attributed to hydrogen bonding stabilization of the bound ligand by distal residue WG8. A set of point mutants in which these residues have been replaced with Phe indicates that the WG8 residue represents the major kinetic barrier to the escape of the bound sulfide species. Accordingly, classical molecular dynamics simulations of SH(-)-bound ferric Tf-trHb show that WG8 plays a key role in the stabilization of coordinated SH(-) whereas the YCD1 and YB10 contributions are negligible. Interestingly, the triple Tf-trHb mutant bearing only Phe residues in the relevant B10, G8, and CD1 positions is endowed with a higher overall affinity for sulfide characterized by a very fast second-order rate constant and 2 order of magnitude faster kinetics of sulfide release with respect to the wild-type protein. Resonance Raman spectroscopy data indicate that the sulfide adducts are typical of a ferric iron low-spin derivative. In analogy with other low-spin ferric sulfide

Quality control considerations for the determination of acid-volatile sulfide and simultaneously extracted metals in sediments

USGS Publications Warehouse

Brumbaugh, William G.; Arms, Jesse W.

1996-01-01

The determination of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEMs) in sediment by treatment with dilute HCl shows promise as a tool for predicting the potential for metal toxicity to sediment-dwelling organisms. Effective quality control measures must be developed if this method is to become a reliable procedure and to ensure comparability of data. However, establishing quality control measures that assess procedural errors for an operationally defined method can be problematic. For example, preextraction spikes added for assessing the accuracy of AVS and SEMs may be poorly recovered due to adsorption or reaction with sediment constituents. For a variety of sediment types, we found preextraction spikes of sulfide, mercury, and copper to be prone to variable recoveries for the AVS/SEM procedure; recoveries averaged 76.3% (SD, 20.9) for sulfide, 61.9% (39.6) for Hg, and 90.1% (12.7) for Cu. The average recovery was near 100% for preextraction spikes of sediments for Cd, Ni, Pb, and Zn, and the recoveries of preextraction blank spikes for all analytes were consistently 95 to 105%. Binding of Cu or Hg with sulfides is sufficiently strong that 1 N hydrochloric acid will not necessarily keep the spiked metal in the dissolved state. This does not mean that the SEM procedure is invalid for these metals, only that the quality control of procedural error is difficult to assess. However, Hg will generally not be detected when measured as an SEM because of its tendency to adsorb onto sulfide minerals even at extremely low pH. Some reference sediments may be useful for assessing consistency of AVS determinations; we measured 5.97 ± 0.65 μmol/g in National Institute of Standards and Technology (NIST) 1645 and 1.34 ± 0.14 μmol/g in NIST 2704 for repeated determinations conducted over the past 3 years. Apparently, some sediments may contain an oxidation-resistant sulfide component that can release low to moderate AVS when treated with dilute HCl.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1987-01-01

A method of 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.

Development of copper recovery process from flotation tailings by a combined method of high‒pressure leaching‒solvent extraction.

PubMed

Han, Baisui; Altansukh, Batnasan; Haga, Kazutoshi; Stevanović, Zoran; Jonović, Radojka; Avramović, Ljiljana; Urosević, Daniela; Takasaki, Yasushi; Masuda, Nobuyuki; Ishiyama, Daizo; Shibayama, Atsushi

2018-06-15

Sulfide copper mineral, typically Chalcopyrite (CuFeS 2 ), is one of the most common minerals for producing metallic copper via the pyrometallurgical process. Generally, flotation tailings are produced as a byproduct of flotation and still consist of un‒recovered copper. In addition, it is expected that more tailings will be produced in the coming years due to the increased exploration of low‒grade copper ores. Therefore, this research aims to develop a copper recovery process from flotation tailings using high‒pressure leaching (HPL) followed by solvent extraction. Over 94.4% copper was dissolved from the sample (CuFeS 2 as main copper mineral) by HPL in a H 2 O media in the presence of pyrite, whereas the iron was co‒dissolved with copper according to an equation given as C Cu  = 38.40 × C Fe . To avoid co‒dissolved iron giving a negative effect on the subsequent process of electrowinning, solvent extraction was conducted on the pregnant leach solution for improving copper concentration. The result showed that 91.3% copper was recovered in a stripped solution and 98.6% iron was removed under the optimal extraction conditions. As a result, 86.2% of copper was recovered from the concentrate of flotation tailings by a proposed HPL‒solvent extraction process. Copyright © 2018 Elsevier B.V. All rights reserved.

Copper speciation in sulfidic solutions at low sulfur activity: Further evidence for cluster complexes?

NASA Astrophysics Data System (ADS)

Thompson, Richard A.; Helz, George R.

1994-07-01

The solubility of two as0-buffering assemblages in the Cu-S system have been studied: chalcocite-djurleite (Cc-Dj) and anilite-covellite (An-Cv). Ion activity products, [Cu +]HS -] 1/2[H +] - 1/2 (25°C, I = 0) at equilibrium, derived from solubility measurements in penicillamine solutions, are 10 -17.01 ± 0.05 (Cc-Dj) and 10 -17.14 ± 0.10 (An-Cv), from which ΔG° f = -82.11 kJ/mol for Cc and -74.77 kJ/mol for An. In the An-Cv assemblage, aCu2S = 0.55 (2 σ = 0.2) vs. 1.00 in the Cc-containing assemblage. The difference in aCu2S between the two assemblages is used in a novel way to estimate stoichiometry of Cu-HS complexes. The solubility of both assemblages (0.7-0.01 M NaHS, pH 7-12.5, 25°C) can be fit with a model incorporating the same two chemical species, one containing an odd number of Cu atoms (Cu(HS) 2-3, CU 3S 4H 2-3, or a higher multimer) and the other containing an even number of Cu atoms (Cu 2S(HS) 22-, Cu 4S 4H 22-, etc.). The trimer-tetramer model fits the combined data for the two assemblages distinctly better than the monomer-dimer model, but this result is very sensitive to uncertainty in aCu2S. Along with EXAFS results, the weight of the evidence favors small cluster complexes (2-5 Cu atoms), but is inconclusive at the present level of resolution. Multimers can be rationalized because condensation of metal-centered monomers to clusters provides a means for soft acid/base elements to maintain favored coordination geometries at low ligand to metal ratios. Based on the fitting methods developed here, previous covellite solubility data from this laboratory are reinterpreted in terms of Cu 2S 2(HS) 33-, Cu 2S 3)(S 4) 2-, and Cu(S 9)S 10) 3-; the last of these could also be represented by the trimer, Cu 3(S 7) 33-, which is homologous with a known complex. With the measured equilibrium constants, the speciation of Cu in the sulfidic zone of the Black Sea is calculated. Covellite is the stable Cu-S mineral, but the sulfidic water column is vastly

Solubility of copper in a sulfur-free mafic melt

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.

1995-12-01

The solubility of Cu in S-free mafic melts has been measured at a series of ƒ O2 values and temperatures of 1245 and 1300°C. At constant temperature Cu solubility increases from 0.04 wt% at log ƒ O2 = -11.9 to 1.10 wt% at log ƒ O 2 = -7.4 . Copper solubilities were in excess of 8 wt% in two runs controlled at very high ƒ O2 conditions of 10 -1.4 and 10 -22 Partitioning of Cu between metal and glass shows a strong ƒ O2 dependence, with D Cumet/gl ranging from 90 at log ƒ O2 = -7.4 to 2190 at log ƒ O2 = -11.9 . Slopes of Cu solubility and DCumet/gl vs. log ƒ O2 suggest that Cu dissolves predominantly in the +1 valence state. Copper solubility decreases with increasing temperature at constant ƒ O2, similar to experimental results for Ni, Co, and Mo (Dingwell et al., 1994; Holzheid et al., 1994). The data are consistent with Cu dissolution as an oxide (represented by CuO 0.5) and suggest that changes in ƒ O2 ( Fe2+/Fe3+ variations and Cu 1+ complexation with Fe 3+) may have large effects on the distribution of Cu between silicate and sulfide magmas. Results also suggest that the extraction of oxide-bonded Cu in mafic magmas by externally derived S may be an important mechanism in the generation of Cu-rich sulfide ores.

Chemical Bonding in Sulfide Minerals

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

Vaughan, David J.; Rosso, Kevin M.

An understanding of chemical bonding and electronic structure in sulfide minerals is central to any attempt at understanding their crystal structures, stabilities and physical properties. It is also an essential precursor to understanding reactivity through modeling surface structure at the molecular scale. In recent decades, there have been remarkable advances in first principles (ab initio) methods for the quantitative calculation of electronic structure. These advances have been made possible by the very rapid development of high performance computers. Several review volumes that chart the applications of these developments in mineralogy and geochemistry are available (Tossell and Vaughan, 1992; Cygan andmore » Kubicki, 2001). An important feature of the sulfide minerals is the diversity of their electronic structures, as evidenced by their electrical and magnetic properties (see Pearce et al. 2006, this volume). Thus, sulfide minerals range from insulators through semiconductors to metals, and exhibit every type of magnetic behavior. This has presented problems for those attempting to develop bonding models for sulfides, and also led to certain misconceptions regarding the kinds of models that may be appropriate. In this chapter, chemical bonding and electronic structure models for sulfides are reviewed with emphasis on more recent developments. Although the fully ab initio quantitative methods are now capable of a remarkable degree of sophistication in terms of agreement with experiment and potential to interpret and predict behavior with varying conditions, both qualitative and more simplistic quantitative approaches will also be briefly discussed. This is because we believe that the insights which they provide are still helpful to those studying sulfide minerals. In addition to the application of electronic structure models and calculations to solid sulfides, work on sulfide mineral surfaces (Rosso and Vaughan 2006a,b) and solution complexes and clusters

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

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.

Surface and capillary forces encountered by zinc sulfide microspheres in aqueous electrolyte.

PubMed

Gillies, Graeme; Kappl, Michael; Butt, Hans-Jürgen

2005-06-21

The colloid probe technique was used to investigate the interactions between individual zinc sulfide (ZnS) microspheres and an air bubble in electrolyte solution. Incorporation of zinc ions into the electrolyte solution overcomes the disproportionate zinc ion dissolution and mimics high-volume-fraction conditions common in flotation. Determined interaction forces revealed a distinct lack of long-ranged hydrophobic forces, indicated by the presence of a DLVO repulsion prior to particle engulfment. Single microsphere contact angles were determined from particle-bubble interactions. Contact angles increased with decreasing radii and with surface oxidation. Surface modification by the absorption of copper and subsequently potassium O-ethyldithiocarbonate (KED) reduced repulsive forces and strongly increased contact angles.

Dzhezkazgan and associated sandstone copper deposits of the Chu-Sarysu basin, Central Kazakhstan

USGS Publications Warehouse

Box, Stephen E.; Seltmann, Reimar; Zientek, Michael L.; Syusyura, Boris; Creaser, Robert A.; Dolgopolova, Alla

2012-01-01

Sandstone-hosted copper (sandstone Cu) deposits occur within a 200-km reach of the northern Chu-Sarysu basin of central Kazakhstan (Dzhezkazgan and Zhaman-Aibat deposits, and the Zhilandy group of deposits). The deposits consist of Cu sulfide minerals as intergranular cement and grain replacement in 10 ore-bearing members of sandstone and conglomerate within a 600- to 1,000-m thick Pennsylvanian fluvial red-bed sequence. Copper metal content of the deposits ranges from 22 million metric tons (Mt, Dzehzkazgan) to 0.13Mt (Karashoshak in the Zhilandy group), with average grades of 0.85 to 1.7% Cu and significant values for silver (Ag) and rhenium (Re). Broader zones of iron reduction (bleaching) of sandstones and conglomerates of the red-bed sequence extend over 10 km beyond each of the deposits along E-NE-trending anticlines, which began to form in the Pennsylvanian. The bleached zones and organic residues within them are remnants of ormer petroleum fluid accumulations trapped by these anticlines. Deposit sites along these F1anticlines are localized at and adjacent to the intersections of nearly orthogonal N-NW-trending F2synclines. These structural lows served to guide the flow of dense ore brines across the petroleum-bearing anticlines, resulting in ore sulfide precipitation where the two fluids mixed. The ore brine was sourced either from the overlying Early Permian lacustrine evaporitic basin, whose depocenter occurs between the major deposits, or from underlying Upper Devonian marine evaporites. Sulfur isotopes indicate biologic reduction of sulfate but do not resolve whether the sulfate was contributed from the brine or from the petroleum fluids. New Re-Os age dates of Cu sulfides from the Dzhezkazgan deposit indicate that mineralization took place between 299 to 309 Ma near the Pennsylvanian-Permian age boundary. At the Dzhezkazgan and some Zhilandy deposits, F2fold deformation continued after ore deposition. Copper orebodies in Lower Permian

The carbonaceous phyllite rock-hosted Pedra Verde copper mine, Borborema Province, Brazil: Stable isotope constraints, structural controls and metallogenic evolution

NASA Astrophysics Data System (ADS)

da Silva Nogueira de Matos, José Henrique; Saraiva dos Santos, Ticiano José; Virgínia Soares Monteiro, Lena

2017-12-01

The Pedra Verde Copper Mine is located in the Viçosa do Ceará municipality, State of Ceará, NE Brazil. The copper mineralization is hosted by the Pedra Verde Phyllite, which is a carbonaceous chlorite-calcite phyllite with subordinate biotite. It belongs to the Neoproterozoic Martinópole Group of the Médio Coreaú Domain, Borborema Province. The Pedra Verde deposit is stratabound and its ore zoning is conspicuous, according to the following sequence, from bottom to top: marcasite/pyrite, native silver, chalcopyrite, bornite, chalcocite, native copper and hematite. Barite and carbonaceous material are reported in ore zones. Zoning reflects the ore formation within a redox boundary developed due to the interaction between oxidized copper- and sulfate-bearing fluids and the reduced phyllite. Structural control on mineralization is evidenced by the association of the ore minerals with veins, hinge folds, shadow pressures, and mylonitic foliation. It was mainly exercised by a dextral transcurrent shear zone developed during the third deformational stage identified in the Médio Coreaú Domain between 590 Ma and 570 Ma. This points to the importance of epigenetic, post-metamorphic deformational events for ore formation. Oxygen isotopic composition (δ18OH2O = 8.94 to 11.28‰, at 250 to 300 °C) estimated for the hydrothermal fluids in equilibrium with calcite indicates metamorphic or evolved meteoric isotopic signatures. The δ13CPDB values (-2.60 to -9.25‰) obtained for hydrothermal calcite indicate mixing of carbon sources derived from marine carbonate rocks and carbonaceous material. The δ34SCDT values (14.88 to 36.91‰) of sulfides suggest evaporites as sulfate sources or a closed system in relation to SO42- availability to form H2S. Carbonaceous matter had a key role in thermochemical sulfate processes and sulfide precipitation. The Pedra Verde Copper Mine is considered the first stratabound meta-sedimentary rock-hosted copper deposit described in Brazil

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

NASA Astrophysics Data System (ADS)

Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

2013-06-01

Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

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...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

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...

The Evolution of Sulfide Tolerance in the Cyanobacteria

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

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...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.504 Section 250.504...-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.604 Section 250.604...-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in...

Anti-inflammatory and cytoprotective properties of hydrogen sulfide.

PubMed

Gemici, Burcu; Wallace, John L

2015-01-01

Hydrogen sulfide is an endogenous gaseous mediator that plays important roles in many physiological processes in microbes, plants, and animals. This chapter focuses on the important roles of hydrogen sulfide in protecting tissues against injury, promoting the repair of damage, and downregulating the inflammatory responses. The chapter focuses largely, but not exclusively, on these roles of hydrogen sulfide in the gastrointestinal tract. Hydrogen sulfide is produced throughout the gastrointestinal tract, and it contributes to maintenance of mucosal integrity. Suppression of hydrogen sulfide synthesis renders the tissue more susceptible to injury and it impairs repair. In contrast, administration of hydrogen sulfide donors can increase resistance to injury and accelerate repair. Hydrogen sulfide synthesis is rapidly and dramatically enhanced in the gastrointestinal tract after injury is induced. These increases occur specifically at the site of tissue injury. Hydrogen sulfide also plays an important role in promoting resolution of inflammation, and restoration of normal tissue function. In recent years, these beneficial actions of hydrogen sulfide have provided the basis for development of novel hydrogen sulfide-releasing drugs. Nonsteroidal anti-inflammatory drugs that release small amounts of hydrogen sulfide are among the most advanced of the hydrogen sulfide-based drugs. Unlike the parent drugs, these modified drugs do not cause injury in the gastrointestinal tract, and do not interfere with healing of preexisting damage. Because of the increased safety profile of these drugs, they can be used in circumstances in which the toxicity of the parent drug would normally limit their use, such as in chemoprevention of cancer. © 2015 Elsevier Inc. All rights reserved.

NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

EPA Science Inventory

An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

Using XAS and SXRF to Study Copper in Wilson Disease at the Molecular and Tissue Level

NASA Astrophysics Data System (ADS)

Ralle, Martina; Blackburn, Ninian J.; Lutsenko, Svetlana

2007-02-01

Wilson disease (WD) is a genetic disorder of copper metabolism associated with severe hepatic, neurological, and psychiatric abnormalities. In WD, the billiary copper excretion is impaired and copper accumulates in tissues, particularly in the liver and the brain. The affected gene, ATP7B, encodes the copper transporting ATPase, Wilson disease protein (WNDP). WNDP has six copper binding sites in the N-terminal portion of the molecule. Each site includes the conserved amino acid sequence MXCXXC, and binds 1 Cu(I) through its 2 cysteine residues. We performed X-ray absorption studies at the Cu Kα-edge on the recombinant N-terminal domain of WNDP (N-WNDP). Copper was bound to N-WNDP either in vivo or in vitro in the presence of different reducing agents. We found that in N-WNDP copper is predominantly coordinated in a linear fashion by two cysteines, with the appearance of a Cu-Cu interaction when all metal binding sites are filled. Increasing amounts of reducing agents containing sulfide or phosphine groups led to binding of the exogenous ligands to copper thereby increasing the coordination number of copper from two to three. To better understand the role of copper in WD, we utilized livers of the 6-weeks-old Atp7b-/- mice (an animal model for WD) in which the copper concentration was 10-20-fold higher compared to that of the control mice. The distribution of copper in hepatocytes was evaluated by synchrotron based X-ray fluorescence microprobe (SXRF). We demonstrate that we can prepare liver slices that retain copper and can detect copper with subcellular resolution. On the same sections μ-XANES (spot size: 5 micron) was used to determine the oxidation state of copper.

The use of ERTS-1 images in the search for large sulfide deposits in the Chagai District, Pakistan

NASA Technical Reports Server (NTRS)

Schmidt, R. G. (Principal Investigator)

1974-01-01

The author has identified the following significant results. Visual examination of color composites was tested under relatively ideal conditions for direct detection of large hydrothermal sulfide deposits at the low-grade porphyry copper deposit at Saindak, western Chagai District, Pakistan. The Saindak deposit is characterized by an elongate zone of easily eroded sulfide-rich rock surrounded by a resistant rim of hornfels and propylitically altered rock. The geomorphic features related to the Saindak deposit are easily distinguished on ERTS-1 images. Attempts to detect a color anomaly using false-color composites were not successful. About 36,000 square km of the western Chagai District were examined on false-color composites for direct evidence of large sulfide deposits. New geologic information acquired from the images was used in conjunction with the known geology to evaluate two previously known proposed areas and to suggest seven additional targets for field checking, one of which is proposed on the basis of tonal anomaly alone. The study also showed that Saindak-type deposits are not likely to be present in some extensive areas of the Chagai District; and also that a rim like that at Saindak does not form if regional metamorphism has increased the resistance of the country rock to erosion.

An ultrasensitive electrochemiluminescence sensor based on reduced graphene oxide-copper sulfide composite coupled with capillary electrophoresis for determination of amlodipine besylate in mice plasma.

PubMed

Wei, Yanfen; Wang, Hao; Sun, Shuangjiao; Tang, Lifu; Cao, Yupin; Deng, Biyang

2016-12-15

A new electrochemiluminescence (ECL) sensor based on reduced graphene oxide-copper sulfide (rGO-CuS) composite coupled with capillary electrophoresis (CE) was constructed for the ultrasensitive detection of amlodipine besylate (AML) for the first time. In this work, rGO-CuS composite was synthesized by one-pot hydrothermal method and used for electrode modification. The electrochemical and ECL behaviors of the sensor were investigated. More than 5-fold enhance in ECL intensity was observed after modified with rGO-CuS composite. The results can be ascribed to the presence of rGO-CuS composite on the electrode surface that facilitates the electron transfer rate between the electroactive center of Ru(bpy)3(2+) and the electrode. The ECL sensor was coupled with CE to improve the selectivity and the CE-ECL parameters that affect separation and detection were optimized. Under the optimum conditions, the linear ranges for AML was 0.008-5.0μg/mL with a detection limit of 2.8ng/mL (S/N=3). The method displayed the advantages of high sensitivity, good selectivity, wide linear range, low detection limit and fine reproducibility, and was used to analyze AML in mice plasma with a satisfactory result, which holds a great potential in the field of pharmaceutical analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

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

NASA Astrophysics Data System (ADS)

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

Sulfur and sulfides in chondrules

NASA Astrophysics Data System (ADS)

Marrocchi, Yves; Libourel, Guy

2013-10-01

The nature and distribution of sulfides within type I PO, POP and PP chondrules of the carbonaceous chondrite Vigarano (CV3) have been studied by secondary electron microscopy and electron microprobe. They occur predominantly as spheroidal blebs composed entirely of low-Ni iron sulfide (troilite, FeS) or troilite + magnetite but in less abundance in association with metallic Fe-Ni beads in opaque assemblages. Troilites are mainly located within the low-Ca pyroxene outer zone and their amounts increase with the abundance of low-Ca pyroxene within chondrules, suggesting co-crystallization of troilite and low-Ca pyroxene during high-temperature events. We show that sulfur concentration and sulfide occurrence in chondrules obey high temperature sulfur solubility and saturation laws. Depending on the fS2 and fO2 of the surrounding gas and on the melt composition, mainly the FeO content, sulfur dissolved in chondrule melts may eventually reach a concentration limit, the sulfur content at sulfide saturation (SCSS), at which an immiscible iron sulfide liquid separates from the silicate melt. The occurrence of both a silicate melt and an immiscible iron sulfide liquid is further supported by the non-wetting behavior of sulfides on silicate phases in chondrules due to the high interfacial tension between their precursor iron-sulfide liquid droplets and the surrounding silicate melt during the high temperature chondrule-forming event. The evolution of chondrule melts from PO to PP towards more silicic compositions, very likely due to high PSiO(g) of the surrounding nebular gas, induces saturation of FeS at much lower S content in PP than in PO chondrules, leading to the co-crystallization of iron sulfides and low-Ca pyroxenes. Conditions of co-saturation of low-Ca pyroxene and FeS are only achieved in non canonical environments characterized by high partial pressures of sulfur and SiO and redox conditions more oxidizing than IW-3. Fe and S mass balance calculations also

The Fate of Malathion on Copper and Iron Piping Within a Water Distribution System

DTIC Science & Technology

2015-03-26

environmental and food conditions of 50 µg cm-2 to 100 µg cm-2 and 200 µg cm-2 of soil and worms, respectively. The results were conclusive; there were...principal technique depends on the detection of molecule absorbance of infrared radiation; the absorbance of radiation is proportionate to increases... Traces of this salt or sulfide may have physically bonded to the copper. H(g) + S(s) H2S(g) (5) Where H, hydrogen gas; reacts with S

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

USGS Publications Warehouse

Learned, R.E.; Chao, T.T.; Sanzolone, R.F.

1981-01-01

In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and "reactive" Fe oxides; (2) "amorphous" Fe oxides; (3) "crystalline" Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments. The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment. The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping. Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended. ?? 1981.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

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

Occurrence model for magmatic sulfide-rich nickel-copper-(platinum-group element) deposits related to mafic and ultramafic dike-sill complexes: Chapter I in Mineral deposit models for resource assessment

USGS Publications Warehouse

Schulz, Klaus J.; Woodruff, Laurel G.; Nicholson, Suzanne W.; Seal, Robert R.; Piatak, Nadine M.; Chandler, Val W.; Mars, John L.

2014-01-01

The sulfides in magmatic Ni-Cu deposits generally constitute a small volume of the host rock(s) and tend to be concentrated in the lower parts of the mafic and/or ultramafic bodies, often in physical depressions or areas marking changes in the geometry of the footwall topography. In most deposits, the sulfide mineralization can be divided into disseminated, matrix or net, and massive sulfide, depending on a combination of the sulfide content of the rock and the silicate texture. The major Ni-Cu sulfide mineralogy typically consists of an intergrowth of pyrrhotite (Fe7S8), pentlandite ([Fe, Ni]9S8), and chalcopyrite (FeCuS2). Cobalt, PGE, and gold (Au) are extracted from most magmatic Ni-Cu ores as byproducts, although such elements can have a significant impact on the economics in some deposits, such as the Noril’sk-Talnakh deposits, which produce much of the world’s palladium. In addition, deposits may contain between 1 and 15 percent magnetite associated with the sulfides.

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

PubMed Central

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 with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored 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. PMID:26030258

The Search for Interstellar Sulfide Grains

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Messenger, Scott

2010-01-01

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

Geochemical Exploration Techniques Applicable in the Search for Copper Deposits

USGS Publications Warehouse

Chaffee, Maurice A.

1975-01-01

Geochemical exploration is an important part of copper-resource evaluation. A large number of geochemical exploration techniques, both proved and untried, are available to the geochemist to use in the search for new copper deposits. Analyses of whole-rock samples have been used in both regional and local geochemical exploration surveys in the search for copper. Analyses of mineral separates, such as biotite, magnetite, and sulfides, have also been used. Analyses of soil samples are widely used in geochemical exploration, especially for localized surveys. It is important to distinguish between residual and transported soil types. Orientation studies should always be conducted prior to a geochemical investigation in a given area in order to determine the best soil horizon and the best size of soil material for sampling in that area. Silty frost boils, caliche, and desert varnish are specialized types of soil samples that might be useful sampling media. Soil gas is a new and potentially valuable geochemical sampling medium, especially in exploring for buried mineral deposits in arid regions. Gaseous products in samples of soil may be related to base-metal deposits and include mercury vapor, sulfur dioxide, hydrogen sulfide, carbon oxysulfide, carbon dioxide, hydrogen, oxygen, nitrogen, the noble gases, the halogens, and many hydrocarbon compounds. Transported materials that have been used in geochemical sampling programs include glacial float boulders, glacial till, esker gravels, stream sediments, stream-sediment concentrates, and lake sediments. Stream-sediment sampling is probably the most widely used and most successful geochemical exploration technique. Hydrogeochemical exploration programs have utilized hot- and cold-spring waters and their precipitates as well as waters from lakes, streams, and wells. Organic gel found in lakes and at stream mouths is an unproved sampling medium. Suspended material and dissolved gases in any type of water may also be useful

Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

NASA Astrophysics Data System (ADS)

Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

2015-01-01

The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

Photocatalytic antibacterial activity of copper-based nanoparticles under visible light illumination

NASA Astrophysics Data System (ADS)

Wu, Zong-Yan; Abdullah, Hairus; Kuo, Dong-Hau

2018-04-01

Copper oxide and sulfide nanoparticles after annealing treatment at 400 °Chave been characterized and tested for their bactericidal properties toward Staphylococcus aureus and Escherichia coli under the dark and LED light illuminated conditions. It was found that the nanoparticles with the formation of CuS/Cu2S/CuO nanoheterostructuresexhibited a great capability of killing Staphylococcus aureus and Escherichia coli with or without light illumination. The antibacterial activity of the nanoparticles was demonstrated and simply observed with colony counting method. A mechanism of the antibacterial behaviour had been proposed and elucidated in this work.

Anomalous concentrations of zinc and copper in highmoor peat bog, southeast coast of Lake Baikal

NASA Astrophysics Data System (ADS)

Bobrov, V. A.; Bogush, A. A.; Leonova, G. A.; Krasnobaev, V. A.; Anoshin, G. N.

2011-08-01

When examining the peat deposit discovered in Vydrinaya bog, South Baikal region, the authors encountered anomalous Zn and Cu concentrations for highmoors being up to 600-500 ppm on a dry matter basis in the Early Holocene beds (360-440 cm) formed 11 000-8500 years ago. It has been demonstrated that Zn and Cu are present inside the plant cells of peat moss in the form of authigenic sulfide minerals of micron size. Apart from Zn and Cu, native Ag particles (5-7 um) have been encountered in the peat of the Vydrinaya bog at a depth of 390-410 cm; these particles formed inside the organic matter of the plasma membrane of peat moss containing Ca, Al, S, and Cu. This study suggests probable patterns of the formation of zinc sulfides, copper sulfides, and native silver in peat moss. The results obtained indicate that biogenic mineral formation plays a significant role in this system, which is a very important argument in the discussion on the ore genesis, in which physicochemical processes are normally favored, while the role of living matter is quite frequently disregarded.

Experimental simulations of sulfide formation in the solar nebula.

PubMed

Lauretta, D S; Lodders, K; Fegley, B

1997-07-18

Sulfurization of meteoritic metal in H2S-H2 gas produced three different sulfides: monosulfide solid solution [(Fe,Ni)1-xS], pentlandite [(Fe,Ni)9-xS8], and a phosphorus-rich sulfide. The composition of the remnant metal was unchanged. These results are contrary to theoretical predictions that sulfide formation in the solar nebula produced troilite (FeS) and enriched the remaining metal in nickel. The experimental sulfides are chemically and morphologically similar to sulfide grains in the matrix of the Alais (class CI) carbonaceous chondrite, suggesting that these meteoritic sulfides may be condensates from the solar nebula.

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide...

Reduction of acid rock drainage using steel slag in cover systems over sulfide rock waste piles.

PubMed

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.

Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

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

Kamiguchi, Satoshi, E-mail: kamigu@riken.jp; Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198; Okumura, Kazu

Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is storedmore » in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.« less

Invisible and microscopic gold in pyrite: Methods and new data for massive sulfide ores of the Urals

NASA Astrophysics Data System (ADS)

Vikentyev, I. V.

2015-07-01

particles was registered in the ores of these deposits by the methods of transmission electron microscopy. The low degree (or absence) of metamorphic recrystallization results in (1) predomination of thin intergrowths of sulfides, which is the main reason for the bad concentration of ores (especially for the Galkinsk deposit) and (2) the high portion of "invisible" gold in the massive sulfide ores, which explains the low yield of Au in copper and zinc concentrates, since it is lost in tailings with predominating pyrite.

Mineralogy and Geochemical Processes of Carbonate Mineral-rich Sulfide Mine Tailings, Zimapan, Mexico

NASA Astrophysics Data System (ADS)

McClure, R. J.; Deng, Y.; Loeppert, R.; Herbert, B. E.; Carrillo, R.; Gonzalez, C.

2009-12-01

Mining for silver, lead, zinc, and copper in Zimapan, Hidalgo State, Mexico has been ongoing since 1576. High concentrations of heavy metals have been found in several mine tailing heaps in the Zimapan area, with concentrations of arsenic observed as high as 28,690 mg/kg and levels of Pb as high as 2772 mg/kg. Unsecured tailings heaps and associated acid mine drainage has presented tremendous problems to revegetation, water quality, and dust emission control in the Zimapan area. Although acid mine drainage problems related to weathering of sulfide minerals have been extensively studied and are well known, the weathering products of sulfides in areas with a significant presence of carbonate minerals and their effect on the mobility of heavy metals warrant further study. Carbonate minerals are expected to neutralize sulfuric acid produced from weathering of sulfide minerals, however, in the Zimapan area localized areas of pH as low as 1.8 were observed within carbonate mineral-rich tailing heaps. The objectives of this study are to characterize (1) the heavy metal-containing sulfide minerals in the initial tailing materials, (2) the intermediate oxidation products of sulfide minerals within the carbonate-rich tailings, (3) chemical species of heavy metals within pH gradients between 1.8 and 8.2, the approximate natural pH of limestone, and (4) the mobility of soluble and colloidal heavy metals and arsenic within the carbonate-rich tailings. Representative mine tailings and their intermediate oxidation products have been sampled from the Zimapan area. Mineralogical characterization will be conducted with X-ray diffraction, infrared spectroscopy, electron microscopes and microprobes, and chemical methods. Chemical species will be extracted by selective dissolution methods. Preliminary results have identified calcite as the dominant mineral in the tailing heaps with a pH of 7, suggesting non-equilibrium with the acidic weathering products. Other minerals identified in

Trace hydrogen sulfide gas sensor based on tungsten sulfide membrane-coated thin-core fiber modal interferometer

NASA Astrophysics Data System (ADS)

Deng, Dashen; Feng, Wenlin; Wei, Jianwei; Qin, Xiang; Chen, Rong

2017-11-01

A novel fiber-optic hydrogen sulfide sensor based on a thin-core Mach-Zehnder fiber modal interferometer (TMZFI) is demonstrated and fabricated. This in-line interferometer is composed of a short section of thin-core fiber sandwiched between two standard single mode fibers, and the fast response to hydrogen sulfide is achieved via the construction of tungsten sulfide film on the outside surface of the TMZFI using the dip-coating and calcination technique. The fabricated sensing nanofilm is characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) spectrometer, Fourier transform infrared (FTIR) and spectroscopic analysis technology, etc. Experimental results showed that the WS2 sensing film has a hexagonal structure with a compact and porous morphology. The XPS and FTIR indicate that the existence of two elements (W and S) is demonstrated. With the increasing concentration of hydrogen sulfide, the interference spectra appear blue shift. In addition, a high sensitivity of 18.37 pm/ppm and a good linear relationship are obtained within a measurement range from 0 to 80 ppm. In addition, there is an excellent selectivity for H2S, which has also been proved by the surface adsorption energy results of tungsten sulfide with four gases (H2S, N2, O2 and CO2) by using the density functional theory calculations. This interferometer has the advantages of simple structure, high sensitivity and easy manufacture, and could be used in the safety monitoring field of hydrogen sulfide gas.

Microbial oxidation of mixtures of methylmercaptan and hydrogen sulfide.

PubMed

Subramaniyan, A; Kolhatkar, R; Sublette, K L; Beitle, R

1998-01-01

Refinery spent-sulfidic caustic, containing only inorganic sulfides, has previously been shown to be amenable to biotreatment with Thiobacillus denitrificans strain F with complete oxidation of sulfides to sulfate. However, many spent caustics contain mercaptans that cannot be metabolized by this strict autotroph. An aerobic enrichment culture was developed from mixed Thiobacilli and activated sludge that was capable of simultaneous oxidation of inorganic sulfide and mercaptans using hydrogen sulfide (H2S) and methylmercaptan (MeSH) gas feeds used to simulate the inorganic and organic sulfur of a spent-sulfidic caustic. The enrichment culture was also capable of biotreatment of an actual mercaptan-containing, spent-sulfidic caustic but at lower rates than predicted by operation on MeSH and H2S fed to the culture in the gas phase, indicating that the caustic contained other inhibitory components.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

2001-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

1999-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, B.S.; Gupta, R.P.

1999-06-22

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

Latent volcanic heat and further unique aspects of early diagenetic stratiform copper mineralization in the White Pine-Presque Isle District, northern Michigan

NASA Astrophysics Data System (ADS)

Brown, Alex C.

2018-06-01

The curious occurrence of copper-rich early diagenetic sediment-hosted stratiform copper mineralization in the finest-grained facies of Nonesuch greybeds in northern Michigan has been previously attributed to the warming of cupriferous brines in the footwall Copper Harbor Conglomerate by latent volcanic heat from the subjacent Porcupine Volcanics shield volcano. That anomalous footwall warming is employed here to explain other unique aspects of the White Pine-Presque Isle mineralization: the abrupt downward sulfide zoning from disseminated pyrite to chalcocite across the top of the cupriferous zone; the absence of bornite and chalcopyrite in the cupriferous zone proper; and the essential absence of pseudomorphs after pyrite euhedra and framboidal aggregates within the cupriferous zone proper, as well as the relatively coarse-grained character of disseminated chalcocite in the cupriferous zone.

Influences on copper bioaccumulation, growth, and survival of the midge, Chironomus tentans, in metal-contaminated sediments

USGS Publications Warehouse

Besser, John M.; Kubitz, Jody A.; Ingersoll, Chris G.; Braselton, W. Emmett; Giesy, John P.

1995-01-01

Sediment bioassays with larvae of the midge, Chironomus tentans, were used to evaluate influences on the bioavailability and toxicity of copper (Cu) in sediments with a wide range of concentrations of metals, acid-volatile sulfide (AVS), and other physicochemical characteristics. Sediments were collected from sixteen lakes in Michigan, USA, and from twelve sites in the Clark Fork River drainage of Montana, USA, which are contaminated with metals from mining activities and from other anthropogenic sources. Bioassays with C. tentans larvae were conducted for ten days in a static-renewal test system, with endpoints of survival, growth, and metal bioaccumulation. Bioaccumulation of copper (Cu) was strongly correlated with Cu concentrations in porewater, and was increased significantly at Cu concentrations less than those affecting growth or survival. Midge survival and growth were not significantly correlated with concentrations of Cu in sediment or porewater, and were poorly predicted by ratios of acid-extractable metals to AVS in sediments. Principal components analysis indicated that Cu concentrations in porewater and bioaccumulation of Cu by midge larvae were influenced by AVS, sediment organic carbon, and porewater pH, and that toxicity was associated with high concentrations of Cu, high concentrations of zinc (Zn) and ammonia. No toxicity was observed in several sediments which contained low concentrations of AVS and high concentrations of Cu and Zn. In sediments which contain little AVS, bioavailability of metals may be controlled by constituents other than sulfides, such as organic matter and metal hydrous oxides. These results indicate that assessments of toxicity in metal-contaminated sediments should evaluate the importance of metal-binding phases other than sulfides, and the possible contributions of ammonia or other toxicants to toxicity in sediment bioassays.

Experimental Investigation on the Topotaxy of Sulfide and Silicate Melts in Peridotite: Implications for the Origin of PGE-depleted Cu-Ni Sulfide Deposit

NASA Astrophysics Data System (ADS)

Wang, Z.; Zhang, J.; Jin, Z.

2016-12-01

Cu-Ni sulfide deposit is generally considered partial melt originated from the mantle which is usually PGE-enriched. However, the largest Cu-Ni sulfide deposits of China (the Jinchuan Cu-Ni deposit) is PGE-depleted. Comparing to silicate melt, the nature and topotaxy of sulfide melt have remained poorly understood. Here we report experimental investigation on the topotaxy of sulfide and silicate melts in peridotite using a piston-cylinder press and a 5GPa Griggs-type deformation apparatus. The starting material consists of polycrystalline olivine or pyrolite and 1 wt% Fe-Ni-Cu sulfide. Hydrostatic and deformation experiments were conducted at a pressure of 1.5 GPa and a temperature of 1250°. Under hydrostatic conditions, our results reveal that the apparent dihedral angle of sulfide melt in an olivine matrix( 96°) is much larger than that of silicate + sulfide melt in pyrolite(<60°) under hydrostatic conditions. The sulfide melt pockets appear mostly as blobs in triple junctions with an immiscible Ni-poor center surrounded by a Ni-rich layer. Under deformation conditions, olivine develops pronounced fabrics with the pole of the (010) forming high concentrations approximately normal to the foliation plane and the [100] axes forming a girdle in the foliation plane. EBSD phase mapping analyses reveal strong shape preferred orientations (SPO) of sulfide +silicate melt in the 45, 90, 135 degree directions for deformation experiments indicating complete wetting of grain boundaries and forming a favorable source for ore deposits. Deformation also causes mixing of the Ni-rich and the Ni-poor sulfide melts. As the platinum-group elements(PGE) prefer to concentrate in the Ni-rich sulfide melt at high temperatures, our results suggest that the metallogenetic source of the PGE-depleted Cu-Ni deposits may have formed under relatively intense deformation and low temperatures with a small fraction of mixed sulfide and silicate melts.

Thin film photovoltaic cells having increased durability and operating life and method for making same

DOEpatents

Barnett, Allen M.; Masi, James V.; Hall, Robert B.

1980-12-16

A solar cell having a copper-bearing absorber is provided with a composite transparent encapsulating layer specifically designed to prevent oxidation of the copper sulfide. In a preferred embodiment, the absorber is a layer of copper sulfide and the composite layer comprises a thin layer of copper oxide formed on the copper sulfide and a layer of encapsulating glass formed on the oxide. It is anticipated that such devices, when exposed to normal operating conditions of various terrestrial applications, can be maintained at energy conversion efficiencies greater than one-half the original conversion efficiency for periods as long as thirty years.

Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: I. Iron-copper-zinc-lead sulfide solubility relations

USGS Publications Warehouse

Hemley, J.J.; Cygan, G.L.; Fein, J.B.; Robinson, G.R.; d'Angelo, W. M.

1992-01-01

Experimental studies, using cold-seal and extraction vessel techniques, were conducted on Fe, Pb, Zn, and Cu sulfide solubilities in chloride soultions at temperatures from 300?? to 700??C and pressures from 0.5 to 2 kbars. The solutions were buffered in pH by quartz monzonite and the pure potassium feldspar-muscovite-quartz assemblage and in fS2-fO2 largely by the assemblage pyrite-pyrrhotite-magnetite. Solubilities increase with increasing temperature and total chloride, and decrease with increasing pressure. The effect of increasing chloride concentration on solubility reflects primarily a shift to lower pH via the silicate buffer reactions. Similarity in behaviour with respect to the temperature and pressure of Fe, Zn, and Pb sulfide solubilities points to similarity in chloride speciation, and the neutral species appear to be dominant in the high-temperature region. -from Authors

Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide-copper sulfide heterostructured nanorods.

PubMed

Zheng, Haimei; Sadtler, Bryce; Habenicht, Carsten; Freitag, Bert; Alivisatos, A Paul; Kisielowski, Christian

2013-11-01

The atomic structure and interfaces of CdS/Cu2S heterostructured nanorods are investigated with the aberration-corrected TEAM 0.5 electron microscope operated at 80 kV and 300 kV applying in-line holography and complementary techniques. Cu2S exhibits a low-chalcocite structure in pristine CdS/Cu2S nanorods. Under electron beam irradiation the Cu2S phase transforms into a high-chalcocite phase while the CdS phase maintains its wurtzite structure. Time-resolved experiments reveal that Cu(+)-Cd(2+) cation exchange at the CdS/Cu2S interfaces is stimulated by the electron beam and proceeds within an undisturbed and coherent sulfur sub-lattice. A variation of the electron beam current provides an efficient way to control and exploit such irreversible solid-state chemical processes that provide unique information about system dynamics at the atomic scale. Specifically, we show that the electron beam-induced copper-cadmium exchange is site specific and anisotropic. A resulting displacement of the CdS/Cu2S interfaces caused by beam-induced cation interdiffusion equals within a factor of 3-10 previously reported Cu diffusion length measurements in heterostructured CdS/Cu2S thin film solar cells with an activation energy of 0.96 eV. © 2013 Elsevier B.V. All rights reserved.

Thermoelectric Properties of Lanthanum Sulfide

NASA Technical Reports Server (NTRS)

Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

1987-01-01

Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, REGULATION, AND ENFORCEMENT, DEPARTMENT OF THE... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen...

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture.

PubMed

Simpson, Stuart L; Spadaro, David A; O'Brien, Dom

2013-11-01

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically<10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Method for inhibiting oxidation of metal sulfide-containing material

DOEpatents

Elsetinow, Alicia; Borda, Michael J.; Schoonen, Martin A.; Strongin, Daniel R.

2006-12-26

The present invention provides means for inhibiting the oxidation of a metal sulfide-containing material, such as ore mine waste rock or metal sulfide taiulings, by coating the metal sulfide-containing material with an oxidation-inhibiting two-tail lipid coating (12) thereon, thereby inhibiting oxidation of the metal sulfide-containing material in acid mine drainage conditions. The lipids may be selected from phospholipids, sphingolipids, glycolipids and combinations thereof.

Carbonyl sulfide

Integrated Risk Information System (IRIS)

Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

Selenium sulfide

Integrated Risk Information System (IRIS)

Selenium sulfide ; CASRN 7446 - 34 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

Methods for producing hydrogen (BI) sulfide and/or removing metals

DOEpatents

Truex, Michael J [Richland, WA; Peyton, Brent M [Pullman, WA; Toth, James J [Kennewick, WA

2002-05-14

The present invention is a process wherein sulfide production by bacteria is efficiently turned on and off, using pH adjustment. The adjustment of pH impacts sulfide production by bacteria by altering the relative amounts of H.sub.2 S and HS-- in solution and thereby control the inhibition of the bacterial metabolism that produces sulfide. This process can be used to make a bioreactor produce sulfide "on-demand" so that the production of sulfide can be matched to its use as a metal precipitation reagent. The present invention is of significance because it enables the use of a biological reactor, a cost effective sulfide production system, by making the biological reactor produce hydrogen sulfide "on demand", and therefore responsive to production schedules, waste stream generation rate, and health and safety requirements/goals.

Smelling Sulfur: Copper and Silver Regulate the Response of Human Odorant Receptor OR2T11 to Low-Molecular-Weight Thiols.

PubMed

Li, Shengju; Ahmed, Lucky; Zhang, Ruina; Pan, Yi; Matsunami, Hiroaki; Burger, Jessica L; Block, Eric; Batista, Victor S; Zhuang, Hanyi

2016-10-03

Mammalian survival depends on ultrasensitive olfactory detection of volatile sulfur compounds, since these compounds can signal the presence of rancid food, O 2 depleted atmospheres, and predators (through carnivore excretions). Skunks exploit this sensitivity with their noxious spray. In commerce, natural and liquefied gases are odorized with t-BuSH and EtSH, respectively, as warnings. The 100-million-fold difference in olfactory perception between structurally similar EtSH and EtOH has long puzzled those studying olfaction. Mammals detect thiols and other odorants using odorant receptors (ORs), members of the family of seven transmembrane G-protein-coupled receptors (GPCRs). Understanding the regulator cofactors and response of ORs is particularly challenging due to the lack of X-ray structural models. Here, we combine computational modeling and site-directed mutagenesis with saturation transfer difference (STD) NMR spectroscopy and measurements of the receptor response profiles. We find that human thiol receptor OR2T11 responds specifically to gas odorants t-BuSH and EtSH requiring ionic copper for its robust activation and that this role of copper is mimicked by ionic and nanoparticulate silver. While copper is both an essential nutrient for life and, in excess, a hallmark of various pathologies and neurodegenerative diseases, its involvement in human olfaction has not been previously demonstrated. When screened against a series of alcohols, thiols, sulfides, and metal-coordinating ligands, OR2T11 responds with enhancement by copper to the mouse semiochemical CH 3 SCH 2 SH and derivatives, to four-membered cyclic sulfide thietane and to one- to four-carbon straight- and branched-chain and five-carbon branched-chain thiols but not to longer chain thiols, suggesting compact receptor dimensions. Alcohols are unreactive.

A Reaction Involving Oxygen and Metal Sulfides.

ERIC Educational Resources Information Center

Hill, William D. Jr.

1986-01-01

Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

Role of reactive oxygen species and sulfide-quinone oxoreductase in hydrogen sulfide-induced contraction of rat pulmonary arteries

PubMed Central

Prieto-Lloret, Jesus; Snetkov, Vladimir A.; Shaifta, Yasin; Docio, Inmaculada; Connolly, Michelle J.; MacKay, Charles E.; Knock, Greg A.

2018-01-01

Application of H2S (“sulfide”) elicits a complex contraction in rat pulmonary arteries (PAs) comprising a small transient contraction (phase 1; Ph1) followed by relaxation and then a second, larger, and more sustained contraction (phase 2; Ph2). We investigated the mechanisms causing this response using isometric myography in rat second-order PAs, with Na2S as a sulfide donor. Both phases of contraction to 1,000 μM Na2S were attenuated by the pan-PKC inhibitor Gö6983 (3 μM) and by 50 μM ryanodine; the Ca2+ channel blocker nifedipine (1 μM) was without effect. Ph2 was attenuated by the mitochondrial complex III blocker myxothiazol (1 μM), the NADPH oxidase (NOX) blocker VAS2870 (10 μM), and the antioxidant TEMPOL (3 mM) but was unaffected by the complex I blocker rotenone (1 μM). The bath sulfide concentration, measured using an amperometric sensor, decreased rapidly following Na2S application, and the peak of Ph2 occurred when this had fallen to ~50 μM. Sulfide caused a transient increase in NAD(P)H autofluorescence, the offset of which coincided with development of the Ph2 contraction. Sulfide also caused a brief mitochondrial hyperpolarization (assessed using tetramethylrhodamine ethyl ester), followed immediately by depolarization and then a second more prolonged hyperpolarization, the onset of which was temporally correlated with the Ph2 contraction. Sulfide application to cultured PA smooth muscle cells increased reactive oxygen species (ROS) production (recorded using L012); this was absent when the mitochondrial flavoprotein sulfide-quinone oxoreductase (SQR) was knocked down using small interfering RNA. We propose that the Ph2 contraction is largely caused by SQR-mediated sulfide metabolism, which, by donating electrons to ubiquinone, increases electron production by complex III and thereby ROS production. PMID:29351439

Removal of insoluble heavy metal sulfides from water.

PubMed

Banfalvi, Gaspar

2006-05-01

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

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.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2003-01-01

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.

Process for producing cadmium sulfide on a cadmium telluride surface

DOEpatents

Levi, Dean H.; Nelson, Art J.; Ahrenkiel, Richard K.

1996-01-01

A process for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness.

Lifting of Administrative Stay for Hydrogen Sulfide

EPA Pesticide Factsheets

EPA lifted the Administrative Stay of the TRI reporting requirements for hydrogen sulfide. Hydrogen sulfide can reasonably be anticipated to cause chronic health effects in humans and significant adverse effects in aquatic organisms.

Use of ERTS-1 images in the search for porphyry copper deposits in Pakistani Baluchistan

NASA Technical Reports Server (NTRS)

Schmidt, R. G.

1973-01-01

Geomorphic features related to a known porphyry copper deposit at Saindak, western Chagai District, Pakistan, are easily distinguished on ERTS-1 images. New geologic information from the images was used in conjunction with known geology to evaluate one previously known prospect area and to suggest two additional ones, but no new prospects were recognized on the basis of the images alone. The study also showed that Saindak-type deposits are not likely to be present in some extensive areas of the Chagai District. The Saindak deposit is in an area of relatively easily eroded folded sedimentary and volcanic rocks. The deposit is characterized by an elongate zone of easily eroded sulfide-rich rock surrounded by this rim and the central sulfide-rich valley are conspicuous features on the images. Swarms of dikes are probably useful for distinguishing real rims from other resistant rock types, but there is no expression of them on the image, although they are easily seen on aerial photographs of the Saindak rim.

Hydrogen sulfide

Integrated Risk Information System (IRIS)

EPA / 635 / R - 03 / 005 www.epa.gov / iris TOXICOLOGICAL REVIEW OF HYDROGEN SULFIDE ( CAS No . 7783 - 06 - 4 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2003 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been

High-quality draft genome sequence of Kocuria marina SO9-6, an actinobacterium isolated from a copper mine

PubMed Central

Castro, Daniel B.A.; Pereira, Letícia Bianca; Silva, Marcus Vinícius M. e; Silva, Bárbara P. da; Palermo, Bruna Rafaella Z.; Carlos, Camila; Belgini, Daiane R.B.; Limache, Elmer Erasmo G.; Lacerda, Gileno V. Jr; Nery, Mariana B.P.; Gomes, Milene B.; Souza, Salatiel S. de; Silva, Thiago M. da; Rodrigues, Viviane D.; Paulino, Luciana C.; Vicentini, Renato; Ferraz, Lúcio F.C.; Ottoboni, Laura M.M.

2015-01-01

An actinobacterial strain, designated SO9-6, was isolated from a copper iron sulfide mineral. The organism is Gram-positive, facultatively anaerobic, and coccoid. Chemotaxonomic and phylogenetic properties were consistent with its classification in the genus Kocuria. Here, we report the first draft genome sequence of Kocuria marina SO9-6 under accession JROM00000000 (http://www.ncbi.nlm.nih.gov/nuccore/725823918), which provides insights for heavy metal bioremediation and production of compounds of biotechnological interest. PMID:26484219

Copper tolerance and copper accumulation of herbaceous plants colonizing inactive California copper mines

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

Kruckeberg, A.L.; Wu, L.

1992-06-01

Herbaceous plant species colonizing four copper mine waste sites in northern California were investigated for copper tolerance and copper accumulation. Copper tolerance was found in plant species colonizing soils with high concentrations of soil copper. Seven of the eight plant species tested were found at more than one copper mine. The mines are geographically isolated, which makes dispersal of seeds from one mine to another unlikely. Tolerance has probably evolved independently at each site. The nontolerant field control population of Vulpia microstachya displays significantly higher tolerance to copper at all copper concentration levels tested than the nontolerant Vulpia myrous population,more » and the degree of copper tolerance attained by V. microstachya at the two copper mines was much greater than that found in V. myrous. It suggests that even in these two closely related species, the innate tolerance in their nontolerant populations may reflect their potential for evolution of copper tolerance and their ability to initially colonize copper mine waste sites. The shoot tissue of the copper mine plants of Arenaria douglasii, Bromous mollis, and V. microstachya accumulated less copper than those plants of the same species from the field control sites when the two were grown in identical conditions in nutrient solution containing copper. The root tissue of these mine plants contain more copper than the roots of the nonmine plants. This result suggests that exclusion of copper from the shoots, in part by immobilization in the roots, may be a feature of copper tolerance. No difference in the tissue copper concentration was detected between tolerant and nontolerant plants of Lotus purshianus, Lupinus bicolor, and Trifolium pratense even though the root tissue had more copper than the leaves.« less

Membrane for hydrogen recovery from streams containing hydrogen sulfide

DOEpatents

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.

Sulfide scaling in low enthalpy geothermal environments; A survey

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

Criaud, A.; Fouillac, C.

1989-01-01

A review of the sulfide scaling phenomena in low-temperature environments is presented. While high-temperature fluids tend to deposit metal sulfides because of their high concentrations of dissolved metals and variations of temperature, pressure and fluid chemistry, low temperature media are characterized by very low metal content but much higher dissolved sulfide. In the case of the goethermal wells of the Paris Basin, detailed studies demonstrate that the relatively large concentrations of chloride and dissolved sulfide are responsible for corrosion and consequent formation of iron sulfide scale composed of mackinawite, pyrite and pyrrhotite. The effects of the exploitation schemes are farmore » less important than the corrosion of the casings. The low-enthalpy fluids that do not originate from sedimentary aquifers (such as in Iceland and Bulgaria), have a limited corrosion potential, and the thin sulfide film that appears may prevent the progress of corrosion.« less

Process for producing cadmium sulfide on a cadmium telluride surface

DOEpatents

Levi, D.H.; Nelson, A.J.; Ahrenkiel, R.K.

1996-07-30

A process is described for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness. 12 figs.

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides.

PubMed

Jood, Priyanka; Ohta, Michihiro

2015-03-16

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.

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides

PubMed Central

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

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

NASA Technical Reports Server (NTRS)

Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

2008-01-01

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

Simultaneous ultrasound-assisted ternary adsorption of dyes onto copper-doped zinc sulfide nanoparticles loaded on activated carbon: optimization by response surface methodology.

PubMed

Asfaram, Arash; Ghaedi, Mehrorang; Hajati, Shaaker; Goudarzi, Alireza; Bazrafshan, Ali Akbar

2015-06-15

The simultaneous and competitive ultrasound-assisted removal of Auramine-O (AO), Erythrosine (Er) and Methylene Blue (MB) from aqueous solutions were rapidly performed onto copper-doped zinc sulfide nanoparticles loaded on activated carbon (ZnS:Cu-NP-AC). ZnS:Cu nanoparticles were studied by FESEM, XRD and TEM. First, the effect of pH was optimized in a one-at-a-time procedure. Then the dependency of dyes removal percentage in their ternary solution on the level and magnitude of variables such as sonication time, initial dyes concentrations and adsorbent dosage was fully investigated and optimized by central composite design (CCD) under response surface methodology (RSM) as well as by regarding desirability function (DF) as a good and general criterion. The good agreement found between experimental and predicted values supports and confirms the suitability of the present model to predict adsorption state. The applied ultrasound strongly enhanced mass transfer process and subsequently performance. Hence, a small amount of the adsorbent (0.04 g) was capable to remove high percentage of dyes, i.e. 100%, 99.6% and 100% for MB, AO and Er, respectively, in very short time (2.5 min). The experimental equilibrium data fitting to Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models showed that the Langmuir model applies well for the evaluation and description of the actual behavior of adsorption. The small amount of proposed adsorbent (0.015 g) was applicable for successful removal of dyes (RE>99.0%) in short time (2.5 min) with high adsorption capacity in single component system (123.5 mg g(-1) for MB, 123 mg g(-1) for AO and 84.5 mg g(-1) for Er). Kinetics evaluation of experiments at various time intervals reveals that adsorption processes can be well predicated and fitted by pseudo-second-order and Elovich models. Copyright © 2015 Elsevier B.V. All rights reserved.

Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Jackson, Simon E.; Pearson, Norman J.; Graham, Stuart

2010-07-01

Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ 65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1 σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ˜-0.4‰ (-0.25 ± 0.36‰, 1 σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1 σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ 65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.

Compositions of Magmatic and Impact Melt Sulfides in Tissint And EETA79001: Precursors of Immiscible Sulfide Melt Blebs in Shergottite Impact Melts

NASA Technical Reports Server (NTRS)

Ross, D. K.; Rao, M. N.; Nyquist, L.; Agee, C.; Sutton, S.

2013-01-01

Immiscible sulfide melt spherules are locally very abundant in shergottite impact melts. These melts can also contain samples of Martian atmospheric gases [1], and cosmogenic nuclides [2] that are present in impact melt, but not in the host shergottite, indicating some components in the melt resided at the Martian surface. These observations show that some regolith components are, at least locally, present in the impact melts. This view also suggests that one source of the over-abundant sulfur in these impact melts could be sulfates that are major constituents of Martian regolith, and that the sulfates were reduced during shock heating to sulfide. An alternative view is that sulfide spherules in impact melts are produced solely by melting the crystalline sulfide minerals (dominantly pyrrhotite, Fe(1-x)S) that are present in shergottites [3]. In this abstract we report new analyses of the compositions of sulfide immiscible melt spherules and pyrrhotite in the shergottites Tissint, and EETA79001,507, and we use these data to investigate the possible origins of the immiscible sulfide melt spherules. In particular, we use the metal/S ratios determined in these blebs as potential diagnostic criteria for tracking the source material from which the numerous sulfide blebs were generated by shock in these melts.

SULFIDE METHOD PLUTONIUM SEPARATION

DOEpatents

Duffield, R.B.

1958-08-12

A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

Environmental Durability of Coated GRCop-84 Copper Alloys

NASA Technical Reports Server (NTRS)

Raj, Sai V.; Robinson, C.; Barrett, C.; Humphrey, D.

2005-01-01

An advanced Cu-8(at.%)Cr-4%Nb alloy developed at NASA's Glenn Research Center, and designated as GRCop-84, is currently being considered for use as liners in combustor chambers and nozzle ramps in NASA s future generations of reusable launch vehicles (RLVs). However, past experience has shown that unprotected copper alloys undergo an environmental attack called "blanching" in rocket engines using liquid hydrogen as fuel and liquid oxygen as the oxidizer. Potential for sulfidation attack of the liners in hydrocarbon-fueled engines is also of concern. As a result, protective overlay coatings alloys are being developed for GRCop-84. The oxidation behavior of several new coating alloys has been evaluated. GRCop-84 specimens were coated with several copper and nickel-based coatings, where the coatings were deposited by either vacuum plasma spraying or cold spraying techniques. Coated and uncoated specimens were thermally cycled in a furnace at different temperatures in order to evaluate the performance of the coatings. Additional studies were conducted in a high pressure burner rig using a hydrocarbon fuel and subjected to a high heat flux hydrogen-oxygen combustion flame in NASA s Quick Access Rocket Exhaust (QARE) rig. The performance of these coatings are discussed.

Geochemical Characterization of Mine Waste, Mine Drainage, and Stream Sediments at the Pike Hill Copper Mine Superfund Site, Orange County, Vermont

USGS Publications Warehouse

Piatak, Nadine M.; Seal, Robert R.; Hammarstrom, Jane M.; Kiah, Richard G.; Deacon, Jeffrey R.; Adams, Monique; Anthony, Michael W.; Briggs, Paul H.; Jackson, John C.

2006-01-01

The Pike Hill Copper Mine Superfund Site in the Vermont copper belt consists of the abandoned Smith, Eureka, and Union mines, all of which exploited Besshi-type massive sulfide deposits. The site was listed on the U.S. Environmental Protection Agency (USEPA) National Priorities List in 2004 due to aquatic ecosystem impacts. This study was intended to be a precursor to a formal remedial investigation by the USEPA, and it focused on the characterization of mine waste, mine drainage, and stream sediments. A related study investigated the effects of the mine drainage on downstream surface waters. The potential for mine waste and drainage to have an adverse impact on aquatic ecosystems, on drinking- water supplies, and to human health was assessed on the basis of mineralogy, chemical concentrations, acid generation, and potential for metals to be leached from mine waste and soils. The results were compared to those from analyses of other Vermont copper belt Superfund sites, the Elizabeth Mine and Ely Copper Mine, to evaluate if the waste material at the Pike Hill Copper Mine was sufficiently similar to that of the other mine sites that USEPA can streamline the evaluation of remediation technologies. Mine-waste samples consisted of oxidized and unoxidized sulfidic ore and waste rock, and flotation-mill tailings. These samples contained as much as 16 weight percent sulfides that included chalcopyrite, pyrite, pyrrhotite, and sphalerite. During oxidation, sulfides weather and may release potentially toxic trace elements and may produce acid. In addition, soluble efflorescent sulfate salts were identified at the mines; during rain events, the dissolution of these salts contributes acid and metals to receiving waters. Mine waste contained concentrations of cadmium, copper, and iron that exceeded USEPA Preliminary Remediation Goals. The concentrations of selenium in mine waste were higher than the average composition of eastern United States soils. Most mine waste was

Reduction of produced elementary sulfur in denitrifying sulfide removal process.

PubMed

Zhou, Xu; Liu, Lihong; Chen, Chuan; Ren, Nanqi; Wang, Aijie; Lee, Duu-Jong

2011-05-01

Denitrifying sulfide removal (DSR) processes simultaneously convert sulfide, nitrate, and chemical oxygen demand from industrial wastewater into elemental sulfur, dinitrogen gas, and carbon dioxide, respectively. The failure of a DSR process is signaled by high concentrations of sulfide in reactor effluent. Conventionally, DSR reactor failure is blamed for overcompetition for heterotroph to autotroph communities. This study indicates that the elementary sulfur produced by oxidizing sulfide that is a recoverable resource from sulfide-laden wastewaters can be reduced back to sulfide by sulfur-reducing Methanobacterium sp. The Methanobacterium sp. was stimulated with excess organic carbon (acetate) when nitrite was completely consumed by heterotrophic denitrifiers. Adjusting hydraulic retention time of a DSR reactor when nitrite is completely consumed provides an additional control variable for maximizing DSR performance.

Understanding Cu release into environment from Kure massive sulfide ore deposits, Kastamonu, NW Turkey

NASA Astrophysics Data System (ADS)

Demirel, Cansu; Sonmez, Seref; Balci, Nurgul

2014-05-01

Covering a wide range on the earth's crust, oxidation of metal sulfide minerals have vital environmental impacts on the aquatic environment, causing one of the major environmental problems known as acid mine drainage (AMD). Located in the Kastamonu province of the Western Black Sea region, Kure district is one of the major copper mining sites in Turkey. Mining activities in the area heads back to ancient times, such that operation is thought to be started with the Roman Empire. Currently, only the underground mining tunnels of Bakibaba and Asikoy are being operated. Thus, mining heaps and ores of those pyritic deposits have been exposed to the oxidative conditions for so long. As a result of weathering processes of past and recent heaps of the Kure volcanic massive sulfide deposits in addition to the main ore mineral (chalcopyrite), significant amount of metals, especially Cu, are being released into the environment creating undesirable environmental conditions. In order to elucidate Cu release mechanisms from Kure pyritic ore deposits and mining wastes, field and laboratory approaches were used. Surface water and sediment samples from the streams around the mining and waste sites were collected. Groundwater samples from the active underground mining site were also collected. Physical parameters (pH, Eh, T°C, and EC) of water samples were determined in situ and in the laboratory using probes (WTW pH 3110, WTW Multi 9310 and CRISON CM 35). Metal and ion concentrations of the water samples were analysed using ICP-MS and DR 2800 spectrophotometer, respectively. High Cu, Co, Zn and Fe concentrations were determined in the water samples with pH values ranging from 2.9- 4. Cu concentrions ranges from 345 ppm to 36 ppm in the water samples. Consistent with the water samples, high Cu, Fe, Zn and Co were also determined in the sediment samples. Laboratory chalcopyrite oxidation experiments under the conditions representing the field site were set up as biological and

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

NASA Astrophysics Data System (ADS)

Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

2015-12-01

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do

Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

NASA Technical Reports Server (NTRS)

Bandy, Alan R.; Thornton, Donald C.; Driedger, Arthur R., III

1993-01-01

A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

Discovery and characterization of iron sulfide and polyphosphate bodies coexisting in Archaeoglobus fulgidus cells

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

Toso, Daniel B.; Javed, Muhammad Mohsin; Czornyj, Elizabeth

Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidusstrain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent inA. fulgiduscells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell containsmore » not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications.« less

Discovery and characterization of iron sulfide and polyphosphate bodies coexisting in Archaeoglobus fulgidus cells

DOE PAGES

Toso, Daniel B.; Javed, Muhammad Mohsin; Czornyj, Elizabeth; ...

2016-01-01

Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidusstrain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent inA. fulgiduscells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell containsmore » not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications.« less

Sulfide intrusion in the tropical seagrasses Thalassia testudinum and Syringodium filiforme

NASA Astrophysics Data System (ADS)

Holmer, Marianne; Pedersen, Ole; Krause-Jensen, Dorte; Olesen, Birgit; Hedegård Petersen, Malene; Schopmeyer, Stephanie; Koch, Marguerite; Lomstein, Bente Aa.; Jensen, Henning S.

2009-11-01

Sulfur and oxygen dynamics in the seagrasses Thalassia testudinum and Syringodium filiforme and their sediments were studied in the US Virgin Islands (USVI) in order to explore sulfide intrusion into tropical seagrasses. Four study sites were selected based on the iron concentration in sediments and on proximity to anthropogenic nutrient sources. Meadow characteristics (shoot density, above- and below-ground biomass, nutrient content) were sampled along with sediment biogeochemistry. Sulfide intrusion was high in T. testudinum, as up to 96% of total sulfur in the plant was derived from sediment-derived sulfides. The sulfide intrusion was negatively correlated to the turnover of sulfides in the sediments regulated by both plant parameters and sediment sulfur pools. Sediment iron content played an indirect role by affecting sulfide turnover rates. Leaf production was negatively correlated with sulfide intrusion suggesting that active growth reduced sulfide intrusion. Sulfide intrusion was lower in S. filiforme (up to 44%) compared to T. testudinum consistent with a higher internal nighttime oxygen concentrations found for S. filiforme. When S. filiforme can take advantage of its ability to maintain high internal oxygen concentrations, as was the case on the USVI, it could increase its success in colonizing unvegetated disturbed sediments with potentially high sulfide concentrations.

Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits

NASA Astrophysics Data System (ADS)

Li, Chusi; Ripley, Edward M.

2005-03-01

Empirical equations to predict the sulfur content of a mafic magma at the time of sulfide saturation have been developed based on several sets of published experimental data. The S content at sulfide saturation (SCSS) can be expressed as: ln X_{text S} = 1.229 - 0.74(10^4/T) - 0.021(P) - 0.311 ln X_{{text{FeO}}} - 6.166X_{{text{SiO}}_{text{2}}} - 9.153X_{{text{Na}}_{text{2}} {text{O + K}}_{text{2}} {text{O}}} - 1.914X_{{text{MgO}}} + 6.594X_{{text{FeO}}} where T is in degrees Kelvin, X is mole fraction and P is in kbar. The squared multiple correlation coefficient ( r 2) for the equation is 0.88. Application of the equation to data from sulfide-saturated mid-ocean ridge basalts (MORB) samples show that the SCSS is closely predicted for primitive MORBs, but that accuracy decreases for lower T (<1,130°C) and more evolved MORB samples. This suggests that because the calibrations are based on anhydrous experimental runs done at temperatures of 1,200°C and above, it is not possible to extrapolate them to significantly lower temperatures and hydrous conditions. Because the SCSS of a primitive MORB magma increases with decreasing P, sulfide saturation in MORB appears to be a function of the degree of en route assimilation of S from country rocks as well as the degree of fractional crystallization in shallow staging chambers. Application of the equation to the high- T impact melt sheet that produced the Sudbury Igneous Complex and associated Ni-Cu sulfide ores indicates that sulfide-saturation was reached at 1,500°C, well above the start of orthopyroxene crystallization at 1,190°C. This would permit ample time for the gravitational settling and collection of immiscible sulfide liquid that produced the high-grade ore bodies. The development of a platinum group element (PGE)-enriched layer in the Sonju Lake Intrusion of the Duluth Complex is thought to be due to the attainment of sulfide saturation in the magma after a period of fractional crystallization. Using the

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem

Temperature and cell-type dependency of sulfide effects on mitochondrial respiration.

PubMed

Groeger, Michael; Matallo, Jose; McCook, Oscar; Wagner, Florian; Wachter, Ulrich; Bastian, Olga; Gierer, Saskia; Reich, Vera; Stahl, Bettina; Huber-Lang, Markus; Szabó, Csaba; Georgieff, Michael; Radermacher, Peter; Calzia, Enrico; Wagner, Katja

2012-10-01

Previous studies suggest that sulfide-induced inhibition of cytochrome c oxidase (cCox) and, consequently, the metabolic and toxic effects of sulfide are less pronounced at low body temperature. Because the temperature-dependent effects of sulfide on the inflammatory response are still a matter of debate, we investigated the impact of varying temperature on the cCox excess capacity and the mitochondrial sulfide oxidation by the sulfide-ubiquinone oxidoreductase in macrophage-derived cell lines (AMJ2-C11 and RAW 264.7). Using an oxygraph chamber, the inhibition of mitochondrial respiration was measured by stepwise titrations with sulfide and the nonmetabolizable cCox inhibitor sodium azide at 25°C and 37°C. Using the latter of the two inhibitors, the excess capacity of the cCox was obtained. Furthermore, we quantified the capacity of these cells to withstand sulfide inhibition by measuring the amount required to inhibit respiration by 50% and 90% and the viability of the cells after 24-h exposure to 100 ppm of hydrogen sulfide. At low titration rates, the AMJ2-C11 cells, but not the RAW 264.7 cells, increased their capacity to withstand exogenously added sulfide. This effect was even greater at 25°C than at 37°C. Furthermore, only the AMJ2-C11 cells remained viable after sulfide exposure for 24 h. In contrast, only in the RAW 264.7 cells that an increase in cCox excess capacity was found at low temperatures. In macrophage-derived cell lines, both the excess capacity of cCox and the efficiency of sulfide elimination may increase at low temperatures. These properties may modify the effects of sulfide in immune cells and, potentially, the inflammatory response during sulfide exposure at different body temperatures.

Distribution of Ag in Cu-sulfides in Kupferschiefer deposit, SW Poland

NASA Astrophysics Data System (ADS)

Kozub, Gabriela A.

2014-05-01

The Cu-Ag Kupferschiefer deposit located at the Fore-Sudetic Monocline (SW Poland) is a world class deposit of stratabound type. The Cu-Ag mineralization in the deposit occurs in the Permian sedimentary rocks (Rotliegend and Zechstein) in three lithological types of ore: the dolomite, the black shale and the sandstone. Silver, next to copper, is the most important element in the Kupferschiefer deposit (Salamon 1979; Piestrzyński 2007; Pieczonka 2011). Although occurrence of the Ag-minerals such as native silver, silver amalgams, stromeyerite, jalpaite and mckinstryite, silver is mainly present in the deposit due to isomorphic substitutions in Cu-minerals such as chalcocite, bornite, tennantite, covellite and chalcopyrite. The aim of the study was to define distribution of silver in Cu-minerals and correlate occurrence of Ag-enriched Cu-sulfides with native silver and silver amalgams. Identification of minerals and textural observation were performed using field emission scanning electron microscope. Analyzes of chemical composition of Cu-sulfides were performed utilizing electron microprobe. Silver concentration in Cu sulfides ranges from 0.1 to 10.4 wt.% in chalcocite, 0.2-15.8 wt.% in bornite, 0.1-2.9 wt.% in tennantite, 0.05-0.3 wt.% in chalcopyrite and ca. 0.4 wt.% in covellite. In general, distribution of silver in Cu-minerals is irregular, as indicated by high variations of Ag concentration in each mineral. Content of Ag in Cu-sulphides, in samples where native silver and silver amalgams are not found, is lower than in samples, where native silver and silver amalgams are noted. The chemical analyzes of Ag-bearing Cu-minerals indicate decrease of Cu content in minerals with high Ag concentration. In such case, decrease of Fe content is also noted in bornite. Lack of micro-inclusions of the native silver or silver amalgams in the Cu-minerals indicates that presence of Ag is mainly related to the isomorphic substitutions. This is in agreement with previous

Sulfide and methane production in sewer sediments.

PubMed

Liu, Yiwen; Ni, Bing-Jie; Ganigué, Ramon; Werner, Ursula; Sharma, Keshab R; Yuan, Zhiguo

2015-03-01

Recent studies have demonstrated significant sulfide and methane production by sewer biofilms, particularly in rising mains. Sewer sediments in gravity sewers are also biologically active; however, their contribution to biological transformations in sewers is poorly understood at present. In this study, sediments collected from a gravity sewer were cultivated in a laboratory reactor fed with real wastewater for more than one year to obtain intact sediments. Batch test results show significant sulfide production with an average rate of 9.20 ± 0.39 g S/m(2)·d from the sediments, which is significantly higher than the areal rate of sewer biofilms. In contrast, the average methane production rate is 1.56 ± 0.14 g CH4/m(2)·d at 20 °C, which is comparable to the areal rate of sewer biofilms. These results clearly show that the contributions of sewer sediments to sulfide and methane production cannot be ignored when evaluating sewer emissions. Microsensor and pore water measurements of sulfide, sulfate and methane in the sediments, microbial profiling along the depth of the sediments and mathematical modelling reveal that sulfide production takes place near the sediment surface due to the limited penetration of sulfate. In comparison, methane production occurs in a much deeper zone below the surface likely due to the better penetration of soluble organic carbon. Modelling results illustrate the dependency of sulfide and methane productions on the bulk sulfate and soluble organic carbon concentrations can be well described with half-order kinetics. Copyright © 2014 Elsevier Ltd. All rights reserved.

Geochemical and Hydrologic Controls of Copper-Rich Surface Waters in the Yerba Loca-Mapocho System

NASA Astrophysics Data System (ADS)

Pasten, P.; Montecinos, M.; Coquery, M.; Pizarro, G. E.; Abarca, M. I.; Arce, G. J.

2015-12-01

Andean watersheds in Northern and Central Chile are naturally enriched with metals, many of them associated to sulfide mineralizations related to copper mining districts. The natural and anthropogenic influx of toxic metals into drinking water sources pose a sustainability challenge for cities that need to provide safe water with the smallest footprint. This work presents our study of the transformations of copper in the Yerba Loca-Mapocho system. Our sampling campaign started from the headwaters at La Paloma Glacier and continues to the inlet of the San Enrique drinking water treatment plant, a system feeding municipalities in the Eastern area of Santiago, Chile. Depending on the season, total copper concentrations go as high as 22 mg/L for the upper sections, which become diluted to <5 mg/L downstream. pH ranged from 3 to 5.6 while suspended solids ranged from <10 to 100 mg/L. We used Geochemist Workbench to assess copper speciation and to evaluate the thermodynamic controls for the formation and dissolution of solid phases. A sediment trap was used to concentrate suspended particulate matter, which was analyzed with ICP-MS, TXRF (total reflection X ray fluorescence) and XRD (X-ray diffraction). Major elements detected in the precipitates were Al (200 g/kg), S (60 g/kg), and Cu (6 g/kg). Likely solid phases include hydrous amorphous phases of aluminum hydroxides and sulfates, and copper hydroxides/carbonates. Efforts are undergoing to find the optimal mixing ratios between the acidic stream and more alkaline streams to maximize attenuation of dissolved copper. The results of this research could be used for enhancing in-stream natural attenuation of copper and reducing treatment needs at the drinking water facility. Acknowledgements to Fondecyt 1130936 and Conicyt Fondap 15110020

Research on the effect of alkali roasting of copper dross on leaching rate of indium

NASA Astrophysics Data System (ADS)

Dafang, Liu; Fan, Xingxiang; Shi, Yifeng; Yang, Kunbin

2017-11-01

The byproduct copper dross produced during refining crude lead was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and fluorescence spectrometer (XRF), which showed that copper dross mainly contained lead, copper, zinc, arsenic, antimony, bismuth, sulfur and a small amount of indium and silver etc. The mineralogical phase change of oxidation roasting of copper dross by adding sodium hydroxide was analyzed with the help of XRD and SEM. The effects of water leaching, ratio of sodium hydroxide, roasting time, and roasting temperature on leaching rate of indium were investigated mainly. The experimental results showed that phase of lead metal and sulfides of lead, copper and zinc disappeared after oxidation roasting of copper dross by adding sodium hydroxide, new phase of oxides of lead, copper, zinc and sodium salt of arsenic and antimony appeared. Water leaching could remove arsenic, and acid leaching residue obtained was then leached with acid. The leaching rate of indium was higher 6.98% compared with alkali roasting of copper dross-acid leaching. It showed that removing arsenic by water leaching and acid leaching could increase the leaching rate of indium and be beneficial to reducing subsequent acid consumption of extracting indium by acid leaching. The roasting temperature had a significant effect on the leaching rate of indium, and leaching rate of indium increased with the rise of roasting temperature. When roasting temperature ranged from 450°C to 600°C, leaching rate of indium increased significantly with the rise of roasting temperature. When roasting temperature rose from 450°C to 600°C, leaching rate of indium increased by 60.29%. The amount of sodium hydroxide had an significant effect on the leaching rate of indium, and the leaching of indium increased with the increase of the amount of sodium hydroxide, and the leaching rate of indium was obviously higher than that of copper dross blank roasting and acid leaching.

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoporous gold-based microbial biosensor for direct determination of sulfide.

PubMed

Liu, Zhuang; Ma, Hanyue; Sun, Huihui; Gao, Rui; Liu, Honglei; Wang, Xia; Xu, Ping; Xun, Luying

2017-12-15

Environmental pollution caused by sulfide compounds has become a major problem for public health. Hence, there is an urgent need to explore a sensitive, selective, and simple sulfide detection method for environmental monitoring and protection. Here, a novel microbial biosensor was developed using recombinant Escherichia coli BL21 (E. coli BL21) expressing sulfide:quinone oxidoreductase (SQR) for sulfide detection. As an important enzyme involved in the initial step of sulfide metabolism, SQR oxidizes sulfides to polysulfides and transfers electrons to the electron transport chain. Nanoporous gold (NPG) with its unique properties was selected for recombinant E. coli BL21 cells immobilization, and then glassy carbon electrode (GCE) was modified by the resulting E. coli/NPG biocomposites to construct an E. coli/NPG/GCE bioelectrode. Due to the catalytic oxidation properties of NPG for sulfide, the electrochemical reaction of the E. coli/NPG/GCE bioelectrode is attributed to the co-catalysis of SQR and NPG. For sulfide detection, the E. coli/NPG/GCE bioelectrode showed a good linear response ranging from 50μM to 5mM, with a high sensitivity of 18.35μAmM -1 cm -2 and a low detection limit of 2.55μM. The anti-interference ability of the E. coli/NPG/GCE bioelectrode is better than that of enzyme-based inhibitive biosensors. Further, the E. coli/NPG/GCE bioelectrode was successfully applied to the detection of sulfide in wastewater. These unique properties potentially make the E. coli/NPG/GCE bioelectrode an excellent choice for reliable sulfide detection. Copyright © 2017 Elsevier B.V. All rights reserved.

In Situ Determination of Sulfide Turnover Rates in a Meromictic Alpine Lake

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

A push-pull method, previously used in groundwater analyses, was successfully adapted for measuring sulfide turnover rates in situ at different depths in the meromictic Lake Cadagno. In the layer of phototrophic bacteria at about 12 m in depth net sulfide consumption was observed during the day, indicating active bacterial photosynthesis. During the night the sulfide turnover rates were positive, indicating a net sulfide production from the reduction of more-oxidized sulfur compounds. Because of lack of light, no photosynthesis takes place in the monimolimnion; thus, only sulfide formation is observed both during the day and the night. Sulfide turnover rates in the oxic mixolimnion were always positive as sulfide is spontaneously oxidized by oxygen and as the rates of sulfide oxidation depend on the oxygen concentrations present. Sulfide oxidation by chemolithotrophic bacteria may occur at the oxicline, but this cannot be distinguished from spontaneous chemical oxidation. PMID:10653740

Inhibition of acid mine drainage and immobilization of heavy metals from copper flotation tailings using a marble cutting waste

NASA Astrophysics Data System (ADS)

Tozsin, Gulsen

2016-01-01

Acid mine drainage (AMD) with high concentrations of sulfates and metals is generated by the oxidation of sulfide bearing wastes. CaCO3-rich marble cutting waste is a residual material produced by the cutting and polishing of marble stone. In this study, the feasibility of using the marble cutting waste as an acid-neutralizing agent to inhibit AMD and immobilize heavy metals from copper flotation tailings (sulfide- bearing wastes) was investigated. Continuous-stirring shake-flask tests were conducted for 40 d, and the pH value, sulfate content, and dissolved metal content of the leachate were analyzed every 10 d to determine the effectiveness of the marble cutting waste as an acid neutralizer. For comparison, CaCO3 was also used as a neutralizing agent. The average pH value of the leachate was 2.1 at the beginning of the experiment ( t = 0). In the experiment employing the marble cutting waste, the pH value of the leachate changed from 6.5 to 7.8, and the sulfate and iron concentrations decreased from 4558 to 838 mg/L and from 536 to 0.01 mg/L, respectively, after 40 d. The marble cutting waste also removed more than 80wt% of heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn) from AMD generated by copper flotation tailings.

An assessment of silver copper sulfides for photovoltaic applications: theoretical and experimental insights† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ta03376h Click here for additional data file. Click here for additional data file.

PubMed Central

Savory, Christopher N.; Ganose, Alex M.; Travis, Will; Atri, Ria S.; Palgrave, Robert G.

2016-01-01

As the worldwide demand for energy increases, low-cost solar cells are being looked to as a solution for the future. To attain this, non-toxic earth-abundant materials are crucial, however cell efficiencies for current materials are limited in many cases. In this article, we examine the two silver copper sulfides AgCuS and Ag3CuS2 as possible solar absorbers using hybrid density functional theory, diffuse reflectance spectroscopy, XPS and Hall effect measurements. We show that both compounds demonstrate promising electronic structures and band gaps for high theoretical efficiency solar cells, based on Shockley–Queisser limits. Detailed analysis of their optical properties, however, indicates that only AgCuS should be of interest for PV applications, with a high theoretical efficiency. From this, we also calculate the band alignment of AgCuS against various buffer layers to aid in future device construction. PMID:27774149

Pressures of skarn formation at Casting Copper NV, USA, based on Raman spectroscopy and elastic modeling of apatite inclusions in garnet

NASA Astrophysics Data System (ADS)

Steele-MacInnis, M.; Barkoff, D. W.; Ashley, K.

2017-12-01

Thermobarometry of metasomatic rocks is commonly challenging, owing to the high variance of hydrothermal mineral assemblages, thermodynamic disequilibrium and overprinting by subsequent hydrothermal episodes. Here, we estimate formation pressures of a Cu-Fe-sulfide-bearing andradite-diopside skarn deposit at Casting Copper (Yerington district, NV) using Raman spectroscopy and elastic modeling of apatite inclusions in garnet. Andradite garnet from the Casting Copper skarn contains inclusions of hydroxyl-fluorapatite, calcite, hematite, magnetite, and ilmenite. Raman spectroscopy reveals that the apatite inclusions are predominantly under tension of -23 to -123 MPa at ambient conditions. Elastic modeling of apatite-in-garnet suggest entrapment occurred at 10 to 115 MPa, assuming a trapping temperature of 400 °C, which is consistent with paleodepth estimates of 2-3 km. These results provide independent constraints on the conditions of hydrothermal skarn formation at Casting Copper, and suggest that this approach may be applied to other, less-constrained skarn systems.

[Fatal outcome of an hydrogen sulfide poisoning].

PubMed

Querellou, E; Jaffrelot, M; Savary, D; Savry, C; Perfus, J-P

2005-10-01

We report a case of fatal outcome poisoning by massive exposure to hydrogen sulfide of a sewer worker. This rare event was associated with a moderate intoxication of two members of the rescue team. The death was due to asystole and massive lung oedema. Autopsy analysis showed diffuse necrotic lesions in lungs. Hydrogen sulfide is a direct and systemic poison, produced by organic matter decomposition. The direct toxicity mechanism is still unclear. The systemic toxicity is due to an acute toxicity by oxygen depletion at cellular level. It is highly diffusable and potentially very dangerous. At low concentration, rotten egg smell must trigger hydrogen sulfide suspicion since at higher concentration it is undetectable, making intoxication possible. In case of acute intoxication, there is an almost instantaneous cardiovascular failure and a rapid death. Hydrogen sulfide exposure requires prevention measures and more specifically the use of respiratory equipment for members of the rescue team.

Atomic layer deposition of metal sulfide materials

DOE PAGES

Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; ...

2015-01-12

The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivatingmore » interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H 2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application

Hydrogen sulfide production from cysteine and homocysteine by periodontal and oral bacteria.

PubMed

Yoshida, Akihiro; Yoshimura, Mamiko; Ohara, Naoya; Yoshimura, Shigeru; Nagashima, Shiori; Takehara, Tadamichi; Nakayama, Koji

2009-11-01

Hydrogen sulfide is one of the predominant volatile sulfur compounds (VSCs) produced by oral bacteria. This study developed and evaluated a system for detecting hydrogen sulfide production by oral bacteria. L-methionine-alpha-deamino-gamma-mercaptomethane-lyase (METase) and beta carbon-sulfur (beta C-S) lyase were used to degrade homocysteine and cysteine, respectively, to produce hydrogen sulfide. Enzymatic reactions resulting in hydrogen sulfide production were assayed by reaction with bismuth trichloride, which forms a black precipitate when mixed with hydrogen sulfide. The enzymatic activities of various oral bacteria that result in hydrogen sulfide production and the capacity of bacteria from periodontal sites to form hydrogen sulfide in reaction mixtures containing L-cysteine or DL-homocysteine were assayed. With L-cysteine as the substrate, Streptococcus anginosus FW73 produced the most hydrogen sulfide, whereas Porphyromonas gingivalis American Type Culture Collection (ATCC) 33277 and W83 and Fusobacterium nucleatum ATCC 10953 produced approximately 35% of the amount produced by the P. gingivalis strains. Finally, the hydrogen sulfide found in subgingival plaque was analyzed. Using bismuth trichloride, the hydrogen sulfide produced by oral bacteria was visually detectable as a black precipitate. Hydrogen sulfide production by oral bacteria was easily analyzed using bismuth trichloride. However, further innovation is required for practical use.

Gold and copper partitioning in magmatic-hydrothermal systems at 800 °C and 100 MPa

NASA Astrophysics Data System (ADS)

Frank, Mark R.; Simon, Adam C.; Pettke, Thomas; Candela, Philip A.; Piccoli, Philip M.

2011-05-01

at the higher aS2sys of 3.5 × 10 -2 where D b/v were 10(±5) for copper and 7(±6) for gold. Thus, there is an inverse relationship between the aS2sys and the D b/v for both copper and gold with increasing aS2sys resulting in a decrease in the D b/v signifying increased importance of the vapor phase for copper and gold transport. This suggests that copper and gold may complex with volatile S-species as well as Cl-species at magmatic conditions, however, none of the experiments of our study at 800 °C and 100 MPa had a D b/v ⩽ 1. We did not directly determine speciation, but infer the existence of some metal-sulfur complexes based on the reported data. We suggest that copper and gold partition preferentially into the brine in most instances at or above the wet solidus. However, in most systems, the mass of vapor is greater than the mass of brine, and vapor transport of copper and gold may become more important in the magmatic environment at higher aS2sys, lower fO2sys, or near the critical point in a salt-water system. A D b/v ⩽ 1 at subsolidus hydrothermal conditions may also occur in response to changes in temperature, fO2sys, aS2sys, and/or acidity. Additionally, both copper and gold were observed to partition into intermediate solid solution and bornite much more strongly than into vapor, brine or silicate melt. This suggests that, although vapor and brine are both efficient at removing copper and gold from a silicate melt, the presence of Cu-Fe sulfides can sequester a substantial portion of the copper and gold contained within a silicate melt if the Cu-Fe sulfides are abundant.

Persistency-field Eh-pH diagrams for sulfides and their application to supergene oxidation and enrichment of sulfide ore bodies

USGS Publications Warehouse

Sato, M.

1992-01-01

At temperatures prevailing near the Earth's surface, metastable co-existence of chemical substances is common because chemical reactions that would directly lead to the attainment of thermody-namically most stable equilibria are often blocked by high activation energy barriers. The persistency of a metastable assemblage is then governed by alternative reaction paths that provide lower activation energy barriers. Comparison of observed mineral assemblages in the supergene oxidized and enriched sulfide ores with corresponding stability Eh-pH diagrams reveals that the supergene assemblages are mostly metastable due primarily to the persistency of sulfide minerals beyond stability boundaries. A new set of diagrams called persistency-field Eh-pH diagrams has been constructed for binary metal sulfides on the basis of electrochemical and other experimental data. Each diagram delineates the persistency field, which is a combined field of thermodynamic stability and reaction path-controlled metastability, for a specific sulfide mineral. When applied to the supergene assemblages, these new diagrams show much better correspondence to the field observations. Although there may still be room for further refinement, the new diagrams appear to provide a strong visual aid to the understanding of the behavior of sulfide minerals in the supergene conditions. ?? 1992.

21 CFR 872.1870 - Sulfide detection device.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Sulfide detection device. 872.1870 Section 872.1870 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Diagnostic Devices § 872.1870 Sulfide detection device. (a) Identification...

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

USGS Publications Warehouse

Zhu, W.; Young, L.Y.; Yee, N.; Serfes, M.; Rhine, E.D.; Reinfelder, J.R.

2008-01-01

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black

Geologic setting, genesis and transformation of sulfide deposits in the northern part of Khetri copper belt, Rajasthan, India — an outline

NASA Astrophysics Data System (ADS)

Sarkar, S. C.; Dasgupta, Somnath

1980-07-01

The present study is confined to the northern part of the Khetri copper belt that extends for about 100 km in northern Rajasthan. Mineralization is more or less strata-bound and is confined to the garnetiferous chlorite schist and banded amphibolite quartzite, occurring towards the middle of the Proterozoic Delhi Supergroup. Preserved sedimentary features and re-estimation of the composition of the pre-metamorphic rocks suggest that the latter were deposited in shallow marine environment characterized by tidal activity. Cordierite-orthoamphibole-cummingtonite rock occurring in the neighbourhood of the ores is discussed, and is suggested to be isochemically metamorphosed sediment. The rocks together with the ores were deformed in two phases and metamorphosed in two progressive and one retrogressive events of metamorphism. Study of the host rocks suggests that the maximum temperature and pressure attained during metamorphism are respectively 550 600°C and < 5.5 kb. Principal ore minerals in Madan Kudan are chalcopyrite, pyrrhotite, pyrite and locally magnetite. In Kolihan these are chalcophyrite, pyrrhotite and cubanite. Subordinate phases are sphalerite, ilmenite, arsenopyrite, mackinawite, molybdenite, cobaltite and pentlandite. The last two are very rare. Gangue minerals comprise quartz, chlorite, garnet, amphiboles, biotite, scapolite, plagioclase and graphite. The ores are metamorphosed at temperatures > 491°C. Sulfide assemblages are explained in terms of fS 2 during metamorphism. Co-folding of the ore zone with the host rocks, confinement of the ores to the carbonaceous pelites or semi-pelitic rocks, strata-bound and locally even stratiform nature of the orebodies, lack of finite ‘wall rock alteration’, metamorphism of the ores in the thermal range similar to that for the host rocks, absence of spatial and temporal relationship with the granitic rocks of the region led the authors to conclude that the entire mineralization was originally sedimentary

Simulation of sulfide buildup in wastewater and atmosphere of sewer networks.

PubMed

Nielsen, A H; Yongsiri, C; Hvitved-Jacobsen, T; Vollertsen, J

2005-01-01

A model concept for prediction of sulfide buildup in sewer networks is presented. The model concept is an extension to--and a further development of--the WATS model (Wastewater Aerobic-anaerobic Transformations in Sewers), which has been developed by Hvitved-Jacobsen and co-workers at Aalborg University. In addition to the sulfur cycle, the WATS model simulates changes in dissolved oxygen and carbon fractions of different biodegradability. The sulfur cycle was introduced via six processes: 1. sulfide production taking place in the biofilm covering the permanently wetted sewer walls; 2. biological sulfide oxidation in the permanently wetted biofilm; 3. chemical and biological sulfide oxidation in the water phase; 4. sulfide precipitation with metals present in the wastewater; 5. emission of hydrogen sulfide to the sewer atmosphere and 6. adsorption and oxidation of hydrogen sulfide on the moist sewer walls where concrete corrosion may take place.

Corrosion of copper and authigenic sulfide mineral growth in hydrothermal bentonite experiments

NASA Astrophysics Data System (ADS)

Caporuscio, F. A.; Palaich, S. E. M.; Cheshire, M. C.; Jové Colón, C. F.

2017-03-01

The focus of this experimental work is to characterize interaction of bentonite with possible used-fuel waste container materials. Experiments were performed up to 300 °C at 150-160 bars for five to six weeks. Bentonite was saturated with a 1900 ppm K-Ca-Na-Cl-bearing water with Cu-foils. Copper rapidly degrades into chalcocite (CuS2) and minor covellite (CuS) in the presence of H2S. Chalcocite growth and corrosion pit depths were measured for four different experimental runs yielding corrosion rates between 8.8 and 116 μm/yr depending on duration of experiment, brine composition, and clay type (bentonite vs. Opalinus Clay). Results of this research show that although pit-corrosion is demonstrated on Cu substrates, experiments show that the reactions that ensue, and the formation of minerals that develop, are extraordinarily slow. This supports the use of Cu in nuclide-containment systems as a possible engineered barrier system material.

Corrosion of copper and authigenic sulfide mineral growth in hydrothermal bentonite experiments

DOE PAGES

Caporuscio, F. A.; Palaich, Sarah E. M.; Cheshire, M. C.; ...

2016-12-29

The focus of this experimental paper is to characterize interaction of bentonite with possible used-fuel waste container materials. Experiments were performed up to 300 °C at 150–160 bars for five to six weeks. Bentonite was saturated with a 1900 ppm K-Ca-Na-Cl-bearing water with Cu-foils. Copper rapidly degrades into chalcocite (CuS 2) and minor covellite (CuS) in the presence of H 2S. Chalcocite growth and corrosion pit depths were measured for four different experimental runs yielding corrosion rates between 8.8 and 116 μm/yr depending on duration of experiment, brine composition, and clay type (bentonite vs. Opalinus Clay). Results of this researchmore » show that although pit-corrosion is demonstrated on Cu substrates, experiments show that the reactions that ensue, and the formation of minerals that develop, are extraordinarily slow. Finally, this supports the use of Cu in nuclide-containment systems as a possible engineered barrier system material.« less

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity...

Friction and transfer of copper, silver, and gold to iron in the presence of various adsorbed surface films

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1979-01-01

Sliding friction experiments were conducted with the noble metals copper, silver, and gold and two binary alloys of these metals contacting iron in the presence of various adsorbates including, oxygen, methyl mercaptan, and methyl chloride. A pin on disk specimen configuration was used with a load of 100 grams, sliding velocity of 60 mm/min; at 25 C with the surfaces saturated with the adsorbates. Auger emission spectroscopy was used to monitor surface films. Results of the experiments indicate that friction and transfer characteristics are highly specific with respect to both the noble metal and surface film present. With all three metals and films transfer of the noble metal to iron occurred very rapidly. With all metals and films transfer of the noble metal to iron continuously increased with repeated passes except for silver and copper sliding on iron sulfide.

Copper and Copper Proteins in Parkinson's Disease

PubMed Central

Rivera-Mancia, Susana; Diaz-Ruiz, Araceli; Tristan-Lopez, Luis; Rios, Camilo

2014-01-01

Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson's disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson's disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased protein-bound copper in brain may enhance iron accumulation and the associated oxidative stress. The function of other copper-binding proteins such as Cu/Zn-SOD and metallothioneins is also beneficial to prevent neurodegeneration. Copper may regulate neurotransmission since it is released after neuronal stimulus and the metal is able to modulate the function of NMDA and GABA A receptors. Some of the proteins involved in copper transport are the transporters CTR1, ATP7A, and ATP7B and the chaperone ATOX1. There is limited information about the role of those biomolecules in the pathophysiology of Parkinson's disease; for instance, it is known that CTR1 is decreased in substantia nigra pars compacta in Parkinson's disease and that a mutation in ATP7B could be associated with Parkinson's disease. Regarding copper-related therapies, copper supplementation can represent a plausible alternative, while copper chelation may even aggravate the pathology. PMID:24672633

Regulation of extracellular copper-binding proteins in copper-resistant and copper-sensitive mutants of Vibrio alginolyticus.

PubMed Central

Harwood, V J; Gordon, A S

1994-01-01

Extracellular proteins of wild-type Vibrio alginolyticus were compared with those of copper-resistant and copper-sensitive mutants. One copper-resistant mutant (Cu40B3) constitutively produced an extracellular protein with the same apparent molecular mass (21 kDa) and chromatographic behavior as copper-binding protein (CuBP), a copper-induced supernatant protein which has been implicated in copper detoxification in wild-type V. alginolyticus. Copper-sensitive V. alginolyticus mutants displayed a range of alterations in supernatant protein profiles. CuBP was not detected in supernatants of one copper-sensitive mutant after cultures had been stressed with 50 microM copper. Increased resistance to copper was not induced by preincubation with subinhibitory levels of copper in the wild type or in the copper-resistant mutant Cu40B3. Copper-resistant mutants maintained the ability to grow on copper-amended agar after 10 or more subcultures on nonselective agar, demonstrating the stability of the phenotype. A derivative of Cu40B3 with wild-type sensitivity to copper which no longer constitutively expressed CuBP was isolated. The simultaneous loss of both constitutive CuBP production and copper resistance in Cu40B3 indicates that constitutive CuBP production is necessary for copper resistance in this mutant. These data support the hypothesis that the extracellular, ca. 20-kDa protein(s) of V. alginolyticus is an important factor in survival and growth of the organism at elevated copper concentrations. The range of phenotypes observed in copper-resistant and copper-sensitive V. alginolyticus indicate that altered sensitivity to copper was mediated by a variety of physiological changes. Images PMID:8031076

A method for measuring sulfide toxicity in the nematode Caenorhabditis elegans.

PubMed

Livshits, Leonid; Gross, Einav

2017-01-01

Cysteine catabolism by gut microbiota produces high levels of sulfide. Excessive sulfide can interfere with colon function, and therefore may be involved in the etiology and risk of relapse of ulcerative colitis, an inflammatory bowel disease affecting millions of people worldwide. Therefore, it is crucial to understand how cells/animals regulate the detoxification of sulfide generated by bacterial cysteine catabolism in the gut. Here we describe a simple and cost-effective way to explore the mechanism of sulfide toxicity in the nematode Caenorhabditis elegans ( C. elegans ). •A rapid cost-effective method to quantify and study sulfide tolerance in C. elegans and other free-living nematodes.•A cost effective method to measure the concentration of sulfide in the inverted plate assay.

Chemical Data for Rock, Sediment, Biological, Precipitate, and Water Samples from Abandoned Copper Mines in Prince William Sound, Alaska

USGS Publications Warehouse

Koski, Randolph A.; Munk, LeeAnn

2007-01-01

In the early 20th century, approximately 6 million metric tons of copper ore were mined from numerous deposits located along the shorelines of fjords and islands in Prince William Sound, Alaska. At the Beatson, Ellamar, and Threeman mine sites (fig. 1), rocks containing Fe, Cu, Zn, and Pb sulfide minerals are exposed to chemical weathering in abandoned mine workings and remnant waste piles that extend into the littoral zone. Field investigations in 2003 and 2005 as well as analytical data for rock, sediment, precipitate, water, and biological samples reveal that the oxidation of sulfides at these sites is resulting in the generation of acid mine drainage and the transport of metals into the marine environment (Koski and others, 2008; Stillings and others, 2008). At the Ellamar and Threeman sites, plumes of acidic and metal-enriched water are flowing through beach gravels into the shallow offshore environment. Interstitial water samples collected from beach sediment at Ellamar have low pH levels (to ~3) and high concentrations of metals including iron, copper, zinc, cobalt, lead, and mercury. The abundant precipitation of the iron sulfate mineral jarosite in the Ellamar gravels also signifies a low-pH environment. At the Beatson mine site (the largest copper mine in the region) seeps containing iron-rich microbial precipitates drain into the intertidal zone below mine dumps (Foster and others, 2008). A stream flowing down to the shoreline from underground mine workings at Beatson has near-neutral pH, but elevated levels of zinc, copper, and lead (Stillings and others, 2008). Offshore sediment samples at Beatson are enriched in these metals. Preliminary chemical data for tissue from marine mussels collected near the Ellamar, Threeman, and Beatson sites reveal elevated levels of copper, zinc, and lead compared to tissue in mussels from other locations in Prince William Sound (Koski and others, 2008). Three papers presenting results of this ongoing investigation of

Chemical Data for Rock, Sediment, Biological, Precipitate, and Water Samples from Abandoned Copper Mines in Prince William Sound, Alaska

USGS Publications Warehouse

Koski, Randolph A.; Munk, LeeAnn

2007-01-01

Introduction In the early 20th century, approximately 6 million metric tons of copper ore were mined from numerous deposits located along the shorelines of fjords and islands in Prince William Sound, Alaska. At the Beatson, Ellamar, and Threeman mine sites (fig. 1), rocks containing Fe, Cu, Zn, and Pb sulfide minerals are exposed to chemical weathering in abandoned mine workings and remnant waste piles that extend into the littoral zone. Field investigations in 2003 and 2005 as well as analytical data for rock, sediment, precipitate, water, and biological samples reveal that the oxidation of sulfides at these sites is resulting in the generation of acid mine drainage and the transport of metals into the marine environment (Koski and others, 2008; Stillings and others, 2008). At the Ellamar and Threeman sites, plumes of acidic and metal-enriched water are flowing through beach gravels into the shallow offshore environment. Interstitial water samples collected from beach sediment at Ellamar have low pH levels (to ~3) and high concentrations of metals including iron, copper, zinc, cobalt, lead, and mercury. The abundant precipitation of the iron sulfate mineral jarosite in the Ellamar gravels also signifies a low-pH environment. At the Beatson mine site (the largest copper mine in the region) seeps containing iron-rich microbial precipitates drain into the intertidal zone below mine dumps (Foster and others, 2008). A stream flowing down to the shoreline from underground mine workings at Beatson has near-neutral pH, but elevated levels of zinc, copper, and lead (Stillings and others, 2008). Offshore sediment samples at Beatson are enriched in these metals. Preliminary chemical data for tissue from marine mussels collected near the Ellamar, Threeman, and Beatson sites reveal elevated levels of copper, zinc, and lead compared to tissue in mussels from other locations in Prince William Sound (Koski and others, 2008). Three papers presenting results of this ongoing

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

PubMed

Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

2007-04-01

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

A comparative study of stream water and stream sediment as geochemical exploration media in the Rio Tanama porphyry copper district, Puerto Rico

USGS Publications Warehouse

Learned, R.E.; Chao, T.T.; Sanzolone, R.F.

1985-01-01

To test the relative effectiveness of stream water and sediment as geochemical exploration media in the Rio Tanama porphyry copper district of Puerto Rico, we collected and subsequently analyzed samples of water and sediment from 29 sites in the rivers and tributaries of the district. Copper, Mo, Pb, Zn, SO42-, and pH were determined in the waters; Cu, Mo, Pb, and Zn were determined in the sediments. In addition, copper in five partial extractions from the sediments was determined. Geochemical contrast (anomaly-to-background quotient) was the principal criterion by which the effectiveness of the two media and the five extractions were judged. Among the distribution patterns of metals in stream water, that of copper most clearly delineates the known porphyry copper deposits and yields the longest discernable dispersion train. The distribution patterns of Mo, Pb, and Zn in water show little relationship to the known mineralization. The distribution of SO42- in water delineates the copper deposits and also the more extensive pyrite alteration in the district; its recognizable downstream dispersion train is substantially longer than those of the metals, either in water or sediment. Low pH values in small tributaries delineate areas of known sulfide mineralization. The distribution patterns of copper in sediments clearly delineate the known deposits, and the dispersion trains are longer than those of copper in water. The partial determinations of copper related to secondary iron and manganese oxides yield the strongest geochemical contrasts and longest recognizable dispersion trains. Significantly high concentrations of molybdenum in sediments were found at only three sites, all within one-half km downstream of the known copper deposits. The distribution patterns of lead and zinc in sediments are clearly related to the known primary lead-zinc haloes around the copper deposits. The recognizable downstream dispersion trains of lead and zinc are shorter than those of

Preparation of silver-activated zinc sulfide thin films

NASA Technical Reports Server (NTRS)

Feldman, C.; Swindells, F. E.

1968-01-01

Silver improves luminescence and reduces contamination of zinc sulfide phosphors. The silver is added after the zinc sulfide phosphors are deposited in thin films by vapor evaporation, but before calcining, by immersion in a solution of silver salt.

DISSOLUTION OF PLUTONIUM CONTAINING CARRIER PRECIPITATE BY CARBONATE METATHESIS AND SEPARATION OF SULFIDE IMPURITIES THEREFROM BY SULFIDE PRECIPITATION

DOEpatents

Duffield, R.B.

1959-07-14

A process is described for recovering plutonium from foreign products wherein a carrier precipitate of lanthanum fluoride containing plutonium is obtained and includes the steps of dissolving the carrier precipitate in an alkali metal carbonate solution, adding a soluble sulfide, separating the sulfide precipitate, adding an alkali metal hydroxide, separating the resulting precipitate, washing, and dissolving in a strong acid.

Optimization of the superconducting phase of hydrogen sulfide

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Masur, E. A.

2015-12-01

The electron and phonon spectra, as well as the densities of electron and phonon states of the SH3 phase and the stable orthorhombic structure of hydrogen sulfide SH2, are calculated for the pressure interval 100-225 GPa. It is found that the I4/ mmm phase can be responsible for the superconducting properties of metallic hydrogen sulfide along with the SH3 phase. Sequential stages for obtaining and conservation of the SH2 phase are proposed. The properties of two (SH2 and SH3) superconducting phases of hydrogen sulfide are compared.

Hydrogen and sulfur recovery from hydrogen sulfide wastes

DOEpatents

Harkness, J.B.L.; Gorski, A.J.; Daniels, E.J.

1993-05-18

A process is described for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is [dis]associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

Hydrogen and sulfur recovery from hydrogen sulfide wastes

DOEpatents

Harkness, John B. L.; Gorski, Anthony J.; Daniels, Edward J.

1993-01-01

A process for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

Chemical dissolution of sulfide minerals

USGS Publications Warehouse

Chao, T.T.; Sanzolone, R.F.

1977-01-01

Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.

A sulfide-saturated lunar mantle?

NASA Astrophysics Data System (ADS)

Brenan, James M.; Mungall, James E.

2017-04-01

Although much work has been done to understand the controls on the sulfur content at sulfide saturation (SCSS) for terrestrial melt compositions, little information exists to evaluate the SCSS for the high FeO compositions typical of lunar magmas, and at the reduced conditions of the Moon's interior. Experiments were done to measure the SCSS for a model low Ti mare basalt with 20 wt% FeO at 1400oC as a function of fO2 and pressure. Synthetic lunar basalt was encapsulated along with stoichiometric FeS in capsules made from Fe-Ir alloy. The fO2 of the experiment can be estimated by the heterogeneous equilibrium: Femetal + 1 /2 O2 = FeOsilicate Variation in the metal composition, by addition of Ir, serves to change the fO2 of the experiment. Capsule compositions spanning the range Fe25Ir75 to Fe96Ir4 (at%) were synthesized by sintering of pressed powders under reducing conditions. Fe100 capsules were fabricated from pure Fe rod. For a melt with 20 wt% FeO, this range in capsule composition spans the fO2 interval of ˜IW-1 (Fe100, Fe96Ir4) to IW+2.2 (Fe25Ir75). Experiments were done over the pressure interval of 0.1 MPa to 2 GPa. Results for experiments involving Fe100capsules indicate that the SCSS decreases from ˜2000 ppm (0.1 MPa) to 700 ppm (2 GPa). Experiments done thus far at 1 GPa, involving the range of capsule compositions indicated, show a marked decrease in SCSS as the Fe content of the capsule increases (fO2 decreases). Complementary to the decrease in SCSS is a drop in the sulfur content of the coexisting sulfide melt, from ˜50 at% at ΔIW = +2.2 to ˜20 at% at ΔIW-1. In fact, both the composition of the sulfide melt and the SCSS are essentially indistinguishable for Fe96Ir4 and Fe100 compositions. Results thus far indicate that at reduced conditions and high pressure, the SCSS for high FeO lunar compositions is low, and overlaps with Apollo 11 melt inclusion data. Importantly, such low SCSS does not require Fe metal saturation, and suggests that some

Synthesis And Characterization of Copper Zinc Tin Sulfide Nanoparticles And Thin Films

NASA Astrophysics Data System (ADS)

Khare, Ankur

Copper zinc tin sulfide (Cu2ZnSnS4, or CZTS) is emerging as an alternative material to the present thin film solar cell technologies such as Cu(In,Ga)Se2 and CdTe. All the elements in CZTS are abundant, environmentally benign, and inexpensive. In addition, CZTS has a band gap of ˜1.5 eV, the ideal value for converting the maximum amount of energy from the solar spectrum into electricity. CZTS has a high absorption coefficient (>104 cm-1 in the visible region of the electromagnetic spectrum) and only a few micron thick layer of CZTS can absorb all the photons with energies above its band gap. CZT(S,Se) solar cells have already reached power conversion efficiencies >10%. One of the ways to improve upon the CZTS power conversion efficiency is by using CZTS quantum dots as the photoactive material, which can potentially achieve efficiencies greater than the present thin film technologies at a fraction of the cost. However, two requirements for quantum-dot solar cells have yet to be demonstrated. First, no report has shown quantum confinement in CZTS nanocrystals. Second, the syntheses to date have not provided a range of nanocrystal sizes, which is necessary not only for fundamental studies but also for multijunction photovoltaic architectures. We resolved these two issues by demonstrating a simple synthesis of CZTS, Cu2SnS3, and alloyed (Cu2SnS3) x(ZnS)y nanocrystals with diameters ranging from 2 to 7 nm from diethyldithiocarbamate complexes. As-synthesized nanocrystals were characterized using high resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and energy dispersive spectroscopy to confirm their phase purity. Nanocrystals of diameter less than 5 nm were found to exhibit a shift in their optical absorption spectra towards higher energy consistent with quantum confinement and previous theoretical predictions. Thin films from CZTS nanocrystals deposited on Mo-coated quartz substrates using drop casting were found to be continuous

Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

PubMed Central

Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

2016-01-01

This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

Potential for improved extraction of tellurium as a byproduct of current copper mining processes

NASA Astrophysics Data System (ADS)

Hayes, S. M.; Spaleta, K. J.; Skidmore, A. E.

2016-12-01

Tellurium (Te) is classified as a critical element due to its increasing use in high technology applications, low average crustal abundance (3 μg kg-1), and primary source as a byproduct of copper extraction. Although Te can be readily recovered from copper processing, previous studies have estimated a 4 percent extraction efficiency, and few studies have addressed Te behavior during the entire copper extraction process. The goals of the present study are to perform a mass balance examining Te behavior during copper extraction and to connect these observations with mineralogy of Te-bearing phases which are essential first steps in devising ways to optimize Te recovery. Our preliminary mass balance results indicate that less than 3 percent of Te present in copper ore is recovered, with particularly high losses during initial concentration of copper ore minerals by flotation. Tellurium is present in the ore in telluride minerals (e.g., Bi-Te-S phases, altaite, and Ag-S-Se-Te phases identified using electron microprobe) with limited substitution into sulfide minerals (possibly 10 mg kg-1 Te in bulk pyrite and chalcopyrite). This work has also identified Te accumulation in solid-phase intermediate extraction products that could be further processed to recover Te, including smelter dusts (158 mg kg-1) and pressed anode slimes (2.7 percent by mass). In both the smelter dusts and anode slimes, X-ray absorption spectroscopy indicates that about two thirds of the Te is present as reduced tellurides. In anode slimes, electron microscopy shows that the remaining Te is present in an oxidized form in a complex Te-bearing oxidate phase also containing Pb, Cu, Ag, As, Sb, and S. These results clearly indicate that more efficient, increased recovery of Te may be possible, likely at minimal expense from operating copper processing operations, thereby providing more Te for manufacturing of products such as inexpensive high-efficiency solar panels.

Study on the sulfidation behavior of smithsonite

NASA Astrophysics Data System (ADS)

Wu, Dandan; Wen, Shuming; Deng, Jiushuai; Liu, Jian; Mao, Yingbo

2015-02-01

Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pHIEP of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, CS in the solution declined from 1000 × 10-6 mol/L to 1.4 × 10-6 mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S2- and CO32- ions.

Copper tolerance of the thermoacidophilic archaeon Sulfolobus metallicus: possible role of polyphosphate metabolism.

PubMed

Remonsellez, Francisco; Orell, Alvaro; Jerez, Carlos A

2006-01-01

It has been postulated that inorganic polyphosphate (polyP) and transport of metal-phosphate complexes could participate in heavy metal tolerance in some bacteria. To study if such a system exists in archaea, the presence of polyP was determined by the electron energy loss spectroscopy (EELS) procedure and quantified by using specific enzymic methods in Sulfolobus acidocaldarius, Sulfolobus metallicus and Sulfolobus solfataricus. All three micro-organisms synthesized polyP during growth, but only S. metallicus greatly accumulated polyP granules. The differences in the capacity to accumulate polyP between these archaea may reflect adaptive responses to their natural environment. Thus, S. metallicus could grow in and tolerate up to 200 mM copper sulfate, with a concomitant decrease in its polyP levels with increasing copper concentrations. On the other hand, S. solfataricus could not grow in or tolerate more than 1-5 mM copper sulfate, most likely due to its low levels of polyP. Shifting S. metallicus cells to copper sulfate concentrations up to 100 mM led to a rapid increase in their exopolyphosphatase (PPX) activity which was concomitant in time with a decrease in their polyP levels and a stimulation of phosphate efflux. Furthermore, copper in the range of 10 microM greatly stimulated PPX activity in cell-free extracts from S. metallicus. The results strongly suggest that a metal tolerance mechanism mediated through polyP is functional in members of the genus Sulfolobus. This ability to accumulate and hydrolyse polyP may play an important role not only in the survival of these micro-organisms in sulfidic mineral environments containing high toxic metals concentrations, but also in their applications in biomining.

A preliminary cost analysis of the biotreatment of refinery spent-sulfidic caustic.

PubMed

Sublette, K L

1997-01-01

Caustics are used in petroleum refining to remove hydrogen sulfide from various hydrocarbon streams. Spent-sulfidic caustics from three refineries have been successfully biotreated on the bench and pilot scale, resulting in neutralization and removal of active Sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans strain F. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic. A commercial-scale treatment system has been designed that features a bioreactor with a suspended culture of flocculated T. denitrificans, a settler and acid and nutrient storage and delivery systems. A cost analysis has been performed for nine cases representing a range of spent caustic sulfide and hydroxide concentrations at a base treatment rate of 10 gpm. This analysis shows that refinery spent-sulfidic caustic can be biotreated for 4-8.3 cent/gal.

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

Optimization of biological sulfide removal in a CSTR bioreactor.

PubMed

Roosta, Aliakbar; Jahanmiri, Abdolhossein; Mowla, Dariush; Niazi, Ali; Sotoodeh, Hamidreza

2012-08-01

In this study, biological sulfide removal from natural gas in a continuous bioreactor is investigated for estimation of the optimal operational parameters. According to the carried out reactions, sulfide can be converted to elemental sulfur, sulfate, thiosulfate, and polysulfide, of which elemental sulfur is the desired product. A mathematical model is developed and was used for investigation of the effect of various parameters on elemental sulfur selectivity. The results of the simulation show that elemental sulfur selectivity is a function of dissolved oxygen, sulfide load, pH, and concentration of bacteria. Optimal parameter values are calculated for maximum elemental sulfur selectivity by using genetic algorithm as an adaptive heuristic search. In the optimal conditions, 87.76% of sulfide loaded to the bioreactor is converted to elemental sulfur.

Thermoelectric properties of non-stoichiometric lanthanum sulfides

NASA Technical Reports Server (NTRS)

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 C. The non-stoichiometric lanthanum sulfides (LaS(x), where x is in the range 1.33-1.50) appear to possess the most favorable thermoelectric properties. The Seebeck coefficient and resistivity vary significantly with composition, so that an optimum value of alpha sq/rho (where alpha is the Seebeck coefficient and rho is the resistivity) can be chosen. The thermal conductivity remains approximately constant with stoichiometry, so a material with an optimum value of alpha sq/rho should possess the optimum figure-of-merit. Data for the Seebeck coefficient and electrical resistivity of non-stoichiometric lanthanum sulfides will be pressed, together with structural properties of these materials.

Monitoring sulfide and sulfate-reducing bacteria

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

Tanner, R.S.

1995-12-31

Simple yet precise and accurate methods for monitoring sulfate-reducing bacteria (SRB) and sulfide remain useful for the study of bacterial souring and corrosion. Test kits are available to measure sulfide in field samples. A more precise methylene blue sulfide assay for both field and laboratory studies is described here. Improved media, compared to that in API RP-38, for enumeration of SRB have been formulated. One of these, API-RST, contained cysteine (1.1 mM) as a reducing agent, which may be a confounding source of sulfide. While cysteine was required for rapid enumeration of SRB from environmental samples, the concentration of cysteinemore » in medium could be reduced to 0.4 mM. It was also determined that elevated levels of yeast extract (>1 g/liter) could interfere with enumeration of SRB from environmental samples. The API-RST medium was modified to a RST-11 medium. Other changes in medium composition, in addition to reduction of cysteine, included reduction of the concentration of phosphate from 3.4 mM to 2.2 mM, reduction of the concentration of ferrous iron from 0.8 mM to 0.5 mM and preparation of a stock mineral solution to ease medium preparation. SRB from environmental samples could be enumerated in a week in this medium.« less

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

NASA Astrophysics Data System (ADS)

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 <1 µm to 43 µm, with a modal diameter of 14-17 µm (by number). Sulfides are not uniformly distributed, and are commonly observed in association with either sub-millimetre-scale plagioclase-clinopyroxene-olivine glomerocrysts or with bubbles. Maximum dissolved sulfur concentrations of 1750 ppm in melt inclusions and matrix glass

Replacement of hazardous chromium impregnating agent from silver/copper/chromium-impregnated active carbon using triethylenediamine to remove hydrogen sulfide, trichloromethane, ammonia, and sulfur dioxide.

PubMed

Wu, Li-Chun; Chung, Ying-Chien

2009-03-01

Activated carbon (AC) is widely used as an effective adsorbent in many applications, including industrial-scale air purification systems and air filter systems in gas masks. In general, ACs without chemical impregnation are good adsorbents of organic vapors but poor adsorbents of low-molecular-weight or polar gases such as chlorine, sulfur dioxide (SO2), formaldehyde, and ammonia (NH3). Impregnated ACs modified with metallic impregnating agents (ASC-carbons; e.g., copper, chromium, and silver) enhance the adsorbing properties of the ACs for simultaneously removing specific poisonous gases, but disposal of the chromium metal salt used to impregnate the ACs has the potential to result in situations that are toxic to both humans and the environment, thereby necessitating the search for replaceable organic impregnating agents that represent a much lower risk. The aim of this study was to assess the gas removal efficiency of an AC in which the organic impregnating agent triethylenediamine (TEDA) largely replaced the metallic impregnating agent chromium. We assessed batch and continuous adsorption capacities in situ for removing simulated hydrogen sulfide (H2S), trichloromethane (CHCl3), NH3, and SO2 gases. Brunauer-Emmet-Teller measurements and scanning electron microscopy analyses identified the removal mechanism by which TEDA-impregnated AS-carbon (dechromium ASC-carbon) adsorbs gases and determined the removal capacity for H2S, CHCl3, NH3, and SO2 to be 311, 258, 272, and 223 mg/g-C, respectively. These results demonstrate that TEDA-impregnated AS-carbon is significantly more efficient than ASC-carbon in adsorbing these four gases. Organic TEDA-impregnating agents have also been proven to be a reliable and environmental friendly agent and therefore a safe replacement of the hazardous chromium found in conventional ASC-carbon used in removing toxic gases from the airstream.

Measurement of plasma hydrogen sulfide in vivo and in vitro

PubMed Central

Shen, Xinggui; Pattillo, Christopher B.; Pardue, Sibile; Bir, Shyamal C.; Wang, Rui; Kevil, Christopher G.

2015-01-01

The gasotransmitter hydrogen sulfide is known to regulate multiple cellular functions during normal and pathophysiological states. However, a paucity of concise information exists regarding quantitative amounts of hydrogen sulfide involved in physiological and pathological responses. This is primarily due to disagreement among various methods employed to measure free hydrogen sulfide. In this article, we describe a very sensitive method of measuring the presence of H2S in plasma down to nanomolar levels, using monobromobimane (MBB). The current standard assay using methylene blue provides erroneous results that do not actually measure H2S. The method presented herein involves derivatization of sulfide with excess MBB in 100 mM Tris–HCl buffer (pH 9.5, 0.1 mM DTPA) for 30 min in 1% oxygen at room temperature. The fluorescent product sulfide-dibimane (SDB) is analyzed by RP-HPLC using an eclipse XDB-C18 (4.6×250 mm) column with gradient elution by 0.1% (v/v) trifluoroacetic acid in acetonitrile. The limit of detection for sulfide-dibimane is 2 nM and the SDB product is very stable over time, allowing batch storage and analysis. In summary, our MBB method is suitable for sensitive quantitative measurement of free hydrogen sulfide in multiple biological samples such as plasma, tissue and cell culture lysates, or media. PMID:21276849

A Study of Knowledge-Based Systems for Photo Interpretation.

DTIC Science & Technology

1980-06-01

special models have been developed by V. F. Hollister and A. N. Campbell to aid in the selection of drilling targets for porphyry copper and...type lead/zinc N. Campbell 20 Kuroko-type massive sulfide C. F. Park, Jr. 34 Komatiitic-type nickel sulfide A. J. Naldrett 72 Butte-type porphyry copper ...M. T. Einaudi 104 Yerington-type porphyry copper M. T. Einaudi 143 Island-arc-type porphyry copper D. Cox 116 Roll-front sandstone uranium R. I

Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Ohsumi, Kazumasa; Mikouchi, Takashi; Hagiya, Kenji; Le, Loan

2008-01-01

The main long-term goal of this research is to understand the physical conditions in the early solar nebula through the detailed characterization of a key class of mineral present in all primitive materials: Fe-Ni sulfides [1&2]. Fe-Ni sulfides can take dozens of structures, depending on the temperature of formation, as well as other physico-chemical factors which are imperfectly understood. Add to this the additional varying factor of Ni content, and we have a potentially sensitive cosmothermometer [3]. Unfortunately, this tool requires exact knowledge of the crystal structure of each grain being considered, and there have been few (none?) studies of the detailed structures of sulfides in chondritic materials. We report here on coordinated compositional and crystallographic investigation of Fe-Ni sulfides in diverse carbonaceous chondrites, initially Acfer 094 (the most primitive CM2 [4]) Tagish Lake (a unique type C2 [5]), a C1 lithology in Kaidun [6], Bali (oxidized CV3 [7]), and Efremovka (reduced CV3 [7]).

Sulfide bonded atomic radii

NASA Astrophysics Data System (ADS)

Gibbs, G. V.; Ross, N. L.; Cox, D. F.

2017-09-01

The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2016-06-14

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.

Iron-sulfide redox flow batteries

DOEpatents

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.

The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

PubMed Central

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

Cooperative oscillations of electron-copper-oxygen interaction: Possible relevance for superconduction theory

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

Tributsch, H.

1989-01-01

Interfaces of copper containing crystallized materials (Cu/sub 5/FeS/sub 4/, CuFeS/sub 2/, Cu/sub 2/S, CuS, CuInS/sub 2/, and CuInSe/sub 2/), exposed to oxidation by H/sub 2/O/sub 2/, undergo sustained electrochemical oscillations. They involve electronic (Cu/sup +/), (Cu/sup 2 +/), and (Cu/sup 3 +/) interactions with chemically bound oxygen similar as in superconducting YBa/sub 2/Cu/sub 3/O/sub 7/ or (La,Sr)/sub 2/CuO/sub 4/ and may be a phenomenon of irreversible thermodynamics which is related to the kind of cooperative electron-copper-oxygen interactions which also give rise to high-temperature superconduction. The relevance of the model system is supported by the formation of the H/sub 2/O/sub 2/more » species on the surface of high-temperature superconducting materials in contact with ambiental humidity. It is shown how, by a simple modification of the interaction mechanism, an oscillatory phenomenon such as that observed with oxidized copper sulfide interfaces, which follows a limiting cycle, can be converted into a triple-state phenomenon. Such a cooperative mechanism that involves a lowest steady state which is unable to turn over energy may be the background for the pairing of electrons or a related cooperative interaction process in superconduction. As a possible support, no interfacial oscillations could yet be induced with Ba/sub 2/Cu/sub 3/Y/sub 7/.« less

Reviewing sulfidation corrosion—Yesterday and today

NASA Astrophysics Data System (ADS)

Bornstein, Norman S.

1996-11-01

At one time, sulfidation corrosion threatened to severely limit the use of gas turbines in marine applications, markedly reduce the life of industrial gas turbines, and affect the performance of aircraft engines. Today, gas turbine engines drive U.S. naval ships, produce electricity, and power aircraft. However, the problem of sulfidation corrosion has not disappeared. The rapid rate of degradation of airfoil materials in the presence of condensed sulfates is still a concern for gas turbine engines that operate in industrial and marine environments.

Photochemical Dual-Catalytic Synthesis of Alkynyl Sulfides.

PubMed

Santandrea, Jeffrey; Minozzi, Clémentine; Cruché, Corentin; Collins, Shawn K

2017-09-25

A photochemical dual-catalytic cross-coupling to form alkynyl sulfides via C(sp)-S bond formation is described. The cross-coupling of thiols and bromoalkynes is promoted by a soluble organic carbazole-based photocatalyst using continuous flow techniques. Synthesis of alkynyl sulfides bearing a wide range of electronically and sterically diverse aromatic alkynes and thiols can be achieved in good to excellent yields (50-96 %). The simple continuous flow setup also allows for short reaction times (30 min) and high reproducibility on gram scale. In addition, we report the first application of photoredox/nickel dual catalysis towards macrocyclization, as well as the first example of the incorporation of an alkynyl sulfide functional group into a macrocyclic scaffold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thiol-based copper handling by the copper chaperone Atox1.

PubMed

Hatori, Yuta; Inouye, Sachiye; Akagi, Reiko

2017-04-01

Human antioxidant protein 1 (Atox1) plays a crucial role in cellular copper homeostasis. Atox1 captures cytosolic copper for subsequent transfer to copper pumps in trans Golgi network, thereby facilitating copper supply to various copper-dependent oxidereductases matured within the secretory vesicles. Atox1 and other copper chaperones handle cytosolic copper using Cys thiols which are ideal ligands for coordinating Cu(I). Recent studies demonstrated reversible oxidation of these Cys residues in copper chaperones, linking cellular redox state to copper homeostasis. Highlighted in this review are unique redox properties of Atox1 and other copper chaperones. Also, summarized are the redox nodes in the cytosol which potentially play dominant roles in the redox regulation of copper chaperones. © 2016 IUBMB Life, 69(4):246-254, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

PubMed Central

Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

2016-01-01

Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

Copper sulfide nanoparticle-based localized drug delivery system as an effective cancer synergistic treatment and theranostic platform.

PubMed

Hou, Lin; Shan, Xiaoning; Hao, Lisha; Feng, Qianhua; Zhang, Zhenzhong

2017-05-01

with multi-mechanism therapy may be a promising method for cancer treatment. In recent years, localized cancer treatment using different biomaterials has attracted increasing attention for effective inhibition of tumor growth. However, it is still challenging for this kind of system to achieve a high drug loading, overcome biological barriers from the site of injection to the site of action, and combine synergetic therapy with diagnosis without adversely affecting the formation process. This study provides a localized diffusion molecular retention (DMR) tumor targeting drug delivery system based on hollow mesoporous copper sulfide nanoparticles (HMCuS NPs) entrapment of anticancer drug for the first time, which can achieve high drug loading, improve local drug accumulation and retention, accomplish synergistic combination of chemo-phototherapy, and finally enhance antitumor effect. In addition, HMCuS NPs also possesses the property suitable for photoacoustic imaging, which could offer us a theranostic platform. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface Charge Development on Transition Metal Sulfides: An Electrokinetic Study

NASA Astrophysics Data System (ADS)

Bebie, Joakim; Schoonen, Martin A. A.; Fuhrmann, Mark; Strongin, Daniel R.

1998-02-01

The isoelectric points, pH i.e.p., of ZnS, PbS, CuFeS 2, FeS, FeS 2, NiS 2, CoS 2, and MnS 2 in NaCl supported electrolyte solutions are estimated to be between pH 3.3 and 0.6, with most of the isoelectric points below pH 2. The first electrokinetic measurements on NiS 2, CoS 2, and MnS 2 are reported here. Below pH i.e.p. the metal-sulfide surfaces are positively charged, above pH i.e.p. the surfaces are negatively charged. The addition of Me 2+ ions shifts the pH i.e.p. and changes the pH dependence considerably. The isoelectric points of the measured transition metal sulfides in the absence of metal ions or dissolved sulfide (H 2S or HS -) are in agreement with those found in earlier studies. The pH range of observed isoelectric points for metal sulfides (0.6-3.3) is compared to the considerably wider pH i.e.p. range (2-12) found for oxides. The correlation between pH i.e.p. and the electronegativities of the metal sulfides suggests that all metal sulfides will have an isoelectric point between pH 0.6 and 3.3. Compared to metal oxides, sulfides exhibit an isoelectric point that is largely independent of the nature of the metal cation in the solid.

Sulfidation behavior and mechanism of zinc silicate roasted with pyrite

NASA Astrophysics Data System (ADS)

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.

Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

DOE PAGES

Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, III, Jack R.; ...

2017-04-06

We consider catalytic hydroprocessing of pyrolysis oils from biomass which produces hydrocarbons for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. Here, we present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consistingmore » of RuS/C and xMoS/Al 2O 3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractions as well as the surprising similarity in content in some sulfided and non-sulfided fractions. Our results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less

Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

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

Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, III, Jack R.

We consider catalytic hydroprocessing of pyrolysis oils from biomass which produces hydrocarbons for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. Here, we present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consistingmore » of RuS/C and xMoS/Al 2O 3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractions as well as the surprising similarity in content in some sulfided and non-sulfided fractions. Our results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less

Sulfur speciation and sulfide oxidation in the water column of the Black Sea

NASA Astrophysics Data System (ADS)

Luther, George W., III; Church, Thomas M.; Powell, David

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on

Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

PubMed

Liu, Xue; Huang, Jia-Qi; Zhang, Qiang; Mai, Liqiang

2017-05-01

Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling of Sulfide Microenvironments on Mars

NASA Technical Reports Server (NTRS)

Schwenzer, S. P.; Bridges, J. C.; McAdam, A.; Steer, E. D.; Conrad, P. G.; Kelley, S. P.; Wiens, R. C.; Mangold, N.; Grotzinger, J.; Eigenbrode, J. L.;

Iron-Nickel Sulfide Compositional Ranges in CM Chondrites: No Simple Plan

NASA Technical Reports Server (NTRS)

Zolensky, Michael; Le, Loan

2003-01-01

Iron-nickel sulfides are found in most or all solar system environments, and are probably the only minerals found in all extraterrestrial materials on hand. Despite this ubiquity, they have only just begun the attention they deserve. The most common Fe-Ni sulfides in chondrites are troilite (FeS), pyrrhotite (Fe(1-x)S) and pentlandite (Fe,Ni)9S8. Troilite is believed to have resulted from sulfidation of metal (Fe-Ni) grains in an H2S-containing environment. Pyrrhotite is produced when friable troilite grains, which are exfoliated from the metal nucleus, are submitted to continued sulfidation. Some asteroids are known to have experienced aqueous alteration, forming products including new generations of sulfides (pyrrhotite and pentlandite). Pentlandite in particular is known to form during such alteration. However, experimental work by Lauretta has indicated that pentlandite may also have been formed during the initial sulfidation process, due to the faster diffusion rate of nickel into the forming sulfide, as compared to iron. Finally, there is considerable evidence for a family of phases intermediate between pyrrhotite and pentlandite, following the trend of the high temperature monosulfide solid solution, something not encountered in terrestrial rocks. Each sulfide has its own particular stability conditions, which have been determined for most phases. The long-term objective of our research is to characterize sulfides in chondritic materials in order to better establish the conditions under which they formed, and the subsequent processes they experienced. Ultimately, it will be possible to infer whether the sulfides in the chondrites were formed in the solar nebula or on asteroids, and if formed on the asteroids, deduce how much alteration has occurred there. Here we explore the relationships between the finest grain size portions of carbonaceous chondrites, these being matrix and chondrule rims; fine-grained materials are the most sensitive to their environment

Selective Sulfidation of Lead Smelter Slag with Sulfur

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

2016-02-01

The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

Lanthanide complexes as luminogenic probes to measure sulfide levels in industrial samples.

PubMed

Thorson, Megan K; Ung, Phuc; Leaver, Franklin M; Corbin, Teresa S; Tuck, Kellie L; Graham, Bim; Barrios, Amy M

2015-10-08

A series of lanthanide-based, azide-appended complexes were investigated as hydrogen sulfide-sensitive probes. Europium complex 1 and Tb complex 3 both displayed a sulfide-dependent increase in luminescence, while Tb complex 2 displayed a decrease in luminescence upon exposure to NaHS. The utility of the complexes for monitoring sulfide levels in industrial oil and water samples was investigated. Complex 3 provided a sensitive measure of sulfide levels in petrochemical water samples (detection limit ∼ 250 nM), while complex 1 was capable of monitoring μM levels of sulfide in partially refined crude oil. Copyright © 2015 Elsevier B.V. All rights reserved.

Denitrifying sulfide removal process on high-salinity wastewaters.

PubMed

Liu, Chunshuang; Zhao, Chaocheng; Wang, Aijie; Guo, Yadong; Lee, Duu-Jong

2015-08-01

Denitrifying sulfide removal (DSR) process comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide, and acetate into nitrogen gas, elemental sulfur (S(0)), and carbon dioxide, respectively. Sulfide- and nitrate-laden wastewaters at 2-35 g/L NaCl were treated by DSR process. A C/N ratio of 3:1 was proposed to maintain high S(0) conversion rate. The granular sludge with a compact structure and smooth outer surface was formed. The microbial communities of DSR consortium via high-throughput sequencing method suggested that salinity shifts the predominating heterotrophic denitrifiers at <10 g/L NaCl to autotrophic denitrifiers at >10 g/L NaCl.

Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi

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

Powell, M.A.; Somero, G.N.

1986-08-01

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide asmore » an inorganic energy source.« less

Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

NASA Astrophysics Data System (ADS)

Gainov, R. R.; Vagizov, F. G.; Golovanevskiy, V. A.; Ksenofontov, V. A.; Klingelhöfer, G.; Klekovkina, V. V.; Shumilova, T. G.; Pen'kov, I. N.

2014-04-01

Nuclear resonance methods, including Mössbauer spectroscopy,are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mössbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu5FeS4) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by 57Fe Mössbauer spectroscopy. Two aspects were considered: reexamination of 57Fe Mössbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mössbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mössbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary 63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mössbauer techniques for bornite detection discussed.

Precursors for formation of copper selenide, indium selenide, copper indium diselenide, and/or copper indium gallium diselenide films

DOEpatents

Curtis, Calvin J; Miedaner, Alexander; Van Hest, Maikel; Ginley, David S

2014-11-04

Liquid-based precursors for formation of Copper Selenide, Indium Selenide, Copper Indium Diselenide, and/or copper Indium Galium Diselenide include copper-organoselenides, particulate copper selenide suspensions, copper selenide ethylene diamine in liquid solvent, nanoparticulate indium selenide suspensions, and indium selenide ethylene diamine coordination compounds in solvent. These liquid-based precursors can be deposited in liquid form onto substrates and treated by rapid thermal processing to form crystalline copper selenide and indium selenide films.

New cyclic sulfides, garlicnins I2, M, N, and O, from Allium sativum.

PubMed

Nohara, Toshihiro; Ono, Masateru; Nishioka, Naho; Masuda, Fuka; Fujiwara, Yukio; Ikeda, Tsuyoshi; Nakano, Daisuke; Kinjo, Junei

2018-01-01

One atypical thiolane-type sulfide, garlicnin I 2 (1), two 3,4-dimethylthiolane-type sulfides, garlicnins M (2) and N (3), and one thiabicyclic-type sulfide, garlicnin O (4), were isolated from the acetone extracts of Chinese garlic bulbs, Allium sativum and their structures were characterized. Hypothetical pathways for the production of the respective sulfides were discussed.

Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing.

PubMed

Ganigué, Ramon; Jiang, Guangming; Liu, Yiqi; Sharma, Keshab; Wang, Yue-Cong; Gonzalez, José; Nguyen, Tung; Yuan, Zhiguo

2018-05-15

Water utilities worldwide spend annually billions of dollars to control sulfide-induced corrosion in sewers. Iron salts chemically oxidize and/or precipitate dissolved sulfide in sewage and are especially used in medium- and large-size sewers. Iron salt dosing rates are defined ad hoc, ignoring variation in sewage flows and sulfide levels. This often results in iron overdosing or poor sulfide control. Online dosing control can adjust the chemical dosing rates to current (and future) state of the sewer system, allowing high-precision, stable and cost-effective sulfide control. In this paper, we report a novel and robust online control strategy for the dosing of ferrous salt in sewers. The control considers the fluctuation of sewage flow, pH, sulfide levels and also the perturbation from rainfall. Sulfide production in the pipe is predicted using auto-regressive models (AR) based on current flow measurements, which in turn can be used to determine the dose of ferrous salt required for cost-effective sulfide control. Following comprehensive model-based assesment, the control was successfully validated and its effectiveness demonstrated in a 3-week field trial. The online control algorithm controlled sulfide below the target level (0.5 mg S/L) while reducing chemical dosing up to 30%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Copper Metallochaperones

PubMed Central

Robinson, Nigel J.; Winge, Dennis R.

2014-01-01

The current state of knowledge on how copper metallochaperones support the maturation of cuproproteins is reviewed. Copper is needed within mitochondria to supply the CuA and intramembrane CuB sites of cytochrome oxidase, within the trans-Golgi network to supply secreted cuproproteins and within the cytosol to supply superoxide dismutase 1 (Sod1). Subpopulations of copper-zinc superoxide dismutase also localize to mitochondria, the secretory system, the nucleus and, in plants, the chloroplast, which also requires copper for plastocyanin. Prokaryotic cuproproteins are found in the cell membrane and in the periplasm of gram-negative bacteria. Cu(I) and Cu(II) form tight complexes with organic molecules and drive redox chemistry, which unrestrained would be destructive. Copper metallochaperones assist copper in reaching vital destinations without inflicting damage or becoming trapped in adventitious binding sites. Copper ions are specifically released from copper metallochaperones upon contact with their cognate cuproproteins and metal transfer is thought to proceed by ligand substitution. PMID:20205585

Bioaccessibility and Solubility of Copper in Copper-Treated Lumber

EPA Science Inventory

Micronized copper (MC)-treated lumber is a recent replacement for Chromated Copper Arsenate (CCA) and Ammonium Copper (AC)-treated lumbers; though little is known about the potential risk of copper (Cu) exposure from incidental ingestion of MC-treated wood. The bioaccessibility o...

Adaptation of cyanobacteria to the sulfide-rich microenvironment of black band disease of coral.

PubMed

Myers, Jamie L; Richardson, Laurie L

2009-02-01

Black band disease (BBD) is a cyanobacteria-dominated microbial mat that migrates across living coral colonies lysing coral tissue and leaving behind exposed coral skeleton. The mat is sulfide-rich due to the presence of sulfate-reducing bacteria, integral members of the BBD microbial community, and the sulfide they produce is lethal to corals. The effect of sulfide, normally toxic to cyanobacteria, on the photosynthetic capabilities of five BBD cyanobacterial isolates of the genera Geitlerinema (3), Leptolyngbya (1), and Oscillatoria (1) and six non-BBD cyanobacteria of the genera Leptolyngbya (3), Pseudanabaena (2), and Phormidium (1) was examined. Photosynthetic experiments were performed by measuring the photoincorporation of [(14)C] NaHCO(3) under the following conditions: (1) aerobic (no sulfide), (2) anaerobic with 0.5 mM sulfide, and (3) anaerobic with 0.5 mM sulfide and 10 microM 3-(3',4'-dichlorophenyl)-1,1-dimethylurea (DCMU). All five BBD cyanobacterial isolates tolerated sulfide by conducting sulfide-resistant oxygenic photosynthesis. Five of the non-BBD cyanobacterial isolates did not tolerate sulfide, although one Pseudanabaena isolate continued to photosynthesize in the presence of sulfide at a considerably reduced rate. None of the isolates conducted anoxygenic photosynthesis with sulfide as an electron donor. This is the first report on the physiology of a culture of Oscillatoria sp. found globally in BBD.

Non-hydrolytic Sol-gel Synthesis of Tin Sulfides

NASA Astrophysics Data System (ADS)

Kaur, Rajvinder

The non-hydrolytic sol-gel (NHSG) process is an effective low temperature route well known for preparing homogeneous metal oxides. Thermodynamically as well as kinetically favored products, which cannot be prepared with the traditional solid-state routes, can be produced using NHSG. This project is focused on the exploration of NHSG synthesis of binary tin sulfides. In the past few years, metal sulfides have been the subject of significant interest. Much effort has been devoted to understand these materials because of their potential applications in electronic, optical, and superconductor devices.4 Among these materials, tin sulfides are materials of technological importance, which are being explored as semiconductors, anode materials for Li ion batteries, photoconductors, photocatalysts and absorber layer materials in photovoltaic solar cell devices. All of these applications depend upon features like homogeneity, oxidation state, high surface area and purity of the materials. These properties can be difficult to achieve by employing traditional synthetic routes, which require high temperatures due to slow diffusion, limiting the products to thermodynamically stable phases and prohibiting control over properties like particle size and surface area. A variety of low temperature methods are being explored due to the increased demand for such advanced materials. This project is focused on exploring the NHSG approach to synthesize binary tin sulfides, with the main goal of establishing conditions for the targeted synthesis of different tin sulfide polymorphs with controlled particle size. Being non-oxide materials, tin sulfides can be air sensitive, which requires special attention in handling. All reactions were carried out in absence of oxygen. This project explores the reaction of tin halides with thioethers in a dry solvent medium, leading to the formation of tin sulfides. There are a number of synthetic parameters that can be varied for the NHSG approach. A

Advantages and challenges of increased antimicrobial copper use and copper mining.

PubMed

Elguindi, Jutta; Hao, Xiuli; Lin, Yanbing; Alwathnani, Hend A; Wei, Gehong; Rensing, Christopher

2011-07-01

Copper is a highly utilized metal for electrical, automotive, household objects, and more recently as an effective antimicrobial surface. Copper-containing solutions applied to fruits and vegetables can prevent bacterial and fungal infections. Bacteria, such as Salmonellae and Cronobacter sakazakii, often found in food contamination, are rapidly killed on contact with copper alloys. The antimicrobial effectiveness of copper alloys in the healthcare environment against bacteria causing hospital-acquired infections such as methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli O157:H7, and Clostridium difficile has been described recently. The use of copper and copper-containing materials will continue to expand and may lead to an increase in copper mining and production. However, the copper mining and manufacturing industry and the consumer do not necessarily enjoy a favorable relationship. Open pit mining, copper mine tailings, leaching products, and deposits of toxic metals in the environment often raises concerns and sometimes public outrage. In addition, consumers may fear that copper alloys utilized as antimicrobial surfaces in food production will lead to copper toxicity in humans. Therefore, there is a need to mitigate some of the negative effects of increased copper use and copper mining. More thermo-tolerant, copper ion-resistant microorganisms could improve copper leaching and lessen copper groundwater contamination. Copper ion-resistant bacteria associated with plants might be useful in biostabilization and phytoremediation of copper-contaminated environments. In this review, recent progress in microbiological and biotechnological aspects of microorganisms in contact with copper will be presented and discussed, exploring their role in the improvement for the industries involved as well as providing better environmental outcomes.

Nanostructured silver sulfide: synthesis of various forms and their application

NASA Astrophysics Data System (ADS)

Sadovnikov, S. I.; Rempel, A. A.; Gusev, A. I.

2018-04-01

The results of experimental studies on nanostructured silver sulfide are analyzed and generalized. The influence of small particle size on nonstoichiometry of silver sulfide is discussed. Methods for the synthesis of various forms of nanostructured Ag2S including nanopowders, stable colloidal solutions, quantum dots, core–shell nanoparticles and heteronanostructures are described. The advantages and drawbacks of different synthetic procedures are analyzed. Main fields of application of nanostructured silver sulfide are considered. The bibliography includes 184 references.

Production and Preservation of Sulfide Layering in Mercury's Magma Ocean

NASA Astrophysics Data System (ADS)

Boukare, C.-E.; Parman, S. W.; Parmentier, E. M.; Anzures, B. A.

2018-05-01

Mercury's magma ocean (MMO) would have been sulfur-rich. At some point during MMO solidification, it likely became sulfide saturated. Here we present physiochemical models exploring sulfide layer formation and stability.

Copper as a target for prostate cancer therapeutics: copper-ionophore pharmacology and altering systemic copper distribution.

PubMed

Denoyer, Delphine; Pearson, Helen B; Clatworthy, Sharnel A S; Smith, Zoe M; Francis, Paul S; Llanos, Roxana M; Volitakis, Irene; Phillips, Wayne A; Meggyesy, Peter M; Masaldan, Shashank; Cater, Michael A

2016-06-14

Copper-ionophores that elevate intracellular bioavailable copper display significant therapeutic utility against prostate cancer cells in vitro and in TRAMP (Transgenic Adenocarcinoma of Mouse Prostate) mice. However, the pharmacological basis for their anticancer activity remains unclear, despite impending clinical trails. Herein we show that intracellular copper levels in prostate cancer, evaluated in vitro and across disease progression in TRAMP mice, were not correlative with copper-ionophore activity and mirrored the normal levels observed in patient prostatectomy tissues (Gleason Score 7 & 9). TRAMP adenocarcinoma cells harbored markedly elevated oxidative stress and diminished glutathione (GSH)-mediated antioxidant capacity, which together conferred selective sensitivity to prooxidant ionophoric copper. Copper-ionophore treatments [CuII(gtsm), disulfiram & clioquinol] generated toxic levels of reactive oxygen species (ROS) in TRAMP adenocarcinoma cells, but not in normal mouse prostate epithelial cells (PrECs). Our results provide a basis for the pharmacological activity of copper-ionophores and suggest they are amendable for treatment of patients with prostate cancer. Additionally, recent in vitro and mouse xenograft studies have suggested an increased copper requirement by prostate cancer cells. We demonstrated that prostate adenocarcinoma development in TRAMP mice requires a functional supply of copper and is significantly impeded by altered systemic copper distribution. The presence of a mutant copper-transporting Atp7b protein (tx mutation: A4066G/Met1356Val) in TRAMP mice changed copper-integration into serum and caused a remarkable reduction in prostate cancer burden (64% reduction) and disease severity (grade), abrogating adenocarcinoma development. Implications for current clinical trials are discussed.

Copper as a target for prostate cancer therapeutics: copper-ionophore pharmacology and altering systemic copper distribution

PubMed Central

Denoyer, Delphine; Pearson, Helen B.; Clatworthy, Sharnel A.S.; Smith, Zoe M.; Francis, Paul S.; Llanos, Roxana M.; Volitakis, Irene; Phillips, Wayne A.; Meggyesy, Peter M.; Masaldan, Shashank; Cater, Michael A.

2016-01-01

Copper-ionophores that elevate intracellular bioavailable copper display significant therapeutic utility against prostate cancer cells in vitro and in TRAMP (Transgenic Adenocarcinoma of Mouse Prostate) mice. However, the pharmacological basis for their anticancer activity remains unclear, despite impending clinical trails. Herein we show that intracellular copper levels in prostate cancer, evaluated in vitro and across disease progression in TRAMP mice, were not correlative with copper-ionophore activity and mirrored the normal levels observed in patient prostatectomy tissues (Gleason Score 7 & 9). TRAMP adenocarcinoma cells harbored markedly elevated oxidative stress and diminished glutathione (GSH)-mediated antioxidant capacity, which together conferred selective sensitivity to prooxidant ionophoric copper. Copper-ionophore treatments [CuII(gtsm), disulfiram & clioquinol] generated toxic levels of reactive oxygen species (ROS) in TRAMP adenocarcinoma cells, but not in normal mouse prostate epithelial cells (PrECs). Our results provide a basis for the pharmacological activity of copper-ionophores and suggest they are amendable for treatment of patients with prostate cancer. Additionally, recent in vitro and mouse xenograft studies have suggested an increased copper requirement by prostate cancer cells. We demonstrated that prostate adenocarcinoma development in TRAMP mice requires a functional supply of copper and is significantly impeded by altered systemic copper distribution. The presence of a mutant copper-transporting Atp7b protein (tx mutation: A4066G/Met1356Val) in TRAMP mice changed copper-integration into serum and caused a remarkable reduction in prostate cancer burden (64% reduction) and disease severity (grade), abrogating adenocarcinoma development. Implications for current clinical trials are discussed. PMID:27175597

Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

PubMed Central

Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

2016-01-01

As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1–40 μM in sulfide detection with a high sensitivity of 1720 μA mM−1 cm−2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported. PMID:27515253

Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

NASA Astrophysics Data System (ADS)

Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

2016-08-01

As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1-40 μM in sulfide detection with a high sensitivity of 1720 μA mM-1 cm-2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported.

Effects of Wood Pollution on Pore-Water Sulfide Levels and Eelgrass Germination

NASA Astrophysics Data System (ADS)

Ekelem, C.

2016-02-01

Historically, sawmills released wood waste onto coastal shorelines throughout the Pacific Northwest of the USA, enriching marine sediments with organic material. The increase in organic carbon boosts the bacterial reduction of sulfate and results in the production of a toxic metabolite, hydrogen sulfide. Hydrogen sulfide is a phytotoxin and can decrease the growth and survival of eelgrass. This is a critical issue since eelgrass, Zostera marina, forms habitat for many species, stabilizes sediment, and plays a role in nutrient cycling and sediment chemistry. The objective of our study was to determine the effects of wood debris on sediment pore-water hydrogen sulfide concentrations and eelgrass germination. To test the impact of wood inputs on sulfide production and seed germination, we conducted a laboratory mesocosm experiment, adding sawdust to marine sediments and measuring the sulfide levels weekly. We subsequently planted seeds in the mesocosms and measured germination rates. Higher concentrations of sawdust led to higher levels of pore-water hydrogen sulfide and drastically slower eelgrass germination rates. Treatments with greater than 10% wood enrichment developed free sulfide concentrations of 0.815 (± 0.427) mM after 118 days, suggesting sediments with greater than 10% wood pollution may have threateningly high pore-water hydrogen sulfide levels. These results can be used to set thresholds for remediation efforts and guide seed distribution in wood polluted areas.

THE WEATHERING OF A SULFIDE OREBODY: SPECIATION AND FATE OF SOME POTENTIAL CONTAMINANTS

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

Courtin-Nomade, Alexandra; Grosbois, Cecile; Marcus, Matthew A.

2010-07-16

Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogenically modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., {approx}500 mg/L Cu, {approx}3700 mg/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less thanmore » 10 {mu}m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (mXAS), scanning X-ray diffraction (mSXRD) and scanning X-ray fluorescence (mSXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According

The weathering of a sulfide orebody: Speciation and fate of some potential contaminants

USGS Publications Warehouse

Courtin-Nomade, A.; Grosbois, C.; Marcus, M.A.; Fakra, S.C.; Beny, J.-M.; Foster, A.L.

2009-01-01

Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogeni- cally modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., ??500 ??g/L Cu, ??3700 ??g/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 ??m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (??XAS), scanning X-ray diffraction ((??SXRD) and scanning X-ray fluorescence (??-SXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace

Advanced Copper Composites Against Copper-Tolerant Xanthomonas perforans and Tomato Bacterial Spot.

PubMed

Strayer-Scherer, A; Liao, Y Y; Young, M; Ritchie, L; Vallad, G E; Santra, S; Freeman, J H; Clark, D; Jones, J B; Paret, M L

2018-02-01

Bacterial spot, caused by Xanthomonas spp., is a widespread and damaging bacterial disease of tomato (Solanum lycopersicum). For disease management, growers rely on copper bactericides, which are often ineffective due to the presence of copper-tolerant Xanthomonas strains. This study evaluated the antibacterial activity of the new copper composites core-shell copper (CS-Cu), multivalent copper (MV-Cu), and fixed quaternary ammonium copper (FQ-Cu) as potential alternatives to commercially available micron-sized copper bactericides for controlling copper-tolerant Xanthomonas perforans. In vitro, metallic copper from CS-Cu and FQ-Cu at 100 μg/ml killed the copper-tolerant X. perforans strain within 1 h of exposure. In contrast, none of the micron-sized copper rates (100 to 1,000 μg/ml) from Kocide 3000 significantly reduced copper-tolerant X. perforans populations after 48 h of exposure compared with the water control (P < 0.05). All copper-based treatments killed the copper-sensitive X. perforans strain within 1 h. Greenhouse studies demonstrated that all copper composites significantly reduced bacterial spot disease severity when compared with copper-mancozeb and water controls (P < 0.05). Although there was no significant impact on yield, copper composites significantly reduced disease severity when compared with water controls, using 80% less metallic copper in comparison with copper-mancozeb in field studies (P < 0.05). This study highlights the discovery that copper composites have the potential to manage copper-tolerant X. perforans and tomato bacterial spot.

Functional consortium for denitrifying sulfide removal process.

PubMed

Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

2010-03-01

Denitrifying sulfide removal (DSR) process simultaneously converts sulfide, nitrate, and chemical oxygen demand from industrial wastewaters to elemental sulfur, nitrogen gas, and carbon dioxide, respectively. This investigation utilizes a dilution-to-extinction approach at 10(-2) to 10(-6) dilutions to elucidate the correlation between the composition of the microbial community and the DSR performance. In the original suspension and in 10(-2) dilution, the strains Stenotrophomonas sp., Thauera sp., and Azoarcus sp. are the heterotrophic denitrifiers and the strains Paracoccus sp. and Pseudomonas sp. are the sulfide-oxidizing denitrifers. The 10(-4) dilution is identified as the functional consortium for the present DSR system, which comprises two functional strains, Stenotrophomonas sp. strain Paracoccus sp. At 10(-6) dilution, all DSR performance was lost. The functions of the constituent cells in the DSR granules were discussed based on data obtained using the dilution-to-extinction approach.

Activation mechanism of ammonium ions on sulfidation of malachite (-201) surface by DFT study

NASA Astrophysics Data System (ADS)

Wu, Dandan; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-07-01

The activation mechanism of ammonium ions on the sulfidation of malachite (-201) was determined by density functional theory (DFT) calculations. Results of DFT calculations indicated that interlayer sulfidation occurs during the sulfidation process of malachite (-201). The absorption of both the ammonium ion and sulfide ion on the malachite (-201) surface is stronger than that of sulfur ion. After sulfidation was activated with ammonium ion, the Cu 3d orbital peak is closer to the Fermi level and characterized by a stronger peak value. Therefore, the addition of ammonium ions activated the sulfidation of malachite (-201), thereby improving the flotation performance.

Negative Regulation of Autophagy by Sulfide Is Independent of Reactive Oxygen Species.

PubMed

Laureano-Marín, Ana M; Moreno, Inmaculada; Romero, Luis C; Gotor, Cecilia

2016-06-01

Accumulating experimental evidence in mammalian, and recently plant, systems has led to a change in our understanding of the role played by hydrogen sulfide in life processes. In plants, hydrogen sulfide mitigates stress and regulates important plant processes such as photosynthesis, stomatal movement, and autophagy, although the underlying mechanism is not well known. In this study, we provide new experimental evidence that, together with our previous findings, demonstrates the role of hydrogen sulfide in regulating autophagy. We used green fluorescent protein fluorescence associated with autophagic bodies and immunoblot analysis of the ATG8 protein to show that sulfide (and no other molecules such as sulfur-containing molecules or ammonium) was able to inhibit the autophagy induced in Arabidopsis (Arabidopsis thaliana) roots under nitrogen deprivation. Our results showed that sulfide was unable to scavenge reactive oxygen species generated by nitrogen limitation, in contrast to well-established reducers. In addition, reducers were unable to inhibit the accumulation of autophagic bodies and ATG8 protein forms to the same extent as sulfide. Therefore, we conclude that sulfide represses autophagy via a mechanism that is independent of redox conditions. © 2016 American Society of Plant Biologists. All Rights Reserved.

A hydrogeologic model of stratiform copper mineralization in the Midcontinent Rift System, Northern Michigan, USA

USGS Publications Warehouse

Swenson, J.B.; Person, M.; Raffensperger, Jeff P.; Cannon, W.F.; Woodruff, L.G.; Berndt, M.E.

2004-01-01

This paper presents a suite of two-dimensional mathematical models of basin-scale groundwater flow and heat transfer for the middle Proterozoic Midcontinent Rift System. The models were used to assess the hydrodynamic driving mechanisms responsible for main-stage stratiform copper mineralization of the basal Nonesuch Formation during the post-volcanic/pre-compressional phase of basin evolution. Results suggest that compaction of the basal aquifer (Copper Harbor Formation), in response to mechanical loading during deposition of the overlying Freda Sandstone, generated a pulse of marginward-directed, compaction-driven discharge of cupriferous brines from within the basal aquifer. The timing of this pulse is consistent with the radiometric dates for the timing of mineralization. Thinning of the basal aquifer near White Pine, Michigan, enhanced stratiform copper mineralization. Focused upward leakage of copper-laden brines into the lowermost facies of the pyrite-rich Nonesuch Formation resulted in copper sulfide mineralization in response to a change in oxidation state. Economic-grade mineralization within the White Pine ore district is a consequence of intense focusing of compaction-driven discharge, and corresponding amplification of leakage into the basal Nonesuch Formation, where the basal aquifer thins dramatically atop the Porcupine Mountains volcanic structure. Equilibrium geochemical modeling and mass-balance calculations support this conclusion. We also assessed whether topography and density-driven flow systems could have caused ore genesis at White Pine. Topography-driven flow associated with the Ottawan orogeny was discounted because it post-dates main-stage ore genesis and because recent seismic interpretations of basin inversion indicates that basin geometry would not be conductive to ore genesis. Density-driven flow systems did not produce focused discharge in the vicinity of the White Pine ore district.

Sulfide and ammonium oxidation, acetate mineralization by denitrification in a multipurpose UASB reactor.

PubMed

Beristain-Cardoso, Ricardo; Gómez, Jorge; Méndez-Pampín, Ramón

2011-02-01

The physiological and kinetic behavior of a denitrifying granular sludge exposed to different sulfide loading rates (55-295 mg/L d) were evaluated in a UASB reactor fed with acetate, ammonium and nitrate. At any sulfide loading rates, the consumption efficiencies of sulfide, acetate and ammonium were above 95%, while nitrate consumption efficiencies were around 62-72%. At the highest sulfide loading rate the ammonium was used as electron donor for N(2) production. The increase of sulfide loading rate also affected the fate of sulfide oxidation, since elemental sulfur was the main end product instead of sulfate. However, the lithotrophic denitrifying kinetic was not affected. FISH oligonucleotide probes for Thiobacillus denitrificans, Thiomiscropira denitrificans, genus Paracoccus and Pseudomonas spp. were used to follow the microbial ecology. The results of this work have shown that four pollutants could simultaneously be removed, namely, sulfide, ammonium, acetate and nitrate under well defined denitrifying conditions. Copyright © 2010 Elsevier Ltd. All rights reserved.

Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades

USGS Publications Warehouse

Reddy, M.M.; Aiken, G.R.

2001-01-01

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.

A Plasmodium falciparum copper-binding membrane protein with copper transport motifs

PubMed Central

2012-01-01

Background Copper is an essential catalytic co-factor for metabolically important cellular enzymes, such as cytochrome-c oxidase. Eukaryotic cells acquire copper through a copper transport protein and distribute intracellular copper using molecular chaperones. The copper chelator, neocuproine, inhibits Plasmodium falciparum ring-to-trophozoite transition in vitro, indicating a copper requirement for malaria parasite development. How the malaria parasite acquires or secretes copper still remains to be fully elucidated. Methods PlasmoDB was searched for sequences corresponding to candidate P. falciparum copper-requiring proteins. The amino terminal domain of a putative P. falciparum copper transport protein was cloned and expressed as a maltose binding fusion protein. The copper binding ability of this protein was examined. Copper transport protein-specific anti-peptide antibodies were generated in chickens and used to establish native protein localization in P. falciparum parasites by immunofluorescence microscopy. Results Six P. falciparum copper-requiring protein orthologs and a candidate P. falciparum copper transport protein (PF14_0369), containing characteristic copper transport protein features, were identified in PlasmoDB. The recombinant amino terminal domain of the transport protein bound reduced copper in vitro and within Escherichia coli cells during recombinant expression. Immunolocalization studies tracked the copper binding protein translocating from the erythrocyte plasma membrane in early ring stage to a parasite membrane as the parasites developed to schizonts. The protein appears to be a PEXEL-negative membrane protein. Conclusion Plasmodium falciparum parasites express a native protein with copper transporter characteristics that binds copper in vitro. Localization of the protein to the erythrocyte and parasite plasma membranes could provide a mechanism for the delivery of novel anti-malarial compounds. PMID:23190769

Coenzyme Q deficiency causes impairment of the sulfide oxidation pathway.

PubMed

Ziosi, Marcello; Di Meo, Ivano; Kleiner, Giulio; Gao, Xing-Huang; Barca, Emanuele; Sanchez-Quintero, Maria J; Tadesse, Saba; Jiang, Hongfeng; Qiao, Changhong; Rodenburg, Richard J; Scalais, Emmanuel; Schuelke, Markus; Willard, Belinda; Hatzoglou, Maria; Tiranti, Valeria; Quinzii, Catarina M

2017-01-01

Coenzyme Q (CoQ) is an electron acceptor for sulfide-quinone reductase (SQR), the first enzyme of the hydrogen sulfide oxidation pathway. Here, we show that lack of CoQ in human skin fibroblasts causes impairment of hydrogen sulfide oxidation, proportional to the residual levels of CoQ. Biochemical and molecular abnormalities are rescued by CoQ supplementation in vitro and recapitulated by pharmacological inhibition of CoQ biosynthesis in skin fibroblasts and ADCK3 depletion in HeLa cells. Kidneys of Pdss2 kd/kd mice, which only have ~15% residual CoQ concentrations and are clinically affected, showed (i) reduced protein levels of SQR and downstream enzymes, (ii) accumulation of hydrogen sulfides, and (iii) glutathione depletion. These abnormalities were not present in brain, which maintains ~30% residual CoQ and is clinically unaffected. In Pdss2 kd/kd mice, we also observed low levels of plasma and urine thiosulfate and increased blood C4-C6 acylcarnitines. We propose that impairment of the sulfide oxidation pathway induced by decreased levels of CoQ causes accumulation of sulfides and consequent inhibition of short-chain acyl-CoA dehydrogenase and glutathione depletion, which contributes to increased oxidative stress and kidney failure. © 2016 The Authors. Published under the terms of the CC BY 4.0 license.

Metal sulfide electrodes and energy storage devices thereof

DOEpatents

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.

Survival of hydrogen sulfide oxidizing bacteria on corroded concrete surfaces of sewer systems.

PubMed

Jensen, H S; Nielsen, A H; Hvitved-Jacobsen, T; Vollertsen, J

2008-01-01

The activity of hydrogen sulfide oxidizing bacteria within corroded concrete from a sewer manhole was investigated. The bacteria were exposed to hydrogen sulfide starvation for up till 18 months, upon which their hydrogen sulfide oxidizing activity was measured. It was tested whether the observed reduction in biological activity was caused by a biological lag phase or by decay of the bacteria. The results showed that the bacterial activity declined with approximately 40% pr. month during the first two months of hydrogen sulfide starvation. After 2-3 months of starvation, the activity stabilized. Even after 6 months of starvation, exposure to hydrogen sulfide for 6 hours a day on three successive days could restore the bacteriological activity to about 80% of the initial activity. After 12 months of starvation, the activity could, however, not be restored, and after 18 months the biological activity approached zero. The long-term survival aspect of concrete corroding bacteria has implications for predicting hydrogen sulfide corrosion in sewer systems subject to irregular hydrogen sulfide loadings, e.g. as they occur in temperate climates where hydrogen sulfide often is a summer-problem only.

Formation of nanocolloidal metacinnabar in mercury-DOM-sulfide systems

USGS Publications Warehouse

Gerbig, Chase A.; Kim, Christopher S.; Stegemeier, John P.; Ryan, Joseph N.; Aiken, George R.

2011-01-01

Direct determination of mercury (Hg) speciation in sulfide-containing environments is confounded by low mercury concentrations and poor analytical sensitivity. Here we report the results of experiments designed to assess mercury speciation at environmentally relevant ratios of mercury to dissolved organic matter (DOM) (i.e., <4 nmol Hg (mg DOM)−1) by combining solid phase extraction using C18 resin with extended X-ray absorption fine structure (EXAFS) spectroscopy. Aqueous Hg(II) and a DOM isolate were equilibrated in the presence and absence of 100 μM total sulfide. In the absence of sulfide, mercury adsorption to the resin increased as the Hg:DOM ratio decreased and as the strength of Hg-DOM binding increased. EXAFS analysis indicated that in the absence of sulfide, mercury bonds with an average of 2.4 ± 0.2 sulfur atoms with a bond length typical of mercury-organic thiol ligands (2.35 Å). In the presence of sulfide, mercury showed greater affinity for the C18 resin, and its chromatographic behavior was independent of Hg:DOM ratio. EXAFS analysis showed mercury–sulfur bonds with a longer interatomic distance (2.51–2.53 Å) similar to the mercury–sulfur bond distance in metacinnabar (2.53 Å) regardless of the Hg:DOM ratio. For all samples containing sulfide, the sulfur coordination number was below the ideal four-coordinate structure of metacinnabar. At a low Hg:DOM ratio where strong binding DOM sites may control mercury speciation (1.9 nmol mg–1) mercury was coordinated by 2.3 ± 0.2 sulfur atoms, and the coordination number rose with increasing Hg:DOM ratio. The less-than-ideal coordination numbers indicate metacinnabar-like species on the nanometer scale, and the positive correlation between Hg:DOM ratio and sulfur coordination number suggests progressively increasing particle size or crystalline order with increasing abundance of mercury with respect to DOM. In DOM-containing sulfidic systems nanocolloidal metacinnabar-like species may form

Enhanced performance of denitrifying sulfide removal process under micro-aerobic condition.

PubMed

Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

2010-07-15

The denitrifying sulfide removal (DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate into di-nitrogen gas, elementary sulfur and carbon dioxide, respectively, at high loading rates. This study determines the reaction rate of sulfide oxidized into sulfur, as well as the reduction of nitrate to nitrite, would be enhanced under a micro-aerobic condition. The presence of limited oxygen mitigated the inhibition effects of sulfide on denitrifier activities, and enhanced the performance of DSR granules. The advantages and disadvantages of applying the micro-aerobic condition to the DSR process are discussed. 2010 Elsevier B.V. All rights reserved.

Vesicle-metal-sulfide assemblages from the Chelyabinsk meteorite

NASA Astrophysics Data System (ADS)

Andronikov, A.; Lauretta, D.; Hill, D.; Andronikova, I.

2014-07-01

On February 15, 2013, an ET object entered the Earth's atmosphere over the Russian city of Chelyabinsk. It entered at a preatmospheric velocity of 18.6 km/sec at the angle of 17--20°. The bolide responsible for this event was estimated to be 17-20 m in diameter and had a mass of ˜10 Ktons; the ensuing airburst occurred at an altitude >20 km and released a total energy of ˜440 kT [1,2]. The Chelyabinsk meteorite is an equilibrated LL5 ordinary chondrite, shock stage S4, and weathering grade WG0 similar to other LL5 falls [1,2]. Our studied sample is an impact melt breccia consisting of shock-darkened chondrite clasts (SDC) and vesicular impact melt lithology (IML). The SDC have recrystallized textures and contain barred- and porphyritic-olivine, porphyritic-olivine-pyroxene and radial-pyroxene chondrules in the intrachondrule matrix. A dense network of thin fractures in the SDC is filled up with opaque minerals [cf. 3]. Metals in the SDC are kamacite (4.7--8.5 % Ni), taenite (21.4--33.5 % Ni), and martensite (14.5--18.6 % Ni). The IML consists mostly of tiny (<10 microns) silicate grains surrounded by patches of glass. The IML is characterized by the presence of multiple vesicles (up to 1 mm) in silicate matrix. The vesicles are often filled up with sulfide-metal assemblages or only with sulfide. Metals in the IML are martensite (12.9--18.4 % Ni) and taenite (19.3--47.3 % Ni). Sulfides from both SDC and IML are Ni-bearing troilite (62.2--64.2 % Fe; 35.2--37.2 % S; 3000--5000 ppm Ni), with rare pentlandite (41.2--48.6 % Fe, 33.2--34.3 % S, 19.4--23.9 % Ni). The presence of abundant vesicles in the IML indicates strong heating and volatilization. Since no other phase except for sulfide-metal assemblages were observed to fill up vesicles, the likely source of volatiles is S vapor formed by vaporization of FeS during impact melting [cf. 4]. Molten metal and sulfide coalesced into droplets of metal-sulfide liquids forming eventually sulfide-metal assemblages. A

Dispersion strengthened copper

DOEpatents

Sheinberg, Haskell; Meek, Thomas T.; Blake, Rodger D.

1989-01-01

A composition of matter comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide, and a method for making this composition of matter.

Dispersion strengthened copper

DOEpatents

Sheinberg, Haskell; Meek, Thomas T.; Blake, Rodger D.

1990-01-01

A composition of matter comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide, and a method for making this composition of matter.

p-Chlorophenyl methyl sulfide

Integrated Risk Information System (IRIS)

p - Chlorophenyl methyl sulfide ; CASRN 123 - 09 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for N

Sulfide in the core and the composition of the silicate Earth

NASA Astrophysics Data System (ADS)

Burton, K. W.

2015-12-01

The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive 'chondritic' meteorites. It now appears, however, that the silicate Earth is not 'chondritic', but depleted in incompatible elements, including refractory lithophile and heat-producing elements. Either Earth lost material during planet-building due to collisional erosion or else internal differentiation processes produced a hidden reservoir deep in the early Earth. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [1]. Pioneering work using the short-lived 146Sm-142Nd system strongly suggests that Earth's silicate mantle is non-chondritic [e.g. 2]. The drawback of such radiogenic isotope systems is that it is not possible to distinguish the fractionation of Sm/Nd that occurs during silicate melting from that occurring during the segregation of a sulfide-melt to form the core. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavy values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd Stable isotope

Formation of copper-indium-selenide and/or copper-indium-gallium-selenide films from indium selenide and copper selenide precursors

DOEpatents

Curtis, Calvin J [Lakewood, CO; Miedaner, Alexander [Boulder, CO; Van Hest, Maikel [Lakewood, CO; Ginley, David S [Evergreen, CO; Nekuda, Jennifer A [Lakewood, CO

2011-11-15

Liquid-based indium selenide and copper selenide precursors, including copper-organoselenides, particulate copper selenide suspensions, copper selenide ethylene diamine in liquid solvent, nanoparticulate indium selenide suspensions, and indium selenide ethylene diamine coordination compounds in solvent, are used to form crystalline copper-indium-selenide, and/or copper indium gallium selenide films (66) on substrates (52).

Microbial oxidation of soluble sulfide in produced water from the Bakkeen Sands

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

Gevertz, D.; Zimmerman, S.; Jenneman, G.E.

1995-12-31

The presence of soluble sulfide in produced water results in problems for the petroleum industry due to its toxicity, odor, corrosive nature, and potential for wellbore plugging. Sulfide oxidation by indigenous nitrate-reducing bacteria (NRB) present in brine collected from wells at the Coleville Unit (CVU) in Saskatchewan, Canada, was investigated. Sulfide oxidation took place readily when nitrate and phosphate were added to brine enrichment cultures, resulting in a decrease in sulfide levels of 99-165 ppm to nondetectable levels (< 3.3 ppm). Produced water collected from a number of producing wells was screened to determine the time required for complete sulfidemore » oxidation, in order to select candidate wells for treatment. Three wells were chosen, based on sulfide removal in 48 hours or less. These wells were treated down the backside of the annulus with a solution containing 10 mM KNO{sub 3} and 100 {mu}M NaH{sub 2}PO{sub 4}. Following a 24- to 72-hour shut-in, reductions in pretreatment sulfide levels of greater than 90% were observed for two of the wells, as well as sustained sulfide reductions of 50% for at least two days following startup. NRB populations in the produced brine were observed to increase significantly following treatment, but no significant increases in sulfate-reducing bacteria were observed. These results demonstrate the technical feasibility of stimulating indigenous populations of NRB to remediate and control sulfide in produced brine.« less

Isolation and characterization of lost copper and molybdenum particles in the flotation tailings of Kennecott copper porphyry ores

NASA Astrophysics Data System (ADS)

Tserendavga, Tsend-Ayush

The importance of flotation separation has long been, and continues to be, an important technology for the mining industry, especially to metallurgical engineers. However, the flotation process is quite complex and expensive, in addition to being influenced by many variables. Understanding the variables affecting flotation efficiency and how valuable minerals are lost to the tailings gives metallurgists an advantage in their attempts to increase efficiency by designing operations to target the areas of greatest potential value. A successful, accurate evaluation of lost minerals in the tailings and appropriate solutions to improve flotation efficiency can save millions of dollars in the effective utilization of our mineral resources. In this dissertation research, an attempt has been made to understand the reasons for the loss of valuable mineral particles in the tailings from Kennecott Utah Copper ores. Possibilities include liberation, particle aggregation (slime coating) and surface chemistry issues associated with the flotation separation. This research generally consisted of three main aspects. The first part involved laboratory flotation experiments and factors, which affect the flotation efficiency. Results of flotation testing are reported that several factors such as mineral exposure/liberation and slime coating and surface oxidation strongly affect the flotation efficiency. The second part of this dissertation research was to develop a rapid scan dual energy (DE) methodology using 2D radiography to identify, isolate, and prepare lost sulfide mineral particles with the advantages of simple sample preparation, short analysis time, statistically reliable accuracy and confident identification. The third part of this dissertation research was concerned with detailed characterization of lost particles including such factors as liberation, slime coating, and surface chemistry characteristics using advanced analytical techniques and instruments. Based on the

Process for thin film deposition of cadmium sulfide

DOEpatents

Muruska, H. Paul; Sansregret, Joseph L.; Young, Archie R.

1982-01-01

The present invention teaches a process for depositing layers of cadmium sulfide. The process includes depositing a layer of cadmium oxide by spray pyrolysis of a cadmium salt in an aqueous or organic solvent. The oxide film is then converted into cadmium sulfide by thermal ion exchange of the O.sup.-2 for S.sup.-2 by annealing the oxide layer in gaseous sulfur at elevated temperatures.

Comparison of the mineralogy of the Boss-Bixby, Missouri copper-iron deposit, and the Olympic Dam copper-uranium-gold deposit, South Australia

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

Brandom, R.T.; Hagni, R.D.; Allen, C.R.

1985-01-01

An ore microscopic examination of 80 polished sections prepared from selected drill core specimens from the Boss-Bixby, Missouri copper-iron deposit has shown that its mineral assemblage is similar to that of the Olympic Dam (Roxby Downs) copper-uranium-gold deposit in South Australia. A comparison with the mineralogy reported for Olympic Dam shows that both deposits contain: 1) the principal minerals, magnetite, hematite, chalcopyrite, and bornite, 2) the cobalt-bearing phases, carrollite and cobaltian pyrite, 3) the titanium oxides, rutile and anatase, 4) smaller amounts of martite, covellite, and electrum, 5) fluorite and carbonates, and 6) some alteration minerals. The deposits also aremore » similar with regard to the sequence of mineral deposition: 1) early oxides, 2) then sulfide minerals, and 3) a final oxide generation. The deposits, however, are dissimilar with regard to their host rock lithologies and structural settings. The Boss-Bixby ores occupy breccia zones within a hydrothermally altered basic intrusive and intruded silicic volcanics, whereas the Olympic Dam ores are contained in sedimentary breccias in a graben or trough. Also, some minerals have been found thus far to occur at only one of the deposits. The similarity of mineralogy in these deposits suggests that they were formed from ore fluids that had some similarities in character and that the St. Francois terrane of Missouri is an important region for further exploration for deposits with this mineral assemblage.« less

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Fonseca, Raúl O. C.

2017-11-01

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700 °C in evacuated silica tubes. At 1050 °C, Se partially partitions into a vapor phase. At 980 °C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700 °C. Instead cooperite (PtS) forms at 900 °C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium's high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

Study on the surface sulfidization behavior of smithsonite at high temperature

NASA Astrophysics Data System (ADS)

Lv, Jin-fang; Tong, Xiong; Zheng, Yong-xing; Xie, Xian; Wang, Cong-bing

2018-04-01

Surface sulfidization behavior of smithsonite at high temperature was investigated by X-ray powder diffractometer (XRD) along with thermodynamic calculation, X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA). The XRD and thermodynamic analyses indicated that the smithsonite was decomposed into zincite at high temperatures. After introducing a small amount of pyrite, artificial sulfides were formed at surface of the obtained zincite. The XPS analyses revealed that the sulfide species including zinc sulfide and zinc disulfide were generated at the zincite surface. The EPMA analyses demonstrated that the film of sulfides was unevenly distributed at the zincite surface. The average concentration of elemental sulfur at the sample surface increased with increasing of pyrite dosage. A suitable mole ratio of FeS2 to ZnCO3 for the surface thermal modification was determined to be about 0.3. These findings can provide theoretical support for improving the process during which the zinc recovery from refractory zinc oxide ores is achieved by xanthate flotation.

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

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

Hubbard, Susan; Personna, Y.R.; Ntarlagiannis, D.

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 datamore » 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.« less

Toxicity of sulfide to early life stages of wild rice (Zizania palustris).

PubMed

Fort, Douglas J; Todhunter, Kevin; Fort, Troy D; Mathis, Michael B; Walker, Rachel; Hansel, Mike; Hall, Scott; Richards, Robin; Anderson, Kurt

2017-08-01

The sensitivity of wild rice (Zizania palustris) to sulfide is not well understood. Because sulfate in surface waters is reduced to sulfide by anaerobic bacteria in sediments and historical information indicated that 10 mg/L sulfate in Minnesota (USA) surface water reduced Z. palustris abundance, the Minnesota Pollution Control Agency established 10 mg/L sulfate as a water quality criterion in 1973. A 21-d daily-renewal hydroponic study was conducted to evaluate sulfide toxicity to wild rice and the potential mitigation of sulfide toxicity by iron (Fe). The hydroponic design used hypoxic test media for seed and root exposure and aerobic headspace for the vegetative portion of the plant. Test concentrations were 0.3, 1.6, 3.1, 7.8, and 12.5 mg/L sulfide in test media with 0.8, 2.8, and 10.8 mg/L total Fe used to evaluate the impact of iron on sulfide toxicity. Visual assessments (i.e., no plants harvested) of seed activation, mesocotyl emergence, seedling survival, and phytoxicity were conducted 10 d after dark-phase exposure. Each treatment was also evaluated for time to 30% emergence (ET30), total plant biomass, root and shoot lengths, and signs of phytotoxicity at study conclusion (21 d). The results indicate that exposure of developing wild rice to sulfide at ≥3.1 mg sulfide/L in the presence of 0.8 mg/L Fe reduced mesocotyl emergence. Sulfide toxicity was mitigated by the addition of Fe at 2.8 mg/L and 10.8 mg/L relative to the control value of 0.8 mg Fe/L, demonstrating the importance of iron in mitigating sulfide toxicity to wild rice. Ultimately, determination of site-specific sulfate criteria taking into account factors that alter toxicity, including sediment Fe and organic carbon, are necessary. Environ Toxicol Chem 2017;36:2217-2226. © 2017 SETAC. © 2017 SETAC.

In situ Fe-sulfide coating for arsenic removal under reducing conditions

NASA Astrophysics Data System (ADS)

Xie, Xianjun; Liu, Yaqing; Pi, Kunfu; Liu, Chongxuan; Li, Junxia; Duan, Mengyu; Wang, Yanxin

2016-03-01

An in situ Fe-sulfide coating approach has been developed for As-contaminated groundwater remediation. Alternate injection of Fe(II), O2-free water and S2- can realize Fe-sulfide coating onto quartz sands with minor changes in porosity. As(III) uptake experiment indicated that the retardation factor for As(III) was 37 and dynamic retention capacity was 44.94 mg As(III)/g Fe, which was much higher than the maximum adsorption capacity for As(III) by FeS and FeS2. This result indicated that adsorption cannot be the only mechanism for As(III) uptake by Fe-sulfide coating layer. The SEM image and FTIR spectra results suggested that interaction between As(III) and Fe-sulfides and formation of As-sulfide precipitates could significantly contribute to As(III) uptake by Fe-sulfide coating layer. Alternate injection of Fe(II) + As(III) and S2- was conducted to simulate in situ As immobilization from real groundwater. The SEM image showed that the quartz sands were mainly covered by crystalline framboidal pyrite after such amendment. The breakthrough of As(III) was not observed during this experiment and the removal capacity for As(III) was 109.7 mg As/g Fe. The As(III) immobilization mechanism during alternate injection of Fe(II) + As(III) and S2- was significantly different from that of As(III) uptake by Fe-sulfide coating. The direct interaction between As(III) and S2- produced As-sulfides contributed to the high As(III) removal capacity during alternate injection of Fe(II) + As(III) and S2-. This result indicated that alternate injection of Fe(II) and S2- approach has an attractive application for As-contaminated groundwater remediation under strongly reducing environment.

In situ Fe-sulfide coating for arsenic removal under reducing conditions

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

Xie, Xianjun; Liu, Yaqing; Pi, Kunfu

2016-03-01

An in situ Fe-sulfide coating approach has been developed for As-contaminated groundwater remediation. Alternate injection of Fe(II), O 2-free water and S 2$-$ can realize Fe-sulfide coating onto quartz sands with minor changes in porosity. As(III) uptake experiment indicated that the retardation factor for As(III) was 37 and dynamic retention capacity was 44.94 mg As(III)/g Fe, which was much higher than the maximum adsorption capacity for As(III) by FeS and FeS 2. This result indicated that adsorption cannot be the only mechanism for As(III) uptake by Fe-sulfide coating layer. The SEM image and FTIR spectra results suggested that interaction betweenmore » As(III) and Fe-sulfides and formation of As-sulfide precipitates could significantly contribute to As(III) uptake by Fe-sulfide coating layer. Alternate injection of Fe(II) + As(III) and S 2$-$ was conducted to simulate in situ As immobilization from real groundwater. The SEM image showed that the quartz sands were mainly covered by crystalline framboidal pyrite after such amendment. The breakthrough of As(III) was not observed during this experiment and the removal capacity for As(III) was 109.7 mg As/g Fe. The As(III) immobilization mechanism during alternate injection of Fe(II) + As(III) and S 2$-$ was significantly different from that of As(III) uptake by Fe-sulfide coating. The direct interaction between As(III) and S 2$-$ produced As-sulfides contributed to the high As(III) removal capacity during alternate injection of Fe(II) + As(III) and S 2$-$. This result indicated that alternate injection of Fe(II) and S 2$-$ approach has an attractive application for As-contaminated groundwater remediation under strongly reducing environment.« less

Electrochemical sulfide removal and caustic recovery from spent caustic streams.

PubMed

Vaiopoulou, Eleni; Provijn, Thomas; Prévoteau, Antonin; Pikaar, Ilje; Rabaey, Korneel

2016-04-01

Spent caustic streams (SCS) are produced during alkaline scrubbing of sulfide containing sour gases. Conventional methods mainly involve considerable chemical dosing or energy expenditures entailing high cost but limited benefits. Here we propose an electrochemical treatment approach involving anodic sulfide oxidation preferentially to sulfur coupled to cathodic caustic recovery using a two-compartment electrochemical system. Batch experiments showed sulfide removal efficiencies of 84 ± 4% with concomitant 57 ± 4% efficient caustic production in the catholyte at a final concentration of 6.4 ± 0.1 wt% NaOH (1.6 M) at an applied current density of 100 A m(-2). Subsequent long-term continuous experiments showed that stable cell voltages (i.e. 2.7 ± 0.1 V) as well as constant sulfide removal efficiencies of 67 ± 5% at a loading rate of 47 g(S) L(-1) h(-1) were achieved over a period of 77 days. Caustic was produced at industrially relevant strengths for scrubbing (i.e. 5.1 ± 0.9 wt% NaOH) at current efficiencies of 96 ± 2%. Current density between 0 and 200 A m(-2) and sulfide loading rates of 50-200 g(S) L(-1) d(-1) were tested. The higher the current density the more oxidized the sulfur species produced and the higher the sulfide oxidation. On the contrary, high loading rate resulted in a reduction of sulfide oxidation efficiency. The results obtained in this study together with engineering calculations show that the proposed process could represent a cost-effective approach for sodium and sulfur recovery from SCS. Copyright © 2016 Elsevier Ltd. All rights reserved.

Redetermination of piperidinium hydrogen sulfide structure

NASA Technical Reports Server (NTRS)

Andras, Maria T.; Hepp, Aloysius F.; Fanwick, Phillip E.; Duraj, Stan A.; Gordon, Edward M.

1994-01-01

The presence of adventitious water in a reaction between dicyclopentamethylene thiuram-disulfide (C5H10NCS2)(sub 2) and a picoline solution of tricyclopentadienyl indium(III) (C5H5)(sub 3). It resulted in the formation of piperidinium hydrogen sulfide (C5H13NS). The piperidinium hydrogen sulfide produced in this way was unambiguously characterized by X-ray crystallography. The structure determination showed that the piperidinium hydrogen sulfide crystal (MW = 119.23 g/mol) has an orthorhombic (Pbcm) unit cell whose parameters are: a = 9.818(2), b = 7.3720(1), c = 9.754(1) A, V = 706.0(3) A(exp 3), Z=4. D(sub chi) = 1.122 g cm(exp -3), Mo K(alpha) (lamda = 0.71073), mu= 3.36 cm(exp -1), F(000) = 264.0, T =293 K, R = 0.036 for 343 reflections with F(sub O)(sup 2) greater than 3 sigma (F(sub O)(sup 2)) and 65 variables. The compound consists of (C5H10NH2)(+) cations and (SH)(-) anions with both species residing on crystallographic mirror planes. N-H -- S hydrogen bonding contributes to the interconnection of neighboring piperidinium components of the compound.

Atomic layer deposition of metal sulfide thin films using non-halogenated precursors

DOEpatents

Martinson, Alex B. F.; Elam, Jeffrey W.; Pellin, Michael J.

2015-05-26

A method for preparing a metal sulfide thin film using ALD and structures incorporating the metal sulfide thin film. The method includes providing an ALD reactor, a substrate, a first precursor comprising a metal and a second precursor comprising a sulfur compound. The first and the second precursors are reacted in the ALD precursor to form a metal sulfide thin film on the substrate. In a particular embodiment, the metal compound comprises Bis(N,N'-di-sec-butylacetamidinato)dicopper(I) and the sulfur compound comprises hydrogen sulfide (H.sub.2S) to prepare a Cu.sub.2S film. The resulting metal sulfide thin film may be used in among other devices, photovoltaic devices, including interdigitated photovoltaic devices that may use relatively abundant materials for electrical energy production.

Hydrogen sulfide emission in sewer networks: a two-phase modeling approach to the sulfur cycle.

PubMed

Yongsiri, C; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Wherever transport of anaerobic wastewater occurs, potential problems associated with hydrogen sulfide in relation to odor nuisance, health risk and corrosion exist. Improved understanding of prediction of hydrogen sulfide emission into the sewer atmosphere is needed for better evaluation of such problems in sewer networks. A two-phase model for emission of hydrogen sulfide along stretches of gravity sewers is presented to estimate the occurrence of both sulfide in the water phase and hydrogen sulfide in the sewer atmosphere. The model takes into account air-water mass transfer of hydrogen sulfide and interactions with other processes in the sulfur cycle. Various emission scenarios are simulated to illustrate the release characteristics of hydrogen sulfide.

Effect of inoculum and sulfide type on simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry and microbial mechanism.

PubMed

Wang, Lan; Wei, Benping; Chen, Ziai; Deng, Liangwei; Song, Li; Wang, Shuang; Zheng, Dan; Liu, Yi; Pu, Xiaodong; Zhang, Yunhong

2015-12-01

Four reactors were initiated to study the effect of inoculum and sulfide type on the simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry (Ssu-Nir) process. Anaerobic sludge, aerobic sludge, and water were used as inocula, and Na2S and biogas were used as a sulfide substrate, respectively. Additionally, 454 pyrosequencing of the 16S rRNA gene was used to explore the bacterial diversity. The results showed that sulfur-oxidizing bacteria (Thiobacillus, 42.2-84.4 %) were dominant in Ssu-Nir process and led to the excellent performance. Aerobic sludge was more suitable for inoculation of the Ssu-Nir process because it is better for rapidly enriching dominant sulfur-oxidizing bacteria (Thiobacillus, 54.4 %), denitrifying sulfur-oxidizing bacteria (40.0 %) and denitrifiers (23.9 %). Lower S(2-) removal efficiency (72.6 %) and NO3 (-) removal efficiency (<90 %) of the Ssu-Nir process were obtained using biogas as a sulfide substrate than when Na2S was used. For the Ssu-Nir process with biogas as the sulfide substrate, limiting H2S absorption caused a high relative abundance of sulfur-oxidizing bacteria, Thiobacillus (84.8 %) and Thiobacillus sayanicus (39.6 %), which in turn led to low relative abundance of denitrifiers (1.6 %) and denitrifying sulfur-oxidizing bacteria (24.4 %), low NO3 (-) removal efficiency, and eventually poor performance.

Zinc sulfide liquefaction catalyst

DOEpatents

Garg, Diwakar

1984-01-01

A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

USGS Publications Warehouse

Visscher, P.T.; Taylor, B.F.

1993-01-01

A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

Properties of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions through photoelectron spectroscopy and density functional theory calculations.

PubMed

Yin, Shi; Bernstein, Elliot R

2016-10-21

A new magnetic-bottle time-of-flight photoelectron spectroscopy (PES) apparatus is constructed in our laboratory. The PES spectra of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide [FeS m (SH) n - ; m, n = 0-3, 0 < (m + n) ≤ 3] cluster anions, obtained at 2.331 eV (532 nm) and 3.492 eV (355 nm) photon energies, are reported. The electronic structure and bonding properties of these clusters are additionally investigated at different levels of density functional theory. The most probable structures and ground state spin multiplicity for these cluster anions are tentatively assigned by comparing their theoretical first vertical detachment energies (VDEs) with their respective experiment values. The behavior of S and (SH) as ligands in these iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions is investigated and compared. The experimental first VDEs for Fe(SH) 1-3 - cluster anions are lower than those found for their respective FeS 1-3 - cluster anions. The experimental first VDEs for FeS 1-3 - clusters are observed to increase for the first two S atoms bound to Fe - ; however, due to the formation of an S-S bond for the FeS 3 - cluster, its first VDE is found to be ∼0.41 eV lower than the first VDE for the FeS 2 - cluster. The first VDEs of Fe(SH) 1-3 - cluster anions are observed to increase with the increasing numbers of SH groups. The calculated partial charges of the Fe atom for ground state FeS 1-3 - and Fe(SH) 1-3 - clusters are apparently related to and correlated with their determined first VDEs. The higher first VDE is correlated with a higher, more positive partial charge for the Fe atom of these cluster anions. Iron sulfide/hydrosulfide mixed cluster anions are also explored in this work: the first VDE for FeS(SH) - is lower than that for FeS 2 - , but higher than that for Fe(SH) 2 - ; the first VDEs for FeS 2 (SH) - and FeS(SH) 2 - are close to that for FeS 3 - , but higher than that for Fe(SH) 3 - . The first VDEs of

Properties of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions through photoelectron spectroscopy and density functional theory calculations

NASA Astrophysics Data System (ADS)

Yin, Shi; Bernstein, Elliot R.

2016-10-01

A new magnetic-bottle time-of-flight photoelectron spectroscopy (PES) apparatus is constructed in our laboratory. The PES spectra of iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide [FeSm(SH)n-; m, n = 0-3, 0 < (m + n) ≤ 3] cluster anions, obtained at 2.331 eV (532 nm) and 3.492 eV (355 nm) photon energies, are reported. The electronic structure and bonding properties of these clusters are additionally investigated at different levels of density functional theory. The most probable structures and ground state spin multiplicity for these cluster anions are tentatively assigned by comparing their theoretical first vertical detachment energies (VDEs) with their respective experiment values. The behavior of S and (SH) as ligands in these iron sulfide, hydrosulfide, and mixed sulfide/hydrosulfide cluster anions is investigated and compared. The experimental first VDEs for Fe(SH)1-3- cluster anions are lower than those found for their respective FeS1-3- cluster anions. The experimental first VDEs for FeS1-3- clusters are observed to increase for the first two S atoms bound to Fe-; however, due to the formation of an S-S bond for the FeS3- cluster, its first VDE is found to be ˜0.41 eV lower than the first VDE for the FeS2- cluster. The first VDEs of Fe(SH)1-3- cluster anions are observed to increase with the increasing numbers of SH groups. The calculated partial charges of the Fe atom for ground state FeS1-3- and Fe(SH)1-3- clusters are apparently related to and correlated with their determined first VDEs. The higher first VDE is correlated with a higher, more positive partial charge for the Fe atom of these cluster anions. Iron sulfide/hydrosulfide mixed cluster anions are also explored in this work: the first VDE for FeS(SH)- is lower than that for FeS2-, but higher than that for Fe(SH)2-; the first VDEs for FeS2(SH)- and FeS(SH)2- are close to that for FeS3-, but higher than that for Fe(SH)3-. The first VDEs of general iron sulfide, hydrosulfide, and

Biological removal of air loaded with a hydrogen sulfide and ammonia mixture.

PubMed

Chen, Ying-xu; Yin, Jun; Fang, Shi

2004-01-01

The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH2S/(m3 x d) and 230 gNH3/(m3 x d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of ammonia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.

Kinetics of Ni3S2 sulfide dissolution in solutions of sulfuric and hydrochloric acids

NASA Astrophysics Data System (ADS)

Palant, A. A.; Bryukvin, V. A.; Vinetskaya, T. N.; Makarenkova, T. A.

2008-02-01

The kinetics of Ni3S2 sulfide (heazlewoodite) dissolution in solutions of hydrochloric and sulfuric acids is studied. The process under study in the temperature range of 30 90°C is found to occur in a kinetic regime and is controlled by the corresponding chemical reactions of the Ni3S2 decomposition by solutions of inorganic acids ( E a = 67 92 kJ/mol, or 16 22 kcal/mol). The only exception is the Ni3S2-HCl system at elevated temperatures (60 90°C). In this case, the apparent activation energy decreases sharply to 8.8 kJ/mol (2.1 kcal/mol), which is explained by the catalytic effect of gaseous chlorine formed under these conditions. The studies performed are related to the physicochemical substantiation of the hydrometallurgical processing of the copper-nickel converter mattes produced in the industrial cycle of the Norilsk Mining Company.

Transition of Blast Furnace Slag from Silicate Based to Aluminate Based: Sulfide Capacity

NASA Astrophysics Data System (ADS)

Yan, Zhiming; Lv, Xuewei; Pang, Zhengde; He, Wenchao; Liang, Dong; Bai, Chenguang

2017-10-01

The effect of Al2O3 and Al2O3/SiO2 ratio on the sulfide capacity of the molten aluminosilicate CaO-SiO2-Al2O3-MgO-TiO2 slag system with high Al2O3 content was measured at 1773 K (1500 °C) using a metal-slag equilibration method. The sulfide capacity between silicate-based and aluminate-based slag was also compared based on the thermodynamic analysis and structural characteristics of melts. At a fixed CaO/SiO2 ratio of 1.20, the sulfide capacity decreases with increasing Al2O3 content primarily due to the decrease of free oxygen (FO) and the activity of O2-. Increasing the Al2O3/SiO2 ratio from 0.47 to 0.79 causes a significant increase in the sulfide capacity of the slags, and a slight increase is found when the Al2O3/SiO2 ratio is more than 0.79. The effect of the substitution of silica by alumina on the sulfide capacity of the slags was not only due to an increase in the activity of basic oxides ( a_{{{O}^{2 - } }} ) but also to a decrease in the stability of sulfide ( γ_{{{S}^{2 - } }} ). Moreover, a_{{{O}^{2 - } }} and γ_{{{S}^{2 - } }} increase in a similar degree, and the weaker binding electronegativity of Al3+ with oxygen atoms results in a slight increase in the final sulfide capacity in the aluminate-based slag system with Al2O3 ↔ SiO2 substitution. Five different sulfide capacity models were employed to predict the sulfide capacity, and the iso-sulfide capacity distribution diagram based on the Young's model was obtained in the high Al2O3 corner of the diagram.

Technological aspects of the microbial treatment of sulfide-rich wastewaters: a case study.

PubMed

Sublette, K L; Kolhatkar, R; Raterman, K

1998-01-01

Thiobacillus denitrificans has been shown to be an effective biocatalyst for the treatment of a variety of sulfide-laden waste streams including sour water, sour gases, and refinery spent-sulfidic caustics. The term 'sour' originated in the petroleum industry to describe a waste contaminated with hydrogen sulfide or salts of sulfide and bisulfide. The microbial treatment of sour waste streams resulting from the production or refining of natural gas and crude oil have been investigated in this laboratory for many years. The application of this technology to the treatment of sour wastes on a commercially useful scale has presented several technical barriers including substrate inhibition (sulfide), product inhibition (sulfate), the need for septic operation, biomass recycle and recovery, mixed waste issues, and the need for large-scale cultivation of the organism for process startup. The removal of these barriers through process improvements are discussed in terms of a case study of the full-scale treatment of sulfide-rich wastewater. The ability of T. denitrificans to deodorize and detoxify an oil-field produced water containing sulfides was evaluated under full-scale field conditions at Amoco Production Co. Salt Creek Field in Midwest, WY. More than 800 m3/d of produced water containing 100 mg/L sulfide and total dissolved solids of 4800 mg/L were successfully biotreated in an earthen pit (3000 m3) over a six-month period. Complete removal of sulfides and elimination of associated odors were observed. The system could be upset by severe hydraulic disturbances; however, the system recovered rapidly when normal influent flow rates were restored.

Sulfide Generation by Dominant Halanaerobium Microorganisms in Hydraulically Fractured Shales

PubMed Central

Booker, Anne E.; Borton, Mikayla A.; Daly, Rebecca A.; Welch, Susan A.; Nicora, Carrie D.; Hoyt, David W.; Wilson, Travis; Purvine, Samuel O.; Wolfe, Richard A.; Sharma, Shikha; Mouser, Paula J.; Cole, David R.; Lipton, Mary S.; Wrighton, Kelly C.

2017-01-01

ABSTRACT Hydraulic fracturing of black shale formations has greatly increased United States oil and natural gas recovery. However, the accumulation of biomass in subsurface reservoirs and pipelines is detrimental because of possible well souring, microbially induced corrosion, and pore clogging. Temporal sampling of produced fluids from a well in the Utica Shale revealed the dominance of Halanaerobium strains within the in situ microbial community and the potential for these microorganisms to catalyze thiosulfate-dependent sulfidogenesis. From these field data, we investigated biogenic sulfide production catalyzed by a Halanaerobium strain isolated from the produced fluids using proteogenomics and laboratory growth experiments. Analysis of Halanaerobium isolate genomes and reconstructed genomes from metagenomic data sets revealed the conserved presence of rhodanese-like proteins and anaerobic sulfite reductase complexes capable of converting thiosulfate to sulfide. Shotgun proteomics measurements using a Halanaerobium isolate verified that these proteins were more abundant when thiosulfate was present in the growth medium, and culture-based assays identified thiosulfate-dependent sulfide production by the same isolate. Increased production of sulfide and organic acids during the stationary growth phase suggests that fermentative Halanaerobium uses thiosulfate to remove excess reductant. These findings emphasize the potential detrimental effects that could arise from thiosulfate-reducing microorganisms in hydraulically fractured shales, which are undetected by current industry-wide corrosion diagnostics. IMPORTANCE Although thousands of wells in deep shale formations across the United States have been hydraulically fractured for oil and gas recovery, the impact of microbial metabolism within these environments is poorly understood. Our research demonstrates that dominant microbial populations in these subsurface ecosystems contain the conserved capacity for the

Sulfide Generation by Dominant Halanaerobium Microorganisms in Hydraulically Fractured Shales

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

Booker, Anne E.; Borton, Mikayla A.; Daly, Rebecca A.

ABSTRACT Hydraulic fracturing of black shale formations has greatly increased United States oil and natural gas recovery. However, the accumulation of biomass in subsurface reservoirs and pipelines is detrimental because of possible well souring, microbially induced corrosion, and pore clogging. Temporal sampling of produced fluids from a well in the Utica Shale revealed the dominance ofHalanaerobiumstrains within thein situmicrobial community and the potential for these microorganisms to catalyze thiosulfate-dependent sulfidogenesis. From these field data, we investigated biogenic sulfide production catalyzed by aHalanaerobiumstrain isolated from the produced fluids using proteogenomics and laboratory growth experiments. Analysis ofHalanaerobiumisolate genomes and reconstructed genomes frommore » metagenomic data sets revealed the conserved presence of rhodanese-like proteins and anaerobic sulfite reductase complexes capable of converting thiosulfate to sulfide. Shotgun proteomics measurements using aHalanaerobiumisolate verified that these proteins were more abundant when thiosulfate was present in the growth medium, and culture-based assays identified thiosulfate-dependent sulfide production by the same isolate. Increased production of sulfide and organic acids during the stationary growth phase suggests that fermentativeHalanaerobiumuses thiosulfate to remove excess reductant. These findings emphasize the potential detrimental effects that could arise from thiosulfate-reducing microorganisms in hydraulically fractured shales, which are undetected by current industry-wide corrosion diagnostics. IMPORTANCEAlthough thousands of wells in deep shale formations across the United States have been hydraulically fractured for oil and gas recovery, the impact of microbial metabolism within these environments is poorly understood. Our research demonstrates that dominant microbial populations in these subsurface ecosystems contain the conserved capacity for the reduction

Crustal contamination and sulfide immiscibility history of the Permian Huangshannan magmatic Ni-Cu sulfide deposit, East Tianshan, NW China

NASA Astrophysics Data System (ADS)

Mao, Ya-Jing; Qin, Ke-Zhang; Tang, Dong-Mei; Feng, Hong-Ye; Xue, Sheng-Chao

2016-11-01

The Huangshannan mafic-ultramafic intrusion is a Permian Ni-Cu sulfide-bearing intrusion in the southern margin of the Central Asian Orogenic Belt. The intrusion consists of an ultramafic unit, which is composed of lherzolite and olivine websterite, and a mafic unit, which is composed of olivine gabbronorite, gabbronorite and leuco-gabbronorite. This intrusion was formed by two separate pulses of magma: a more primitive magma for the early ultramafic unit and a more evolved magma for the late mafic unit. U-Pb isotope geochronology of zircon from the mafic unit yields an age of 278 ± 2 Ma. According to its olivine and Cr-rich spinel compositions, the estimated parental magma of lherzolite for the Huangshannan intrusion has 12.4 wt.% MgO, indicating picritic affinity. Fractional crystallization modeling results and the presence of rounded sulfide inclusions in an olivine crystal (Fo 86.7) indicate that sulfide immiscibility was achieved at the beginning of olivine fractionation. Co-magmatic zircon crystals from gabbronorite have a δ18O value close to 6.5‰, which is 1.2‰ higher than the typical mantle value and suggests significant crustal contamination (∼20%). The positive εHf(t) values of co-magmatic zircon (which vary from +9.2 to +15.3) and positive whole rock εNd(t) values (which vary from +4.7 to +7.8) also indicate that the parental magma was derived from a depleted mantle source and contaminated by 5-20% juvenile arc crust and then by ∼5% upper crustal materials. However, modeling results of sulfur content at sulfide saturation reveal that such a large amount of crustal contamination is not sufficient to trigger sulfide saturation in the parental magma, which strongly suggests that external sulfur addition, probably during contamination, has played a critical role in causing sulfide immiscibility. Furthermore, the arc magmatism geochemical signatures of the Huangshannan intrusion, such as significant Nb and Ta depletion relative to La and low Ca

Sulfide toxicity: Mechanical ventilation and hypotension determine survival rate and brain necrosis

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

Baldelli, R.J.; Green, F.H.Y.; Auer, R.N.

1993-09-01

Occupational exposure to hydrogen sulfide is one of the leading causes of sudden death in the workplace, especially in the oil and gas industry. High-dose exposure causes immediate neurogenic apnea and death; lower doses cause [open quotes]knockdown[close quotes] (transient loss of consciousness, with apnea). Because permanent neurological sequelae have been reported, the authors sought to determine whether sulfide can directly kill central nervous system neurons. Ventilated and unventilated rats were studied to allow administration of higher doses of sulfide and to facilitate physiological monitoring. It was extremely difficult to produce cerebral necrosis with sulfide. Only one of eight surviving unventilatedmore » rats given high-dose sulfide (a dose that was lethal in [ge]50% of animals) showed cerebral necrosis. Mechanical ventilation shifted the dose that was lethal in 50% of the animals to 190 mg/kg from 94 mg/kg in the unventilated rats. Sulfide was found to potently depress blood pressure. Cerebral necrosis was absent in the ventilated rats (n = 11), except in one rat that showed profound and sustained hypotension to [le]35 Torr. Electroencephalogram activity ceased during exposure but recovered when the animals regained consciousness. The authors conclude that very-high-dose sulfide is incapable of producing cerebral necrosis by a direct histotoxic effect. 32 refs., 5 figs.« less

The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

NASA Astrophysics Data System (ADS)

Lajin, Bassam; Francesconi, Kevin A.

2016-06-01

Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools.

Molybdenum-copper and tungsten-copper alloys and method of making

DOEpatents

Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

1989-05-23

Molybdenum-copper and tungsten-copper alloys are prepared by a consumable electrode method in which the electrode consists of a copper matrix with embedded strips of refractory molybdenum or tungsten. The electrode is progressively melted at its lower end with a superatmospheric inert gas pressure maintained around the liquifying electrode. The inert gas pressure is sufficiently above the vapor pressure of copper at the liquidus temperature of the alloy being formed to suppress boiling of liquid copper.

Molybdenum-copper and tungsten-copper alloys and method of making

DOEpatents

Schmidt, F.A.; Verhoeven, J.D.; Gibson, E.D.

1989-05-23

Molybdenum-copper and tungsten-copper alloys are prepared by a consumable electrode method in which the electrode consists of a copper matrix with embedded strips of refractory molybdenum or tungsten. The electrode is progressively melted at its lower end with a superatmospheric inert gas pressure maintained around the liquefying electrode. The inert gas pressure is sufficiently above the vapor pressure of copper at the liquidus temperature of the alloy being formed to suppress boiling of liquid copper. 6 figs.

Negative Regulation of Autophagy by Sulfide Is Independent of Reactive Oxygen Species1

PubMed Central

Laureano-Marín, Ana M.; Moreno, Inmaculada

2016-01-01

Accumulating experimental evidence in mammalian, and recently plant, systems has led to a change in our understanding of the role played by hydrogen sulfide in life processes. In plants, hydrogen sulfide mitigates stress and regulates important plant processes such as photosynthesis, stomatal movement, and autophagy, although the underlying mechanism is not well known. In this study, we provide new experimental evidence that, together with our previous findings, demonstrates the role of hydrogen sulfide in regulating autophagy. We used green fluorescent protein fluorescence associated with autophagic bodies and immunoblot analysis of the ATG8 protein to show that sulfide (and no other molecules such as sulfur-containing molecules or ammonium) was able to inhibit the autophagy induced in Arabidopsis (Arabidopsis thaliana) roots under nitrogen deprivation. Our results showed that sulfide was unable to scavenge reactive oxygen species generated by nitrogen limitation, in contrast to well-established reducers. In addition, reducers were unable to inhibit the accumulation of autophagic bodies and ATG8 protein forms to the same extent as sulfide. Therefore, we conclude that sulfide represses autophagy via a mechanism that is independent of redox conditions. PMID:27208225

Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

NASA Astrophysics Data System (ADS)

Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

2016-09-01

With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

Alkaline sulfide pretreatment of an antimonial refractory Au-Ag ore for improved cyanidation

NASA Astrophysics Data System (ADS)

Alp, Ibrahim; Celep, Oktay; Deveci, Haci

2010-11-01

This paper presents the alkaline sulfide pretreatment of an antimonial refractory gold and silver ore. In the ore, gold occurs mainly as gold-silver alloys and as associated with quartz and framboidal pyrite grains, and, to a small extent, as the inclusions within antimonial sulfides. Silver is present extensively as antimonial sulfides such as andorite. Alkaline sulfide pretreatment was shown to allow the decomposition of the antimonial sulfide minerals (up to 98% Sb removal) and to remarkably improve the amenability of gold (e.g., from <49% up to 83%) and silver (e.g., from <18% up to 90%) to subsequent cyanide leaching. An increase in reagent concentration (1-4 mol/L Na2S or NaOH) and temperature (20-80°C), and a decrease in particle size seem to produce an enhancing effect on metal extraction. These findings suggest that alkaline sulfide leaching can be suitably used as a chemical pretreatment method prior to the conventional cyanidation for antimonial refractory gold and silver ores.

Preliminary study on copper isotopes of the Zijinshan ore field, Fujian Province, SE China

NASA Astrophysics Data System (ADS)

Zhao, Hai-Xiang

2017-04-01

Zijinshan Cu-Au polymetallic ore field is located in Southeast China, tectonically belonging to the Interior Cathaysia Block. It is a complete porphyry-epithermal mineralization system, including Luoboling porphyry Cu-Mo deposit, Zijinshan high sulfidation Cu-Au deposit, Yueyang low sulfidation Ag-Au deposit, Wuziqilong and Longjiangting transitional style Cu deposits, etc. Main ore minerals from Zijinshan and Wuziqilong deposits are covellite and digenite. Copper isotopic compositions of these two minerals were analyzed. Copper isotope ratios are reported in the standard delta notation: δ65 Cu‰¯[ (65Cu/63Cu)Sample/(65Cu/63Cu) ERM-AE633-1] ×1000. The overall δ65Cu values for the analysed samples vary from -2.76 to 1.33‰Ṫhe Zijinshan Cu-Au deposit show large Cu isotopic variability (-2.76 to 1.33), among which covellite samples range from -2.76‰ to 0.38‰ with -0.79‰ in average and digenite samples range from -1.8‰ to 1.33‰ with -0.11‰ in average. During the leaching process of hypogene sulphides, 65Cu was leached more easily and then trapped in the supergene enrichment zone. Therefore, enrichment minerals should be enriched in 65Cu and the leached cap enriched in 63Cu. Thus the relationship of δ65Cu values for different Cu reservoirs should be leached cap minerals < hypogene sulphides < enrichment minerals. Nonexistence of enriched δ65Cu values indicate that the major copper minerals (mainly covellite and digenite) in the Zijinshan Cu-Au deposit and Wuziqilong Cu deposit are of hypogene origin rather than secondary origin. At the Wuziqilong Cu deposit, Cu isotopes has narrow range from 0.16‰ to 0.43‰ with 0.31‰ in average, which is typically of hypogene origin. Two coexisting covellite -digenite fractionations (δ65Cu =δ65Cucovellite - δ65Cudigenite) are 0.27‰ and 0.18‰ relatively. For minerals of the Cu-S system, from chalcocite (Cu2S) to covellite (CuS), proportions of Cu(II) become higher and higher. The classical definition of

Sulfides in the Garnet Pyroxenite xenoliths from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Sen, I. S.; Sen, G.; Bizimis, M.

2007-12-01

Oahu is known for its garnet bearing xenoliths that occur in the Honolulu Volcanics. Clinopyroxene is the dominant minerals of these rocks, and modes of other silicate minerals - orthopyroxene, olivine, garnet, amphibole, and phlogopite vary considerably. Ilmenite and Spinels of diverse variety also occur (Keshav et al. 2007, J. Petrol.). In this report we present new electron microprobe and LA-ICPMS data on the sulfides that are always present in these xenoliths although they make up only trace amounts. In terms of morphology and mode of occurrence the sulfides can be divided fundamentally into two types - Type I occurs as poikilitic inclusions in the silicate phases mostly in clinopyroxene and Type II occurs in the interstitial spaces between the silicates, along grain boundaries and along cracks within individual silicate grains. Sizes of both types vary considerably. Type I sulfides are generally globular and appear to have formed from immiscible sulfide melts that got enclosed by the silicate minerals that grew from the main body of silicate melt. Keshav et al. (2007) estimate the average solidus temperatures of garnet pyroxenites from Oahu to range from 1215 to 1600°C (average 1325°C) at 3-5 GPa. Therefore, the Type I sulfides are high temperature sulfides that formed above the silicate solidus. Type II sulfides take various forms - from vein-like to dendritic. Compositionally, both types include Ni rich pyrrhotites (Ni content varies from 3-5 wt%) and monosulfide solid solutions(MSS). The MSS are divided into Ni rich MSS containing as much as 20 wt% of Ni, the average is 15 wt% while the Ni poor MSS has 5-9 wt% of Ni in it. We have limited data on PGE so far but the Type II sulfides have a very low PGE content. Two recent papers have noted that Hawaiian plume-derived shield tholeiites are too rich in Ni for a given SiO2% to be produced by partial melting of a peridotite and called for an unusual Ni-rich pyroxenite source in which the large Ni content is

Dispersion strengthened copper

DOEpatents

Sheinberg, H.; Meek, T.T.; Blake, R.D.

1990-01-09

A composition of matter is described which is comprised of copper and particles which are dispersed throughout the copper, where the particles are comprised of copper oxide and copper having a coating of copper oxide. A method for making this composition of matter is also described. This invention relates to the art of powder metallurgy and, more particularly, it relates to dispersion strengthened metals.

The effects of sulfide composition on the solubility of sulfur in coexisting silicate melts

NASA Astrophysics Data System (ADS)

Smythe, Duane; Wood, Bernard; Kiseeva, Ekaterina

2016-04-01

The extent to which sulfur dissolves in silicate melts saturated in an immiscible sulfide phase is a fundamental question in igneous petrology and plays a primary role in the generation of magmatic ore deposits, volcanic degassing and planetary differentiation. Terrestrial sulfide melts often contain over 20 weight percent Ni + Cu, however, most experimental studies investigating sulfur solubility in silicate melt have been primarily concerned with the effects of silicate melt composition, and pure FeS has been use as the immiscible sulfide melt (O'Neill and Mavrogenes, 2002; Li and Ripley, 2005). To investigation of the effects of sulfide composition, in addition to those of temperature, pressure and silicate melt composition, on sulfur solubility in silicate melts, we have carried out a series of experiments done at pressures between 1.5 and 3 GPa and temperatures from 1400 to 1800C over a range of compositions of both the silicate and sulfide melt. We find that the solubility of sulfur in silicate melts drops significantly with the substitution of Ni and Cu for Fe in the immiscible sulfide melt, decreasing by approximately 40% at mole fractions of NiS + Cu2S of 0.4. Combining our results with those from the previous studies investigating sulfur solubility in silicate melts we have also found that solubility increases with increasing temperature and decreases pressure. These results show that without considering the composition of the immiscible sulfide phase the sulfur content of silicate melts can be significantly overestimated. This may serve to explain the relatively low sulfur concentrations in MORB melts, which previous models predict to be undersaturated in a sulfide phase despite showing chemical and textural evidence for sulfide saturation. Li, C. & Ripley, E. M. (2005). Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits. Mineralium Deposita 40, 218-230. O'Neill, H. S. C

Formation of Titanium Sulfide from Titanium Oxycarbonitride by CS2 Gas

NASA Astrophysics Data System (ADS)

Ahmadi, Eltefat; Yashima, Yuta; Suzuki, Ryosuke O.; Rezan, Sheikh Abdul

2018-05-01

Previously this group reported that a good quality titanium metal powder can be produced from titanium sulfides by electrochemical OS process. In this study, the sulfurization procedure was examined to synthesize titanium sulfide from titanium oxycarbonitride by CS2 gas. The experiments were carried out in the temperature range of 1173 K to 1523 K (900 °C to 1250 °C) in a tube reactor with continuously flowing argon (Ar) as carrier gas of CS2. The formation of titanium sulfide phases from the commercial TiN, TiC, and TiO powders was studied as the initial step. Then, TiO0.02C0.13N0.85 coming from ilmenite was sulfurized to prepare single phase of titanium sulfide. The products were characterized by X-ray diffraction, and the morphology of the sulfides was rigorously investigated, and the sulfur, oxygen, and carbon contents in the products were analyzed. The process was remarkably dependent on the temperature and time. TiN and TiO0.02C0.13N0.85 powders could be fully converted to the single phase of Ti2.45S4 (Ti2+x S4) at 1473 K (1200 °C) in 3.6 ks. The maximum weight gain of TiN sample was 55.3 pct indicating a full conversion of TiN to Ti2S3 phase. The carbon and oxygen contents in this sulfide prepared from the oxycarbonitride were about 1.8 wt pct C and 1.4 wt pct O, respectively. Therefore, the titanium sulfide could be a promising feedstock for the production of commercial grade titanium powder.