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 potassic, phillic, argillic and prophylitic in the area and silicious alteration near the mineralized veins, indicate probable existence of porphyry copper ore and imply epithermal gold in the Jolfa area, north west of Iran. Key words: Masjid Dagi, Alteration, Pyrite, Sulfide, Mineralography, Stock work.

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.

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.

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.

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.

Synthesis and molecular structure of a spheroidal binary nanoscale copper sulfide cluster.

PubMed

Bestgen, Sebastian; Fuhr, Olaf; Roesky, Peter W; Fenske, Dieter

2016-09-27

The reaction of copper(4-(tert-butyl)phenyl)methanethiolate [CuSCH 2 C 6 H 4 t Bu] with bis(trimethylsilyl)sulfide S(SiMe 3 ) 2 in the presence of triphenylphosphine PPh 3 afforded the binary 52 nuclear copper cluster [Cu 52 S 12 (SCH 2 C 6 H 4 t Bu) 28 (PPh 3 ) 8 ]. The molecular structure of this intensely red coloured nanoscale Cu 2 S mimic was established by single crystal X-ray diffraction.

Fabrication and applications of copper sulfide (CuS) nanostructures

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

Shamraiz, Umair, E-mail: umairshamraiz@gmail.com; Hussain, Raja Azadar, E-mail: hussainazadar@gamil.com; Badshah, Amin, E-mail: aminbadshah@yahoo.com

2016-06-15

This review article presents different fabrication procedures (under the headlines of solvothermal routes, aerosol methods, solution methods and thermolysis), and applications (photocatalytic degradation, ablation of cancer cells, electrode material in lithium ion batteries and in gas sensing, organic solar cells, field emission properties, super capacitor applications, photoelectrochemical performance of QDSCs, photocatalytic reduction of organic pollutants, electrochemical bio sensing, enhanced PEC characteristics of pre-annealed CuS film electrodes) of copper sulfide (Covellite). - Highlights: • This review article presents the synthesis and applications of copper sulfide. • CuS has been used over the years for different applications in nanoscience. • Different syntheticmore » protocols are followed for their preparation which help in the possible modifications in the morphology of CuS.« 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.

The use of ethanol to remove sulfur from coal. Final report, September 1991--December 1992

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

Not Available

1993-04-15

In developing the new Ohio University procedure the thermodynamic limitations of the reactions for removal of both pyritic and organic sulfur from coal at 400--600{degrees}C were studied using copper as a very strong H{sub 2}S-acceptor. Copper serves as a catalyst for ethanol dehydrogenation to form nascent hydrogen. Copper also serves as a scavenger to form copper sulfide from the hydrogen sulfide evolved during the reaction. Copper sulfide in turn serves as a catalyst for organic sulfur hydrodesulfurization reactions. If the coal to be desulfurized contains pyrite (FeS{sub 2}) or FeS, the copper scavenger effect reduces any back reaction of hydrogenmore » sulfide with the iron and increases the removal of sulfur from the carbonaceous material. The desired effect of using copper can be achieved by using copper or copper containing alloys as materials of construction or as liners for a regenerable reactor. During the time period that Ohio Coal Development Office supported this work, small scale (560 grams) laboratory experiments with coals containing about 3.5% sulfur have achieved up to 90% desulfurization at temperatures of 500{degrees}C when using a copper reactor. Results from the autoclave experiments have identified the nature of the chemical reactions taking place. Because the process removes both pyritic and organic sulfur in coal, the successful scale up of the process would have important economic significance to the coal industry. Even though this and other chemical processes may be relatively expensive and far from being commercial, the reason for further development is that this process may hold the promise of achieving much greater sulfur reduction and of producing a cleaner coal than other methods. This would be especially important for small or older power plants and industrial boilers.« less

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 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 resolution are needed to precisely verify surface structures formed after copper activation. Sphalerite and pyrite surfaces are characterised by varying amounts of steps and defects, and this heterogeneity suggests co-existence of more than one copper-sulfide structure after activation.

Experimentally Determined Phase Diagram for the Barium Sulfide-Copper(I) Sulfide System Above 873 K (600 °C)

NASA Astrophysics Data System (ADS)

Stinn, Caspar; Nose, Katsuhiro; Okabe, Toru; Allanore, Antoine

2017-12-01

The phase diagram of the barium sulfide-copper(I) sulfide system was investigated above 873 K (600 °C) using a custom-built differential thermal analysis (DTA) apparatus. The melting point of barium sulfide was determined utilizing a floating zone furnace. Four new compounds, Ba2Cu14S9, Ba2Cu2S3, Ba5Cu4S7, and Ba9Cu2S10, were identified through quench experiments analyzed with wavelength dispersive X-ray spectroscopy (WDS) and energy dispersive X-ray analysis (EDS). A miscibility gap was observed between 72 and 92 mol pct BaS using both DTA experiments and in situ melts observation in a floating zone furnace. A monotectic was observed at 94.5 mol pct BaS and 1288 K (1015 °C).

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.

Copper solubility in a basaltic melt and sulfide liquid/silicate melt partition coefficients of Cu and Fe

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.; Li, Chusi

2002-09-01

The solubility of copper in a sulfur-saturated basaltic melt has been determined at 1245°C as a function of fO 2 and fS 2. Copper solubilities at log fO 2 values between -8 and -11 fall into two distinct populations as a function of fS 2. At log fS 2 values < -1.65, sulfide liquid that coexists with the basaltic glass quenches to sulfur-poor bornite solid solution. At log fS 2 values in excess of -1.65, the sulfide liquid quenches to a complex intergrowth of sulfur-rich bornite and intermediate solid solution. Copper solubilities in the low-fS 2 population range from 594 to 1550 ppm, whereas those in the high-fS 2 population range from 80 to 768 ppm. Sulfide liquid/silicate liquid partition coefficients (D) for Cu and Fe range from 480 to 1303 and 0.7 to 13.6, respectively. Metal-sulfur complexing in the silicate liquid is shown to be insignificant relative to metal-oxide complexing for Fe but permissible for Cu at high fS 2 values. On log D Fe (sulfide-silicate) and log D Cu (sulfide-silicate) vs. 1/2 (log fS 2 - log fO 2) diagrams, both fS 2 populations show distinct but parallel trends. The observation of two D values for any fS 2/fO 2 ratio indicates nonideal mixing of species involved in the exchange reaction. The two distinct trends observed for both Cu and Fe are thought to be due to variations in activity coefficient ratios (e.g., γ FeO/γ FeS and γ CuO 0.5/γ CuS 0.5). Results of the experiments suggest that accurate assessments of fS 2/fO 2 ratios are required for the successful numerical modeling of processes such as the partial melting of sulfide-bearing mantle and the crystallization of sulfide-bearing magmas, as well as the interpretation of sulfide mineralogical zoning. In addition, the experiments provide evidence for oxide or oxy-sulfide complexing for Cu in silicate magmas and suggest that the introduction of externally derived sulfur to mafic magma may be an important process for the formation of Cu-rich disseminated magmatic sulfide ore deposits.

Explosibility of Metal Powders

DTIC Science & Technology

1964-01-01

299 1832 - Copper ore, sulfide , Mexic.................................................- - 100 - - - 300 1873 - Iron ore, magnetite...100 - - - 302 2076.............................................. do...................................... - - 100 - - - 303 749 - Iron ore, sulfide ...9 Pyrophoricity ............................................................... 9 Prevention of ignition and explosion

Sulfobacillus thermosulfidooxidans strain Cutipay enhances chalcopyrite bioleaching under moderate thermophilic conditions in the presence of chloride ion.

PubMed

Bobadilla-Fazzini, Roberto A; Cortés, Maria Paz; Maass, Alejandro; Parada, Pilar

2014-12-01

Currently more than 90% of the world's copper is obtained through sulfide mineral processing. Among the copper sulfides, chalcopyrite is the most abundant and therefore economically relevant. However, primary copper sulfide bioleaching is restricted due to high ionic strength raffinate solutions and particularly chloride coming from the dissolution of ores. In this work we describe the chalcopyrite bioleaching capacity of Sulfobacillus thermosulfidooxidans strain Cutipay (DSM 27601) previously described at the genomic level (Travisany et al. (2012) Draft genome sequence of the Sulfobacillus thermosulfidooxidans Cutipay strain, an indigenous bacterium isolated from a naturally extreme mining environment in Northern Chile. J Bacteriol 194:6327-6328). Bioleaching assays with the mixotrophic strain Cutipay showed a strong increase in copper recovery from chalcopyrite concentrate at 50°C in the presence of chloride ion, a relevant inhibitory element present in copper bioleaching processes. Compared to the abiotic control and a test with Sulfobacillus acidophilus DSM 10332, strain Cutipay showed an increase of 42 and 69% in copper recovery, respectively, demonstrating its high potential for chalcopyrite bioleaching. Moreover, a genomic comparison highlights the presence of the 2-Haloacid dehalogenase predicted-protein related to a potential new mechanism of chloride resistance in acidophiles. This novel and industrially applicable strain is under patent application CL 2013-03335.

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 are more likely to have a higher proportion of free gold and may require different ore processing strategies.

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 cement around quartz sand grains, and brecciated pyrite grains are surrounded by rims of hematite and goethite. Dolomite is the principal sandstone cement. Cathodoluminescence microscopic study of the mineral has shown that it was deposited during seven periods before the copper sulfide mineralization. ?? 1991.

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.

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.

Publications - IC 49 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

Survey; Antimony; Arsenic; Base Metals; Bismuth; Chromium; Coal; Copper; Diamonds; Drilling; Economic Sampling; Stibnite; Sulfides; Tantalum; Tin; True North; Ultramafic; Volcanogenic Massive Sulfide; Wulik

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.

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 lower model Th/U. These Pb isotope differences are inferred to result from differences in their respective post-1.7 Ga magmatic histories. Throughout Arizona, Pb isotope compositions of Late Cretaceous and early Tertiary plutons and associated sulfide minerals are distinct from those of Jurassic plutons and also middle Tertiary igneous rocks and sulfide minerals. These differences most likely reflect changes in tectonic setting and magmatic sources. Within Late Cretaceous and early Tertiary igneous complexes that host economic porphyry copper deposits, there is commonly a decrease in Pb isotope composition from older to younger plutons. This decrease in Pb isotope values with time suggests an increasing involvement of crust with lower U/Pb than average crust in the source(s) of Late Cretaceous and early Tertiary magmas. Lead isotope compositions of the youngest porphyries in the igneous complexes are similar to those in most sulfide minerals within the associated porphyry copper deposit. This Pb isotope similarity argues for a genetic link between them. However, not all Pb in the sulfide minerals in porphyry copper deposits is magmatically derived. Some sulfide minerals, particularly those that are late stage, or distal to the main orebody, or in Proterozoic or Paleozoic rocks, have elevated Pb isotope compositions displaced toward the gross average Pb isotope composition of the local country rocks. The more radiogenic isotopic compositions argue for a contribution of Pb from those rocks at the site of ore deposition. Combining the Pb isotope data with available geochemical, isotopic, and petrologic data suggests derivation of the young porphyry copper-related plutons, most of their Pb, and other metals from a hybridized lower continental crustal source. Because of the likely involvement of subduction-related mantle-derived basaltic magma in the hybridized lower crustal source, an indiscernible mantle contribution is probable in the porphyry magmas. Clearly, in addition

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.

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).

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

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.

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.

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.

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.

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.

Real-time control data wrangling for development of mathematical control models of technological processes

NASA Astrophysics Data System (ADS)

Vasilyeva, N. V.; Koteleva, N. I.; Fedorova, E. R.

2018-05-01

The relevance of the research is due to the need to stabilize the composition of the melting products of copper-nickel sulfide raw materials in the Vanyukov furnace. The goal of this research is to identify the most suitable methods for the aggregation of the real time data for the development of a mathematical model for control of the technological process of melting copper-nickel sulfide raw materials in the Vanyukov furnace. Statistical methods of analyzing the historical data of the real technological object and the correlation analysis of process parameters are described. Factors that exert the greatest influence on the main output parameter (copper content in matte) and ensure the physical-chemical transformations are revealed. An approach to the processing of the real time data for the development of a mathematical model for control of the melting process is proposed. The stages of processing the real time information are considered. The adopted methodology for the aggregation of data suitable for the development of a control model for the technological process of melting copper-nickel sulfide raw materials in the Vanyukov furnace allows us to interpret the obtained results for their further practical application.

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.

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.

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.

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 Au are contained in pyrite assemblages as micro- to nano-sized inclusions, especially in the high grade fertile porphyry deposits. However, unexpectedly high concentrations of Te, Se, and Re may be associated with early stage of sulfide mineralization, especially when there is no epithermal lithocap. This may highlight the significance of trace metals partitioning in the sulfides formed at the early stages of mineralization in PCDs.

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.

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.

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.

ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

PubMed Central

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

1963-01-01

Razzell, W. E. (British Columbia Research Council, Vancouver, Canada) and P. C. Trussell. Isolation and properties of an iron-oxidizing Thiobacillus. J. Bacteriol. 85:595–603. 1963. — An organism isolated from acidic copper-leaching waters has been shown to oxidize ferrous ions, sulfur, and metallic sulfides but exhibit peculiar responses to thiosulfate. The name Thiobacillus ferrooxidans has been used to describe it. A pH of 2.5 is optimal for growth on iron, sulfur, and metallic sulfides, but cells free from iron can be obtained from growth at pH 1.6, and sulfur cultures adjusted to pH 5.5 readily attain a pH of 1.8. A stationary cultivation procedure appears superior to percolation techniques for studying the oxidation of finely divided metallic sulfides. Concentrations of soluble copper in excess of 1 g per liter were obtained from chalcopyrite in less than 4 weeks. Chalcocite oxidation proceeded in the absence of iron. Sodium chloride inhibits iron oxidation without preventing oxidation of metallic sulfides by the organism. PMID:14042937

Progress in bioleaching: part B: applications of microbial processes by the minerals industries.

PubMed

Brierley, Corale L; Brierley, James A

2013-09-01

This review presents developments and applications in bioleaching and mineral biooxidation since publication of a previous mini review in 2003 (Olson et al. Appl Microbiol Biotechnol 63:249-257, 2003). There have been discoveries of newly identified acidophilic microorganisms that have unique characteristics for effective bioleaching of sulfidic ores and concentrates. Progress has been made in understanding and developing bioleaching of copper from primary copper sulfide minerals, chalcopyrite, covellite, and enargite. These developments point to low oxidation-reduction potential in concert with thermophilic bacteria and archaea as a potential key to the leaching of these minerals. On the commercial front, heap bioleaching of nickel has been commissioned, and the mineral biooxidation pretreatment of sulfidic-refractory gold concentrates is increasingly used on a global scale to enhance precious metal recovery. New and larger stirred-tank reactors have been constructed since the 2003 review article. One biooxidation-heap process for pretreatment of sulfidic-refractory gold ores was also commercialized. A novel reductive approach to bioleaching nickel laterite minerals has been proposed.

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.

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.

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. The pitchblende in the deposit forms a steeply plunging ore shoot that has a horizontal length of more than 50 feet and a vertical height of about 85 feet. The thickness of the ore shoot averages about 2 feet, but it ranges from a feather edge to about 4 feet. The hard pitch-blende is intimately intergrown with siderite; other gangue minerals include pyrite, quartz, and finely comminuted fragments of the wall rocks. The vein was repeatedly reopened during mineral deposition as shown by several stages of brecciation and recommended by the vein matter. The pitchblende deposit probably formed at intermediate temperatures and depths and, according to the Pb/U ratio, is about 60 million years old--an early Tertiary age.

An Improved Process for Precipitating Cyanide Ions from the Barren Solution at Different pHs

NASA Astrophysics Data System (ADS)

Figueroa, Gabriela V.; Parga, José R.; Valenzuela, Jesus L.; Vázquez, Victor; Valenzuela, Alejandro; Rodriguez, Mario

2016-02-01

In recent decades, the use of metal sulfides instead of hydroxide precipitation in hydrometallurgical processes has gained prominence. Some arguments for its preferential use are as follows: a high degree of metal removal at relatively low pH values, the sparingly soluble nature of sulfide precipitates, favorable dewatering characteristics, and the stability of the formed metal sulfides. The Merrill-Crowe zinc-precipitation process has been applied worldwide in a large number of operations for the recovery of gold and silver from cyanide solutions. However, in some larger plants, the quality of this precious precipitate is low because copper, zinc and especially lead are precipitated along with gold and silver. This results in higher consumption of zinc dust and flux during the smelting of the precipitate, the formation of the matte, and a shorter crucible life. The results show that pH has a significant effect on the removal efficiency of zinc and copper cyanide ions. The optimal pH range was determined to be 3-4, and the removal efficiency of zinc and copper cyanide ions was up to 99%.

Workshop proceedings: Photovoltaic conversion of solar energy for terrestrial applications. Volume 2: Invited papers

NASA Technical Reports Server (NTRS)

1973-01-01

A photovoltaic device development plan is reported that considers technological as well as economical aspects of single crystal silicon, polycrystal silicon, cadmium sulfide/copper sulfide thin films, as well as other materials and devices for solar cell energy conversion systems.

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 ...

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.

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.

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.

Workshop proceedings: Photovoltaic conversion of solar energy for terrestrial applications. Volume 1: Working group and panel reports

NASA Technical Reports Server (NTRS)

1973-01-01

Technological aspects of solar energy conversion by photovoltaic cells are considered. The advantage of the single crystal silicon solar cell approach is developed through comparisons with polycrystalline silicon, cadmium sulfide/copper sulfide thin film cells, and other materials and devices.

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.

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.

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.

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.

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.

Method of forming components for a high-temperature secondary electrochemical cell

DOEpatents

Mrazek, Franklin C.; Battles, James E.

1983-01-01

A method of forming a component for a high-temperature secondary electrochemical cell having a positive electrode including a sulfide selected from the group consisting of iron sulfides, nickel sulfides, copper sulfides and cobalt sulfides, a negative electrode including an alloy of aluminum and an electrically insulating porous separator between said electrodes. The improvement comprises forming a slurry of solid particles dispersed in a liquid electrolyte such as the lithium chloride-potassium chloride eutetic, casting the slurry into a form having the shape of one of the components and smoothing the exposed surface of the slurry, cooling the cast slurry to form the solid component, and removing same. Electrodes and separators can be thus formed.

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.

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.

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 undeveloped source of copper and nickel on Earth. Microorganisms are important catalysts for sulfide mineral oxidation, and research on extreme acidophiles has improved our ability to manage and remediate mine wastes. We found that the microbial assemblages associated with weathered rock from the Duluth Complex are dominated by organisms not widely associated with mine waste or mining-impacted environments, and we describe geochemical and experimental influences on community composition. This report will be a useful foundation for understanding the microbial biogeochemistry of moderately acidic mine waste from these and similar deposits. PMID:28600313

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 undeveloped source of copper and nickel on Earth. Microorganisms are important catalysts for sulfide mineral oxidation, and research on extreme acidophiles has improved our ability to manage and remediate mine wastes. We found that the microbial assemblages associated with weathered rock from the Duluth Complex are dominated by organisms not widely associated with mine waste or mining-impacted environments, and we describe geochemical and experimental influences on community composition. This report will be a useful foundation for understanding the microbial biogeochemistry of moderately acidic mine waste from these and similar deposits. Copyright © 2017 American Society for Microbiology.

The origin of Cu/Au ratios in porphyry-type ore deposits.

PubMed

Halter, Werner E; Pettke, Thomas; Heinrich, Christoph A

2002-06-07

Microanalysis of major and trace elements in sulfide and silicate melt inclusions by laser-ablation inductively coupled plasma mass spectrometry indicates a direct link between a magmatic sulfide liquid and the composition of porphyry-type ore deposits. Copper (Cu), gold (Au), and iron (Fe) are first concentrated in a sulfide melt during magmatic evolution and then released to an ore-forming hydrothermal fluid exsolved late in the history of a magma chamber. The composition of sulfide liquids depends on the initial composition and source of the magma, but it also changes during the evolution of the magma in the crust. Magmatic sulfide melts may exert the dominant direct control on the economic metal ratios of porphyry-type ore deposits.

Method of forming components for a high-temperature secondary electrochemical cell

DOEpatents

Mrazek, F.C.; Battles, J.E.

1981-05-22

A method of forming a component for a high-temperature secondary electrochemical cell having a positive electrode including a sulfide selected from the group consisting of iron sulfides, nickel sulfides, copper sulfides and cobalt sulfides, a negative electrode including an alloy of aluminum and an electrically insulating porous separator between said electrodes is described. The improvement comprises forming a slurry of solid particles dispersed in a liquid electrolyte such as the lithium chloride-potassium chloride eutectic, casting the slurry into a form having the shape of one of the components and smoothing the exposed surface of the slurry, cooling the cast slurry to form the solid component, and removing same. Electrodes and separators can be thus formed.

Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

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

Bruhn, D F; Thompson, D N; Noah, K S

1999-06-01

Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, Leptospirillum, Ferromicrobium, and Acidiphilium. Two temperatures (30C and 45C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. Aftermore » acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to the low pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.« less

Cu(I)/Cu(II) mixed-valence surface complexes of S-[(2-hydroxyamino)-2-oxoethyl]-N,N-dibutyldithiocarbamate: Hydrophobic mechanism to malachite flotation.

PubMed

Liu, Sheng; Zhong, Hong; Liu, Guangyi; Xu, Zhenghe

2018-02-15

Hydroxamate and sulfhydryl surfactants are effective collectors for flotation of copper minerals. The combination application of hydroxamate and sulfhydryl collectors has been proved to be an effective approach for improving the flotation recovery of non-sulfide copper minerals. A surfactant owing both hydroxamate and dithiocarbamate groups might exhibit strong affinity to non-sulfide copper minerals through double sites adsorption, rendering an enhanced hydrophobization to non-sulfide copper minerals flotation. The flotation performance of S-[(2-hydroxyamino)-2-oxoethyl]- N,N-dibutyldithiocarbamate (HABTC) to malachite, calcite and quartz were first evaluated through systematic micro-flotation experiments. HABTC's hydrophobic mechanism to malachite was further investigated and analyzed by zeta potential, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The micro-flotation results demonstrated HABTC was an excellent collector for malachite flotation and exhibited favorable selectivity for flotation separation of malachite from quartz or calcite under pH 8.5-10.3. Zeta potential and FTIR implied that HABTC might bond with the surface copper atoms of malachite, with releasing the H + ions of its hydroxamate group into pulp. ToF-SIMS provided clear evidences that the Cu-hydroxamate and Cu-dithiocarbamate groups were formed on malachite surfaces after HABTC adsorption. XPS revealed that Cu(I)/Cu(II) mixed-valence surface complexes of HABTC anchored on malachite through formation of Cu(I)S and Cu(II)O bonds, accompanying with reduction of partial surface Cu(II) to Cu(I). The Cu(I)/Cu(II) mixed-valence double chelating character and "chair"-shape N,N-dibutyldithiocarbamate hydrophobic group, resulting in an enhanced affinity and hydrophobization of HABTC to malachite flotation. Copyright © 2017 Elsevier Inc. All rights reserved.

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

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.

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.

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.

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

NASA Astrophysics Data System (ADS)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

Rhenium: a rare metal critical in modern transportation

USGS Publications Warehouse

John, David A.

2015-01-01

Rhenium rarely occurs as a native element or as its own sulfide mineral—rheniite (ReS2)—and often occurs as a substitute for molybdenum in molybdenite (MoS2). Most extracted rhenium is a byproduct of copper mining, with about 80 percent recovered from flue dust during the processing of molybdenite concentrates from porphyry copper deposits.

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.

Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

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

Bruhn, Debby Fox; Thompson, David Neal; Noah, Karl Scott

1999-06-01

Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, “Leptospirillum”, “Ferromicrobium”, and Acidiphilium. Two temperatures (30°C and 45°C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. Aftermore » acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to low the pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.« less

Facile and low temperature route to synthesis of CuS nanostructure in mesoporous material by solvothermal method.

PubMed

Sohrabnezhad, Sh; Zanjanchi, M A; Hosseingholizadeh, S; Rahnama, R

2014-04-05

The synthesis of CuS nanomaterial in MCM-41 matrix has been realized by chemical synthesis between MCM-41, copper sulfate pentahydrate and thiourea via a solvothermal method in ethylene glycol and water, separately. X-ray diffraction analysis (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and fourier transform infrared (FT-IR) were used to characterize the products. At synthesized CuS/MCM-41 sample in ethylene glycol, X-ray diffraction and diffuse reflectance spectroscopy showed pure covellite phase of copper sulfide with high crystality. But prepared CuS/MCM-41 sample in water shows the covellite, chalcocite and the djurleite phase of copper sulfide nanostructures. The formation of CuS nanostructures was confirmed by FT-IR. Photocatalytic activity of CuS/MCM-41 nanocomposites was studied for degradation of Methylene Blue (MB) under visible light. The CuS/MCM-41 nanocomposite is more effective nanocatalyst than synthesized CuS/MCM-41 sample in water for degradation of methylene blue. Several parameters were examined, catalyst amount (0.1-1gL(-1)), pH (1-13) and initial concentration of MB (0.96-10ppm). The extent of degradation was estimated from the residual concentration by spectrophotometrically. The support size was obtained in the range 60-145nm by TEM. In the same way, the average size of copper sulfide in CuSMCM-41E and CuS/MCM-41W nanostructures were obtained about 10nm and 16nm, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Metallogeny of the midcontinent rift system of North America

USGS Publications Warehouse

Nicholson, S.W.; Cannon, W.F.; Schulz, K.J.

1992-01-01

The 1.1 Ga Midcontinent rift system of North America is one of the world's major continental rifts and hosts a variety of mineral deposits. The rocks and mineral deposits of this 2000 km long rift are exposed only in the Lake Superior region. In the Lake Superior region, the rift cuts across Precambrian basement terranes ranging in age from ??? 1850 Ma to more than 3500 Ma. Where exposed, the rift consists of widespread tholeiitic basalt flows with local interlayered rhyolite and clastic sedimentary rocks. Beneath the center of Lake Superior the volcanic and sedimentary rocks are more than 30 km deep as shown by recent seismic reflection profiles. This region hosts two major classes of mineral deposits, magmatic and hydrothermal. All important mineral production in this region has come from hydrothermal deposits. Rift-related hydrothermal deposits include four main types: (1) native copper deposits in basalts and interflow sediments; (2) sediment-hosted copper sulfide and native copper; (3) copper sulfide veins and lodes hosted by rift-related volcanic and sedimentary rocks; and (4) polymetallic (five-element) veins in the surrounding Archean country rocks. The scarcity of sulfur within the rift rocks resulted in the formation of very large deposits of native metals. Where hydrothermal sulfides occur (i.e., shale-hosted copper sulfides), the source of sulfur was local sedimentary rocks. Magmatic deposits have locally supported exploration and minor production, but most are subeconomic presently. These deposits occur in intrusions exposed near the margins of the rift and include CuNiPGE and TiFe (V) in the Duluth Complex, U-REE-Nb in small carbonatites, and breccia pipes resulting from local hydrothermal activity around small felsic intrusions. Mineralization associated with some magmatic bodies resulted from the concentration of incompatible elements during fractional crystallization. Most of the sulfide deposits in intrusions, however, contain sulfur derived from country rocks; the interaction between magma and country rocks was important in generation of the magmatic CuNi sulfide deposits. A mantle plume origin has been proposed for the formation of the Midcontinent rift. More than 1 million km3 of mafic magma was erupted in the rift and a comparable volume of mafic intrusions are inferred beneath the rift, providing a ready and structurally confined supply of mafic source rocks that were available for leaching of metals by basinal brines. These brines were heated by a steep geothermal gradient that resulted from the melting and underplating of magma derived from the plume. Hydrothermal deposits were emplaced for at least 30-40 m.y. after rift magmatism and extension ceased. This time lag may reflect either the time required to heat deeply buried rocks and fluids within the rift, or may be due to the timing of post-rift compression that may have provided the driving mechanism for expulsion of hydrothermal fluids from deep portions of the rift. ?? 1992.

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].

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.

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

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.

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 underway with enzimes without the bacteria may confirm this hypothesis. The data obtained in these experiments will provide some constraints in the use of copper isotopes as proxy for life in the rock record.

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

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

Geological and geochemical studies of the Shujiadian porphyry Cu deposit, Anhui Province, Eastern China: Implications for ore genesis

NASA Astrophysics Data System (ADS)

Wang, Shiwei; Zhou, Taofa; Yuan, Feng; Fan, Yu; White, Noel C.; Lin, Fengjie

2015-05-01

Most porphyry deposits in the world occur in magmatic arc settings and are related to subduction of oceanic plates. A small proportion of porphyry deposits occur in intracontinental settings, however they are still poorly understood. Shujiadian, a newly-discovered porphyry Cu deposit, is located in the Middle-Lower Yangtze River Valley metallogenic belt and belongs to the intracontinental class. The deposit has classic alteration zones defined by a core of potassic alteration and local Ca-silicate alteration, which is overprinted by a feldspar-destructive alteration zone and cut by veins containing epidote and chlorite. Wallrocks of the deposit are unreactive quartz-rich sedimentary rocks. Three main paragenetic stages have been recognized based on petrographic observations; silicate stage, quartz-sulfide stage, and sulfide-carbonate stage. Quartz + pyrite + chalcopyrite ± molybdenite veins, and quartz + chalcopyrite + pyrite veins of the quartz-sulfide stage contribute most of the copper, and chalcopyrite + chlorite ± pyrite ± pyrrhotite ± quartz ± illite veins of the sulfide-carbonate stage also contribute part of the copper; all the mineralized veins are associated with feldspar-destructive alteration. Investigations on the fluid inclusions in Shujiadian indicate that the ore-forming fluids had four evolutionary episodes: immiscibility and overpressure in the silicate stage, boiling in the quartz-sulfide stage and mixing with meteoric water in the sulfide-carbonate stage. Sulfur and strontium isotope studies suggest that ore metals were mainly derived from magmatic-hydrothermal fluids, and combined with our study of fluid inclusions, we infer that decompression, changes in oxygen fugacity and sulfur content were the main factors that caused Cu precipitation. Compared with porphyry deposits in magmatic arc settings, there are some differences in the ore-bearing rock, alteration, and the composition of ore-forming fluids.

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.

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

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

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.

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.

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 during supergene oxidation. Isotopic measurements of oxygen in supergene kaolinite from Boyongan suggest that local paleometeoric water involved in weathering had a ??180 composition of approximately -5.7 per mil. At the latitude of the southern Philippines, this value corresponds to Pleistocene rain water condensing at elevations between 750 and 1,050 m above contemporary sea level, providing a maximum estimate for the surface elevation during weathering of the porphyry systems. Physiographic reconstuctions suggest that the deep oxidation profile at Boyongan formed in an environment of high topographic relief immediately east of a prominent (>550 m) escarpment. The high permeability contrast between the breccia complex and the surrounding wall rocks, coupled with the proximity of the breccia complex to the escarpment, led to a depressed groundwater table and a vertically extensive unsaturated zone in the immediate vicinity of Boyongan. This thick vadose zone and the low hypogene pyrite/copper sulfide ratios (0.6) at Boyongan promoted in situ oxidation of copper sulfides with only modest (<200 m) supergene remobilization of copper. In contrast, higher hypogene pyrite/chalcopyrite ratios (2.3) at Bayugo led to greater acid production during weathering and more complete leaching of copper above the base of oxidation. This process promoted significant (600 m) lateral dispersion of copper down the paleohydraulic gradient into the diatreme breccia comple, ultimately leading to the formation of an exotic copper deposit. ?? 2009 Society of Economices Geologists, 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.

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.

Effect of Heat and Laser Treatment on Cu2S Thin Film Sprayed on Polyimide Substrate

NASA Astrophysics Data System (ADS)

Magdy, Wafaa; Mahmoud, Fawzy A.; Nassar, Amira H.

2018-02-01

Three samples of copper sulfide Cu2S thin film were deposited on polyimide substrate by spray pyrolysis using deposition temperature of 400°C and deposition time of about 45 min. One of the samples was left as deposited, another was heat treated, while the third was laser treated. The structural, surface morphological, optical, mechanical, and electrical properties of the films were investigated. X-ray diffraction (XRD) analysis showed that the copper sulfide films were close to copper-rich phase (Cu2S). Increased crystallite size after heat and laser treatment was confirmed by XRD analysis and scanning electron microscopy. Vickers hardness measurements showed that the samples' hardness values were enhanced with increasing crystallite size, representing an inverse Hall-Petch (H-P) effect. The calculated optical bandgap of the treated films was lower than that of the deposited film. Finally, it was found that both heat and laser treatment enhanced the physical properties of the sprayed Cu2S films on polyimide substrate for use in solar energy applications.

Oxidation kinetics of molten copper sulfide

NASA Astrophysics Data System (ADS)

Alyaser, A. H.; Brimacombe, J. K.

1995-02-01

The oxidation kinetics of molten Cu2S baths, during top lancing with oxygen/nitrogen (argon) mixtures, have been investigated as a function of oxygen partial pressure (0.2 to 0.78), bath temperature (1200 °C to 1300 °C), gas flow rate (1 to 4 L/min), and bath mixing. Surface-tension-driven flows (the Marangoni effect) were observed both visually and photographically. Thus, the oxidation of molten Cu2S was found to progress in two distinct stages, the kinetics of which are limited by the mass transfer of oxygen in the gas phase to the melt surface. During the primary stage, the melt is partially desulfurized while oxygen dissolves in the liquid sulfide. Upon saturation of the melt with oxygen, the secondary stage commences in which surface and bath reactions proceed to generate copper and SO2 electrochemically. A mathematical model of the reaction kinetics has been formulated and tested against the measurements. The results of this study shed light on the process kinetics of the copper blow in a Peirce-Smith converter or Mitsubishi reactor.

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.

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.

Kinetic comparison of microbial assemblages for the anaerobic treatment of wastewater with high sulfate and heavy metal contents.

PubMed

Sinbuathong, Nusara; Sirirote, Pramote; Liengcharernsit, Winai; Khaodhiar, Sutha; Watts, Daniel J

2009-01-01

Mixed-microbial assemblages enriched from a septic tank, coastal sediment samples, the digester sludge of a brewery wastewater treatment plant and acidic sulfate soil samples were compared on the basis of growth rate, waste and sulfate reduction rate under sulfate reducing conditions at 30 degrees C. The specific growth rate of various cultures was in the range 0.0013-0.0022 hr(-1). Estimates of waste and sulfate reduction rate were obtained by fitting substrate depletion and sulfate reduction data with the Michaelis-Menten equation. The waste reduction rates were in the range 4x10(-8)-1x10(-7) I mg(-1) hr(-1) and generally increased in the presence of copper, likely by copper sulfide precipitation that reduced sulfide and copper toxicity and thus protected the anaerobic microbes. Anaerobic microorganisms from a brewery digester sludge were found to be the most appropriate culture for the treatment of wastewater with high sulfate and heavy metal content due to their growth rate, and waste and sulfate reduction rate.

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

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.

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.

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

Arsenic leaching and speciation in C&D debris landfills and the relationship with gypsum drywall content.

PubMed

Zhang, Jianye; Kim, Hwidong; Dubey, Brajesh; Townsend, Timothy

2017-01-01

The effects of sulfide levels on arsenic leaching and speciation were investigated using leachate generated from laboratory-scale construction and demolition (C&D) debris landfills, which were simulated lysimeters containing various percentages of gypsum drywall. The drywall percentages in lysimeters were 0, 1, 6, and 12.4wt% (weight percent) respectively. With the exception of a control lysimeter that contained 12.4wt% of drywall, each lysimeter contained chromated copper arsenate (CCA) treated wood, which accounts for 10wt% of the C&D waste. During the period of study, lysimeters were mostly under anaerobic conditions. Leachate analysis results showed that sulfide levels increased as the percentage of drywall increased in landfills, but arsenic concentrations in leachate were not linearly correlated with sulfide levels. Instead, the arsenic concentrations decreased as sulfide increased up to approximately 1000μg/L, but had an increase with further increase in sulfide levels, forming a V-shape on the arsenic vs. sulfide plot. The analysis of arsenic speciation in leachate showed different species distribution as sulfide levels changed; the fraction of arsenite (As(III)) increased as the sulfide level increased, and thioarsenate anions (As(V)) were detected when the sulfide level further increased (>10 4 μg/L). The formation of insoluble arsenic sulfide minerals at a lower range of sulfide and soluble thioarsenic anionic species at a higher range of sulfide likely contributed to the decreasing and increasing trend of arsenic leaching. Copyright © 2016. Published by Elsevier Ltd.

[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.

Mineralogical and geochemical characterization of waste rocks from a gold mine in northeastern Thailand: application for environmental impact protection.

PubMed

Assawincharoenkij, Thitiphan; Hauzenberger, Christoph; Ettinger, Karl; Sutthirat, Chakkaphan

2018-02-01

Waste rocks from gold mining in northeastern Thailand are classified as sandstone, siltstone, gossan, skarn, skarn-sulfide, massive sulfide, diorite, and limestone/marble. Among these rocks, skarn-sulfide and massive sulfide rocks have the potential to generate acid mine drainage (AMD) because they contain significant amounts of sulfide minerals, i.e., pyrrhotite, pyrite, arsenopyrite, and chalcopyrite. Moreover, both sulfide rocks present high contents of As and Cu, which are caused by the occurrence of arsenopyrite and chalcopyrite, respectively. Another main concern is gossan contents, which are composed of goethite, hydrous ferric oxide (HFO), quartz, gypsum, and oxidized pyroxene. X-ray maps using electron probe micro-analysis (EPMA) indicate distribution of some toxic elements in Fe-oxyhydroxide minerals in the gossan waste rock. Arsenic (up to 1.37 wt.%) and copper (up to 0.60 wt.%) are found in goethite, HFO, and along the oxidized rim of pyroxene. Therefore, the gossan rock appears to be a source of As, Cu, and Mn. As a result, massive sulfide, skarn-sulfide, and gossan have the potential to cause environmental impacts, particularly AMD and toxic element contamination. Consequently, the massive sulfide and skarn-sulfide waste rocks should be protected from oxygen and water to avoid an oxidizing environment, whereas the gossan waste rocks should be protected from the formation of AMD to prevent heavy metal contamination.

METHOD OF REMOVING IODINE FROM GASES AND FILTER MEDIUM THEREFOR

DOEpatents

Silverman, L.

1961-08-01

A method for the removal of iodine from large gas volumes is described. The gaseous medium is heated to a temperature not exceeding 400 deg C. Water vapor is then added to the medium in approximate amounts of 1 lb/cu ft of the medium. The medium is then passed through a porous copper fibrous pad having deposited thereon a coating of silver, the silver coating being treated with hydrogen sulfide forming a layer of silver sulfide. (AEC)

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.

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.

Demonstration and Validation of a Regenerated Cellulose Dialysis Membrane Diffusion Sampler for Monitoring Groundwater Quality and Remediation Progress at DoD Sites

DTIC Science & Technology

2007-02-01

years if kept refrigerated in its preservative solution of ethanol, sodium benzoate , and ethylene diamine tetra-acetic acid (EDTA). Alternatively... sodium bicarbonate solution, EDTA, and sodium azide solution to remove residual gylcerol, sulfide, cadmium, chromium, copper, iron, nickel, zinc, and lead...Magnesium Cadmium Nickel Potassium Chromium Selenium Sodium Copper Vanadium Aluminum Iron Zinc Arsenic Lead Antimony Manganese Anions (1-3 days

Corrosion issues in high-level nuclear waste containers

NASA Astrophysics Data System (ADS)

Asl, Samin Sharifi

In this dissertation different aspects of corrosion and electrochemistry of copper, candidate canister material in Scandinavian high-level nuclear waste disposal program, including the thermodynamics and kinetics of the reactions that are predicted to occur in the practical system have been studied. A comprehensive thermodynamic study of copper in contact with granitic groundwater of the type and composition that is expected in the Forsmark repository in Sweden has been performed. Our primary objective was to ascertain whether copper would exist in the thermodynamically immune state in the repository, in which case corrosion could not occur and the issue of corrosion in the assessment of the storage technology would be moot. In spite of the fact that metallic copper has been found to exist for geological times in granitic geological formations, copper is well-known to be activated from the immune state to corrode by specific species that may exist in the environment. The principal activator of copper is known to be sulfur in its various forms, including sulfide (H2S, HS-, S2-), polysulfide (H2Sx, HSx -, Sx 2-), poly sulfur thiosulfate ( SxO3 2-), and polythionates (SxO6 2-). A comprehensive study of this aspect of copper chemistry has never been reported, and yet an understanding of this issue is vital for assessing whether copper is a suitable material for fabricating canisters for the disposal of HLNW. Our study identifies and explores those species that activate copper; these species include sulfur-containing entities as well as other, non-sulfur species that may be present in the repository. The effects of temperature, solution pH, and hydrogen pressure on the kinetics of the hydrogen electrode reaction (HER) on copper in borate buffer solution have been studied by means of steady-state polarization measurements, including electrochemical impedance spectroscopy (EIS). In order to obtain electrokinetic parameters, such as the exchange current density and the cathodic Tafel slope, two stages of optimization have been performed. From the optimization process, the activation energy (Eac) of the HER on copper was obtained as ≈32 kJ mol-1. Moreover, the mechanism of the hydrogen evolution reaction (HER) on copper in mildly alkaline media has been studied by means of EIS over the frequency range of 0.01 Hz ≤ f ≤ 5 kHz. The impedance spectra were modeled using a mechanism based upon the Volmer-Heyrovsky-Tafel steps for hydrogen evolution and by considering the reactions involved in hydrogen atom and hydroxyl group adsorption on the copper surface. A single set of kinetic parameters, including the rate constants and transfer coefficient, have been derived for each pH by optimization of the mechanistic model on the experimental impedance (EIS) data. It is postulated that the HER proceeds through the Volmer-Heyrovsky-Tafel mechanism with the Volmer reaction being the rate-determining step. The kinetics of growth of the passive sulfide film on copper in deaerated aqueous sodium chloride solution as a function of applied potential, sulfide species concentrations and temperature were explored by means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The electronic and compositional properties of the passive layer were investigated with Mott-Schottky analysis and X-ray photoelectron spectroscopy (XPS). It is found that metal vacancies are predominant defects in the barrier layer which is in agreement with the p-type character of the film observed experimentally. A point defect model (PDM) for formation and dissolution of the passive sulfide film on copper is proposed. Finally, the behavior of the system interpreted in terms of reaction mechanisms and kinetic parameters extracted from the experimental impedance data by mathematical optimization using a genetic algorithm approach. The diffusion coefficient of cation vacancies is obtained directly from optimization of the proposed model onto the EIS experimental data and was found to be essentially independent from the applied potential within the passive range. The diffusivity of the predominance defects (cation vacancies) found to increase with increase in solution temperature from approx. 10-13 (cm2 s-1 ) at 25 °C to 10-11 (cm2 S -1) at 75 °C.

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.

Multiple episodes of mineralization revealed by Re-Os molybdenite geochronology in the Lala Fe-Cu deposit, SW China

NASA Astrophysics Data System (ADS)

Zhu, Zhimin; Tan, Hongqi; Liu, Yingdong; Li, Chao

2018-03-01

The Lala Fe-Cu deposit is one of the largest iron oxide-copper-gold (IOCG) deposits in the Kangdian copper belt, southwest China. The paragenetic sequence of the Lala deposit includes six hydrothermal stages: pre-ore pervasive Na alteration (I); magnetite stage with K-feldspar and apatite (II); polymetallic disseminated/massive magnetite-sulfide stage (III); banded magnetite-sulfide stage (IV); sulfide vein stage (V); and late quartz-carbonate vein stage (VI). Fifteen molybdenite separates from stages III to VI were analyzed for Re-Os dating. Our new Re-Os data, together with previous studies, identify four distinct hydrothermal events at the Lala deposit. Molybdenite from the stage III disseminated to massive chalcopyrite-magnetite ores yielded a weighted average Re-Os age of 1306 ± 8 Ma (MSWD = 1.1, n = 6) which represents the timing of main ore formation. Molybdenite from the stage IV-banded magnetite-chalcopyrite ores yielded a weighted average Re-Os age of 1086 ± 8 Ma (MSWD = 2.2, n = 7), i.e., a second ore-forming event. Molybdenite from the stage V sulfide veins yielded a weighted average Re-Os age of 988 ± 8 Ma (MSWD = 1.3, n = 7) which represents the timing of a third hydrothermal event. Molybdenite from the quartz-carbonate veins (stage VI) yielded a weighted average Re-Os age at 835 ± 4 Ma (MSWD = 0.66, n = 10) and documented the timing of a late hydrothermal event. Our results indicate that the Lala deposit formed during multiple, protracted mineralization events over several hundred million years. The first three Mesoproterozoic mineralization events are coeval with intra-continental rifting (breakup of the supercontinent Nuna) and share a temporal link to other IOCG-style deposits within the Kangdian Copper Belt, and the last Neoproterozoic hydrothermal event is coeval with the Sibao orogeny which culminated with the amalgamation of the Yangtze Block with the Cathaysia Block at 860-815 Ma.

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.

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.

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.

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.

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

Resistive coating for current conductors in cryogenic applications

DOEpatents

Hirayama, Chikara; Wagner, George R.

1982-05-18

This invention relates to a resistive or semiconducting coating for use on current conductors in cryogenic applications. This includes copper-clad superconductor wire, copper wire used for stabilizing superconductor magnets, and for hyperconductors. The coating is a film of cuprous sulfide (Cu.sub.2 S) that has been found not to degrade the properties of the conductors. It is very adherent to the respective conductors and satisfies the mechanical, thermal and electrical requirements of coatings for the conductors.

Method of producing .sup.67 Cu

DOEpatents

O'Brien, Jr., Harold A.; Barnes, John W.; Taylor, Wayne A.; Thomas, Kenneth E.; Bentley, Glenn E.

1984-01-01

A method of producing carrier-free .sup.67 Cu by proton spallation combined with subsequent chemical separation and purification is disclosed. A target consisting essentially of pressed zinc oxide is irradiated with a high energy, high current proton beam to produce a variety of spallogenic nuclides, including .sup.67 Cu and other copper isotopes. The irradiated target is dissolved in a concentrated acid solution to which a palladium salt is added. In accordance with the preferred method, the spallogenic copper is twice coprecipitated with palladium, once with metallic zinc as the precipitating agent and once with hydrogen sulfide as the precipitating agent. The palladium/copper precipitate is then dissolved in an acid solution and the copper is separated from the palladium by liquid chromatography on an anion exchange resin.

Method for producing /sup 67/Cu

DOEpatents

O'Brien, H.A. Jr.; Barnes, J.W.; Taylor, W.A.; Thomas, K.E.; Bentley, G.E.

A method of producing carrier-free /sup 67/Cu by proton spallation combined with subsequent chemical separation and purification is disclosed. A target consisting essentially of pressed zinc oxide is irradiated with a high energy, high current proton beam to produce a variety of spallogenic nuclides, including /sup 67/Cu and other copper isotopes. The irradiated target is dissolved in a concentrated acid solution to which a palladium salt is added. In accordance with the preferred method, the spallogenic copper is twice coprecipitated with palladium, once with metallic zinc as the precipitating agent and once with hydrogen sulfide as the precipitating agent. The palladium/copper precipitate is then dissolved in an acid solution and the copper is separated from the palladium by liquid chromatography on an anion exchange resin.

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

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

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 impact of aging wine in high and low oxygen conditions on the fractionation of Cu and Fe in Chardonnay wine.

PubMed

Kontoudakis, Nikolaos; Guo, Anque; Scollary, Geoffrey R; Clark, Andrew C

2017-08-15

Solid-phase extraction has previously been used to fractionate copper and iron into hydrophobic, cationic and residual forms. This study showed the change in fractionated copper and iron in Chardonnay wines with 1-year of bottle aging under variable oxygen and protein concentrations. Wines containing protein in low oxygen conditions induced a decrease (20-50%) in total copper and increased the proportion of the hydrophobic copper fraction, associated with copper(I) sulfide. In contrast, protein stabilised wines showed a lower proportion of the hydrophobic copper fraction after 1-year of aging. In oxidative storage conditions, the total iron decreased by 60% when at high concentration, and the concentration of the residual fraction of both copper and iron increased. The results show that oxidative storage increases the most oxidative catalytic form of the metal, whilst changes during reductive storage depend on the extent of protein stabilisation of the wine. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photovoltaic energy technologies: Health and environmental effects document

NASA Astrophysics Data System (ADS)

Moskowitz, P. D.; Hamilton, L. D.; Morris, S. C.; Rowe, M. D.

1980-09-01

The potential health and environmental consequences of producing electricity by photovoltaic energy systems was analyzed. Potential health and environmental risks are identified in representative fuel and material supply cycles including extraction, processing, refining, fabrication, installation, operation, and isposal for four photovoltaic energy systems (silicon N/P single crystal, silicon metal/insulator/semiconductor (MIS) cell, cadmium sulfide/copper sulfide backwall cell, and gallium arsenide heterojunction cell) delivering equal amounts of useful energy. Each step of the fuel and material supply cycles, materials demands, byproducts, public health, occupational health, and environmental hazards is identified.

Solar Photovoltaic Cells.

ERIC Educational Resources Information Center

Mickey, Charles D.

1981-01-01

Reviews information on solar radiation as an energy source. Discusses these topics: the key photovoltaic material; the bank theory of solids; conductors, semiconductors, and insulators; impurity semiconductors; solid-state photovoltaic cell operation; limitations on solar cell efficiency; silicon solar cells; cadmium sulfide/copper (I) sulfide…

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.

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 removal of heavy metals from contaminated soil by a combination of sulfidisation and flotation.

PubMed

Vanthuyne, Mathias; Maes, André

2002-05-06

The possibility of removing cadmium, copper, lead and zinc from Belgian loamy soil by a combination of sulfidisation pre-treatment and Denver flotation was investigated. The potentially available--sulfide convertible--metal content of the metal polluted soil was estimated by EDTA (0.1 M, pH 4.65) extraction and BCR sequential extraction. EDTA extraction is better at approximating the metal percentage that is expected to be convertible into a metal sulfide phase, in contrast to the sequential extraction procedure of 'Int. J. Environ. Anal. Chem. 51 (1993) pp. 135-151' in which transition metals present as iron oxide co-precipitates are dissolved by hydroxylammoniumchloride in the second extraction step. To compare the surface characteristics of metal sulfides formed by sulfidisation with those of crystalline metal sulfides, two types of synthetic sediments were prepared and extracted with 0.1 M EDTA (pH 4.65) in anoxic conditions. Separate metal sulfides or co-precipitates with iron sulfide were formed by sulfide conditioning. The Denver flotation of both types of synthetic sediments (kerosene as collector at high background electrolyte concentrations) resulted in similar concentrating factors for freshly formed metal sulfides as for fine-grained crystalline metal sulfides. The selective flotation of metal sulfides after sulfide conditioning of a polluted soil, using kerosene or potassium ethyl xanthate as collectors and MIBC as frother, was studied at high background electrolyte concentrations. The sulfidisations were made in ambient air and inside an anoxic glove box. The concentrating factors corrected by the potentially available metal percentage, determined by 0.1 M EDTA extraction, lie between 2 and 3. The selective flotation of these finely dispersed, amorphous, metal sulfides can possibly be improved by optimising the bubble-particle interaction.

Corrosion Behavior of Plasma-Passivated Cu

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

Barbour, J.C.; Braithwaite, J.W.; Son, K.A.

1999-07-09

A new approach is being pursued to study corrosion in Cu alloy systems by using combinatorial analysis combined with microscopic experimentation (the Combinatorial Microlab) to determine mechanisms for copper corrosion in air. Corrosion studies are inherently difficult because of complex interactions between materials and environment, forming a multidimensional phase space of corrosion variables. The Combinatorial Microlab was specifically developed to address the mechanism of Cu sulfidation, which is an important reliability issue for electronic components. This approach differs from convention by focusing on microscopic length scales, the relevant scale for corrosion. During accelerated aging, copper is exposed to a varietymore » of corrosive environments containing sulfidizing species that cause corrosion. A matrix experiment was done to determine independent and synergistic effects of initial Cu oxide thickness and point defect density. The CuO{sub x} was controlled by oxidizing Cu in an electron cyclotron resonance (ECR) O{sub 2} plasma, and the point defect density was modified by Cu ion irradiation. The matrix was exposed to 600 ppb H{sub 2}S in 65% relative humidity air atmosphere. This combination revealed the importance of oxide quality in passivating Cu and prevention of the sulfidizing reaction. A native oxide and a defect-laden ECR oxide both react at 20 C to form a thick Cu{sub 2}S layer after exposure to H{sub 2}S, while different thicknesses of as-grown ECR oxide stop the formation of Cu{sub 2}S. The species present in the ECR oxide will be compared to that of an air oxide, and the sulfide layer growth rate will be presented.« less

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.

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.

The bioleaching potential of a bacterial consortium.

PubMed

Latorre, Mauricio; Cortés, María Paz; Travisany, Dante; Di Genova, Alex; Budinich, Marko; Reyes-Jara, Angélica; Hödar, Christian; González, Mauricio; Parada, Pilar; Bobadilla-Fazzini, Roberto A; Cambiazo, Verónica; Maass, Alejandro

2016-10-01

This work presents the molecular foundation of a consortium of five efficient bacteria strains isolated from copper mines currently used in state of the art industrial-scale biotechnology. The strains Acidithiobacillus thiooxidans Licanantay, Acidiphilium multivorum Yenapatur, Leptospirillum ferriphilum Pañiwe, Acidithiobacillus ferrooxidans Wenelen and Sulfobacillus thermosulfidooxidans Cutipay were selected for genome sequencing based on metal tolerance, oxidation activity and bioleaching of copper efficiency. An integrated model of metabolic pathways representing the bioleaching capability of this consortium was generated. Results revealed that greater efficiency in copper recovery may be explained by the higher functional potential of L. ferriphilum Pañiwe and At. thiooxidans Licanantay to oxidize iron and reduced inorganic sulfur compounds. The consortium had a greater capacity to resist copper, arsenic and chloride ion compared to previously described biomining strains. Specialization and particular components in these bacteria provided the consortium a greater ability to bioleach copper sulfide ores. Copyright © 2016 Elsevier Ltd. All rights reserved.

Report on accelerated corrosion studies.

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

Mowry, Curtis Dale; Glass, Sarah Jill; Sorensen, Neil Robert

2011-03-01

Sandia National Laboratories (SNL) conducted accelerated atmospheric corrosion testing for the U.S. Consumer Product Safety Commission (CPSC) to help further the understanding of the development of corrosion products on conductor materials in household electrical components exposed to environmental conditions representative of homes constructed with problem drywall. The conditions of the accelerated testing were chosen to produce corrosion product growth that would be consistent with long-term exposure to environments containing humidity and parts per billion (ppb) levels of hydrogen sulfide (H{sub 2}S) that are thought to have been the source of corrosion in electrical components from affected homes. This report documentsmore » the test set-up, monitoring of electrical performance of powered electrical components during the exposure, and the materials characterization conducted on wires, screws, and contact plates from selected electrical components. No degradation in electrical performance (measured via voltage drop) was measured during the course of the 8-week exposure, which was approximately equivalent to 40 years of exposure in a light industrial environment. Analyses show that corrosion products consisting of various phases of copper sulfide, copper sulfate, and copper oxide are found on exposed surfaces of the conductor materials including wires, screws, and contact plates. The morphology and the thickness of the corrosion products showed a range of character. In some of the copper wires that were observed, corrosion product had flaked or spalled off the surface, exposing fresh metal to the reaction with the contaminant gasses; however, there was no significant change in the wire cross-sectional area.« less

Biomining: metal recovery from ores with microorganisms.

PubMed

Schippers, Axel; Hedrich, Sabrina; Vasters, Jürgen; Drobe, Malte; Sand, Wolfgang; Willscher, Sabine

2014-01-01

Biomining is an increasingly applied biotechnological procedure for processing of ores in the mining industry (biohydrometallurgy). Nowadays the production of copper from low-grade ores is the most important industrial application and a significant part of world copper production already originates from heap or dump/stockpile bioleaching. Conceptual differences exist between the industrial processes of bioleaching and biooxidation. Bioleaching is a conversion of an insoluble valuable metal into a soluble form by means of microorganisms. In biooxidation, on the other hand, gold is predominantly unlocked from refractory ores in large-scale stirred-tank biooxidation arrangements for further processing steps. In addition to copper and gold production, biomining is also used to produce cobalt, nickel, zinc, and uranium. Up to now, biomining has merely been used as a procedure in the processing of sulfide ores and uranium ore, but laboratory and pilot procedures already exist for the processing of silicate and oxide ores (e.g., laterites), for leaching of processing residues or mine waste dumps (mine tailings), as well as for the extraction of metals from industrial residues and waste (recycling). This chapter estimates the world production of copper, gold, and other metals by means of biomining and chemical leaching (bio-/hydrometallurgy) compared with metal production by pyrometallurgical procedures, and describes new developments in biomining. In addition, an overview is given about metal sulfide oxidizing microorganisms, fundamentals of biomining including bioleaching mechanisms and interface processes, as well as anaerobic bioleaching and bioleaching with heterotrophic microorganisms.

Fabrication of an Inexpensive Ion-Selective Electrode.

ERIC Educational Resources Information Center

Palanivel, A.; Riyazuddin, P.

1984-01-01

The preparation and performance of a graphite (silver/copper sulfide) electrode is described. This rod, extracted from a used dry cell, is an acceptable substitute for ion-selective electrodes after it has been cleaned by abrasion followed by an overnight treatment with hydrochloric acid. (JN)

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.

Molybdenum toxicity and hypocuprosis in ruminants: a review

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

Ward, G.M.

1978-01-01

Elevated Mo intakes depress Cu availability and may produce a physiological Cu deficiency in ruminants. Total sulfur or sulfate in the ration generally potentiates the effect of Mo. The ratio of Cu to Mo in feed is important regardless of the absolute amount of each. For this reason, and because of the importance of the S content of the diet, it is impossible to define safe dietary limits for Cu and Mo. Physiological Cu deficiencies are produced by four classes of feeds: (1) high Mo, generally above 100 ppM, (2) low Cu:Mo ratio, 2:1 or less, (3) Cu deficiency, belowmore » 5 ppM, and (4) high protein, 20 to 30% protein in fresh forage. The latter situation probably results from higher levels of sulfide produced from sulfur amino acids during rumen fermentation. Copper sulfide is largely unabsorbed. Future instances of hypocuprosis in the US are most likely to occur from marginal copper deficiencies in forages.« less

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.

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.

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

High-temperature sorbent method for removal of sulfur-containing gases from gaseous mixtures

DOEpatents

Young, J.E.; Jalan, V.M.

1982-07-07

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorbtion capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

High-temperature sorbent method for removal of sulfur containing gases from gaseous mixtures

DOEpatents

Young, J.E.; Jalan, V.M.

1984-06-19

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorption capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

High-temperature sorbent method for removal of sulfur containing gases from gaseous mixtures

DOEpatents

Young, John E.; Jalan, Vinod M.

1984-01-01

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorption capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

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 and shares similarities with the syn-orogenic copper deposits of the Congo-Zambian Copperbelt formed during the Gondwana amalgamation.

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.

Small-scale and large-scale testing of photo-electrochemically activated leaching technology in Aprelkovo and Delmachik Mines

NASA Astrophysics Data System (ADS)

Sekisov, AG; Lavrov, AYu; Rubtsov, YuI

2017-02-01

The paper gives a description of tests and trials of the technology of heap gold leaching from rebellious ore in Aprelkovo and Delmachik Mines. Efficiency of leaching flowsheets with the stage-wise use of activated solutions of different reagents, including active forms of oxygen, is evaluated. Carbonate-peroxide solutions are used at the first stage of leaching to oxidize sulfide and sulfide-arsenide ore minerals to recover iron and copper from them. The second stage leaching uses active cyanide solutions to leach encapsulated and disperse gold and silver.

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.

RESPIROMETRY AS A TOOL TO DETERMINE METAL TOXICITY IN A SULFATE REDUCING BACTERIAL CULTURE

EPA Science Inventory

A novel method under development for treatment of acid mine drainage waste uses biologically- generated hydrogen sulfide (H2S) to precipitate the metals in acid mine drainage (principally zinc, copper, aluminum, nickel, cadmium, arsenic, manganese, iron, and cobalt). The insolub...

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 high Hg content (up to 11 mass %). The Cu-Au deposits in the Flatschach area show similarities with meso- to epizonal orogenic lode gold deposits regarding the geological setting, the structural control of mineralization, the type of alteration, the early (stage 1) sulfide assemblage and composition of gold. Unique about the Flatschach district is the lower-temperature overprint of copper arsenides (domeykite and koutekite) and copper sulfides (djurleite, yarrowite/spionkopite) on earlier formed sulfide mineralization. Based on mineralogical considerations temperature of stage 2 mineralization was between about 70 °C and 160 °C. Gold was locally mobilized during this low-temperature hydrothermal overprint as well as during stage 3 supergene oxidation and cementation processes.

KALMIOPSIS WILDERNESS, OREGON.

USGS Publications Warehouse

Page, Norman J; Miller, Michael S.

1984-01-01

Geologic, geochemical, geophysical field and laboratory, and mine and prospect studies conducted in the Kalmiopsis Wilderness, Oregon indicate that areas within and immediately adjacent to the wilderness have substantiated mineral-resource potential. The types of mineral resources which occur in these areas include massive sulfide deposits containing copper, zinc, lead, silver and gold; podiform chromite deposits; laterite deposits containing nickel, cobalt, and chromium; lode gold deposits; and placer gold deposits. Past production from existing mines is estimated to have been at least 7000 troy oz of gold, 4000 long tons of chromite, and few tens of tons of copper ore.

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

Biomineralization of metal-containing ores and concentrates.

PubMed

Rawlings, Douglas E; Dew, David; du Plessis, Chris

2003-01-01

Biomining is the use of microorganisms to extract metals from sulfide and/or iron-containing ores and mineral concentrates. The iron and sulfide is microbially oxidized to produce ferric iron and sulfuric acid, and these chemicals convert the insoluble sulfides of metals such as copper, nickel and zinc to soluble metal sulfates that can be readily recovered from solution. Although gold is inert to microbial action, microbes can be used to recover gold from certain types of minerals because as they oxidize the ore, they open its structure, thereby allowing gold-solubilizing chemicals such as cyanide to penetrate the mineral. Here, we review a strongly growing microbially-based metal extraction industry, which uses either rapid stirred-tank or slower irrigation technology to recover metals from an increasing range of minerals using a diversity of microbes that grow at a variety of temperatures.

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.

A highly active and magnetically retrievable nanoferrite-DOPA-copper catalyst for the coupling of thiophenols with aryl halides

EPA Science Inventory

Diaryl sulfides were synthesized using magnetically recoverable heterogeneous Cu catalyst via one-pot multi component reaction using MW irradiation; the use of isopropanol as a benign reaction medium, easy recovery of the catalyst using an external magnet, efficient recycling...

Post-depositional behavior of Cu in a metal-mining polishing pond (East Lake, Canada).

PubMed

Martin, Alan J; Jambor, John L; Pedersen, Tom F; Crusius, John

2003-11-01

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactorthat permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 microg L(-1) and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 microg cm(-2) yr(-1)) can account for the elevated levels of dissolved Cu in lake waters (approximately 50 microg L(-1)). Implications for lake recovery are discussed.

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.

Post-Depositional Behavior of Cu in a Metal-Mining Polishing Pond (East Lake, Canada)

USGS Publications Warehouse

Martin, A.J.; Jambor, J.L.; Pedersen, Thomas F.; Crusius, John

2003-01-01

The post-depositional behavior of Cu in a gold-mining polishing pond (East Lake, Canada) was assessed after mine closure by examination of porewater chemistry and mineralogy. The near-surface (upper 1.5 cm) sediments are enriched in Cu, with values ranging from 0.4 to 2 wt %. Mineralogical examination revealed that the bulk of the Cu inventory is present as authigenic copper sulfides. Optical microscopy, energy-dispersion spectra, and X-ray data indicate that the main Cu sulfide is covellite (CuS). The formation of authigenic Cu-S phases is supported by the porewater data, which demonstrate that the sediments are serving as a sink for dissolved Cu below sub-bottom depths of 1-2 cm. The zone of Cu removal is consistent with the occurrence of detectable sulfide and the consumption of sulfate. The sediments can be viewed as a passive bioreactor that permanently removes Cu as insoluble copper sulfides. This process is not unlike that which occurs in other forms of bioremediation, such as wetlands and permeable reactive barriers. Above the zone of Cu removal, dissolved Cu maxima in the interfacial porewaters range from 150 to 450 ??g L-1 and reflect the dissolution of a Cu-bearing phase in the surface sediments. The reactive phase is thought to be a component of treatment sludges delivered to the lake as part of cyanide treatment. Flux calculations indicate that the efflux of dissolved Cu from the sediments to the water column (14-51 ??g cm-2 yr-1) can account for the elevated levels of dissolved Cu in lake waters (???50 ??g L-1). Implications for lake recovery are discussed.

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.

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.

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.

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.

Tunable intraparticle frameworks for creating complex heterostructured nanoparticle libraries

NASA Astrophysics Data System (ADS)

Fenton, Julie L.; Steimle, Benjamin C.; Schaak, Raymond E.

2018-05-01

Complex heterostructured nanoparticles with precisely defined materials and interfaces are important for many applications. However, rationally incorporating such features into nanoparticles with rigorous morphology control remains a synthetic bottleneck. We define a modular divergent synthesis strategy that progressively transforms simple nanoparticle synthons into increasingly sophisticated products. We introduce a series of tunable interfaces into zero-, one-, and two-dimensional copper sulfide nanoparticles using cation exchange reactions. Subsequent manipulation of these intraparticle frameworks yielded a library of 47 distinct heterostructured metal sulfide derivatives, including particles that contain asymmetric, patchy, porous, and sculpted nanoarchitectures. This generalizable mix-and-match strategy provides predictable retrosynthetic pathways to complex nanoparticle features that are otherwise inaccessible.

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.

Gold in minerals and the composition of native gold

USGS Publications Warehouse

Jones, Robert Sprague; Fleischer, Michael

1969-01-01

Gold occurs in nature mainly as the metal and as various alloys. It forms complete series of solid solutions with silver, copper, nickel, palladium, and platinum. In association with the platinum metals, gold occurs as free gold as well as in solid solution. The native elements contain the most gold, followed by the sulfide minerals. Several gold tellurides are known, but no gold selenides have been reported, and only one sulfide, the telluride-sulfide mineral nagyagite, is known. The nonmetallic minerals carry the least gold, and the light-colored minerals generally contain less gold than the dark minerals. Some conclusions in the literature are conflicting in regard to the relation of fineness of native gold to its position laterally and vertically within a lode, the nature of the country rocks, and the location and size of nuggets in a streambed, as well as to the variation of fineness within an individual nugget.

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

Biomining-biotechnologies for extracting and recovering metals from ores and waste materials.

PubMed

Johnson, D Barrie

2014-12-01

The abilities of acidophilic chemolithotrophic bacteria and archaea to accelerate the oxidative dissolution of sulfide minerals have been harnessed in the development and application of a biotechnology for extracting metals from sulfidic ores and concentrates. Biomining is currently used primarily to leach copper sulfides and as an oxidative pretreatment for refractory gold ores, though it is also used to recover other base metals, such as cobalt, nickel and zinc. Recent developments have included using acidophiles to process electronic wastes, to extract metals from oxidized ores, and to selectively recover metals from process waters and waste streams. This review describes the microorganisms and mechanisms involved in commercial biomining operations, how the technology has developed over the past 50 years, and discusses the challenges and opportunities for mineral biotechnologies in the 21st century. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

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.

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

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

Base and precious metal occurrences along the San Andreas Fault, Point Delgada, California

USGS Publications Warehouse

McLaughlin, Robert J.; Sorg, D.H.; Ohlin, H.N.; Heropoulos, Chris

1979-01-01

Previously unrecognized veins containing lead, zinc, and copper sulfide minerals at Point Delgada, Calif., are associated with late Mesozoic(?) and Tertiary volcanic and sedimentary rocks of the Franciscan assemblage. Sulfide minerals include pyrite, sphalerite, galena, and minor chalcopyrite, and galena-rich samples contain substantial amounts of silver. These minerals occur in a quartz-carbonate gangue along northeast-trending faults and fractures that exhibit (left?) lateral and vertical slip. The sense of fault movement and the northeasterly strike are consistent with predicted conjugate fault sets of the present San Andreas fault system. The sulfide mineralization is younger than the Franciscan rocks of Point Delgada and King Range, and it may have accompanied or postdated the inception of San Andreas faulting. Mineralization largely preceded uplift, the formation of a marine terrace, and the emplacement of landslide-related debris-flow breccias that overlie the mineralized rocks and truncate the sulfide veins. These field relations indicate that the sulfide mineralization and inception of San Andreas faulting were clearly more recent than the early Miocene and that the mineralization could be younger than about 1.2 m.y. The sulfide veins at Point Delgada may be of economic significance. However, prior to any exploitation of the occurrence, economic and environmental conflicts of interest involving private land ownership, the Shelter Cove home development, and proximity of the coast must be resolved.

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.

Sorbent for use in hot gas desulfurization

DOEpatents

Gasper-Galvin, Lee D.; Atimtay, Aysel T.

1993-01-01

A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.

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 Carboniferous fore-arc setting in the Beishan orogenic belt.

Characterisation of [Cu4S], the catalytic site in nitrous oxide reductase, by EPR spectroscopy.

PubMed

Oganesyan, Vasily S; Rasmussen, Tim; Fairhurst, Shirley; Thomson, Andrew J

2004-04-07

The enzyme nitrous oxide reductase (N(2)OR) has a unique tetranuclear copper centre [Cu(4)S], called Cu(Z), at the catalytic site for the two-electron reduction of N(2)O to N(2). The X- and Q-band EPR spectra have been recorded from two forms of the catalytic site of the enzyme N(2)OR from Paracoccus pantotrophus, namely, a form prepared anaerobically, Cu(Z), that undergoes a one-electron redox cycle and Cu(Z)*, prepared aerobically, which cannot be redox cycled. The spectra of both species are axial with that of Cu(Z) showing a rich hyperfine splitting in the g||-region at X-band. DFT calculations were performed to gain insight into the electronic configuration and ground-state properties of Cu(Z) and to calculate EPR parameters. The results for the oxidation state [Cu(+1)(3)Cu(+2)(1)S](3+) are in good agreement with values obtained from the fitting of experimental spectra, confirming the absolute oxidation state of Cu(Z). The unpaired spin density in this configuration is delocalised over four copper ions, thus, Cu(I) 20.1%, Cu(II) 9.5%, Cu(III) 4.8% and Cu(IV) 9.2%, the mu(4)-sulfide ion and oxygen ligand. The three copper ions carrying the highest spin density plus the sulfide ion lie approximately in the same plane while the fourth copper ion is perpendicular to this plane and carries only 4.8% spin density. It is suggested that the atoms in this plane represent the catalytic core of Cu(Z), allowing electron redistribution within the plane during interaction with the substrate, N(2)O.

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.

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.

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.

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 shale near the Zhaman-Aibat deposit indicate that at least some of the mineralization there is younger than at Dzhezkazgan, consistent with the Re-Os age and with differences in their ore Pb isotopes.

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

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.

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.

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 samples from the massive sulfide deposits in the Moira Sound unit plot on a different trend (206Pb/204Pb=17.375–19.418, 207Pb/204Pb=15.361–15.519, 208Pb/204Pb=36.856–37.241) from the steep slope defined by the massive sulfide deposits in the Wales Group. In comparison, the Pb-isotopic ratios of Devonian polymetallic (Pb-Zn-Au-Ag) quartz-sulfide veins vary widely ( 206Pb/204Pb=18.339–18.946, 207Pb/204Pb=15.447–15.561, 208Pb/204Pb=37.358–38.354), straddling the slope defined by the massive sulfide deposits in the Moira Sound unit. The general decrease in 207Pb/204Pb ratio in these deposits, relative to the average crustal Pb-evolution curve, suggests that the most likely lead sources were those associated with oceanic volcanic rocks. The massive sulfide deposits in the Wales Group may have resided within an intraoceanic tectonic setting where the mantle was the predominant contributor of metals. Some contribution from reworked arc material or recycled older, hydrothermally altered oceanic crust (including pelagic sediment) is also possible. Lead sources of the massive sulfide deposits in the Moira Sound unit also included an older source region, possibly a Late Proterozoic or Cambrian volcanosedimentary sequence and the massive sulfide deposits in the Wales Group. Preliminary regional comparison of the Pb-isotopic data indicates that the Greens Creek (Admiralty Island, Alaska) and Windy Craggy (northern British Columbia) deposits probably did not share a common lead source with the VMS deposits on Prince of Wales Island. Other sulfide occurrences on Admiralty Island are also more radiogenic than those on Prince of Wales Island. Large differences in 207Pb/204Pb ratio suggest that the lead in the VMS deposits in different parts of the Alexander terrane evolved from sources with heterogeneous U/Pb ratios, resulting from mixing of mantle and crustal components. 

Origins of life systems chemistry

NASA Astrophysics Data System (ADS)

Sutherland, J.

2015-10-01

By reconciling previously conflicting views about the origin of life - in which one or other cellular subsystem emerges first, and then 'invents' the others - a new modus operandi for its study is suggested. Guided by this, a cyanosulfidic protometabolism is uncovered which uses UV light and the stoichiometric reducing power of hydrogen sulfide to convert hydrogen cyanide, and a couple of other prebiotic feedstock molecules which can be derived therefrom, into nucleic acid, peptide and lipid building blocks. Copper plays several key roles in this chemistry, thus, for example, copper(I) catalysed cross coupling and copper(II) driven oxidative crosscoupling reactions generate key feedstock molecules. Geochemical scenarios consistent with this protometabolism are outlined. Finally, the transition of a system from the inanimate to the animate state is considered in the context of there being intermediate stages of partial 'aliveness'.

The mineral resource potential of the Harrat Nawasif, sheet 21/42 C, Ranyah, sheet 21/42 D, and Jabal Dalfa, sheet 21/43 C quadrangles, Kingdom of Saudi Arabia

USGS Publications Warehouse

Fenton, Michael D.

1983-01-01

Areas with mineral resource potential in the Harrat Nawasif, Ranyah, and Jabal Dalfa quadrangles in the central Precambrian Shield of Saudi Arabia have been identified by reconnaissance rock geochemistry and inspection of ancient prospects. Locally anomalous areas in perthitic, alkalic granite terrane in the Ranyah quadrangle possibly contain niobium, zirconium, thorium, fluorite, rare-earth, tin, molybdenum, or copper mineralization. The reconnaissance rock geochemical survey in layered volcanic and volcaniclastic terrane in the Jabal Dalfa quadrangle identified a zinc anomaly in quartzite and a nickel-copper zone that is an extension of the Jabal Judayr prospect, where a low-grade, nickel-copper sulfide deposit is known. The Precambrian terrane in the Harrat Nawasif quadrangle has no known mineral resource potential.

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.

Trace-metal sources and their release from mine wastes: examples from humidity cell tests of hardrock mine waste and from Warrior Basin coal

USGS Publications Warehouse

Diehl, S.F.; Smith, Kathleen S.; Desborough, G.A.; White, W.W.; Lapakko, K.A.; Goldhaber, Martin B.; Fey, David L.

2003-01-01

To assess the potential impact of metal and acid contamination from mine-waste piles, it is important to identify the mineralogic source of trace metals and their mode of occurrence. Microscopic analysis of mine-waste samples from both hard-rock and coalmine waste samples demonstrate a microstructural control, as well as mineralogic control, on the source and release of trace metals into local water systems. The samples discussed herein show multiple periods of sulfide mineralization with varying concentrations of trace metals. In the first case study, two proprietary hard-rock mine-waste samples exposed to a series of humidity cell tests (which simulate intense chemical weathering conditions) generated acid and released trace metals. Some trace elements of interest were: arsenic (45-120 ppm), copper (60-320 ppm), and zinc (30-2,500 ppm). Untested and humidity cell-exposed samples were studied by X-ray diffraction, scanning electron microscope with energy dispersive X-ray (SEM/EDX), and electron microprobe analysis. Studies of one sample set revealed arsenic-bearing pyrite in early iron- and magnesium-rich carbonate-filled microveins, and iron-, copper-, arsenic-, antimony-bearing sulfides in later crosscutting silica-filled microveins. Post humidity cell tests indicated that the carbonate minerals were removed by leaching in the humidity cells, exposing pyrite to oxidative conditions. However, sulfides in the silica-filled veins were more protected. Therefore, the trace metals contained in the sulfides within the silica-filled microveins may be released to the surface and (or) ground water system more slowly over a greater time period. In the second case study, trace metal-rich pyrite-bearing coals from the Warrior Basin, Alabama were analyzed. Arsenic-bearing pyrite was observed in a late-stage pyrite phase in microfaults and microveins that crosscut earlier arsenic.

Velocity of action of oxygen, hydrogen sulfide, and halogens on metals

NASA Technical Reports Server (NTRS)

Tammann, Gustav; Koster, Werner

1952-01-01

This report discusses a method of determining the rate of surface oxidation of a metal by the change in the color of the surface film produced by reactions with oxygen, chlorine, or iodine. The metals studied included iron, nickel, copper, zinc, cadmium, tin, lead, cobalt, and manganese. Tables are given for surface film thickness versus color for various times.

METHOD OF REMOVING RADIOACTIVE IODINE FROM GASES

DOEpatents

Silverman, L.

1962-01-23

A method of removing radioactive iodine from a gaseous medium is given in which the gaseous medium is adjusted to a temperature not exceeding 400 deg C and then passed over a copper fibrous pad having a coating of cupric sulfide deposited thereon. An ionic exchange on the pad results in the formation of cupric iodide and the release of sulfur. (AEC)

N4H9Cu7S4: a hydrazinium-based salt with a layered Cu7S4- framework.

PubMed

Mitzi, David B

2007-02-05

Crystals of a hydrazinium-based copper(I) sulfide salt, N4H9Cu7S4 (1), have been isolated by an ambient temperature solution-based process. In contrast to previously reported hydrazinium salts of main-group metal chalcogenides, which consist of isolated metal chalcogenide anions, and ACu7S4 (A = NH4+, Rb+, Tl+, K+), which contains a more three-dimensional Cu7S4- framework with partial Cu-site occupancy, the structure of 1 [P21, a = 6.8621(4) A, b = 7.9851(4) A, c = 10.0983(5) A, beta = 99.360(1) degrees , Z = 2] is composed of extended two-dimensional Cu7S4- slabs with full Cu-site occupancy. The Cu7S4- slabs are separated by a mixture of hydrazinium and hydrazine moieties. Thermal decomposition of 1 into copper(I) sulfide proceeds at a significantly lower temperature than that observed for analogous hydrazinium salts of previously considered metal chalcogenides, completing the transition at temperatures as low as 120 degrees C. Solutions of 1 may be used in the solution deposition of a range of Cu-containing chalcogenide films.

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.

Geochemical characterization of slags, other mines wastes, and their leachates from the Elizabeth and Ely mines (Vermont), the Ducktown mining district (Tennessee), and the Clayton smelter site (Idaho)

USGS Publications Warehouse

Piatak, Nadine M.; Seal, Robert R.; Hammarstrom, Jane M.; Meier, Allen L.; Briggs, Paul H.

2003-01-01

Waste-rock material produced at historic metal mines contains elevated concentrations of potentially toxic trace elements. Two types of mine waste were examined in this study: sintered waste rock and slag. The samples were collected from the Elizabeth and Ely mines in the Vermont copper belt (Besshi-type massive sulfide deposits), from the Copper Basin mining district near Ducktown, Tennessee (Besshi-type massive sulfide deposits), and from the Clayton silver mine in the Bayhorse mining district, Idaho (polymetallic vein and replacement deposits). The data in this report are presented as a compilation with minimal interpretation or discussion. A detailed discussion and interpretation of the slag data are presented in a companion paper. Data collected from sintered waste rock and slag include: (1) bulk rock chemistry, (2) mineralogy, (3) and the distribution of trace elements among phases for the slag samples. In addition, the reactivity of the waste material under surficial conditions was assessed by examining secondary minerals formed on slag and by laboratory leaching tests using deionized water and a synthetic solution approximating precipitation in the eastern United States.

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.

Raman spectroscopy of efflorescent sulfate salts from Iron Mountain Mine Superfund Site, California.

PubMed

Sobron, Pablo; Alpers, Charles N

2013-03-01

The Iron Mountain Mine Superfund Site near Redding, California, is a massive sulfide ore deposit that was mined for iron, silver, gold, copper, zinc, and pyrite intermittently for nearly 100 years. As a result, both water and air reached the sulfide deposits deep within the mountain, producing acid mine drainage consisting of sulfuric acid and heavy metals from the ore. Particularly, the drainage water from the Richmond Mine at Iron Mountain is among the most acidic waters naturally found on Earth. The mineralogy at Iron Mountain can serve as a proxy for understanding sulfate formation on Mars. Selected sulfate efflorescent salts from Iron Mountain, formed from extremely acidic waters via drainage from sulfide mining, have been characterized by means of Raman spectroscopy. Gypsum, ferricopiapite, copiapite, melanterite, coquimbite, and voltaite are found within the samples. This work has implications for Mars mineralogical and geochemical investigations as well as for terrestrial environmental investigations related to acid mine drainage contamination.

Raman spectroscopy of efflorescent sulfate salts from Iron Mountain Mine Superfund Site, California

USGS Publications Warehouse

Sobron, Pablo; Alpers, Charles N.

2013-01-01

The Iron Mountain Mine Superfund Site near Redding, California, is a massive sulfide ore deposit that was mined for iron, silver, gold, copper, zinc, and pyrite intermittently for nearly 100 years. As a result, both water and air reached the sulfide deposits deep within the mountain, producing acid mine drainage consisting of sulfuric acid and heavy metals from the ore. Particularly, the drainage water from the Richmond Mine at Iron Mountain is among the most acidic waters naturally found on Earth. The mineralogy at Iron Mountain can serve as a proxy for understanding sulfate formation on Mars. Selected sulfate efflorescent salts from Iron Mountain, formed from extremely acidic waters via drainage from sulfide mining, have been characterized by means of Raman spectroscopy. Gypsum, ferricopiapite, copiapite, melanterite, coquimbite, and voltaite are found within the samples. This work has implications for Mars mineralogical and geochemical investigations as well as for terrestrial environmental investigations related to acid mine drainage contamination.

The CsoR-like sulfurtransferase repressor (CstR) is a persulfide sensor in Staphylococcus aureus.

PubMed

Luebke, Justin L; Shen, Jiangchuan; Bruce, Kevin E; Kehl-Fie, Thomas E; Peng, Hui; Skaar, Eric P; Giedroc, David P

2014-12-01

How cells regulate the bioavailability of utilizable sulfur while mitigating the effects of hydrogen sulfide toxicity is poorly understood. CstR [Copper-sensing operon repressor (CsoR)-like sulfurtransferase repressor] represses the expression of the cst operon encoding a putative sulfide oxidation system in Staphylococcus aureus. Here, we show that the cst operon is strongly and transiently induced by cellular sulfide stress in an acute phase and specific response and that cst-encoded genes are necessary to mitigate the effects of sulfide toxicity. Growth defects are most pronounced when S. aureus is cultured in chemically defined media with thiosulfate (TS) as a sole sulfur source, but are also apparent when cystine is used or in rich media. Under TS growth conditions, cells fail to grow as a result of either unregulated expression of the cst operon in a ΔcstR strain or transformation with a non-inducible C31A/C60A CstR that blocks cst induction. This suggests that the cst operon contributes to cellular sulfide homeostasis. Tandem high-resolution mass spectrometry reveals derivatization of CstR by both inorganic tetrasulfide and an organic persulfide, glutathione persulfide, to yield a mixture of Cys31-Cys60' interprotomer cross-links, including di-, tri- and tetrasulfide bonds, which allosterically inhibit cst operator DNA binding by CstR. © 2014 John Wiley & Sons Ltd.

The CsoR-like sulfurtransferase repressor (CstR) is a persulfide sensor in Staphylococcus aureus

PubMed Central

Luebke, Justin L.; Shen, Jiangchuan; Bruce, Kevin E.; Kehl-Fie, Thomas E.; Peng, Hui; Skaar, Eric P.; Giedroc, David P.

2014-01-01

How cells regulate the bioavailability of utilizable sulfur while mitigating the effects of hydrogen sulfide toxicity is poorly understood. CstR (Copper-sensing operon repressor (CsoR)-like sulfurtransferase repressor) represses the expression of the cst operon encoding a putative sulfide oxidation system in Staphylococcus aureus. Here, we show that the cst operon is strongly and transiently induced by cellular sulfide stress in an acute phase and specific response and that cst-encoded genes are necessary to mitigate the effects of sulfide toxicity. Growth defects are most pronounced when S. aureus is cultured in chemically defined media with thiosulfate (TS) as a sole sulfur source, but are also apparent when cystine is used or in rich media. Under TS growth conditions, cells fail to grow as a result of either unregulated expression of the cst operon in a ΔcstR strain or transformation with a non-inducible C31A/C60A CstR that blocks cst induction. This suggests that the cst operon contributes to cellular sulfide homeostasis. Tandem high resolution mass spectrometry reveals derivatization of CstR by both inorganic tetrasulfide and an organic persulfide, glutathione persulfide, to yield a mixture of Cys31-Cys60’ interprotomer crosslinks, including di-, tri- and tetrasulfide bonds, which allosterically inhibit cst operator DNA binding by CstR. PMID:25318663

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 potentially acid generating because of paste-pH values of less than 4 and negative net-neutralization potentials (NNP). The processed flotation-mill tailings, however, had a near neutral paste pH, positive NNP, and a few weight percent calcite. Leachate tests indicated that elements and compounds such as Al, Cd, Cu, Fe, Mn, Se, SO4, and Zn were leached from mine waste in concentrations that exceeded aquatic ecosystem and drinking-water standards. Mine waste from the Pike Hill mines was chemically and mineralogically similar to that from the Elizabeth and Ely mines. In addition, metals were leached and acid was produced from mine waste from the Pike Hill mines in comparable concentrations to those from the Elizabeth and Ely mines, although the host rock of the Pike Hill deposits contains significant amounts of carbonate minerals and, thus, a greater acid-neutralizing capacity when compared to the host rocks of the Elizabeth and Ely deposits. Water samples collected from unimpacted parts of the Waits River watershed generally contained lower amounts of metals compared to water samples from mine drainage, were alkaline, and had a neutral pH, which was likely because of calcareous bedrock. Seeps and mine pools at the mine site had acidic to neutral pH, ranged from oxic to anoxic, and generally contained concentrations of metals, for example, aluminum, cadmium, copper, iron, and zinc, that exceeded aquatic toxicity standards or drinking-water standards, or both. Surface waters directly downstream of the Eureka and Union mines were acidic, as indicated by pH values from 3.1 to 4.2, and contained high concentrations of some elements including as much as 11,400 micrograms per liter (?g/L) Al, as much as 22.9 ?g/L Cd, as much as 6,790 ?g/L Cu, as much as 23,300 ?g/L Fe, as much as 1,400 ?g/L Mn, and as much as 3,570 ?g/L Zn. The concentrations of these elements exceeded water-quality guidelines. Generally, in surface waters, the pH increased and the concentrations of these elemen

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.

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Dilbert, C.A.

1984-01-01

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil. Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones. Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones. ?? 1984.

Geology and regional setting of the Al Masane ancient mine area, southeastern Arabian Shield, Kingdom of Saudi Arabia

USGS Publications Warehouse

Conway, Clay M.

1985-01-01

Chemical characteristics of volcanic rocks at Al Masane and elsewhere, along with features such as zinc-copper-iron sulfide mineralization, rhyolite-basalt bimodality, and the quartz phenocryst-rich nature of the felsic rocks, are compatible with an unusually primitive tholeiitic island-arc origin for the strata and mineral deposits of the Habawnah mineral belt.

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.

Acute toxicity of heavy metals to acetate-utilizing mixed cultures of sulfate-reducing bacteria: EC100 and EC50.

PubMed

Utgikar, V P; Chen, B Y; Chaudhary, N; Tabak, H H; Haines, J R; Govind, R

2001-12-01

Acid mine drainage from abandoned mines and acid mine pit lakes is an important environmental concern and usually contains appreciable concentrations of heavy metals. Because sulfate-reducing bacteria (SRB) are involved in the treatment of acid mine drainage, knowledge of acute metal toxicity levels for SRB is essential for the proper functioning of the treatment system for acid mine drainage. Quantification of heavy metal toxicity to mixed cultures of SRB is complicated by the confounding effects of metal hydroxide and sulfide precipitation, biosorption, and complexation with the constituents of the reaction matrix. The objective of this paper was to demonstrate that measurements of dissolved metal concentrations could be used to determine the toxicity parameters for mixed cultures of sulfate-reducing bacteria. The effective concentration, 100% (EC100), the lowest initial dissolved metal concentrations at which no sulfate reduction is observed, and the effective concentration, 50% (EC50), the initial dissolved metal concentrations resulting in a 50% decrease in sulfate reduction, for copper and zinc were determined in the present study by means of nondestructive, rapid physical and chemical analytical techniques. The reaction medium used in the experiments was designed specifically (in terms of pH and chemical composition) to provide the nutrients necessary for the sulfidogenic activity of the SRB and to preclude chemical precipitation of the metals under investigation. The toxicity-mitigating effects of biosorption of dissolved metals were also quantified. Anaerobic Hungate tubes were set up (at least in triplicate) and monitored for sulfate-reduction activity. The onset of SRB activity was detected by the blackening of the reaction mixture because of formation of insoluble ferrous sulfide. The EC100 values were found to be 12 mg/L for copper and 20 mg/L for zinc. The dissolved metal concentration measurements were effective as the indicators of the effect of the heavy metals at concentrations below EC100. The 7-d EC50 values obtained from the difference between the dissolved metal concentrations for the control tubes (tubes not containing copper or zinc) and tubes containing metals were found to be 10.5 mg/L for copper and 16.5 mg/L for zinc. Measurements of the turbidity and pH, bacterial population estimations by means of a most-probable number technique, and metal recovery in the sulfide precipitate were found to have only a limited applicability in these determinations.

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.

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.

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications

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

Riha, Shannon C.; Koegel, Alexandra A.; Meng, Xiangbo

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure r-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase, consisting of both r- and a-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS) allow the derivation of a self-consistent reaction mechanism. Lastly, MnS thin films were deposited on copper foil and tested as a Li-ion battery anode. The MnS coin cells showed exceptional cyclemore » stability and near-theoretical capacity.« less

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications

DOE PAGES

Riha, Shannon C.; Koegel, Alexandra A.; Meng, Xiangbo; ...

2016-01-19

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure r-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase, consisting of both r- and a-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS) allow the derivation of a self-consistent reaction mechanism. Lastly, MnS thin films were deposited on copper foil and tested as a Li-ion battery anode. The MnS coin cells showed exceptional cyclemore » stability and near-theoretical capacity.« less

I-III-VI.sub.2 based solar cell utilizing the structure CuInGaSe.sub.2 CdZnS/ZnO

DOEpatents

Chen, Wen S.; Stewart, John M.

1992-01-07

A thin film I-III-VI.sub.2 based solar cell having a first layer of copper indium gallium selenide, a second layer of cadmium zinc sulfide, a double layer of zinc oxide, and a metallization structure comprised of a layer of nickel covered by a layer of aluminum. An optional antireflective coating may be placed on said metallization structure. The cadmium zinc sulfide layer is deposited by means of an aqueous solution growth deposition process and may actually consist of two layers: a low zinc content layer and a high zinc content layer. Photovoltaic efficiencies of 12.5% at Air Mass 1.5 illumination conditions and 10.4% under AMO illumination can be achieved.

The behavior of sulfur in industrial pyrometallurgical slags

NASA Astrophysics Data System (ADS)

Nagamori, Meguru

1994-08-01

Dissolution of sulfur in industrial slags, even at such a low level as 1 mass% S or so, increases the solubility of certain valuable metals by an order of magnitude. The phenomenon is accounted for in terms of Flood-Førland-Grjotheim's model for dianionic salt solutions, whereas its rigorous analysis requires the digaseous Gibbs-Duhem integration. In the research described here, the distribution of sulfur among gas, slag, and metallic iron phases in the bath smelting of iron ore was computer-simulated based on a two-sites model coupled with sulfide capacity data. The solubilities of Ag, Cu, Co, and Ni in industrial slags are reviewed by applying the sulfidic-oxidic dissolution model to copper-matte smelting, nickel-slag cleaning (Falconbridge, Canada), and the imperial smelting process for zinc and lead (Hachinohe, Japan).

Method for removing sulfur oxide from waste gases and recovering elemental sulfur

DOEpatents

Moore, Raymond H.

1977-01-01

A continuous catalytic fused salt extraction process is described for removing sulfur oxides from gaseous streams. The gaseous stream is contacted with a molten potassium sulfate salt mixture having a dissolved catalyst to oxidize sulfur dioxide to sulfur trioxide and molten potassium normal sulfate to solvate the sulfur trioxide to remove the sulfur trioxide from the gaseous stream. A portion of the sulfur trioxide loaded salt mixture is then dissociated to produce sulfur trioxide gas and thereby regenerate potassium normal sulfate. The evolved sulfur trioxide is reacted with hydrogen sulfide as in a Claus reactor to produce elemental sulfur. The process may be advantageously used to clean waste stack gas from industrial plants, such as copper smelters, where a supply of hydrogen sulfide is readily available.

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.

Tellurium

USGS Publications Warehouse

Goldfarb, Richard J.; Berger, Byron R.; George, Micheal W.; Seal, Robert R.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Tellurium (Te) is a very rare element that averages only 3 parts per billion in Earth’s upper crust. It shows a close association with gold and may be present in orebodies of most gold deposit types at levels of tens to hundreds of parts per million. In large-tonnage mineral deposits, such as porphyry copper and seafloor volcanogenic massive sulfide deposits, sulfide minerals may contain hundreds of parts per million tellurium, although the orebodies likely have overall concentrations of 0.1 to 1.0 parts per million tellurium. Tellurium is presently recovered as a primary ore from only two districts in the world; these are the gold-tellurium epithermal vein deposits located adjacent to one another at Dashuigou and Majiagou (Sichuan Province) in southwestern China, and the epithermal-like mineralization at the Kankberg deposit in the Skellefteå VMS district of Västerbotten County, Sweden. Combined, these two groups of deposits account for about 15 percent (about 70 metric tons) of the annual global production of between 450 and 470 metric tons of tellurium. Most of the world’s tellurium, however, is produced as a byproduct of the mining of porphyry copper deposits. These deposits typically yield concentrations of 1 to 4 percent tellurium in the anode slimes recovered during copper refining. Present production of tellurium from the United States is solely from the anode slimes at ASARCO LLC’s copper refinery in Amarillo, Texas, and may total about 50 metric tons per year. The main uses of tellurium are in photovoltaic solar cells and as an additive to copper, lead, and steel alloys in various types of machinery. The environmental data available regarding the mining of tellurium are limited; most concerns to date have focused on the more-abundant metals present in the large-tonnage deposits from which tellurium is recovered as a byproduct. Global reserves of tellurium are estimated to be 24,000 metric tons, based on the amount of tellurium likely contained in global copper reserves and on a 50 percent recovery rate from refinery anode slimes during the commonly used electrolytic process, also known as solvent extraction-electrolytic refining. If the more economical solvent-leach process—a process that does not recover tellurium—is increasingly used in the future to recover lower grades of copper from porphyry and other large-tonnage deposits, then additional high-grade tellurium-rich gold deposits may become new primary sources for tellurium, particularly epithermal vein deposits associated with alkaline magmatism.

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 sulfide oxidation in Prince William Sound are in press. Koski and others (2008) provide an overview of rock alteration, surface water chemistry, and the distribution of metals at the Ellamar, Threeman, and Beatson mine sites. Based on a 60-day, stream-discharge experiment at Beatson in 2005, Stillings and others (2008) analyze changes in water chemistry during storm events and the flux of metals to the shoreline. Foster and others (2008) investigate the biomass and diversity of microbial communities present in surface waters (streams, seeps, pore waters) using fatty acid methyl ester (FAMES) data and principal component analysis. The publications cited above contain a subset of the total chemical data for rock, sediment, biological, precipitate, and water samples collected from the three mine sites in 2003 and 2005. The purpose of this report is the presentation of complete chemical data sets for all samples collected during the two field periods of fieldwork. Data for a small number of samples collected at two other mines (Schlosser and Fidalgo, fig. 1), visited in 2003, are also included in the tables.

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 investigation of sulfide oxidation in Prince William Sound are in press. Koski and others (2008) provide an overview of rock alteration, surface water chemistry, and the distribution of metals at the Ellamar, Threeman, and Beatson mine sites. Based on a 60-day, stream-discharge experiment at Beatson in 2005, Stillings and others (2008) analyze changes in water chemistry during storm events and the flux of metals to the shoreline. Foster and others (2008) investigate the biomass and diversity of microbial communities present in surface waters (streams, seeps, pore waters) using fatty acid methyl ester (FAMES) data and principal component analysis. The publications cited above contain a subset of the total chemical data for rock, sediment, biological, precipitate, and water samples collected from the three mine sites in 2003 and 2005. The purpose of this report is the presentation of complete chemical data sets for all samples collected during the two field periods of fieldwork. Data for a small number of samples collected at two other mines (Schlosser and Fidalgo, fig. 1), visited in 2003, are also included in the tables.

CdS thin films prepared by continuous wave Nd:YAG laser

NASA Astrophysics Data System (ADS)

Wang, H.; Tenpas, Eric W.; Vuong, Khanh D.; Williams, James A.; Schuesselbauer, E.; Bernstein, R.; Fagan, J. G.; Wang, Xing W.

1995-08-01

We report new results on continuous wave Nd:YAG laser deposition of cadmium sulfide thin films. Substrates were soda-lime silicate glass, silica glass, silicon, and copper coated formvar sheets. As deposited films were mixtures of cubic and hexagonal phases, with two different grain sizes. As revealed by SEM micrographs, films had smooth surface morphology. As revealed by TEM analysis, grain sizes were extremely small.

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.

Prospects and performance limitations for Cu-Zn-Sn-S-Se photovoltaic technology.

PubMed

Mitzi, David B; Gunawan, Oki; Todorov, Teodor K; Barkhouse, D Aaron R

2013-08-13

While cadmium telluride and copper-indium-gallium-sulfide-selenide (CIGSSe) solar cells have either already surpassed (for CdTe) or reached (for CIGSSe) the 1 GW yr⁻¹ production level, highlighting the promise of these rapidly growing thin-film technologies, reliance on the heavy metal cadmium and scarce elements indium and tellurium has prompted concern about scalability towards the terawatt level. Despite recent advances in structurally related copper-zinc-tin-sulfide-selenide (CZTSSe) absorbers, in which indium from CIGSSe is replaced with more plentiful and lower cost zinc and tin, there is still a sizeable performance gap between the kesterite CZTSSe and the more mature CdTe and CIGSSe technologies. This review will discuss recent progress in the CZTSSe field, especially focusing on a direct comparison with analogous higher performing CIGSSe to probe the performance bottlenecks in Earth-abundant kesterite devices. Key limitations in the current generation of CZTSSe devices include a shortfall in open circuit voltage relative to the absorber band gap and secondarily a high series resistance, which contributes to a lower device fill factor. Understanding and addressing these performance issues should yield closer performance parity between CZTSSe and CdTe/CIGSSe absorbers and hopefully facilitate a successful launch of commercialization for the kesterite-based technology.

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.

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.

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

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.

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

Development of Cu-bearing bake-hardenable steel sheets for automotive exposed panels

NASA Astrophysics Data System (ADS)

Hong, Moon-Hi; Cho, Noi-Ha; Kim, Sung-Il; Kwon, Ohjoon; Lim, Sung-Hwan; Moon, Won-Jin

2010-12-01

Recently, newly developed bake-hardenable (BH) steel sheets strengthened by copper sulfide (CuS) have been successfully employed in commercial production lines that supply automotive outer panels. The metallurgical concepts governing fabrication of these new BH steel sheets require keeping carbon content as low as 0.0015 wt.% without any additional amount of titanium and/or niobium for solute carbon scavenging. The role of CuS precipitates has turned out to raise the yield strength acting as a barrier against dislocation movement. In this paper, we studied the effects of chemical compositions and manufacturing process variables on the microstructure and mechanical properties of newly developed BH steel sheets. We found that the control of carbon and nitrogen showed a good balance between bake-hardenability (BH) and yield point elongation (YP-El). We identified the crystallographic relationship between the nano-size CuS precipitates and the ferrite matrix of (001)sulfide//(001)α-Fe and [001]sulfide//[001]α-Fe. We also found that the BH and YP-El were affected by the formation of aluminium nitride (AlN) and the annealing temperature.

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.

Microwave-assisted Ullmann C-S bond formation: synthesis of the P38alpha MAPK clinical candidate VX-745.

PubMed

Bagley, Mark C; Davis, Terence; Dix, Matthew C; Fusillo, Vincenzo; Pigeaux, Morgane; Rokicki, Michal J; Kipling, David

2009-11-06

Microwave irradiation promotes the rapid and efficient reaction of a thiophenol and aryl or heteroaryl halide using a copper or palladium catalyst and a range of ligands, depending upon substrate. Of particular utility is the use of copper(I) iodide (5 mol %) and trans-cyclohexane-1,2-diol as ligand under basic conditions and microwave irradiation to give the corresponding sulfide in high yield. This method for C-S bond formation is applied in the four-step synthesis of the clinical candidate VX-745 in 38% overall yield. The inhibitory activity of VX-745 against p38alpha MAPK is confirmed in Werner syndrome dermal fibroblasts at 1.0 microM concentration by immunoblot assay.

Auger analysis of oxygen and sulfur interactions with various metals and the effect of sliding on these interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Various gases were adsorbed to copper, aluminum, and chromium surfaces. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Chemisorption was conducted on static surfaces and during dynamic friction experiments. An Auger cyclindrical mirror analyzer was used to monitor surface films. The sulfur containing gases adsorbed readily to all surfaces. Exposures of as little as 0.000001 (torr)(sec) (1 langmuir) were sufficient to reduce friction. Sliding contact did not affect chemisorption of copper or aluminum but did affect chemisorption to chromium surfaces. Oxygen removed sulfur films from all surfaces at room temperature (23 C). Gaseous exposures were from 0.000001 to 0.01 (torr)(sec) (1 to 10,000 langmuirs).

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

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 copper. ?? 1985.

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.

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 Wiley Periodicals, Inc. Biotechnol Bioeng 80: 349-357, 2002.

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.

Alternative for Perchlorates in Incendiary and Pyrotechnic Formulations for Projectiles

DTIC Science & Technology

2009-08-01

although other copper salts including chloride, acetate, sulfate and carbonate are highly bioavailable in animal nutrition. The toxicity of a single oral...6 hours to 820 mg m-3 after 2 hr. In experimental animals, single inhalation exposures to hydrogen sulfide result in death and respiratory...is in general regulated by the equilibria between CO2, HCO3 - and CO3 2-. The buffer capacity depends on the concentration of these substances

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

DOE PAGES

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie; ...

2017-09-22

Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

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

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie

Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

Partitioning of zinc among common ferromagnesian minerals and implications for hydrothermal mobilization

USGS Publications Warehouse

Johnson, C.A.

1994-01-01

In systems where metals are scavenging from crystalline rocks by through-flowing fluids, the important host minerals must be dissolved or must undergo cation-exchange reactions with the fluid. Whereas copper resides in sulfides, zinc resides in magnetic and, to a lesser extent, in biotite, clinopyroxene and olivine. Magnetite is known from petrographic studies to be more resistant to alteration than sulfides. For metals extracted from crystalline rocks, the Cu:Zn mass ratio may thus decrease with progressive alteration. In systems where metals are scavenged from cooling magmas by exsolving fluids, the metals are partitioned among melt, fluid and any crystals that have fractionated. For zinc, crystal fractionation may be an important sink if magnetite or biotite crystallize before fluid saturation. The zinc concentrations of magmatic fluids will thus be reduced. -from Author

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.

Cu{sub 2}ZnSnS{sub 4} nanoflakes prepared by one step microwave irradiation technique: Effect of Cu concentration

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

Kandare, S. P.; Dhole, S. D.; Bhoraskar, V. N.

Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoflakes were synthesized in one step by microwave irradiation method. Controlling the secondary phases in Copper Zinc Tin Sulfide (CZTS) material is critical, but it is necessary to control secondary phases in order to achieve the high efficiency solar cells made from CZTS. In the recent years, CZTS has shown its growing importance in thin film photovoltaic application because of its favorable optical and electrical properties. In this work, a systematic study has been carried out by properly controlling the copper concentration to get the pure phase of CZTS. X-ray diffraction shows the CZTS kesterite structure.more » Optical band gap estimated from UV-Visible spectroscopy was around 1.37eV. Systematic Raman study reveals the suppression of Cu{sub 2}S peak with variation in copper concentration which otherwise was not clear from XRD and UV-visible data.« less

Diffusion-reaction modelling of early diagenesis of sediments affected by acid mine drainage.

NASA Astrophysics Data System (ADS)

Torres, E.; Ayora, C.; Arias, J. L.; Garcia Robledo, E.; Papaspyrou, S.; Corzo, A.

2012-04-01

The Sancho Reservoir (SW Spain) is a monomictic water reservoir affected by acid mine drainage. It has a pH of ~4, with high sulfate (200 ppm) and heavy metal concentrations in the water column. The reservoir develops reducing conditions at the bottom during the stratification period. A laboratory experiment was carried out to study the effect of this oxygen variation on the early diagenesis processes and the cycling of metals. Sediment cores and bottom water were collected during the stratification period and brought to the laboratory. The cores were maintained in an aquarium bubbled with nitrogen gas to maintain hypoxic conditions (~10 µmol O2 L-1) for 1 day. Then, oxic conditions were induced by bubbling with air and maintained for 50 days. Finally, hypoxia was re-established for 10 days. Triplicate cores were sliced in a anaerobic glove box at each stage. Pore water was extracted by centrifugation and: Eh, pH, DO, DOC, sulfate, Fe and trace metals were analyzed. The sediment was freeze-dried and a sequential extraction protocol was applied to determine the exchangeable, AVS, Fe-(oxy)hydroxides, Fe-oxides, organic matter, pyrite sulfur and residual phase iron fractions. Organic carbon and total C, N, H and S were also analyzed in the sediment. A reactive diffusion model has been used to obtain the rates of biogeochemical reactions by fitting to the experimental data. During hypoxic conditions sulfate and Fe-(oxy)hydroxides are reduced, due to the anaerobic oxidation of organic matter, at the very first few cm, releasing sulfide and Fe(II) which precipitate as iron sulfide. When oxygen diffuses in the sediment, sulfate-reduction and the sulfide peaks are displaced deeper into the sediment. Oxygen penetration depth and its consumption rates in the sediment increase quickly, resulting in the reoxidation of the iron sulfides that had precipitated during hypoxic conditions. Sulfide and Fe(II) are released and are again oxidized to Fe(III) and sulfate respectively. Arsenic can be adsorbed onto the iron sulfides and pyrite. During the dissolution of the iron sulfide As will be released and will diffuse to the water column. Copper and zinc can also precipitate as metal sulfides.

Synthesis and characterization of inorganic materials precipitated into polymeric and novel liquid crystalline systems

NASA Astrophysics Data System (ADS)

Lubeck, Christopher Ryan

The use of nanostructured, hybrid materials possesses great future potential. Many examples of nanostructured materials exist within nature, such as animal bone, animal teeth, and seashells. This research, inspired by nature, strove to mimic salient properties of natural materials, utilizing methods observed within nature to produce materials. Further, this research increased the functionality of the templates from "mere" template to functional participant. Different chemical methods to produce hybrid materials were employed within this research to achieve these goals. First, electro-osmosis was utilized to drive ions into a polymeric matrix to form hybrid inorganic polymer material, creating a material inspired by naturally occurring bone or seashell in which the inorganic component provides strength and the polymeric material decreases the brittleness of the combined hybrid material. Second, self-assembled amphiphiles, forming higher ordered structures, acted as a template for inorganic cadmium sulfide. Electronically active molecules based on ethylene oxide and aniline segments were synthesized to create interaction between the templating material and the resulting inorganic cadmium sulfide. The templating process utilized self-assembly to create the inorganic structure through the interaction of the amphiphiles with water. The use of self-assembly is itself inspired by nature. Self-assembled structures are observed within living cells as cell walls and cell membranes are created through hydrophilic and hydrophobic interactions. Finally, the mesostructured inorganic cadmium sulfide was itself utilized as a template to form mesostructured copper sulfide.

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.

A study on the optics of copper indium gallium (di)selenide (CIGS) solar cells with ultra-thin absorber layers.

PubMed

Xu, Man; Wachters, Arthur J H; van Deelen, Joop; Mourad, Maurice C D; Buskens, Pascal J P

2014-03-10

We present a systematic study of the effect of variation of the zinc oxide (ZnO) and copper indium gallium (di)selenide (CIGS) layer thickness on the absorption characteristics of CIGS solar cells using a simulation program based on finite element method (FEM). We show that the absorption in the CIGS layer does not decrease monotonically with its layer thickness due to interference effects. Ergo, high precision is required in the CIGS production process, especially when using ultra-thin absorber layers, to accurately realize the required thickness of the ZnO, cadmium sulfide (CdS) and CIGS layer. We show that patterning the ZnO window layer can strongly suppress these interference effects allowing a higher tolerance in the production process.

Volumetric determination of uranium titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, J.S.; Skinner, D.L.; Rader, L.F.

1957-01-01

Need for a more rapid volumetric method for the routine determination of uranium in uranium-rich materials has led to the development of a method that uses titanous sulfate as a reductant before oxidimetric titration. Separation of the hydrogen sulfide group is not necessary. Interfering elements precipitated by cupferron are removed by automatic filtrations made simultaneously rather than by the longer chloroform extraction method. Uranium is reduced from VI to IV by addition of an excess of titanous sulfate solution, cupric ion serving as an indicator by forming red metallic copper when reduction is complete. The copper is reoxidized by addition of mercuric perchlorate. The reduced uranium is then determined by addition of excess ferric sulfate and titration with ceric sulfate. The method has proved to be rapid, accurate, and economical.

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 media. Samples of ice and snow have been used for limited geochemical surveys. Both geobotanical and biogeochemical surveys have been successful in locating copper deposits in many parts of the world. Micro-organisms, including bacteria and algae, are other unproved media that should be studied. Animals can be used in geochemical-prospecting programs. Dogs have been used quite successfully to sniff out hidden and exposed sulfide minerals. Tennite mounds are commonly composed of subsurface material, but have not as yet proved to be useful in locating buried mineral deposits. Animal tissue and waste products are essentially unproved but potentially valuable sampling media. Knowledge of the location of areas where trace-element-associated diseases in animals and man are endemic as well as a better understanding of these diseases, may aid in identifying regions that are enriched in or depleted of various elements, including copper. Results of analyses of gases in the atmosphere are proving valuable in mineral-exploration surveys. Studies involving metallic compounds exhaled by plants into the atmosphere, and of particulate matter suspended in the atmosphere are reviewed these methods may become important in the future. Remote-sensing techniques are useful for making indirect measurements of geochemical responses. Two techniques applicable to geochemical exploration are neutron-activation analysis and gamma-ray spectrometry. Aerial photography is especially useful in vegetation surveys. Radar imagery is an unproved but potentially valuable method for use in studies of vegetation in perpetually clouded regions. With the advent of modern computers, many new techniques, such as correlation analysis, regression analysis, discriminant analysis, factor analysis, cluster analysis, trend-surface analysis, and moving-average analysis can be applied to geochemical data sets. Selective use of these techniques can provide new insights into the interpretatio

Final Report: Sintered CZTS Nanoparticle Solar Cells on Metal Foil; July 26, 2011 - July 25, 2012

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

Leidholm, C.; Hotz, C.; Breeze, A.

2012-09-01

This is the final report covering 12 months of this subcontract for research on high-efficiency copper zinc tin sulfide (CZTS)-based thin-film solar cells on flexible metal foil. Each of the first three quarters of the subcontract has been detailed in quarterly reports. In this final report highlights of the first three quarters will be provided and details will be given of the final quarter of the subcontract.

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.

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.

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.

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

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.

Geologic history of the Blackbird Co-Cu district in the Lemhi subbasin of the Belt-Purcell Basin

USGS Publications Warehouse

Bookstrom, Arthur A.; Box, Stephen E.; Cossette, Pamela M.; Frost, Thomas P.; Gillerman, Virginia; King, George; Zirakparvar, N. Alex

2016-01-01

The Blackbird cobalt-copper (Co-Cu) district in the Salmon River Mountains of east-central Idaho occupies the central part of the Idaho cobalt belt—a northwest-elongate, 55-km-long belt of Co-Cu occurrences, hosted in grayish siliciclastic metasedimentary strata of the Lemhi subbasin (of the Mesoproterozoic Belt-Purcell Basin). The Blackbird district contains at least eight stratabound ore zones and many discordant lodes, mostly in the upper part of the banded siltite unit of the Apple Creek Formation of Yellow Lake, which generally consists of interbedded siltite and argillite. In the Blackbird mine area, argillite beds in six stratigraphic intervals are altered to biotitite containing over 75 vol% of greenish hydrothermal biotite, which is preferentially mineralized.Past production and currently estimated resources of the Blackbird district total ~17 Mt of ore, averaging 0.74% Co, 1.4% Cu, and 1.0 ppm Au (not including downdip projections of ore zones that are open downward). A compilation of relative-age relationships and isotopic age determinations indicates that most cobalt mineralization occurred in Mesoproterozoic time, whereas most copper mineralization occurred in Cretaceous time.Mesoproterozoic cobaltite mineralization accompanied and followed dynamothermal metamorphism and bimodal plutonism during the Middle Mesoproterozoic East Kootenay orogeny (ca. 1379–1325 Ma), and also accompanied Grenvilleage (Late Mesoproterozoic) thermal metamorphism (ca. 1200–1000 Ma). Stratabound cobaltite-biotite ore zones typically contain cobaltite1 in a matrix of biotitite ± tourmaline ± minor xenotime (ca. 1370–1320 Ma) ± minor chalcopyrite ± sparse allanite ± sparse microscopic native gold in cobaltite. Such cobaltite-biotite lodes are locally folded into tight F2 folds with axial-planar S2 cleavage and schistosity. Discordant replacement-style lodes of cobaltite2-biotite ore ± xenotime2 (ca. 1320–1270 Ma) commonly follow S2fractures and fabrics. Discordant quartz-biotite and quartz-tourmaline breccias, and veins contain cobaltite3 ± xenotime3 (ca. 1058–990 Ma).Mesoproterozoic cobaltite deposition was followed by: (1) within-plate plutonism (530–485 Ma) and emplacement of mafic dikes (which cut cobaltite lodes but are cut by quartz-Fe-Cu-sulfide veins); (2) garnet-grade metamorphism (ca. 151–93 Ma); (3) Fe-Cu-sulfide mineralization (ca. 110–92 Ma); and (4) minor quartz ± Au-Ag ± Bi mineralization (ca. 92–83 Ma).Cretaceous Fe-Cu-sulfide vein, breccia, and replacement-style deposits contain various combinations of chalcopyrite ± pyrrhotite ± pyrite ± cobaltian arsenopyrite (not cobaltite) ± arsenopyrite ± quartz ± siderite ± monazite (ca. 144–88 Ma but mostly 110–92 Ma) ± xenotime (104–93 Ma). Highly radiogenic Pb (in these sulfides) and Sr (in siderite) indicate that these elements resided in Mesoproterozoic source rocks until they were mobilized after ca. 100 Ma. Fe-Cu-sulfide veins, breccias, and replacement deposits appear relatively undeformed and generally lack metamorphic fabrics.Composite Co-Cu-Au ore contains early cobaltite-biotite lodes, cut by Fe-Cu-sulfide veins and breccias, or overprinted by Fe-Cu-sulfide replacement-style deposits, and locally cut by quartz veinlets ± Au-Ag ± Bi minerals.

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

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.

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

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.

Solar electric and thermal conversion system in close proximity to the consumer. [solar panels on house roofs

NASA Technical Reports Server (NTRS)

Boeer, K. W.

1975-01-01

Solar cells may be used to convert sunlight directly into electrical energy and into lowgrade heat to be used for large-scale terrestrial solar-energy conversion. Both forms of energy can be utilized if such cells are deployed in close proximity to the consumer (rooftop). Cadmium-sulfide/copper-sulfide (CdS/Cu2S) solar cells are an example of cells which may be produced inexpensively enough to become economically attractive. Cell parameters relevant for combined solar conversion are presented. Critical issues, such as production yield, life expectancy, and stability of performance, are discussed. Systems-design parameters related to operating temperatures are analyzed. First results obtained on Solar One, the experimental house of the University of Delaware, are given. Economic aspects are discussed. Different modes of operation are discussed in respect to the power utility and consumer incentives.

Eco-friendly p-type Cu2SnS3 thermoelectric material: crystal structure and transport properties

PubMed Central

Shen, Yawei; Li, Chao; Huang, Rong; Tian, Ruoming; Ye, Yang; Pan, Lin; Koumoto, Kunihito; Zhang, Ruizhi; Wan, Chunlei; Wang, Yifeng

2016-01-01

As a new eco-friendly thermoelectric material, copper tin sulfide (Cu2SnS3) ceramics were experimentally studied by Zn-doping. Excellent electrical transport properties were obtained by virtue of 3-dimensionally conductive network for holes, which are less affected by the coexistence of cubic and tetragonal phases that formed upon Zn subsitition for Sn; a highest power factors ~0.84 mW m−1 K−2 at 723 K was achieved in the 20% doped sample. Moreover, an ultralow lattice thermal conductivity close to theoretical minimum was observed in these samples, which could be related to the disordering of atoms in the coexisting cubic and tetragonal phases and the interfaces. Thanks to the phonon-glass-electron-crystal features, a maximum ZT ~ 0.58 was obtained at 723 K, which stands among the tops for sulfide thermoelectrics at the same temperature. PMID:27666524

Resolution of matrix effects on analysis of total and methyl mercury in aqueous samples from the Florida Everglades

USGS Publications Warehouse

Olson, M.L.; Cleckner, L.B.; Hurley, J.P.; Krabbenhoft, D.P.; Heelan, T.W.

1997-01-01

Aqueous samples from the Florida Everglades present several problems for the analysis of total mercury (HgT) and methyl mercury (MeHg). Constituents such as dissolved organic carbon (DOC) and sulfide at selected sites present particular challenges due to interferences with standard analytical techniques. This is manifested by 1) the inability to discern when bromine monochloride (BrCl) addition is sufficient for sample oxidation for HgT analysis; and 2) incomplete spike recoveries using the distillation/ethylation technique for MeHg analysis. Here, we suggest ultra-violet (UV) oxidation prior to addition of BrCl to ensure total oxidation of DOC prior to HgT analysis and copper sulfate (CuSO4) addition to aid in distillation in the presence of sulfide for MeHg analysis. Despite high chloride (Cl-) levels, we observed no effects on MeHg distillation/ethylation analyses. ?? Springer-Verlag 1997.

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.

Geochemical and mineralogical characterization of the abandoned Valzinco (lead-zinc) and Mitchell (gold) mine sites prior to reclamation, Spotsylvania County, Virginia

USGS Publications Warehouse

Hammarstrom, Jane M.; Johnson, Adam N.; Seal, Robert R.; Meier, Allen L.; Briggs, Paul L.; Piatak, Nadine M.

2006-01-01

The Virginia gold-pyrite belt, part of the central Virginia volcanic-plutonic belt, hosts numerous abandoned metal mines. The belt extends from about 50 km south of Washington, D.C., for approximately 175 km to the southwest into central Virginia. The rocks that comprise the belt include metamorphosed volcanic and clastic (noncarbonate) sedimentary rocks that were originally deposited during the Ordovician). Deposits that were mined can be classified into three broad categories: 1. volcanic-associated massive sulfide deposits, 2. low-sulfide quartz-gold vein deposits, 3. gold placer deposits, which result from weathering of the vein deposits The massive sulfide deposits were historically mined for iron and pyrite (sulfur), zinc, lead, and copper but also yielded byproduct gold and silver. The most intensely mineralized and mined section of the belt is southwest of Fredericksburg, in the Mineral district of Louisa and Spotsylvania counties. The Valzinco Piatak lead-zinc mine and the Mitchell gold prospect are abandoned sites in Spotsylvania County. As a result of environmental impacts associated with historic mining, both sites were prioritized for reclamation under the Virginia Orphaned Land Program administered by the Virginia Department of Mines, Minerals, and Energy (VDMME). This report summarizes geochemical data for all solid sample media, along with mineralogical data, and results of weathering experiments on Valzinco tailings and field experiments on sediment accumulation in Knights Branch. These data provide a framework for evaluating water-rock interactionsand geoenvironmental signatures of long-abandoned mines developed in massive sulfide deposits and low-sulfide gold-quartz vein deposits in the humid temperate ecosystem domain in the eastern United States.

Electrochemical Applications in Metal Bioleaching.

PubMed

Tanne, Christoph Kurt; Schippers, Axel

2017-12-10

Biohydrometallurgy comprises the recovery of metals by biologically catalyzed metal dissolution from solids in an aqueous solution. The application of this kind of bioprocessing is described as "biomining," referring to either bioleaching or biooxidation of sulfide metal ores. Acidophilic iron- and sulfur-oxidizing microorganisms are the key to successful biomining. However, minerals such as primary copper sulfides are recalcitrant to dissolution, which is probably due to their semiconductivity or passivation effects, resulting in low reaction rates. Thus, further improvements of the bioleaching process are recommendable. Mineral sulfide dissolution is based on redox reactions and can be accomplished by electrochemical technologies. The impact of electrochemistry on biohydrometallurgy affects processing as well as analytics. Electroanalysis is still the most widely used electrochemical application in mineralogical research. Electrochemical processing can contribute to bioleaching in two ways. The first approach is the coupling of a mineral sulfide to a galvanic partner or electrocatalyst (spontaneous electron transfer). This approach requires only low energy consumption and takes place without technical installations by the addition of higher redox potential minerals (mostly pyrite), carbonic material, or electrocatalytic ions (mostly silver ions). Consequently, the processed mineral (often chalcopyrite) is preferentially dissolved. The second approach is the application of electrolytic bioreactors (controlled electron transfer). The electrochemical regulation of electrolyte properties by such reactors has found most consideration. It implies the regulation of ferrous and ferric ion ratios, which further results in optimized solution redox potential, less passivation effects, and promotion of microbial activity. However, many questions remain open and it is recommended that reactor and electrode designs are improved, with the aim of finding options for simplified biohydrometallurgical processing. This chapter focuses on metal sulfide dissolution via bioleaching and does not include other biohydrometallurgical processes such as microbial metal recovery from solution.

Miocene and early Pliocene epithermal gold-silver deposits in the northern Great Basin, western United States: Characteristics, distribution, and relationship to Magmatism

USGS Publications Warehouse

John, D.A.

2001-01-01

Numerous important Miocene and early Pliocene epithermal Au-Ag deposits are present in the northern Great Basin. Most deposits are spatially and temporally related to two magmatic assemblages: bimodal basalt-rhyolite and western andesite. These magmatic assemblages are petrogenetic suites that reflect variations in tectonic environment of magma generation. The bimodal assemblage is a K-rich tholeiitic series formed during continental rifting. Rocks in the bimodal assemblage consist mostly of basalt to andesite and rhyolite compositions that generally contain anhydrous and reduced mineral assemblages (e.g., quartz + fayalite rhyolites). Eruptive forms include mafic lava flows, dikes, cinder and/or spatter cones, shield volcanoes, silicic flows, domes, and ash-flow calderas. Fe-Ti oxide barometry indicates oxygen fugacities between the magnetite-wustite and fayalite-magnetite-quartz oxygen buffers for this magmatic assemblage. The western andesite assemblage is a high K calc-alkaline series that formed a continental-margin are related to subduction of oceanic crust beneath the western coast of North America. In the northern Great Basin, most of the western andesite assemblage was erupted in the Walker Lane belt, a zone of transtension and strike-slip faulting. The western andesite assemblage consists of stratovolcanoes, dome fields, and subvolcanic plutons, mostly of andesite and dacite composition. Biotite and hornblende phenocrysts are abundant in these rocks. Oxygen fugacities of the western andesite assemblage magmas were between the nickel-nickel oxide and hematite-magnetite buffers, about two to four orders of magnitude greater than magmas of the bimodal assemblage. Numerous low-sulfidation Au-Ag deposits in the bimodal assemblage include deposits in the Midas (Ken Snyder), Sleeper, DeLamar, Mule Canyon, Buckhorn, National, Hog Ranch, Ivanhoe, and Jarbidge districts; high-sulfidation gold and porphyry copper-gold deposits are absent. Both high- and low-sulfidation gold-silver and porphyry copper-gold deposits are affiliated with the western andesite assemblage and include the Comstock Lode, Tonopah, Goldfield, Aurora, Bodie, Paradise Peak, and Rawhide deposits. Low-sulfidation Au-Ag deposits in the bimodal assemblage formed under relatively low oxygen and sulfur fugacities and have generally low total base metal (Cu + Pb + Zn) contents, low Ag/Au ratios, and notably high selenide mineral contents compared to temporally equivalent low-sulfidation deposits in the western andesite assemblage. Petrologic studies suggest that these differences may reflect variations in the magmatic-tectonic settings of the associated magmatic assemblages-deposits in the western andesite assemblage formed from oxidized, water-rich, subduction-related calc-alkaline magmas, whereas deposits in the bimodal assemblage were associated with reduced, water-poor tholeiitic magmas derived from the lithospheric mantle during continental extension. The contrasting types and characteristics of epithermal deposits and their affinities with associated igneous rocks suggest that a genetic relationship is present between these Au-Ag deposits and their temporally associated magmatism, although available data do not prove this relationship for most low-sulfidation deposits.

Engineering and Development Support of General Decon Technology for the DARCOM Installation Restoration Program. Task 4. General Technology Literature Searches (II) Solidification Techniques for Lagoon Waters

DTIC Science & Technology

1980-12-01

40.8 Sodium 70.1 Zinc 0.01 37 The process includes the following steps (Pichat et al., 1979): - neutralization precipitation (silicates, borates...Compressive Strength of Polyester - Encapsulated Sodium Sulfate Waste Composite ....... .............. 64 9. Deep Chemical Mixer Mounted on a Barge...zinc, copper, lead, manganese and tin; sodium salts of arsenate, borate, phosphate, iodate, and sulfide; and sulfate salts. Sulfate salts form calcium

BREAD LOAF ROADLESS AREA, VERMONT.

USGS Publications Warehouse

Slack, John F.; Bitar, Richard F.

1984-01-01

On the basis of mineral-resource survey the Bread Loaf Roadless Area, Vermont, is considered to have probable resource potential for the occurrence of volcanogenic massive sulfide deposits of copper, zinc, and lead, particularly in the north and northeastern section of the roadless area. Nonmetallic commodities include minor deposits of sand and gravel, and abundant rock suitable for crushing. However, large amounts of these materials in more accessible locations are available outside the roadless area. A possibility exists that oil or natural gas resources may be present at great depth.

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.

Geochemical studies of rare earth elements in the Portuguese pyrite belt, and geologic and geochemical controls on gold distribution

USGS Publications Warehouse

Grimes, David J.; Earhart, Robert L.; de Carvalho, Delfim; Oliveira, Vitor; Oliveira, Jose T.; Castro, Paulo

1998-01-01

This report describes geochemical and geological studies which were conducted by the U.S. Geological Survey (USGS) and the Servicos Geologicos de Portugal (SPG) in the Portuguese pyrite belt (PPB) in southern Portugal. The studies included rare earth element (REE) distributions and geological and geochemical controls on the distribution of gold. Rare earth element distributions were determined in representative samples of the volcanic rocks from five west-trending sub-belts of the PPB in order to test the usefulness of REE as a tool for the correlation of volcanic events, and to determine their mobility and application as hydrothermal tracers. REE distributions in felsic volcanic rocks show increases in the relative abundances of heavy REE and a decrease in La/Yb ratios from north to south in the Portuguese pyrite belt. Anomalous amounts of gold are distributed in and near massive and disseminated sulfide deposits in the PPB. Gold is closely associated with copper in the middle and lower parts of the deposits. Weakly anomalous concentrations of gold were noted in exhalative sedimentary rocks that are stratigraphically above massive sulfide deposits in a distal manganiferous facies, whereas anomalously low concentrations were detected in the barite-rich, proximal-facies exhalites. Altered and pyritic felsic volcanic rocks locally contain highly anomalous concentrations of gold, suggesting that disseminated sulfide deposits and the non-ore parts of massive sulfide deposits should be evaluated for their gold potential.

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.

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

Porphyry-type ore deposits sometimes contain fluid inclusion compositions consistent with the partitioning of copper and gold into vapor relative to coexisting brine at the depositional stage. However, this has not been reproduced experimentally at magmatic conditions. In an attempt to determine the conditions under which copper and gold may partition preferentially into vapor relative to brine at temperatures above the solidus of granitic magmas, we performed experiments at 800 °C, 100 MPa, oxygen fugacity ( fO2sys) buffered by Ni-NiO, and aS2sys fixed at either 3.5 × 10 -2 by using intermediate solid solution-pyrrhotite, or 1.2 × 10 -4 by using intermediate solid solution-pyrrhotite-bornite. The coexisting vapor (˜3 wt.% NaCl eq.) and brine (˜68 wt.% NaCl eq.) were composed initially of NaCl + KCl + HCl + H 2O, with starting HCl set to <1000 μg/g in the aqueous mixture. Synthetic vapor and brine fluid inclusions were trapped at run conditions and subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Our experiments demonstrate that copper and gold partitioned strongly into the magmatic volatile phase(s) (MVP) (i.e., vapor or brine) relative to a silicate melt over the entire imposed range of aS2sys. Nernst style partition coefficients between coexisting brine (b) and melt (m), D b/m (±1 σ), range from 3.6(±2.2) × 10 1 to 4(±2) × 10 2 for copper and from 1.2(±0.6) × 10 2 to 2.4(±2.4) × 10 3 for gold. Partition coefficients between coexisting vapor (v) and melt, D v/m range from 2.1 ± 0.7 to 18 ± 5 and 7(±3) × 10 1 to 1.6(±1.6) × 10 2 for copper and gold, respectively. Partition coefficients for all experiments between coexisting brine and vapor, D b/v (±1 σ), range from 7(±2) to 1.0(±0.4) × 10 2 and 1.7(±0.2) to 15(±2) for copper and gold, respectively. Observed average D b/v at an aS2sys of 1.2 × 10 -4 were elevated, 95(±5) and 15 ± 1 for copper and gold, respectively, relative to those 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.

Biosorption of Cu(II) by powdered anaerobic granular sludge from aqueous medium.

PubMed

Zhou, Xu; Chen, Chuan; Wang, Aijie; Jiang, Guangming; Liu, Lihong; Xu, Xijun; Yuan, Ye; Lee, Duu-Jung; Ren, Nanqi

2013-01-01

Copper(II) biosorption processes by two pre-treated powdered anaerobic granular sludges (PAGS) (original sludges were methanogenic anaerobic granules and denitrifying sulfide removal (DSR) anaerobic granules) were investigated through batch tests. Factors affecting the biosorption process, such as pH, temperature and initial copper concentrations, were examined. Also, the physico-chemical characteristics of the anaerobic sludge were analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy image, surface area and elemental analysis. A second-order kinetic model was applied to describe the biosorption process, and the model could fit the biosorption process. The Freundlich model was used for describing the adsorption equilibrium data and could fit the equilibrium data well. It was found that the methanogenic PAGS was more effective in Copper(II) biosorption process than the DSR PAGS, whose maximum biosorption capacity was 39.6% lower. The mechanisms of the biosorption capacities for different PAGS were discussed, and the conclusion suggested that the environment and biochemical reactions during the growth of biomass may have affected the structure of the PAGS. The methanogenic PAGS had larger specific surface area and more biosorption capacity than the DSR PAGS.

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

Au speciation in sulfides (including "invisible" Au), which mostly controls the loss of Au during ore dressing, is discussed. Modern methods of analysis of Au speciation, with discussion of limitations by locality and sensitivity, are reviewed. The results of sulfide investigation by the methods of scanning and transmission electron microscopy, mass spectrometric analysis with laser ablation (LA-ICP-MS), the thermochemical method (study of ionic Au speciation), and automated "quantitative mineralogy," are demonstrated for weakly metamorphosed VHMS deposits of the Urals (Galkinsk and Uchaly). Significant content of Au is scattered in sulfides, such as pyrite, chalcopyrite, and sphalerite, with quantitative predomination of pyrite. The portion of such "invisible" gold ranges from <10% (Galkinsk deposit) to 85% (Uchaly deposit). Major part of "invisible" gold occurs as micron- to nanoscale particles of Au minerals. The portion of gold structurally bound in pyrite lattice (from the bulk concentration of Au in pyrite) is estimated to be from few % (the Galkinsk deposit) to 20-25% (the Uchaly deposit). The presence of As and Sb in pyrite and sphalerite, as well as other trace elements (Te, Co, Mn, Cu, Hg, and Ag in both as well as Fe in sphalerite) stimulates the incorporation of Au in sulfide, but mostly in defect-associated, not isomorphic form. Micron particles of Ag sulfosalts (pyrargyrite, freibergite, stephanite, polybasite, pyrostilpnite, argentotetrahedrite, pearceite, proustite), Au-Ag alloys (from gold of high fineness to küstelite), Ag and Au-Ag tellurides (hessite, empressite, calaverite), and occasional Au-Ag sulfides (petrovskaite, uytenbogaardtite) were registered in the areas of Au enrichment of both deposits; selenotelluride (kurilite) particles were found on the Galkinsk deposit. Nanoscale (1-50 nm) native gold (spherical and disk-shaped particles, flakes) with a monocrystal diffraction pattern of some particles and a ring diffraction pattern of other 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.

Environmental geochemistry of abandoned flotation tailing reservior from the Tonglvshan Fe-Cu sulfide mine in Daye, Central China.

PubMed

Guo, Y; Bao, Z Y; Deng, Y M; Ma, Z Z; Yan, S

2011-07-01

This study investigated metals of tailings from Tonglvshan mine in Daye and assessed the effect of metal contamination in water and sediment near the tailing reservoir. The concentration of copper, lead, zinc, cadmium, chromium and nickel was measured in deposit samples taken from a profile in an abandoned flotation tailing reservoir, as well as in water and sediment samples near the reservoir. The results of this study indicate that copper concentration ranges from 780 to 4390 mg/kg, 2-10 times higher than the limit values in soil, while the contents of other metals are below the limit values. Metal levels in water and sediments are high and varied widely in different sampling sites. The mean concentrations of copper, lead, zinc, cadmium, chromium and nickel in waters are 27.76, 2.28, 8.20, 0.12, 5.30 and 3.04 mg/L, while those in sediments are 557.65, 96.95, 285.20, 0.92, 94.30 and 4.75 mg/kg, respectively. All of the results indicate that the environment near the tailing reservoir is polluted to some extent by some kinds of metals, especially by copper, lead, zinc and cadmium, which may be caused not only by some discharge sources of metals, but also by life garbage and sewage.

Genetic variability of psychrotolerant Acidithiobacillus ferrivorans revealed by (meta)genomic analysis.

PubMed

González, Carolina; Yanquepe, María; Cardenas, Juan Pablo; Valdes, Jorge; Quatrini, Raquel; Holmes, David S; Dopson, Mark

2014-11-01

Acidophilic microorganisms inhabit low pH environments such as acid mine drainage that is generated when sulfide minerals are exposed to air. The genome sequence of the psychrotolerant Acidithiobacillus ferrivorans SS3 was compared to a metagenome from a low temperature acidic stream dominated by an A. ferrivorans-like strain. Stretches of genomic DNA characterized by few matches to the metagenome, termed 'metagenomic islands', encoded genes associated with metal efflux and pH homeostasis. The metagenomic islands were enriched in mobile elements such as phage proteins, transposases, integrases and in one case, predicted to be flanked by truncated tRNAs. Cus gene clusters predicted to be involved in copper efflux and further Cus-like RND systems were predicted to be located in metagenomic islands and therefore, constitute part of the flexible gene complement of the species. Phylogenetic analysis of Cus clusters showed both lineage specificity within the Acidithiobacillus genus as well as niche specificity associated with an acidic environment. The metagenomic islands also contained a predicted copper efflux P-type ATPase system and a polyphosphate kinase potentially involved in polyphosphate mediated copper resistance. This study identifies genetic variability of low temperature acidophiles that likely reflects metal resistance selective pressures in the copper rich environment. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Mineralogical and geochemical controls on the release of trace elements from slag produced by base- and precious-metal smelting at abandoned mine sites

USGS Publications Warehouse

Piatak, N.M.; Seal, R.R.; Hammarstrom, J.M.

2004-01-01

Slag collected from smelter sites associated with historic base-metal mines contains elevated concentrations of trace elements such as Cu, Zn and Pb. Weathering of slag piles, many of which were deposited along stream banks, potentially may release these trace elements into the environment. Slags were sampled from the Ely and Elizabeth mines in the Vermont copper belt, from the copper Basin mining district at Ducktown, Tennessee and from the Clayton silver mine in the Bayhorse mining district, Idaho, in the USA. Primary phases in the slags include: olivine-group minerals, glass, spinels, sulfide minerals and native metals for Vermont samples; glass, sulfide minerals and native metals for the Ducktown sample; and olivine-group minerals, clinopyroxenes, spinels, sulfide minerals, native metals and other unidentified metallic compounds for Clayton slag. Olivine-group minerals and pyroxenes are dominantly fayalitic and hedenbergitic in composition, respectively and contain up to 1.25 wt.% ZnO. Spinel minerals range between magnetite and hercynite in composition and contain Zn (up to 2.07 wt.% ZnO), Ti (up to 4.25 wt.% TiO2) and Cr (up to 1.39 wt.% Cr2O3). Cobalt, Ni, Cu, As, Ag, Sb and Pb occur in the glass phase, sulfides, metallic phases and unidentified metallic compounds. Bulk slag trace-element chemistry shows that the metals of the Vermont and Tennessee slags are dominated by Cu (1900-13,500 mg/kg) and Zn (2310-10,200 mg/kg), whereas the Clayton slag is dominated by Pb (63,000 mg/kg), Zn (19,700 mg/kg), Cu (7550 mg/kg), As (555 mg/kg), Sn (363 mg/kg) and Ag (200 mg/kg). Laboratory-based leach tests indicate metals can be released under simulated natural conditions. Leachates from most slags were found to contain elevated concentrations of Cu and Zn (up to 1800 and 470 ??g/l, respectively), well in excess of the acute toxicity guidelines for aquatic life. For the Idaho slag, the concentration of Pb in the leachate (11,000 ??g/l) is also in excess of the acute toxicity guideline. Geochemical modeling of the leachate chemistry suggests that leachates from the Vermont, Tennessee and Clayton slags are saturated with amorphous silica and Al hydroxide. Therefore, the dissolution of silicate and oxide phases, the oxidation of sulfide phases, as well as the precipitation of secondary phases may control the composition of leachate from slags. The presence of secondary minerals on slag deposits in the field is evidence that these materials are reactive. The petrographic data and results of leaching tests from this study indicate slag may be a source of potentially toxic metals at abandoned mine sites.

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.

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.

Tracing remobilization of nutrients and toxic elements after application of rice straw or derived ash / biochar in paddy soils

NASA Astrophysics Data System (ADS)

Schaller, Jörg; Wang, Jiajia; Planer-Friedrich, Britta

2017-04-01

More than 600 million tons of rice straw are produced each year as byproduct of rice grain production. As an increasing application, besides e.g. composting or fodder for animals, the straw remains on the field for decomposition and nutrient supply. A central concern during rice cultivation is accumulation of arsenic, but it is currently unclear how the application of rice straw or derived ash or biochar to paddy soils will influence arsenic uptake by the next generation of rice plants. Consequently, we assessed the element mobilization via soil microcosm incubations with straw or derived ash or biochar or without those amendments under flooding (40 days) and subsequent drainage (14 days). We focused on elements potentially influencing the uptake of arsenic by the next generation of rice plants (e.g. silicon, phosphorus, iron), or which are nutrients but toxic themselves at higher levels (sulfur, sulfide, iron, iron(II), manganese, copper, and zinc). We found significant differences in the release of arsenic, iron(II), sulfide, total sulfur, DOC, manganese, copper, and zinc . For example highest pore water Mn and As concentrations were found for soil amended with straw, whereas the straw amendment reduced S mobilization, possibly due to sulfate reduction by straw decomposing microbes. For P, we found highest pore water concentrations for straw, followed by biochar, ash and control. In summary, application of rice straw or derived ash or biochar strongly affect the element availability in paddy soil.

Fast synthesis, formation mechanism, and control of shell thickness of CuS–polystyrene core–shell microspheres

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

Zhao, Li-min, E-mail: zhaolimin@lcu.ecu.cn; Shao, Xin; Yin, Yi-bin

2012-09-15

Graphical abstract: Core–shell structure PSt/CuS were prepared using polystyrene which were modified by 3-methacryloxypropyltrimethoxysilane as template. The coating thickness of CuS can be controlled by the amount of 3-methacryloxypropyltrimethoxysilane and the UV–vis absorption intensity of PSt/CuS composite also changed with the coating thickness of CuS. Highlights: ► Core–shell structure PSt/CuS were prepared using silanol-modified polystyrene microspheres as template. ► The coating thickness of core–shell structure PSt/CuS can be controlled by a simple method. ► The UV–vis absorption intensity of PSt/CuS composite also changed with the coating thickness of CuS. -- Abstract: The silanol-modified polystyrene microspheres were prepared through dispersion polymerization.more » Then copper sulfide particles were grown on silanol-modified polystyrene through sonochemical deposition in an aqueous bath containing copper acetate and sulfide, released through the hydrolysis of thioacetamide. The resulting particles were continuous and uniform as characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared, thermogravimetric analysis and UV–vis absorption spectroscopy were used to characterize the structure and properties of core–shell particles. The results showed the coating thickness of CuS shell can be controlled by the amount of silanol and the UV–vis absorption intensity of PSt/CuS composite also changed with the coating thickness of CuS.« less

Assessment of mineral resource tracts in the Chugach National Forest, Alaska

USGS Publications Warehouse

Nelson, Steven W.; Miller, Marti L.

2000-01-01

Locatable minerals have been produced from the Chugach National Forest (CNF) for nearly 100 years. Past gold production has come from the Kenai Peninsula and the Girdwood, Port Wells, and Valdez areas. Copper and by-product gold and silver have been produced from mines at Ellamar, on Latouche Island, and near Valdez. Many of the past-producing properties were not mined out and contain significant inferred reserves of gold, copper, lead, zinc, and silver. This report outlines mineral resource areas (tracts) that contain both identified and undiscovered mineral resources. These tracts were drawn on the basis of one or more of the following criteria: (1) geochemical anomalies, (2) favorable geologic units, (3) presence of mines, prospects or mineral occurrences, and (4) geophysical anomalies. Bliss (1989) used six mineral deposit models to describe the types of deposits known from the CNF. Of these deposit types, only four are sufficiently known and defined in the CNF to be suitable for consideration in outlining and ranking of mineral resource tracts; these deposit types are: (1) Cyprus-type massive sulfide, (2) Chugach-type low-sulfide goldquartz veins, (3) placer gold, and (4) polymetallic vein. The U.S. Bureau of Mines indicated that most of the inferred mineral reserves in the CNF would not be economic to produce under current prices. Small-scale placer gold operations are a possible exception. Other known resources that have recorded past production (oil, coal, rock, sand, and gravel) are not addressed in this report.

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.

Complete genome sequence of Acidihalobacter prosperus strain F5, an extremely acidophilic, iron- and sulfur-oxidizing halophile with potential industrial applicability in saline water bioleaching of chalcopyrite.

PubMed

Khaleque, Himel N; Corbett, Melissa K; Ramsay, Joshua P; Kaksonen, Anna H; Boxall, Naomi J; Watkin, Elizabeth L J

2017-11-20

Successful process development for the bioleaching of mineral ores, particularly the refractory copper sulfide ore chalcopyrite, remains a challenge in regions where freshwater is scarce and source water contains high concentrations of chloride ion. In this study, a pure isolate of Acidihalobacter prosperus strain F5 was characterized for its ability to leach base metals from sulfide ores (pyrite, chalcopyrite and pentlandite) at increasing chloride ion concentrations. F5 successfully released base metals from ores including pyrite and pentlandite at up to 30gL -1 chloride ion and chalcopyrite up to 18gL -1 chloride ion. In order to understand the genetic mechanisms of tolerance to high acid, saline and heavy metal stress the genome of F5 was sequenced and analysed. As well as being the first strain of Ac. prosperus to be isolated from Australia it is also the first complete genome of the Ac. prosperus species to be sequenced. The F5 genome contains genes involved in the biosynthesis of compatible solutes and genes encoding monovalent cation/proton antiporters and heavy metal transporters which could explain its abilities to tolerate high salinity, acidity and heavy metal stress. Genome analysis also confirmed the presence of genes involved in copper tolerance. The study demonstrates the potential biotechnological applicability of Ac. prosperus strain F5 for saline water bioleaching of mineral ores. Copyright © 2017 Elsevier B.V. All rights reserved.

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 results from characterization, the extent to which these factors contribute to the loss of sulfide mineral particles in the tailings were determined.

Ancient mines of the Farah Garan area, southwestern Saudi Arabia

USGS Publications Warehouse

Smith, C.W.; Blank, H. Richard

1979-01-01

Ancient miners, in quest of oxidized copper minerals, gold, silver, and possibly zinc, mined gossans to approximately 20 m depth in an area 1.1 by 0.5 km in extent at Farah Garan. The gossans, derived from sulfides, are ordinarily found at contacts between marble lenses and metavolcanic-metasedimentary rocks, but in the southern part of the mined area, gossans are also within marbles. The gossans are generally lensoidal and discontinuous along strike. The same type of metallization, in similar rocks, was found at the Hemair ancient workings, about 3 km southeast. Both deposits are thought to be of epigenetic origin, and ore deposition was controlled by shearing along marble contacts. Drilling is recommended at Farah Garan. Al Ashyab is 4 km south of Farah Garan, and similar rocks and structures extend through both areas but there are no ancient workings at Al Ashyab. The dominant geologic feature in the area is a high, narrow, light-colored ridge consisting of intensely silicified quartz porphyry. Pyritized metavolcanic rocks envelope the silicified rock, and geochemical sampling revealed weakly anomalous, erratically spaced concentrations of copper and zinc within these rocks. No further work is recommended for the area. Quartz-filled fractures containing gold were mapped at Al Asharfat, Lejourah, and other locations where ancient miners worked the veins. The gold-bearing quartz veins are narrow and have short strike lengths, and potential tonnages are thought to be small. The veins are in younger, more massive rocks than the enclosing metamorphic rocks and are thought to be younger than the adjacent sulfide deposits. No further work is recommended. Pyritized zones and associated sparse copper oxides extend intermittently about 6 km south of Hemair in metasedimentary rocks of the Jiddah group. Similar zones, associated quartz vein swarms, and minor magnetite and gold are found in mafic metavolcanic rocks adjacent to the contact with quartz porphyry about 1 km west of Al Asharfat. Further study of these areas is recommended.

The use of ethanol to remove sulfur from coal. Final report, September 1991--December 1992; Revision

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

Savage, R.L.; Lazarov, L.K.; Prudich, M.E.

1994-03-10

The initial technical goal in the project was to develop a chemical method for the cost effective removal of both inorganic and organic sulfur from Ohio coals. Verifying and using a process of reacting ethanol vapors with coal under conditions disclosed in U.S. Patent 4,888,029, the immediate technical objectives were to convert a small scale laborative batch process to a larger scale continuous process which can serve as the basis for commercial development of the technology. This involved getting as much information as possible from small scale batch autoclave or fluid bed laboratory reactors for use in pilot plant studies.more » The laboratory data included material balances on the coal and sulfur, temperature and pressure ranges for the reaction, minimum reaction times at different conditions, the effectiveness of different activators such as oxygen and nitric oxide, the amount and nature of by-products such as sulfur dioxide, hydrogen sulfide and acetaldehyde, the effect of coal particle size on the speed and completeness of the reaction, and the effectiveness of the reaction on different Ohio coals. Because the laboratory experiments using the method disclosed in U.S. 4,888,029 were not successful, the objective for the project was changed to develop a new laboratory process to use ethanol to remove sulfur from coal. Using copper as a catalyst and as an H{sub 2}S scavenger, a new laboratory procedure to use ethanol to remove sulfur from coal has been developed at Ohio University and a patent application covering this process was filed in March, 1993. The process is based on the use of copper as a catalyst for the dehydrogenation of ethanol to produce nascent hydrogen to remove sulfur from the coal and the use of copper as a scavenger to capture the hydrogen sulfide formed from the sulfur removed from coal.« less

Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Lazarov, Marina; Horn, Ingo

2015-09-01

Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides, carbonates and oxides in situ with a precision of better than 0.1‰ (2SD) without using a matrix-matched standard during laser ablation analyses. Thus, this is a suitable tool to resolve Cu isotopic zoning larger than 0.1‰ in Cu-sulfides, carbonates and oxides.

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

Water characterization and seasonal heavy metal distribution in the Odiel River (Huelva, Spain) by means of principal component analysis.

PubMed

Montes-Botella, C; Tenorio, M D

2003-11-01

The Iberian Pyrite Belt is the largest mass of sulfide and manganese ores in Western Europe. Its sulfide oxidation is the origin of a heavily acidic drainage that affects the Odiel River in southwestern Huelva (Spain). To assess physicochemical, contamination parameters, heavy metal distribution and its seasonal variation in the upper Odiel River and in El Lomero mines, three water samplings were undertaken and analyzed between July 1998 and November 1999. Water from the Odiel River in the polluted zone showed low pH values (2.76-3.51), high heavy metal content, and high values of conductivity (1410-3648 microS/cm) and dissolved solids (1484-5602 mg/L). Principal Component Analysis (PCA) showed that variables related with the products of the pyrite oxidation and the salts that are solubilized by the high acidity generated in the oxidation of sulfides, grouped in the first component, accounted for 40.88% of total variance, and were the main influential factor in physicochemical water sample properties. The second influential factor was minority metals (nickel, cobalt, cadmium). Heavy metals showed three different seasonal patterns, closely related with saline efflorescences formed next to the river bed: majority metals (iron, copper, manganese, zinc); minority metals (lead, nickel, cobalt, cadmium); and chromium, which had a distinctive behavior.

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

Gibbs Energy Modeling of Digenite and Adjacent Solid-State Phases

NASA Astrophysics Data System (ADS)

Waldner, Peter

2017-08-01

All sulfur potential and phase diagram data available in the literature for solid-state equilibria related to digenite have been assessed. Thorough thermodynamic analysis at 1 bar total pressure has been performed. A three-sublattice approach has been developed to model the Gibbs energy of digenite as a function of composition and temperature using the compound energy formalism. The Gibbs energies of the adjacent solid-state phases covelitte and high-temperature chalcocite are also modeled treating both sulfides as stoichiometric compounds. The novel model for digenite offers new interpretation of experimental data, may contribute from a thermodynamic point of view to the elucidation of the role of copper species within the crystal structure and allows extrapolation to composition regimes richer in copper than stoichiometric digenite Cu2S. Preliminary predictions into the ternary Cu-Fe-S system at 1273 K (1000 °C) using the Gibbs energy model of digenite for calculating its iron solubility are promising.

The Interaction of CuS and Halothiobacillus HT1 Biofilm in Microscale Using Synchrotron Radiation-Based Techniques

PubMed Central

Lin, Huirong; Chen, Guangcun; Zhu, Shenhai; Chen, Yingxu; Chen, Dongliang; Xu, Wei; Yu, Xiaohan; Shi, Jiyan

2013-01-01

In order to investigate the microbe-mineral interaction in the micro scale, spatial distribution and speciation of Cu and S in Halothiobacillus HT1 biofilm formed on a CuS surface was examined using synchrotron-based X-ray techniques. Confocal laser scanning microscope (CLSM) results indicated that Halothiobacillus HT1 biofilm formation gave rise to distinct chemical and redox gradients, leading to diverse niches in the biofilm. Live cells were distributed at the air-biofilm and membrane-biofilm interface. CuS was oxidized by Halothiobacillus HT1 biofilm, and copper penetrated into the biofilm. Sulfide was oxidized to cysteine (77.3%), sulfite (3.8%) and sulfonate (18.9%). Cu-cysteine-like species were involved in the copper homeostasis. These results significantly improve our understanding of the interfacial properties of the biofilm-mineral interface. PMID:23708108

An innovative coupling between column leaching and oxygen consumption tests to assess behavior of contaminated marine dredged sediments.

PubMed

Couvidat, Julien; Benzaazoua, Mostafa; Chatain, Vincent; Zhang, Fan; Bouzahzah, Hassan

2015-07-01

Contaminated dredged sediments are often considered hazardous wastes, so they have to be adequately managed to avoid leaching of pollutants. The mobility of inorganic contaminants is a major concern. Metal sulfides (mainly framboïdal pyrite, copper, and zinc sulfides) have been investigated in this study as an important reactive metal-bearing phase sensitive to atmospheric oxygen action. An oxygen consumption test (OC-Test) has been adapted to assess the reactivity of dredged sediments when exposed to atmospheric oxygen. An experimental column set-up has been developed allowing the coupling between leaching and oxygen consumption test to investigate the reactivity of the sediment. This reactivity, which consisted of sulfide oxidation, was found to occur for saturation degree between 60 and 90 % and until the 20th testing week, through significant sulfates releases. These latter were assumed to come from sulfide oxidation in the first step of the test, then probably from gypsum dissolution. Confrontation results of OC-Test and leachate quality shows that Cu was well correlated to sulfates releases, which in turn, leads to Ca and Mg dissolution (buffer effect). Cu, and mostly Zn, was associated to organic matter, phyllosilicates, and other minerals through organo-clay complexes. This research confirmed that the OC-Test, originally developed for mine tailings, could be a useful tool in the dredged sediment field which can allow for intrinsic characterization of reactivity of a material suspected to readily reacting with oxygen and for better understanding of geochemical processes that affect pollutants behavior, conversion, and transfer in the environment.

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.

Status of CdS/CdTe solar cell research at NREL

NASA Astrophysics Data System (ADS)

Ramanathan, K.; Dhere, R. G.; Coutts, T. J.; Chu, T.; Chu, S.

1992-12-01

We report on the deposition of thin cadmium sulfide (CdS) layers from aqueous solutions and their optical properties. CdS layers have been deposited on soda lime glass, tin oxide coated glass and copper indium diselenide (CuInSe2) thin films. A systematic increase in the absorption is found to occur with increasing concentration of the buffer salt used in the bath. CdS/CdTe thin film solar cells have been fabricated by close spaced sublimation of CdTe, yielding 11.3% devices.

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

DOE PAGES

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu; ...

2017-09-21

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

Internal structure of cesium-bearing radioactive microparticles released from Fukushima nuclear power plant

PubMed Central

Yamaguchi, Noriko; Mitome, Masanori; Kotone, Akiyama-Hasegawa; Asano, Maki; Adachi, Kouji; Kogure, Toshihiro

2016-01-01

Microparticles containing substantial amounts of radiocesium collected from the ground in Fukushima were investigated mainly by transmission electron microscopy (TEM) and X-ray microanalysis with scanning TEM (STEM). Particles of around 2 μm in diameter are basically silicate glass containing Fe and Zn as transition metals, Cs, Rb and K as alkali ions, and Sn as substantial elements. These elements are homogeneously distributed in the glass except Cs which has a concentration gradient, increasing from center to surface. Nano-sized crystallites such as copper- zinc- and molybdenum sulfide, and silver telluride were found inside the microparticles, which probably resulted from the segregation of the silicate and sulfide (telluride) during molten-stage. An alkali-depleted layer of ca. 0.2 μm thick exists at the outer side of the particle collected from cedar leaves 8 months after the nuclear accident, suggesting gradual leaching of radiocesium from the microparticles in the natural environment. PMID:26838055

Sulvanite (Cu 3VS 4) nanocrystals for printable thin film photovoltaics

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

Chen, Ching -Chin; Stone, Kevin H.; Lai, Cheng -Yu

Copper Vanadium Sulfide (Cu 3VS 4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The synthesis of Cu 3VS 4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu 3VS 4 nanocrystals has been confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was evaluated by transmission electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface modifications, key element in solution processing. Further annealing ofmore » as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu 3VS 4 powders exhibiting an impurity that could be potentially mitigated by annealing temperature optimization. Furthermore, Cu 3VS 4, formed solely from Earth-abundant elements, could provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.« less

An evaluation of problems arising from acid mine drainage in the vicinity of Shasta Lake, Shasta County, California

USGS Publications Warehouse

Fuller, Richard H.; Shay, J.M.; Ferreira, R.F.; Hoffman, R.J.

1978-01-01

Streams draining the mined areas of massive sulfide ore deposits in the Shasta Mining Districts of northern California are generally acidic and contain large concentrations of dissolved metals, including iron, copper, and zinc. The streams, including Flat, Little Backbone, Spring, West Squaw, Horse, and Zinc Creeks, discharge into Shasta Reservoir and the Sacramento River and have caused numerous fish kills. The sources of pollution are discharge from underground mines, streams that flow into open pits, and streams that flow through pyritic mine dumps where the oxidation of pyrite and other sulfide minerals results in the production of acid and the mobilization of metals. Suggested methods of treatment include the use of air and hydraulic seals in the mines, lime neutralization of mine effluent, channeling of runoff and mine effluent away from mine and tailing areas, and the grading and sealing of mine dumps. A comprehensive preabatement and postabatement program is recommended to evaluate the effects of any treatment method used. (Woodard-USGS)

A ground electromagnetic survey used to map sulfides and acid sulfate ground waters at the abandoned Cabin Branch Mine, Prince William Forest Park, northern Virginia gold-pyrite belt

USGS Publications Warehouse

Wynn, Jeffrey C.

2000-01-01

INTRODUCTION AND BACKGROUND: Prince William Forest Park is situated at the northeastern end of the Virginia Gold-Pyrite belt northwest of the town of Dumfries, VA. The U. S. Marine Corps Reservation at Quantico borders the park on the west and south, and occupies part of the same watershed. Two abandoned mines are found within the park: the Cabin Branch pyrite mine, a historic source of acid mine drainage, and the Greenwood gold mine, a source of mercury contamination. Both are within the watershed of Quantico Creek (Fig.1). The Cabin Branch mine (also known as the Dumfries mine) lies about 2.4 km northwest of the town of Dumfries. It exploited a 300 meter-long, lens-shaped body of massive sulfide ore hosted by metamorphosed volcanic rocks; during its history over 200,000 tons of ore were extracted and processed locally. The site became part of the National Capitol Region of the National Park Service in 1940 and is currently managed by the National Park Service. In 1995 the National Park Service, in cooperation with the Virginia Department of Mines, Minerals, and Energy reclaimed the Cabin Branch site. The Virginia Gold-Pyrite belt, also known as the central Virginia volcanic-plutonic belt, is host to numerous abandoned metal mines (Pavlides and others, 1982), including the Cabin Branch deposit. The belt itself extends from its northern terminus near Cabin Branch, about 50 km south of Washington, D.C., approximately 175 km to the southwest into central Virginia. It is underlain by metamorphosed volcanic and clastic (non-carbonate) sedimentary rocks, originally deposited approximately 460 million years ago during the Ordovician Period (Horton and others, 1998). Three kinds of deposits are found in the belt: volcanic-associated massive sulfide deposits, low-sulfide quartz-gold vein deposits, and gold placer deposits. The massive sulfide deposits such as Cabin Branch were historically mined for their sulfur, copper, zinc, and lead contents, but also yielded byproduct gold and silver. The environmental impact of massive sulfide deposits can be substantial. These deposits are characterized by high concentrations of heavy-metal sulfide minerals, hosted by silicate rocks. Thus, weathering of these deposits and their mine wastes has the potential to generate heavy-metal laden sulfuric acid that can have negative impacts on aquatic ecosystems. In addition, lead associated with solid mine wastes has the potential for human health impacts through ingestion. The heavy metals that are encountered in these deposits and are most likely to cause environmental impacts include copper, zinc, lead, cadmium, and arsenic. In addition, the weathering of pyrite releases large amounts of iron, and the acid generated attacks the country rocks and causes the release of large amounts of aluminum, which also can severely impact aquatic ecosystems. A reclamation attempt was made at the site in 1995, including construction of storm-water diversion trenches around the abandoned mine area, grading tailings away from the stream bank, addition of pulverized limestone and topsoil, and revegetation. The post-reclamation chemistry of shallow groundwaters (<3 meters deep) shows a neutral pH on the southwestern bank of the stream but pH of 4.1 to 4.5 on the northeastern bank. The dominant ions are Fe2+ and SO42- (Seal, Haffner, Meier, and Pollio, 1999) A ground electromagnetic survey was conducted over the site in 1999 as part of a wider study ( Seal, Haffner, and Meier, 1998a,b, 1999). It was hoped that a 3-D map of the soil conductivity derived from the survey could provide insight into the distribution of the mobilized sulfides present under the ground. This study was conducted in cooperation with the National Park Service

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 the crystallographic structure of covellite indicated that one third of the Cu is Cu(II) and digenite (Cu1.8S) has one ninth of Cu(II). Therefore, covellite is more oxidized species and has higher δ65Cu compared with coexisting digenite.

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.

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.

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.

GEOLOGY, SULFUR ISOTOPES AND THE ORIGIN OF THE HEATH STEELE ORE DEPOSITS, NEWCASTLE, N.B., CANADA

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

Dechow, E.

The Heath Steele mine is located 35 miles northwest of Newcastle, New Brunswick, Canada. Middle Ordovician Tetagouche Group rocks, consisting of siliceous and basic volcanic rocks, and fine-grained quartz sericite schists and porphyry, have been folded into a steeply plunging recumbent anticline. The ore deposits of zinc, lead, and copper are associated with minor folding and/or sheared dilatent zones at or near the contact between porphyry and fine-grained senicitic schist. Mineralogically the sulfide bodies consist of early, euhedral arsenopyrite, magnetite, and pyrite, followed by interstitial pyrrhotite, sphalerite, chalcopyrite and galena. Minor minerals are ternantite-tetrahedrite, bismuthinite, marcasite, hematite, and some graphite.more » Supergene minerals consist of chalcocite, covellite, and marcasite with a little native silver. Little hypogene replacement has taken place between the minerals, which show a "porphyritic" texture. Sulfur isotope ratios were determined for over 150 sulfide and sulfate specimens from five of the seven ore bodies, and from granite, acid and basic volcanics, porphyry, and sediments. The results indicate that there is no detectable fractionation either during hypogene mineralization or supergene enrichment. The spread (21.82 to 22.02) covered by the ratios is narrow, and suggestive of a well homogenized source of mineral solutions. The enrichment of S/sup 34/ in the ore sulfides and the presence of graphite, evident from mineralographic studies and mass spectrometric analysis, suggests reduction of original sulfates (known to be enriched in S/sup 34/) by organic carbon at temperatures in excess of 500 deg C. A calculation based on the isotopic exchange reaction between sulfide and sulfate under equilibrium conditions and the spread of the ratios indicates a temperature of 700 to 800 deg C for the source. Finally the ratios determined for sulfides in a gneissic granite close to Heath Steele have the same ratio as the ore. These factors are considered to be diagnostic of a magmatic hydrothermal origin for the orp deposits. It is believed that an original source bed has been buried until suitable temperatures were reached to cause granitization, reduction of sulfates, and mobilization of the resulting sulfides to form ore deposits at favorable loci. (auth)« less

Copper systematics during mantle melting and crustal differentiation in arcs: implications for S and Pb budgets of the continental crust

NASA Astrophysics Data System (ADS)

Lee, C.; Chin, E. J.; Dasgupta, R.; Luffi, P. I.; Le Roux, V.

2010-12-01

During mid-ocean ridge melting, Cu behaves like Sc and is therefore moderately incompatible, as evidenced by the twofold increase in Cu content in MORBs compared to the mantle. However, Cu content in the continental crust is comparable to that of the mantle, implying that during continental crust formation, Cu becomes effectively compatible. Cu is one of the only elements that exhibits Jekyll and Hyde behavior. This switch to being compatible is consistent with the observation that for the majority of arc magmas (as well as MORBs), Cu decreases with increasing SiO2 and decreasing MgO. Using natural samples, we infer new partition coefficients that indicate Cu is incompatible in olivine, pyroxenes, amphiboles, and biotite. The only mineral to exert significant control on Cu partitioning is sulfide. Cu behaves incompatibly during mantle melting because the modal abundance of sulfides relative to silicate minerals is extremely low. The monotonic decrease in Cu in most differentiating arc magmas requires sulfide saturation. In addition, the similar abundances of Cu in many primitive arc magmas compared to MORBs suggests that mantle melting in both environments occurs not only at sulfide saturation but without the need for excess Cu (or S). In a few cases, however, primitive arc magmas begin with high Cu or show increases in Cu with differentiation, which most likely requires unusually high oxygen fugacities in the source or magmatic evolution towards high oxygen fugacity. Such cases may be important for the origin of Cu porphyry deposits, but are generally rare. Because of the close link between Cu and sulfide during magma differentiation, Cu can be used as a proxy for the pre-degassed S content of arc magmas. The S content of continental crust, like many volatile elements, is basically unconstrained, but it can be inferred from Cu, which is much better constrained. Finally, the fact that the continental crust is highly depleted in Cu implies that there is a missing reservoir rich in Cu and by necessity sulfide. Cumulate xenoliths in arc settings fit this persona. Delamination of these cumulates, embedded with sulfides, will have profound implications for the Pb isotopic evolution of the mantle by linking the Pb paradox to continent formation.

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

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.

Krasnotur'insk Skarn copper ore field, Northern Urals: The U-Pb age of ore-controlling diorites and their place in the regional metallogeny

NASA Astrophysics Data System (ADS)

Grabezhev, A. I.; Ronkin, Yu. L.; Puchkov, V. N.; Gerdes, A.; Rovnushkin, M. Yu.

2014-06-01

The Krasnotur'insk skarn copper ore field known from the theoretical works of Academician K.S. Korzhinskii is located in the western part of the Tagil volcanic zone (in the area of the town of Krasnotur'insk). The ore field is composed of layered Devonian (Emsian) volcanosedimentary rocks intruded by small plutons of quartz diorites, diorites, and gabbrodiorites. Widespread pre-ore and intra-ore dikes of similar composition control the abundance of the andradite skarns formed after limestones and the magnetitesulfide and sulfide ore bodies formed after skarns. The LA-ICP-MS U-Pb concordant age of zircon from the quartz diorite of the Vasil'evsko-Moskalevskii pluton calculated by 16 analyses (16 crystals) is 407.7 ± 1.6 Ma (MSWD = 1.5). Taking into account the geological and petrogeochemical similarity of diorites of small plutons and intra-ore dikes, it is assumed that this age corresponds to the period of formation of the ore-magmatic system of the Krasnotur'insk skarn copper ore field. It was probably formed somewhat earlier than the Auerbakh montzonitic pluton and the accompanying skarn magnetite deposits in the south.

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 abiotic in order to elucidate Cu release from ore and wastes. Greater Cu release were measured from the biological experiments carried out with S and Fe oxidizers compared to those from the chemical experiments. Fe-oxide precipitation experiments carried out in the laboratory showed high Cu absorbtion into Fe-oxides produced by biological reactions carried out with Fe oxidizers. Overall, these preliminary experimental results showed that Cu release and migration from the source can be controlled by various microorganims which regulate S and Fe cycles in the field. Key words: Metal sulfide oxidation, Kure pyritic copper mines, AMD, Bioleaching, Secondary Fe-oxide precipitation

Metallogeny of the nikolai large igneous province (LIP) in southern alaska and its influence on the mineral potential of the talkeetna mountains

USGS Publications Warehouse

Schmidt, J.M.; Rogers, R.K.

2007-01-01

Recent geologic mapping has identified areas of extrusive basalts of the Middle to Late Triassic Nikolai Greenstone within the Wrangellia terrane that extend at least 80 km southwest of their previously known extent. Abundant dolerite sills of similar composition intrude Paleozoic and Mesozoic stratigraphy below the Nikolai throughout the central Talkeetna Mountains. The Talkeetna Mountains, therefore, have newly identified potential for copper, nickel, and platinum-group elements (PGEs) as disseminated, net-textured, or massive magmatic sulfide deposits hosted in mafic and ultramafic sill-form complexes related to emplacement of the Nikolai. Because of their potential high grades, similar magmatic sulfide targets have been the focus of increasing mineral exploration activity over the last decade in the Amphitheater Mountains and central Alaska Range, 100-200 km to the northeast. The Nikolai Greenstone, associated intrusions, and their metamorphosed equivalents also have potential to host stratabound disseminated "basaltic copper" deposits. Sedimentary and metasedimentary rocks overlying the Nikolai have the potential to host stratabound, disseminated, or massive "reduced-facies" type Cu-Ag deposits. Ultramafic rocks have been identified only in the extreme northeastern Talkeetna Mountains to date. However, coincident gravity and magnetic highs along the leading (northwestern) edge of and within Wrangellia in the Talkeetna and Clearwater Mountains suggest several areas that are highly prospective for ultramafic rocks related to extrusion of Nikolai lavas. In particular, the distribution, geometry, and composition of sills within the pre-Nikolai stratigraphy and the structural and tectonic controls on intrusive versus extrusive rock distribution deserve serious examination. Copyright ?? 2007 The Geological Society of America.

High temperature neutron powder diffraction study of the Cu12Sb4S13 and Cu4Sn7S16 phases

NASA Astrophysics Data System (ADS)

Lemoine, Pierric; Bourgès, Cédric; Barbier, Tristan; Nassif, Vivian; Cordier, Stéphane; Guilmeau, Emmanuel

2017-03-01

Ternary copper-containing sulfides Cu12Sb4S13 and Cu4Sn7S16 have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu12Sb4S13 and Cu4Sn7S16 phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu12Sb4S13 decomposes above ≈792 K into Cu3SbS3, and (ii) Cu4Sn7S16 decomposes above ≈891 K into Sn2S3 and a copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu3SnS4 stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu12Sb4S13 are in fair agreement with recent published data, the decomposition behavior of Cu4Sn7S16 differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu4Sn7S16 and tetrahedrite Cu12Sb4S13 phases at 300 K, and for the high temperature form of skinnerite Cu3SbS3 at 843 K.

Geology of the Shinarump No. 1 uranium mine, Seven Mile Canyon area, Grand County, Utah

USGS Publications Warehouse

Finch, Warren Irvin

1954-01-01

The geology of the Shinarump No. 1 uranium mine, located about 12 miles northwest of Moab, Utah, in the Seven Mile Canyon area, Grand County, Utah, was studied to determine the habits, ore controls, and possible origin of the deposit. Rocks of Permian, Triassic, and Jurassic age crop out in the area mapped, and uranium deposits are found in three zones in the lower 25 feet of the Chinle formation of Late Triassic age. The Shinarump No. 1 mine, which is in the lowermost zone, is located on the west flank of the Moab anticline near the Moab fault. The Shinarump No. 1 uranium deposit consists of discontinuous lenticular layers of mineralized rock, irregular in outline, that, in general, follow the bedding. Ore minerals, mainly uraninite, impregnate the rock. High-grade ore seams of uraninite and chalcocite occur along bedding planes. Uraninite formed later than, or simultaneous with, most sulfides, and the chalcocite may be of two ages, with some being later than uraninite. Uraninite and chalcocite are concentrated in the more poorly sorted parts of siltstones. In the Seven Mile Canyon area guides to ore inferred from the study of the Shinarump No. 1 deposit are the presence of bleached siltstone, carbonaceous matter, and copper sulfides. Results of spectrographic analysis indicate that the mineralizing solutions contained important amounts of barium, vanadium, uranium, and copper, as well as lesser amounts of strontium, chromium, boron, yttrium, lead, and zinc. The origin of the Shinarump No. 1 deposit is thought to be hydrothermal.

Geology of the Shinarump No. 1 uranium mine, Seven Mile Canyon area, Grand County, Utah

USGS Publications Warehouse

Finch, Warren Irvin

1953-01-01

The Shinarump No. 1 uranium mine is located about 12 miles northwest of Moab, Utah, in the Seven Mile Canyon area, Grand County, Utah. A study was made of the geology of the Shinarump No. 1 mine in order to determine the habits, ore controls, and possible origin of the deposit. Rocks of Permain, Triassic, and Jurassic age crop out in the area mapped. Uranium deposits are found in three zones in the lower 25 feet of the Upper Triassic Chinle formation. The Shinarump No. 1 mine, which is in the lowermost zone, is located on the west flank of the Moab anticline near the Moab fault. The Shinarump No. 1 uranium deposit consists of discontinuous lenticular layers of mineralized rock, irregular in outline, that, in general, follow the bedding. Ore minerals, mainly uranite, impregnate the rock. High-grade seams of uranite and chalcocite occur along bedding planes. Formation of unraninite is later than or simultaneous with most sulfides. Chalcocite may be of two ages, with some being later than uraninite. Uraninite and chalcocite are concentrated in the poorer sorted parts of siltstones. Guides to ore in the Seven Mile Canyon area inferred from the study of the Shinarump No. 1 deposit are the presence of bleached siltstone, copper sulfides, and carbonaceous matter. Results of spectrographic analysis indicated that the mineralizing solutions contained important amounts of barium, vanadium, uranium, and copper as well as lesser amounts of strontium, chromium, boron, yttrium, lead, and zinc. The origin of the Shinarump No. 1 deposit is thought to be hydrothermal, dated as later or early.

A Laughing Gas Greenhouse for the Proterozoic?

NASA Astrophysics Data System (ADS)

Roberson, A. L.; Roadt, J.; Halevy, I.; Kasting, J. F.

2010-12-01

An anoxic, sulfidic ‘Canfield ocean’ during the Proterozoic (0.75-2.3 Ga) would have had limited trace metal abundances because of the low solubility of metal sulfides. The limitation on copper, specifically, would have had a significant impact on marine denitrification. Copper is needed for the enzyme that controls the final step of denitrification, from N2O to N2. Today, only about 5-6 percent of denitrification results in release of N2O. If all denitrification stopped at N2O during the Proterozoic, the N2O flux could have been 15-20 times higher than today. Other parts of the nitrogen cycle should have been able to operate at rates comparable to today, as catalysts for these reactions should have existed. The high N2O flux should have created higher atmospheric N2O concentrations; although this effect may have been offset by faster rates of N2O photolysis if O2 concentrations were lower than today. N2O concentrations of 0.3 to 30 ppmv, along with methane levels of 30-100 ppm, could have kept the surface warm during the Proterozoic without necessitating high CO2 levels. The high methane concentrations were a consequence of lack of dissolved O2 and sulfate in the deep ocean, which should have led to a high CH4 flux from marine sediments. A second oxygenation event at the end of the Proterozoic would have resulted in a shift to a more modern ocean and, consequently, more modern concentrations of atmospheric N2O and CH4.

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.

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

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

PubMed

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

2015-10-01

This paper reports the bioavailability of the metals (cadmium, copper, zinc, lead, and nickel) in sediment samples collected in seven stations from the São Paulo Estuary, Todos os Santos Bay, Brazil. The bioavailability was determined by employing the technique "acid-volatile sulfide (AVS) and simultaneously extracted metal (SEM)". The elements cadmium, copper, lead, and zinc were determined using differential pulse anodic stripping voltammetry (DPASV), while nickel was quantified utilizing electrothermal atomic absorption spectrometry (ET AAS). The accuracy of these methods was confirmed using a certified reference material of estuarine sediment (NIST 1646). The sulfide was quantified using potentiometry with selective electrode and the organic matter determination employing an indirect volumetric method using potassium dichromate and iron(II) sulfate solutions. The bioavailability of the metals was estimated by relationship between the concentration of AVS and the sum of the concentrations of the simultaneously extracted metals (ΣSEM), considering a significant toxicity when (ΣSEM)/(AVS) is higher than 1. The bioavailability values in the seven stations studied varied from 0.93 to 1.31 (June, 2014) and from 0.34 to 0.58 (September, 2014). These results demonstrated a critical condition of toxicity (bioavailability >1) in six of the seven sediment samples collected during the rainy season (June, 2014). In the other period (September, 2014), the bioavailability was always lower than 1 for all sediment samples collected in the seven stations. The individual values of the concentrations of the five metals were compared with the parameters PEL (probable effects level) and TEL (threshold effects level), which are commonly employed for characterization of ecological risk in environmental systems. This comparison revealed that all metals have concentrations lower than the PEL and only zinc and lead in some stations have contents higher than the TEL. The bioavailability evaluation and the concentrations achieved for the five elements in the sediments samples analyzed demonstrated that the ecosystem studied does not present an environmental risk.

Metallogenic and tectonic significance of oxygen isotope data and whole-rock potassium-argon ages of the Nikolai Greenstone, McCarthy Quadrangle, Alaska

USGS Publications Warehouse

Silberman, M.L.; MacKevett, E.M.; Connor, C.L.; Matthews, Alan

1980-01-01

The Middle and (or) Late Triassic Nikolai Greenstone, part of the allochthonous terrane of Wrangellia, is typically altered and locally metamorphosed to prehnite-pumpellyite facies with chlorite and epidote as the most common secondary minerals. Intrinsic copper content averages 155 ppm, and two types of concentrations of copper in the Nikolai are common: (1) native copper fillings of amygdules and rubble zones typically near flow tops, and (2) veins and thin replacement zones that contain native copper and copper-iron sulfides in quartz-epidote or calcite gangue in faults and fractures. Oxygen isotope data from quartz and epidote from three copperbearing veins yield calculated ore fluid temperatures of approximately 200°C and 6180 of approximately +1 per mil in agreement with a metamorphicsegregation origin of these deposits, as suggested by Sinclair (1977). Seven K-Ar ages of chloritized greenstone, including those adjacent to veins fall on an initial argon diagram with a zero intercept and a slope which yields an isochron age of 112 + 11 m.y. The ages define a Cretaceous thermalmetamorphic episode which is responsible for alteration and mineralization. The episode is younger than a major Jurassic progeny, accompanied by granitic intrusion, in the area, and appears to be unaffected by minor granitic intrusion in the middle to late Tertiary. We believe the Cretaceous event is related to accretion of Wrangellia to its present relative position in North America. This age of accretion agrees with stratigraphic and structural evidence cited by other workers. 

Germanium and indium

USGS Publications Warehouse

Shanks, W.C. Pat; Kimball, Bryn E.; Tolcin, Amy C.; Guberman, David E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Germanium and indium are two important elements used in electronics devices, flat-panel display screens, light-emitting diodes, night vision devices, optical fiber, optical lens systems, and solar power arrays. Germanium and indium are treated together in this chapter because they have similar technological uses and because both are recovered as byproducts, mainly from copper and zinc sulfides.The world’s total production of germanium in 2011 was estimated to be 118 metric tons. This total comprised germanium recovered from zinc concentrates, from fly ash residues from coal burning, and from recycled material. Worldwide, primary germanium was recovered in Canada from zinc concentrates shipped from the United States; in China from zinc residues and coal from multiple sources in China and elsewhere; in Finland from zinc concentrates from the Democratic Republic of the Congo; and in Russia from coal.World production of indium metal was estimated to be about 723 metric tons in 2011; more than one-half of the total was produced in China. Other leading producers included Belgium, Canada, Japan, and the Republic of Korea. These five countries accounted for nearly 95 percent of primary indium production.Deposit types that contain significant amounts of germanium include volcanogenic massive sulfide (VMS) deposits, sedimentary exhalative (SEDEX) deposits, Mississippi Valley-type (MVT) lead-zinc deposits (including Irish-type zinc-lead deposits), Kipushi-type zinc-lead-copper replacement bodies in carbonate rocks, and coal deposits.More than one-half of the byproduct indium in the world is produced in southern China from VMS and SEDEX deposits, and much of the remainder is produced from zinc concentrates from MVT deposits. The Laochang deposit in Yunnan Province, China, and the VMS deposits of the Murchison greenstone belt in Limpopo Province, South Africa, provide excellent examples of indium-enriched deposits. The SEDEX deposits at Bainiuchang, China (located in southeastern Yunnan Province), and the Dabaoshan SEDEX deposit (located in the Nanling region of China) contain indium-enriched sphalerite. Another major potential source of indium occurs in the polymetallic tin-tungsten belt in the Eastern Cordillera of the Andes Mountains of Bolivia. Deposits there occur as dense arrays of narrow, elongate, indium-enriched tin oxide-polymetallic sulfide veins in volcanic rocks and porphyry stocks.Information about the behavior of germanium and indium in the environment is limited. In surface weathering environments, germanium and indium may dissolve from host minerals and form complexes with chloride, fluoride, hydroxide, organic matter, phosphate, or sulfate compounds. The tendency for germanium and indium to be dissolved and transported largely depends upon the pH and temperature of the weathering solutions. Because both elements are commonly concentrated in sulfide minerals, they can be expected to be relatively mobile in acid mine drainage where oxidative dissolution of sulfide minerals releases metals and sulfuric acid, resulting in acidic pH values that allow higher concentrations of metals to be dissolved into solution.

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.

2D Inversion of DCR and Time Domain IP data: an example from ore exploration

NASA Astrophysics Data System (ADS)

Adrian, J.; Tezkan, B.

2015-12-01

Ore deposits often appear as disseminated sulfidic materials. Exploring these deposits with the Direct Current Resistivity (DCR) method alone is challenging because the resistivity signatures caused by disseminated material is often hard to detect. The Time-domain Induced Polarization (TDIP) method, on the other hand, is qualified to detect areas with disseminated sulfidic ores due to large electrode polarization effects which result in large chargeability anomalies. By employing both methods we gain information about both, the resistivity and the chargeability distribution of the subsurface.On the poster we present the current state of the development of a 2D smoothness constraint inversion algorithm for DCR and TDIP data. The implemented forward algorithm uses a Finite Element approach with an unstructured mesh. The model parameters resistivity and chargeability are connected by either a simple conductivity pertubation approach or a complex conductivity approach.As a case study, the 2D inversion results of DCR/TDIP and RMT data obtained during a survey on a sulfidic copper ore deposit in Turkey are presented. The presence of an ore deposit is indicated by areas with low resistivity and significantly high chargeability in the inversion models.This work is part of the BMBF/TUEBITAK funded project ``Two-dimensional joint interpretation of Radiomagnetotellurics (RMT), Direct Current Resistivity (DCR) and Induced Polarization (IP) data: an example from ore exploration''.

A strategy to improve the energy conversion efficiency and stability of quantum dot-sensitized solar cells using manganese-doped cadmium sulfide quantum dots.

PubMed

Gopi, Chandu V V M; Venkata-Haritha, M; Kim, Soo-Kyoung; Kim, Hee-Je

2015-01-14

This article describes the effect of manganese (Mn) doping in CdS to improve the photovoltaic performance of quantum dot sensitized solar cells (QDSSCs). The performances of the QDSSCs are examined in detail using a polysulfide electrolyte with a copper sulfide (CuS) counter electrode. Under the illumination of one sun (AM 1.5 G, 100 mW cm(-2)), 10 molar% Mn-doped CdS QDSSCs exhibit a power conversion efficiency (η) of 2.85%, which is higher than the value of 2.11% obtained with bare CdS. The improved photovoltaic performance is due to the impurities from Mn(2+) doping of CdS, which have an impact on the structure of the host material and decrease the surface roughness. The surface roughness and morphology of Mn-doped CdS nanoparticles can be characterised from atomic force microscopy images. Furthermore, the cell device based on the Mn-CdS electrode shows superior stability in the sulfide/polysulfide electrolyte in a working state for over 10 h, resulting in a highly reproducible performance, which is a serious challenge for the Mn-doped solar cell. Our finding provides an effective method for the fabrication of Mn-doped CdS QDs, which can pave the way to further improve the efficiency of future QDSSCs.

Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron.

PubMed

Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A

2016-05-05

This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor. Copyright © 2016 Elsevier B.V. All rights reserved.

Fluid evolution and ore genesis of the Dalingshang deposit, Dahutang W-Cu ore field, northern Jiangxi Province, South China

NASA Astrophysics Data System (ADS)

Peng, Ning-Jun; Jiang, Shao-Yong; Xiong, Suo-Fei; Pi, Dao-Hui

2018-02-01

The Dalingshang W-Cu deposit is located in the North section of the Dahutang ore field, northern Jiangxi Province, South China. Vein- and breccia-style tungsten-copper mineralization is genetically associated with Mesozoic S-type granitic rocks. Infrared and conventional microthermometric studies of both gangue and ore minerals show that the homogenization temperatures for primary fluid inclusions in wolframite ( 340 °C) are similar to those in scheelite ( 330 °C), but about 40 °C higher than those of apatite ( 300 °C) and generally 70 °C higher than those in coexisting quartz ( 270 °C). Laser Raman analysis identifies CH4 and N2 without CO2 in fluid inclusions in scheelite and coexisting quartz, while fluid inclusions in quartz of the sulfide stage have variable CO2 content. The ore-forming fluids overall are characterized by high- to medium-temperature, low-salinity, CH4, N2, and/or CO2-bearing aqueous fluids. Chalcopyrite, muscovite, and sphalerite are the most abundant solids recognized in fluid inclusions from different ores. The H-O-S-Pb isotope compositions favor a dominantly magmatic origin for ores and fluids, while some depleted δ34S values (- 14.4 to - 0.9‰) of sulfides from the sulfide stage are most likely produced by an increase of oxygen fugacity, possibly caused by inflow of oxidized meteoric waters. The microthermometric data also indicate that a simple cooling process formed early scheelite and wolframite. However, increasing involvement of meteoric waters and fluid mixing may trigger a successive deposition of base metal sulfides. Fluid-rock interaction was critical for scheelite mineralization as indicated by in-situ LA-ICP-MS analysis of trace elements in scheelite.

Mineral deposit densities for estimating mineral resources

USGS Publications Warehouse

Singer, Donald A.

2008-01-01

Estimates of numbers of mineral deposits are fundamental to assessing undiscovered mineral resources. Just as frequencies of grades and tonnages of well-explored deposits can be used to represent the grades and tonnages of undiscovered deposits, the density of deposits (deposits/area) in well-explored control areas can serve to represent the number of deposits. Empirical evidence presented here indicates that the processes affecting the number and quantity of resources in geological settings are very general across many types of mineral deposits. For podiform chromite, porphyry copper, and volcanogenic massive sulfide deposit types, the size of tract that geologically could contain the deposits is an excellent predictor of the total number of deposits. The number of mineral deposits is also proportional to the type’s size. The total amount of mineralized rock is also proportional to size of the permissive area and the median deposit type’s size. Regressions using these variables provide a means to estimate the density of deposits and the total amount of mineralization. These powerful estimators are based on analysis of ten different types of mineral deposits (Climax Mo, Cuban Mn, Cyprus massive sulfide, Franciscan Mn, kuroko massive sulfide, low-sulfide quartz-Au vein, placer Au, podiform Cr, porphyry Cu, and W vein) from 108 permissive control tracts around the world therefore generalizing across deposit types. Despite the diverse and complex geological settings of deposit types studied here, the relationships observed indicate universal controls on the accumulation and preservation of mineral resources that operate across all scales. The strength of the relationships (R 2=0.91 for density and 0.95 for mineralized rock) argues for their broad use. Deposit densities can now be used to provide a guideline for expert judgment or used directly for estimating the number of most kinds of mineral deposits.

Radiation resistance of thin-film solar cells for space photovoltaic power

NASA Technical Reports Server (NTRS)

Woodyard, James R.; Landis, Geoffrey A.

1991-01-01

Copper indium diselenide, cadmium telluride, and amorphous silicon alloy solar cells have achieved noteworthy performance and are currently being studied for space power applications. Cadmium sulfide cells had been the subject of much effort but are no longer considered for space applications. A review is presented of what is known about the radiation degradation of thin film solar cells in space. Experimental cadmium telluride and amorphous silicon alloy cells are reviewed. Damage mechanisms and radiation induced defect generation and passivation in the amorphous silicon alloy cell are discussed in detail due to the greater amount of experimental data available.

ARNOLD MESA ROADLESS AREA, ARIZONA.

USGS Publications Warehouse

Wolfe, Edward W.; McColly, Robert A.

1984-01-01

Geologic geochemical, and aeromagnetic investigations and a survey of mines and prospects in the Arnold Mesa Roadless Area, Arizona, provide little evidence for the occurrence of mineral or energy resources. Buried Proterozoic basement rocks are possible hosts of porphyry-type copper and massive sulfide deposits but the thick cover of Paleozoic sedimentary rocks and upper Cenozoic volcanic rocks precluded assessment of this possibility. Chemistry and temperature of spring and well waters suggest that a geothermal resource may exist near the eastern margin of the roadless area, but the anomaly has not been tested by drilling and this resource remains unverified. No other energy resources were identified.

Industrial contributions of arsenic to the environment.

PubMed Central

Nelson, K W

1977-01-01

Arsenic is present in all copper, lead, and zinc sulfide ores and is carried along with those metals in the mining, milling and concentrating process. Separation, final concentration and refining of by-product arsenic as the trioxide is achieved at smelters. Arsenic is the essential consistent element of many compounds important and widely used in agriculture and wood preservation. Lesser amounts are used in metal alloys, glass-making, and feed additives. There is no significant recycling. Current levels of arsenic emissions to the atmosphere from smelters and power plants and ambient air concentrations are given as data of greatest environmental interest. PMID:908308

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

Sequential Extraction Results and Mineralogy of Mine Waste and Stream Sediments Associated With Metal Mines in Vermont, Maine, and New Zealand

USGS Publications Warehouse

Piatak, N.M.; Seal, R.R.; Sanzolone, R.F.; Lamothe, P.J.; Brown, Z.A.; Adams, M.

2007-01-01

We report results from sequential extraction experiments and the quantitative mineralogy for samples of stream sediments and mine wastes collected from metal mines. Samples were from the Elizabeth, Ely Copper, and Pike Hill Copper mines in Vermont, the Callahan Mine in Maine, and the Martha Mine in New Zealand. The extraction technique targeted the following operationally defined fractions and solid-phase forms: (1) soluble, adsorbed, and exchangeable fractions; (2) carbonates; (3) organic material; (4) amorphous iron- and aluminum-hydroxides and crystalline manganese-oxides; (5) crystalline iron-oxides; (6) sulfides and selenides; and (7) residual material. For most elements, the sum of an element from all extractions steps correlated well with the original unleached concentration. Also, the quantitative mineralogy of the original material compared to that of the residues from two extraction steps gave insight into the effectiveness of reagents at dissolving targeted phases. The data are presented here with minimal interpretation or discussion and further analyses and interpretation will be presented elsewhere.

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

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

Effect of thione primers on adhesive bonding between an indirect composite material and Ag-Pd-Cu-Au alloy.

PubMed

Imai, Hideyuki; Koizumi, Hiroyasu; Shimoe, Saiji; Hirata, Isao; Matsumura, Hideo; Nikawa, Hiroki

2014-01-01

The current study evaluated the effect of primers on the shear bond strength of an indirect composite material joined to a silverpalladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell). Disk specimens were cast from the alloy and were air-abraded with alumina. Eight metal primers were applied to the alloy surface. A light-polymerized indirect composite material (Solidex) was bonded to the alloy. Shear bond strength was determined both before and after the application of thermocycling. Two groups primed with Metaltite (thione) and M. L. Primer (sulfide) showed the greatest post-thermocycling bond strength (8.8 and 6.5 MPa). The results of the X-ray photoelectron spectroscopic (XPS) analysis suggested that the thione monomer (MTU-6) in the Metaltite primer was strongly adsorbed onto the Ag-Pd-Cu-Au alloy surface even after repeated cleaning with acetone. The application of either the thione (MTU-6) or sulfide primer is effective for enhancing the bonding between a composite material and Ag-Pd-Cu-Au alloy.

Solvothermal Synthesis of Three-Dimensional Hierarchical CuS Microspheres from a Cu-Based Ionic Liquid Precursor for High-Performance Asymmetric Supercapacitors.

PubMed

Zhang, Jing; Feng, Huijie; Yang, Jiaqin; Qin, Qing; Fan, Hongmin; Wei, Caiying; Zheng, Wenjun

2015-10-07

It is meaningful to exploit copper sulfide materials with desired structure as well as potential application due to their cheapness and low toxicity. A low-temperature and facile solvothermal method for preparing three-dimensional (3D) hierarchical covellite (CuS) microspheres from an ionic liquid precursor [Bmim]2Cu2Cl6 (Bmim = 1-butyl-3-methylimidazolium) is reported. The formation of CuS nanostructures was achieved by decomposition of intermediate complex Cu(Tu)3Cl (thiourea = Tu), which produced CuS microspheres with diameters of 2.5-4 μm assembled by nanosheets with thicknesses of 10-15 nm. The ionic liquid, as an "all-in-one" medium, played a key role for the fabrication and self-assembly of CuS nanosheets. The alkylimidazolium rings ([Bmim](+)) were found to adsorb onto the (001) facets of CuS crystals, which inhibited the crystal growth along the [001] direction, while the alkyl chain had influence on the assembly of CuS nanosheets. The CuS microspheres showed enhanced electrochemical performance and high stability for the application in supercapacitors due to intriguing structural design and large specific surface area. When this well-defined CuS electrode was assembled into an asymmetric supercapacitor (ASC) with an activated carbon (AC) electrode, the CuS//AC-ASC demonstrated good cycle performance (∼88% capacitance after 4000 cycles) and high energy density (15.06 W h kg(-1) at a power density of 392.9 W kg(-1)). This work provides new insights into the use of copper sulfide electrode materials for asymmetric supercapacitors and other electrochemical devices.

Permissive tracts for volcanogenic massive sulfide deposits in Mauritania (phase V, deliverable 76): Chapter L1 in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Taylor, Cliff D.; Horton, John D.

2012-01-01

This report contains the USGS results of the PRISM-II Mauritania Minerals Project and is presented in cooperation with the Ministry of Petroleum, Energy, and Mines of the Islamic Republic of Mauritania. The Report is composed of separate chapters consisting of multidisciplinary interpretive reports with accompanying plates on the geology, structure, geochronology, geophysics, hydrogeology, geochemistry, remote sensing (Landsat TM and ASTER), and SRTM and ASTER digital elevation models of Mauritania. The syntheses of these multidisciplinary data formed the basis for additional chapters containing interpretive reports on 12 different commodities and deposit types known to occur in Mauritania, accompanied by countrywide mineral resource potential maps of each commodity/deposit type. The commodities and deposit types represented include: (1) Ni, Cu, PGE, and Cr deposits hosted in ultramafic rocks; (2) orogenic, Carlin-like, and epithermal gold deposits; (3) polymetallic Pb-Zn-Cu vein deposits; (4) sediment-hosted Pb-Zn-Ag deposits of the SEDEX and Mississippi Valley-type; (5) sediment-hosted copper deposits; ( 6) volcanogenic massive sulfide deposits; (7) iron oxide copper-gold deposits; (8) uranium deposits; (9) Algoma-, Superior-, and oolitic-type iron deposits; (10) shoreline Ti-Zr placer deposits; (11) incompatible element deposits hosted in pegmatites, alkaline rocks, and carbonatites, and; (12) industrial mineral deposits. Additional chapters include the Mauritanian National Mineral Deposits Database are accompanied by an explanatory text and the Mauritania Minerals Project GIS that contains all of the interpretive layers created by USGS scientists. Raw data not in the public domain may be obtained from the Ministry of Petroleum, Energy, and Mines in Nouakchott, Mauritania.

Isotherms and kinetic study of ultrasound-assisted adsorption of malachite green and Pb2+ ions from aqueous samples by copper sulfide nanorods loaded on activated carbon: Experimental design optimization.

PubMed

Sharifpour, Ebrahim; Khafri, Hossein Zare; Ghaedi, Mehrorang; Asfaram, Arash; Jannesar, Ramin

2018-01-01

Copper sulfide nanorods loaded on activated carbon (CuS-NRs-AC) was synthesized and used for simultaneous ultrasound-assisted adsorption of malachite green (MG) and Pb 2+ ions from aqueous solution. Following characterization of CuS-NRs-AC were investigated by SEM, EDX, TEM and XRD, the effects of pH (2.0-10), amount of adsorbent (0.003-0.011g), MG concentration (5-25mgL -1 ), Pb 2+ concentration (3-15mgL -1 ) and sonication time (1.5-7.5min) and their interactions on responses were investigated by central composite design (CCD) and response surface methodology. According to desirability function on the Design Expert optimum removal (99.4%±1.0 for MG and 68.3±1.8 for Pb 2+ ions) was obtained at pH 6.0, 0.009g CuS-NRs-AC, 6.0min mixing by sonication and 15 and 6mgL -1 for MG and Pb 2+ ions, respectively. High determination coefficient (R 2 >0.995), Pred-R 2 -value (>0.920) and Adju-R 2 -value (>0.985) all are good indication of best agreement between the experimental and design modelling. The adsorption kinetics follows the pseudo-second order model and adsorption isotherm follows the Langmuir model with maximum adsorption capacity of 145.98 and 47.892mgg -1 for MG and Pb 2+ ions, respectively. This adsorbent over short contact time is good choice for simultaneous removal of large content of both MG and Pb 2+ ions from wastewater sample. Copyright © 2017 Elsevier B.V. All rights reserved.

ASTER, ALI and Hyperion sensors data for lithological mapping and ore minerals exploration.

PubMed

Beiranvand Pour, Amin; Hashim, Mazlan

2014-01-01

This paper provides a review of the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER), Advanced Land Imager (ALI), and Hyperion data and applications of the data as a tool for ore minerals exploration, lithological and structural mapping. Spectral information extraction from ASTER, ALI, and Hyperion data has great ability to assist geologists in all disciplines to map the distribution and detect the rock units exposed at the earth's surface. The near coincidence of Earth Observing System (EOS)/Terra and Earth Observing One (EO-1) platforms allows acquiring ASTER, ALI, and Hyperion imagery of the same ground areas, resulting accurate information for geological mapping applications especially in the reconnaissance stages of hydrothermal copper and gold exploration, chromite, magnetite, massive sulfide and uranium ore deposits, mineral components of soils and structural interpretation at both regional and district scales. Shortwave length infrared and thermal infrared bands of ASTER have sufficient spectral resolution to map fundamental absorptions of hydroxyl mineral groups and silica and carbonate minerals for regional mapping purposes. Ferric-iron bearing minerals can be discriminated using six unique wavelength bands of ALI spanning the visible and near infrared. Hyperion visible and near infrared bands (0.4 to 1.0 μm) and shortwave infrared bands (0.9 to 2.5 μm) allowed to produce image maps of iron oxide minerals, hydroxyl-bearing minerals, sulfates and carbonates in association with hydrothermal alteration assemblages, respectively. The techniques and achievements reviewed in the present paper can further introduce the efficacy of ASTER, ALI, and Hyperion data for future mineral and lithological mapping and exploration of the porphyry copper, epithermal gold, chromite, magnetite, massive sulfide and uranium ore deposits especially in arid and semi-arid territory.

Microbial communities in a porphyry copper tailings impoundment and their impact on the geochemical dynamics of the mine waste.

PubMed

Diaby, Nouhou; Dold, Bernhard; Pfeifer, Hans-Rudolf; Holliger, Christof; Johnson, D Barrie; Hallberg, Kevin B

2007-02-01

The distribution and diversity of acidophilic bacteria of a tailings impoundment at the La Andina copper mine, Chile, was examined. The tailings have low sulfide (1.7% pyrite equivalent) and carbonate (1.4% calcite equivalent) contents and are stratified into three distinct zones: a surface (0-70-80 cm) 'oxidation zone' characterized by low-pH (2.5-4), a 'neutralization zone' (70-80 to 300-400 cm) and an unaltered 'primary zone' below 400 cm. A combined cultivation-dependent and biomolecular approach (terminal restriction enzyme fragment length polymorphism and 16S rRNA clone library analysis) was used to characterize the indigenous prokaryotic communities in the mine tailings. Total cell counts showed that the microbial biomass was greatest in the top 125 cm of the tailings. The largest numbers of bacteria (10(9) g(-1) dry weight of tailings) were found at the oxidation front (the junction between the oxidation and neutralization zones), where sulfide minerals and oxygen were both present. The dominant iron-/sulfur-oxidizing bacteria identified at the oxidation front included bacteria of the genus Leptospirillum (detected by molecular methods), and Gram-positive iron-oxidizing acidophiles related to Sulfobacillus (identified both by molecular and cultivation methods). Acidithiobacillus ferrooxidans was also detected, albeit in relatively small numbers. Heterotrophic acidophiles related to Acidobacterium capsulatum were found by molecular methods, while another Acidobacterium-like bacterium and an Acidiphilium sp. were isolated from oxidation zone samples. A conceptual model was developed, based on microbiological and geochemical data derived from the tailings, to account for the biogeochemical evolution of the Piuquenes tailings impoundment.

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.

Depth profile composition studies of thin film CdS:Cu2S solar cells using XPS and AES

NASA Astrophysics Data System (ADS)

Bhide, V. G.; Salkalachen, S.; Rastogi, A. C.; Rao, C. N. R.; Hegde, M. S.

1981-09-01

Studies of the surface composition and depth profiles of thin film CdS:Cu2S solar cells based on the techniques of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) are reported. Specimens were fabricated by the thermal deposition of polycrystalline CdS films onto silver-backed electrodes predeposited on window glass substrates, followed by texturization in hot HCl and chemical plating in a hot CuCl(I) bath for a few seconds to achieve the topotaxial growth of CuS films. The XPS and AES studies indicate the junction to be fairly diffused in the as-prepared cell, with heat treatment in air at 210 C sharpening the junction, improving the stoichiometry of the Cu2S layer and thus improving cell performance. The top copper sulfide layer is found to contain impurities such as Cd, Cl, O and C, which may be removed by mild Ar(+) ion beam etching. The presence of copper deep in the junction is invariably detected, apparently in the grain boundary region in the form of CuS or Cu(2+) trapped in the lattice. It is also noted that the nominal valence state of copper changes abruptly from Cu(+) to Cu(2+) across the junction.

Linking leach chemistry and microbiology of low-grade copper ore bioleaching at different temperatures

NASA Astrophysics Data System (ADS)

Jia, Yan; Sun, He-yun; Tan, Qiao-yi; Gao, Hong-shan; Feng, Xing-liang; Ruan, Ren-man

2018-03-01

The effects of temperature on chalcocite/pyrite oxidation and the microbial population in the bioleaching columns of a low-grade chalcocite ore were investigated in this study. Raffinate from the industrial bioleaching heap was used as an irrigation solution for columns operated at 20, 30, 45, and 60°C. The dissolution of copper and iron were investigated during the bioleaching processes, and the microbial community was revealed by using a high-throughput sequencing method. The genera of Ferroplasma, Acidithiobacillus, Leptospirillum, Acidiplasma, and Sulfobacillus dominated the microbial community, and the column at a higher temperature favored the growth of moderate thermophiles. Even though microbial abundance and activity were highest at 30°C, the column at a higher temperature achieved a much higher Cu leaching efficiency and recovery, which suggested that the promotion of chemical oxidation by elevated temperature dominated the dissolution of Cu. The highest pyrite oxidation percentage was detected at 45°C. Higher temperature resulted in precipitation of jarosite in columns, especially at 60°C. The results gave implications to the optimization of heap bioleaching of secondary copper sulfide in both enhanced chalcocite leaching and acid/iron balance, from the perspective of leaching temperature and affected microbial community and activity.

Copper isotope fractionation during partial melting and melt percolation in the upper mantle: Evidence from massif peridotites in Ivrea-Verbano Zone, Italian Alps

NASA Astrophysics Data System (ADS)

Huang, Jian; Huang, Fang; Wang, Zaicong; Zhang, Xingchao; Yu, Huimin

2017-08-01

To investigate the behavior of Cu isotopes during partial melting and melt percolation in the mantle, we have analyzed Cu isotopic compositions of a suite of well-characterized Paleozoic peridotites from the Balmuccia and Baldissero massifs in the Ivrea-Verbano Zone (IVZ, Northern Italy). Our results show that fresh lherzolites and harzburgites have a large variation of δ65Cu ranging from -0.133 to 0.379‰, which are negatively correlated with Al2O3 contents as well as incompatible platinum-group (e.g., Pd) and chalcophile element (e.g., Cu, S, Se, and Te) contents. The high δ65Cu can be explained by Cu isotope fractionation during partial melting of a sulfide-bearing peridotite source, with the light isotope (63Cu) preferentially entering the melts. The low δ65Cu can be attributed to precipitation of sulfides enriched in 63Cu during sulfur-saturated melt percolation. Replacive dunites from the Balmuccia massif display high δ65Cu from 0.544 to 0.610‰ with lower Re, Pd, S, Se, and Te contents and lower Pd/Ir ratios relative to lherzolites, which may result from dissolution of sulfides during interactions between S-undersaturated melts and lherzolites at high melt/rock ratios. Thus, our results suggest that partial melting and melt percolation largely account for the Cu isotopic heterogeneity of the upper mantle. The correlation between δ65Cu and Cu contents of the lherzolites and harzburgites was used to model Cu isotope fractionation during partial melting of a sulfide-bearing peridotite, because Cu is predominantly hosted in sulfide. The modelling results indicate an isotope fractionation factor of αmelt-peridotite = 0.99980-0.99965 (i.e., 103lnαmelt-peridotite = -0.20 to -0.35‰). In order to explain the Cu isotopic systematics of komatiites and mid-ocean ridge basalts reported previously, the estimated αmelt-peridotite was used to simulate Cu isotopic variations in melts generated by variable degrees of mantle melting. The results suggest that high degrees (>25%) of partial melting extracts nearly all source Cu and it cannot produce Cu isotope fractionation in komatiites relative to their mantle source, and that sulfide segregation during magma evolution have modified Cu isotopic compositions of mid-ocean ridge basalts.

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 the tailings include gypsum, quartz, pyrite, mica, talc, amphiboles, and feldspars. Oxidation products identified include copiapite as well as various iron oxides. Future results are expected to reveal most of the heavy metals to be adsorbed by or coprecipitate with iron oxides, with most of the oxidized arsenic staying in the soluble form. The mobility of the colloidal form of the oxides and associated heavy metals within the carbonate mineral-rich tailings need additional study.

Study of earth abundant tco and absorber materials for photovoltaic applications

NASA Astrophysics Data System (ADS)

Prabhakar, Tejas

In order to make photovoltaic power generation a sustainable venture, it is necessary to use cost-effective materials in the manufacture of solar cells. In this regard, AZO (Aluminum doped Zinc Oxide) and CZTS (Copper Zinc Tin Sulfide) have been studied for their application in thin film solar cells. While AZO is a transparent conducting oxide, CZTS is a photovoltaic absorber. Both AZO and CZTS consist of earth abundant elements and are non-toxic in nature. Highly transparent and conductive AZO thin films were grown using RF sputtering. The influence of deposition parameters such as working pressure, RF power, substrate temperature and flow rate on the film characteristics was investigated. The as-grown films had a high degree of preferred orientation along the (002) direction which enhanced at lower working pressures, higher RF powers and lower substrate temperatures. Williamson-Hall analysis on the films revealed that as the working pressure was increased, the nature of stress and strain gradually changed from being compressive to tensile. The fall in optical transmission of the films was a consequence of free carrier absorption resulting from enhanced carrier density due to incorporation of Al atoms or oxygen vacancies. The optical and electrical properties of the films were described well by the Burstein-Moss effect. CZTS absorber layers were grown using ultrasonic spray pyrolysis at a deposition temperature of 350 C and subsequently annealed in a sulfurization furnace. Measurements from XRD and Raman spectra confirmed the presence of pure single phase Cu2ZnSnS4. Texture analysis of as-deposited and annealed CZTS films indicated that the (112) plane which is characteristic of the kesterite phase was preferred. The grain size increased from 50 nm to 100 nm on conducting post-deposition annealing. CZTS films with stoichiometric composition yielded a band gap of 1.5 eV, which is optimal for solar energy conversion. The variation of tin in the film changed its resistivity by several orders of magnitude and subsequently the tin free ternary chalcogenide Cu2ZnS2 having very low resistivity was obtained. By carefully optimization of concentrations of tin, zinc and copper, a zinc-rich/tin-rich/copper-poor composition was found to be most suitable for solar cell applications. Etching of CZTS films using KCN solution reduced their resistivity, possibly due to the elimination of binary copper sulfide phases. CZTS solar cells were fabricated both in the substrate and superstrate configurations.

Preliminary report on the White Canyon area, San Juan county, Utah

USGS Publications Warehouse

Benson, William E.; Trites, Albert F.; Beroni, Ernest P.; Feeger, John A.

1952-01-01

The White Canyon area, in the central part of San Juan County, Utah, consists of approximately two 15-minute quadrangles. Approximately 75 square miles have been mapped by the Geological Survey on a scale of 1 inch equals 1 mile, using a combined aerial photography-plane table method. Structure contours were drawn on top of the Organ Rock member of the Cutler formation. Parts of the Gonway and North Point claims, 1/4 mile east of the Happy Jack mine, were mapped in detail. The principal objectives of the investigations were: (1) to establish ore guides; (2) to select areas favorable for exploration; and (3) to map the general geology and to determine the regional relationships of the uranium deposits. The White Canyon area is comprised of sedimentary rocks of Carboniferous to Jurassic age, more than 2,000 feet thick, having a regional dip of 1° to 2° SW. The nearest igneous rocks are in the Henry Mountains about 7 miles west of the northern part of the area; The Shinarump conglomerate of the late Triassic age, the principal ore horizon in the White Canyon area, consists of lenticular beds of sandstone, conglomeratic sandstone, conglomerate, clay, and siltstone. The Shinarump conglomerate, absent in places, is as much as 75 feet thick. The sandstones locally contain molds of logs and fragments of altered volcanic ash. Some of the logs have been replaced by copper and uranium minerals and iron oxides. The clay and siltstone underlie and are interbedded with the sandstone, and are most common in channels that cut into the underlying Moenkopi formation. The Shinarump conglomerate contains reworked Moenkopi siltstone fragments, clay balls, carbonized wood, and pebbles of quarts, quartzite, and chert. Jointing is prominent in the Western part of the mapped area. The three most prominent joint trends are due east, N. 65°-75° W., and N. 65°-75° E. All joints have vertical dips. The red beds are bleached along some joints, especially those that trend N. 65°-75° W. All uranium ore produced has been from the lower part of the Shinarump conglomerate, where it commonly occurs with copper as disseminations and fracture coatings in sandstone. Uranium and copper minerals also occur in low-grade disseminated deposits in the lower Chinle and in the Moenkopi formation and in veins cutting these formations. Although some uranium deposits occur in Chinarump channels and scours, copper and uranium minerals along fractures suggest that channel control may be secondary. Logs and clay balls apparently have exerted some chemical influences for deposition. The uranium occurs as the oxide in some deposits, and as secondary hydrous sulfates, phosphates, oxides, and silicates in these and several other deposits. Charcoal, iron and manganese oxides, and veinlets of hydrocarbon are abnormally radioactive in most of the deposits. Base-metal sulfides are commonly found inside the oxidized zone. Secondary copper minerals include the hydrous sulfates and carbonate. Gangue minerals include quarts, clay minerals, and manganese oxides, dickite (?), calcite, gypsum, pyrite, and chalcedony (?). Principal wall-rock alteration appears to have been silicification, clay alteration, and bleaching. Most of the shipped ore has contained more than 0.3 percent uranium. The ore also contains copper, commonly in grades lower than 1.0 percent. Criteria believed to be most useful for prospecting for concealed uranium deposits are (1) visible uranium minerals; (2) sulfide minerals; (3) secondary copper minerals; (4) dickite (?); (5) hydrocarbons; and (6) bleaching and alteration of the Moenkopi formation.

Weathering of historical copper slags in dynamic experimental system with rhizosphere-like organic acids.

PubMed

Potysz, Anna; Kierczak, Jakub; Grybos, Malgorzata; Pędziwiatr, Artur; van Hullebusch, Eric D

2018-06-01

This study was undertaken to simulate experimentally the weathering of slags disposed nearby soil rhizosphere. The aim of the research was to differentiate the effect of pH and organics on slags dissolution as well as to indicate weathering sequence of phase components. The studied slags are mainly composed of Fe (34.5 wt%) and Si (17.9 wt%) and contain up to 3761 mg kg -1 of Cu and 3628 mg kg -1 of Zn. The main identified phases are fayalite and glass, whereas sulfides and metallic Cu are volumetrically minor. A 30 days long slag weathering experiment was carried out with artificial root exudates (43.7 mM) and demineralized water at initial pH = 3.5 and pH = 6.7. The highest metal release (up to 10.9% of Zn and 4.6% of Cu) was observed in ARE solution at initial pH 3.5. Dissolution of sulfides and fayalite was mainly driven by pH. Artificial root exudates enhance glass dissolution as compared to demineralized water regardless of initially fixed pH. Based on this study following weathering sequences are delineated: i) under ARE 3.5 conditions: silicates > glass > sulfides, ii) under DW 3.5 conditions: sulfides > silicates > glass, iii) under near-neutral conditions: sulfides > glass > silicates. Copyright © 2018 Elsevier Ltd. All rights reserved.

Covellite CuS as a matrix for "invisible" gold: X-ray spectroscopic study of the chemical state of Cu and Au in synthetic minerals

NASA Astrophysics Data System (ADS)

Tagirov, Boris R.; Trigub, Alexander L.; Kvashnina, Kristina O.; Shiryaev, Andrey A.; Chareev, Dmitriy A.; Nickolsky, Maximilian S.; Abramova, Vera D.; Kovalchuk, Elena V.

2016-10-01

Geological processes leading to formation of sulfide ores often result in precipitation of gold-bearing sulfides which can contain high concentrations of this metal in ;invisible; (or ;refractory;) state. Covellite (CuS) is ubiquitous mineral in many types of the ore deposits, and numerous studies of the natural ores show that covellite can contain high concentrations of Au. At the same time, Au-bearing covellite withstands cooling in contrast to other minerals of the Cu-Fe-S system (chalcocite, bornite, chalcopyrite), where Au exsolves at low temperatures. This makes covellite a convenient model system for investigation of the chemical state (local environment and valence) of the ;invisible; Au in copper-sulfide ores (copper-porphyry, epithermal, volcanogenic massive sulfide, SEDEX deposits). Therefore, it is necessary to determine the location of Au in the covellite matrix as it will have important implications for the methods employed by mineral processing industry to extract Au from sulfide ores. Here we investigate the chemical state of Cu and Au in synthetic covellite containing up to 0.3 wt.% of Au in the ;invisible; state. The covellite crystals were synthesized by hydrothermal and salt flux methods. Formation of the chemically bound Au is indicated by strong dependence of the concentration of Au in covellite on the sulfur fugacity in the experimental system (d(log C(Au))/d(log f(S2)) ∼ 0.65). The Au concentration of covellite grows with increasing temperature from 400 to 450 °C, whereas further temperature increase to 500 °C has only minor effect. The synthesized minerals were studied using X-ray absorption fine structure spectroscopy (XAFS) in high energy resolution fluorescence detection (HERFD) mode. Ab initio simulations of Cu K edge XANES spectra show that the Cu oxidation state in two structural positions in covellite (tetrahedral and triangular coordination with S atoms) is identical: the total loss of electronic charge for the 3d shell is ∼0.3 for both positions of Cu. This result is confirmed by theoretical analysis of electron density performed using quantum theory of atoms in molecules (QTAIM). Modeling of the Au L3 edge EXAFS/XANES spectra showed that Au in covellite exists in the form of the isomorphous solid solution formed by substitution for Cu atoms in triangular coordination with the Me-S distance in the first coordination shell increased by 0.18 Å relative to the pure CuS structure. The ;formal; oxidation state of Au in covellite is +1. The Bader partial atomic charge for Au in covellite is lower than the charge of Cu (+0.2 e vs. +0.5 e) indicating that the degree of covalency for the Au-bearing covellite is higher than that of pure CuS. The analysis of electronic density of states shows that this structural position of Au results in strong interactions between hybridized Au s,p,d, S p, and Cu p,d orbitals. Such chemical bonding of Au to S and Cu can result in the formation of Au-bearing solid solution with other minerals in the Cu-Fe-S system.

Mineral Resources of the Wabayuma Peak Wilderness Study Area, Mohave County, Arizona

USGS Publications Warehouse

Conway, Clay M.; Hassemer, Jerry R.; Knepper, Daniel H.; Pitkin, James A.; Jachens, Robert C.; Chatman, Mark L.

1990-01-01

The Wabayuma Peak Wilderness Study Area (AZ-020-037/043), for which a mineral survey was requested by the U.S. Bureau of land Management, encompasses 40,118 acres in northwestern Arizona. Fieldwork was carried out in 1986-88 by the U.S. Bureau of Mines and the U.S. Geological Survey to appraise the identified (known) resources and assess the mineral resource potential (undiscovered) of the wilderness study area. Within the Wabayuma Peak Wilderness Study Area are 14 private parcels of land totaling 1,315 acres. The Wabayuma Peak Wilderness Study Area, including the 14 private parcels of land, is herein referred to as the 'wilderness study area' or the 'study area'. The Boriana, Antler, and Copper World mines lie near the east boundary of the study area. The Boriana mine was a major tungsten-producing mine of the United States during World War II. The Antler and Copper World mines produced relatively small amounts of copper and zinc prior to 1970. Copper and zinc were mined within 100 ft of the study area at the Antler mine. The Antler mine contains subeconomic resources of 350,000 to 400,000 short tons of copper-zinc ore; a minimum of 2,000 short tons, at grades of 1 to 4 percent copper and 1 to 2 percent zinc, lie within the study area. No other mineral resources were identified within the study area. Four small tracts in the eastern part and one in the central part of the study area have high resource potential for copper, zinc, and minor lead, silver, and gold in massive sulfide deposits. A large central tract and two eastern tracts have moderate resource potential for the same metals. An eastern and a western tract within the wilderness study area have high resource potential for tungsten, copper, and combinations of beryllium, gold, silver, arsenic, bismuth, molybdenum, tin, indium, thorium, niobium, yttrium, lanthanum, scandium, tantalum, rhenium, lead, zinc, and iron in granite-related tungsten-polymetallic vein deposits. Most of the rest of the study area has moderate resource potential for these metals. A northern tract in the study area has moderate resource potential for gold, copper, and combinations of silver, zinc, lead, tungsten, and molybdenum in polymetallic vein deposits of several types.

Rhenium

USGS Publications Warehouse

John, David A.; Seal, Robert R.; Polyak, Désirée E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Rhenium is one of the rarest elements in Earth’s continental crust; its estimated average crustal abundance is less than 1 part per billion. Rhenium is a metal that has an extremely high melting point and a heat-stable crystalline structure. More than 80 percent of the rhenium consumed in the world is used in high-temperature superalloys, especially those used to make turbine blades for jet aircraft engines. Rhenium’s other major application is in platinum-rhenium catalysts used in petroleum refining.Rhenium rarely occurs as a native element or as its own sulfide mineral; most rhenium is present as a substitute for molybdenum in molybdenite. Annual world mine production of rhenium is about 50 metric tons. Nearly all primary rhenium production (that is, rhenium produced by mining rather than through recycling) is as a byproduct of copper mining, and about 80 percent of the rhenium obtained through mining is recovered from the flue dust produced during the roasting of molybdenite concentrates from porphyry copper deposits. Molybdenite in porphyry copper deposits can contain hundreds to several thousand grams per metric ton of rhenium, although the estimated rhenium grades of these deposits range from less than 0.1 gram per metric ton to about 0.6 gram per metric ton.Continental-arc porphyry copper-(molybdenum-gold) deposits supply most of the world’s rhenium production and have large inferred rhenium resources. Porphyry copper mines in Chile account for about 55 percent of the world’s mine production of rhenium; rhenium is also recovered from porphyry copper deposits in the United States, Armenia, Kazakhstan, Mexico, Peru, Russia, and Uzbekistan. Sediment-hosted strata-bound copper deposits in Kazakhstan (of the sandstone type) and in Poland (of the reduced-facies, or Kupferschiefer, type) account for most other rhenium produced by mining. These types of deposits also have large amounts of identified rhenium resources. The future supply of rhenium is likely to depend largely on the capacity of the specialized processing facilities needed to recover rhenium from molybdenite concentrates.The environmental consequences of rhenium recovery are closely linked to the consequences of mining large porphyry copper and strata-bound copper deposits; no additional environmental impact from recovery of rhenium from these deposits has been identified. No information is available regarding the potential toxic effects of rhenium on humans, partly because of the low natural abundance of rhenium.

Geological structure and prospects of noble metal ore mineralization of the Khayrkhan gabbroid massif (Western Mongolia)

NASA Astrophysics Data System (ADS)

Kurumshieva, K. R.; Gertner, I. F.; Tishin, P. A.

2017-12-01

An analysis of the distribution of noble metals in zones of sulfide mineralization makes it possible to justify the isolation of four ore-bearing horizons with a specific geochemical zonation. A rise in the gold content relative to palladium and platinum is observed from the bottom upwards along the section of the stratified series of gabbroids. The study of the mineral phases of sulphides and the noble minerals itself indicates the evolution of hydrothermal solutions, which determines the different activity and mobility of the fluid (mercury, tellurium, sulfur) and ore (copper, nickel, iron, platinum, gold and silver) components.

Geologic, aeromagnetic and mineral resource potential maps of the Whisker Lake Wilderness, Florence County, Wisconsin

USGS Publications Warehouse

Schulz, Klaus J.

1983-01-01

The mineral resource potential of the Whisker Lake Wilderness in the Nicolet National Forest, Florence County, northeastern Wisconsin, was evaluated in 1982. The bedrock consists of recrystallized and deformed volcanic and sedimentary rocks of Early Proterozoic age. Sand and gravel are the only identified resources in the Whisker Lake Wilderness. However, the area is somewhat isolated from current markets and both commodities are abundant regionally. The wilderness also has low potential for peat in swampy lowlands. The southwestern part of the wilderness has a low to moderate mineral resource potential for stratabound massive-sulfide (copper-zinc-lead) deposits.

Copper isotope behavior during extreme magma differentiation and degassing: a case study on Laacher See phonolite tephra (East Eifel, Germany)

NASA Astrophysics Data System (ADS)

Huang, Jian; Liu, Sheng-Ao; Wörner, Gerhard; Yu, Huimin; Xiao, Yilin

2016-09-01

Copper (Cu) isotopic analyses were performed on a set of samples from the Laacher See tephra (LST) (Eifel, Germany) to investigate whether Cu isotopes are fractionated during extreme magma differentiation and degassing. The LST represents a continuous fractional crystallization series from parental basanite through mafic to highly differentiated phonolites. Samples analyzed here include phonolites of variable degrees of differentiation, phonolite-basanite hybrid rocks formed by mixing basanite and phonolite magmas, and basanite-derived mega-crystals (i.e., clinopyroxene, amphibole, phlogopite). In addition, we analyzed a series of mafic parental lavas from surrounding volcanic centers to constrain the Cu isotopic features of the Eifel mantle. Mafic phonolites show strong depletion in Cu compared to their parental basanites from ~50 to ~3 ppm, indicating sulfide fractionation during the basanite-to-phonolite differentiation. Mass balance calculations, based on the most Cu-rich hybrid rock (δ65Cu = -0.21 ‰, [Cu] = 46.2 ppm), show that the parental basanite magmas have δ65Cu of ca. -0.21 ‰, lighter than those of the mafic phonolites (~0.11 ‰). This suggests that sulfide fractionation preferentially removes the lighter Cu isotope (63Cu) in S-saturated magmas. By contrast, all phonolites have a limited range of Cu contents (1.1 to 4.0 ppm) with no systematic variations with S, suggesting that Cu is not controlled by sulfide fractionation during the evolution of mafic to highly differentiated phonolites. The identical δ65Cu values (0.11 ± 0.03 ‰, 2SD, n = 10) of the phonolites, irrespective of highly diverse composition and extents of differentiation, indicate that fractional crystallization of silicates (e.g., plagioclase, sanidine, amphibole, pyroxene, olivine), Fe-Ti-oxides and phosphate (e.g., apatite) generates insignificant Cu isotope fractionation. The lack of correlations between δ65Cu and volatile contents (e.g., S, Cl) in the LST sequence implies that volcanic degassing causes no detectable Cu isotope fractionation of igneous rocks. Eifel basalts and mega-crystals have variable δ65Cu (-0.18 to 0.21 ‰) that are uncorrelated to MgO and Cu, suggesting that such variations were not caused by differentiation but reflect the Cu isotopic heterogeneity of the Eifel mantle source due to metasomatism by fluids derived from hydrothermally altered oceanic lithosphere.

Genesis of the Datuanshan stratabound skarn Cu(-Mo) deposit, Middle-Lower Yangtze Valley, Eastern China: constraints from geology, Re-Os geochronology, mineralogy, and sulfur isotopes

NASA Astrophysics Data System (ADS)

Cao, Yi; Gao, Fuping; Du, Yangsong; Du, Yilun; Pang, Zhenshan

2017-03-01

Stratabound deposits are the most abundant and economically significant ore type in the Middle-Lower Yangtze River Valley, one of the most important metallogenic belts in China. The Datuanshan deposit is one of the largest and most representative stratabound Cu(-Mo) deposits in the Tongling district of the Middle-Lower Yangtze River metallogenic belt. All the orebodies of the Datuanshan deposit occur around Mesozoic quartz monzodiorite and are tabular or semi-tabular bodies along bedding-parallel faults within upper Permian to Lower Triassic strata. However, discordant and crosscutting relationships (e.g., the host rocks crosscut by skarn- and quartz-sulfide veins, with alteration halos around the veins) have also been found, especially along the skarn-host contact and orebody-host contact, indicating that skarnitization and mineralization postdated the deposition of the host sediments. The skarn consists mainly of prograde garnet and pyroxene and retrograde alteration assemblages of amphibole, epidote, and chlorite, as well as quartz and sulfides. Electron microprobe analyses show that the garnets and pyroxenes are grossular-andradite and hedenbergite-diopside series, respectively, and all samples plot in the field of typical skarn copper deposits worldwide. Molybdenite samples from stratiform copper ores yield Re-Os model ages of 138.2-139.9 Ma with a weighted mean age of 139.2 ± 0.9 Ma. This is reasonably consistent with the ages of the stratiform Mo ores (138.0-140.8 Ma) and genetically related quartz monzodiorite (135.2-139.3 Ma) in the Datuanshan deposit, indicating that the stratiform Cu and Mo mineralization was contemporaneous with emplacement of the quartz monzodiorite magmas in the Early Cretaceous. Fifteen δ34S values for sulfides range from -1.8 to +4.7 ‰, with a mean of 0.5 ‰, indicating that the sulfur was derived mainly from a magmatic source. Moreover, the sulfur isotope values of the ores are consistent with those of Mesozoic intermediate-acid intrusions but are different from those of sediments in the Shizishan orefield. Based on these lines of evidence, we conclude that the Datuanshan stratabound Cu(-Mo) deposit is the result of replacement related to Mesozoic magmatic rocks and is not a product of submarine exhalative sedimentary processes.

Classification of mineral deposits into types using mineralogy with a probabilistic neural network

USGS Publications Warehouse

Singer, Donald A.; Kouda, Ryoichi

1997-01-01

In order to determine whether it is desirable to quantify mineral-deposit models further, a test of the ability of a probabilistic neural network to classify deposits into types based on mineralogy was conducted. Presence or absence of ore and alteration mineralogy in well-typed deposits were used to train the network. To reduce the number of minerals considered, the analyzed data were restricted to minerals present in at least 20% of at least one deposit type. An advantage of this restriction is that single or rare occurrences of minerals did not dominate the results. Probabilistic neural networks can provide mathematically sound confidence measures based on Bayes theorem and are relatively insensitive to outliers. Founded on Parzen density estimation, they require no assumptions about distributions of random variables used for classification, even handling multimodal distributions. They train quickly and work as well as, or better than, multiple-layer feedforward networks. Tests were performed with a probabilistic neural network employing a Gaussian kernel and separate sigma weights for each class and each variable. The training set was reduced to the presence or absence of 58 reported minerals in eight deposit types. The training set included: 49 Cyprus massive sulfide deposits; 200 kuroko massive sulfide deposits; 59 Comstock epithermal vein gold districts; 17 quartzalunite epithermal gold deposits; 25 Creede epithermal gold deposits; 28 sedimentary-exhalative zinc-lead deposits; 28 Sado epithermal vein gold deposits; and 100 porphyry copper deposits. The most common training problem was the error of classifying about 27% of Cyprus-type deposits in the training set as kuroko. In independent tests with deposits not used in the training set, 88% of 224 kuroko massive sulfide deposits were classed correctly, 92% of 25 porphyry copper deposits, 78% of 9 Comstock epithermal gold-silver districts, and 83% of six quartzalunite epithermal gold deposits were classed correctly. Across all deposit types, 88% of deposits in the validation dataset were correctly classed. Misclassifications were most common if a deposit was characterized by only a few minerals, e.g., pyrite, chalcopyrite,and sphalerite. The success rate jumped to 98% correctly classed deposits when just two rock types were added. Such a high success rate of the probabilistic neural network suggests that not only should this preliminary test be expanded to include other deposit types, but that other deposit features should be added.

Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments

USGS Publications Warehouse

Hammarstrom, J.M.; Seal, R.R.; Meier, A.L.; Kornfeld, J.M.

2005-01-01

Weathering of metal-sulfide minerals produces suites of variably soluble efflorescent sulfate salts at a number of localities in the eastern United States. The salts, which are present on mine wastes, tailings piles, and outcrops, include minerals that incorporate heavy metals in solid solution, primarily the highly soluble members of the melanterite, rozenite, epsomite, halotrichite, and copiapite groups. The minerals were identified by a combination of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron-microprobe. Base-metal salts are rare at these localities, and Cu, Zn, and Co are commonly sequestered as solid solutions within Fe- and Fe-Al sulfate minerals. Salt dissolution affects the surface-water chemistry at abandoned mines that exploited the massive sulfide deposits in the Vermont copper belt, the Mineral district of central Virginia, the Copper Basin (Ducktown) mining district of Tennessee, and where sulfide-bearing metamorphic rocks undisturbed by mining are exposed in Great Smoky Mountains National Park in North Carolina and Tennessee. Dissolution experiments on composite salt samples from three minesites and two outcrops of metamorphic rock showed that, in all cases, the pH of the leachates rapidly declined from 6.9 to 30 mg L-1), Fe (>47 mg L-1), sulfate (>1000 mg L-1), and base metals (>1000 mg L-1 for minesites, and 2 mg L-1 for other sites). Geochemical modeling of surface waters, mine-waste leachates, and salt leachates using PHREEQC software predicted saturation in the observed ochre minerals, but significant concentration by evaporation would be needed to reach saturation in most of the sulfate salts. Periodic surface-water monitoring at Vermont minesites indicated peak annual metal loads during spring runoff. At the Virginia site, where no winter-long snowpack develops, metal loads were highest during summer months when salts were dissolved periodically by rainstorms following sustained evaporation during dry spells. Despite the relatively humid climate of the eastern United States, where precipitation typically exceeds evaporation, salts form intermittently in open areas, persist in protected areas when temperature and relative humidity are appropriate, and contribute to metal loadings and acidity in surface waters upon dissolution, thereby causing short-term perturbations in water quality.

Cobalt—Styles of deposits and the search for primary deposits

USGS Publications Warehouse

Hitzman, Murray W.; Bookstrom, Arthur A.; Slack, John F.; Zientek, Michael L.

2017-11-30

Cobalt (Co) is a potentially critical mineral. The vast majority of cobalt is a byproduct of copper and (or) nickel production. Cobalt is increasingly used in magnets and rechargeable batteries. More than 50 percent of primary cobalt production is from the Central African Copperbelt. The Central African Copperbelt is the only sedimentary rock-hosted stratiform copper district that contains significant cobalt. Its presence may indicate significant mafic-ultramafic rocks in the local basement. The balance of primary cobalt production is from magmatic nickel-copper and nickel laterite deposits. Cobalt is present in several carbonate-hosted lead-zinc and copper districts. It is also variably present in Besshi-type volcanogenic massive sulfide and siliciclastic sedimentary rock-hosted deposits in back arc and rift environments associated with mafic-ultramafic rocks. Metasedimentary cobalt-copper-gold deposits (such as Blackbird, Idaho), iron oxide-copper-gold deposits, and the five-element vein deposits (such as Cobalt, Ontario) contain different amounts of cobalt. None of these deposit types show direct links to mafic-ultramafic rocks; the deposits may result from crustal-scale hydrothermal systems capable of leaching and transporting cobalt from great depths. Hydrothermal deposits associated with ultramafic rocks, typified by the Bou Azzer district of Morocco, represent another type of primary cobalt deposit.In the United States, exploration for cobalt deposits may focus on magmatic nickel-copper deposits in the Archean and Proterozoic rocks of the Midwest and the east coast (Pennsylvania) and younger mafic rocks in southeastern and southern Alaska; also, possibly basement rocks in southeastern Missouri. Other potential exploration targets include—The Belt-Purcell basin of British Columbia (Canada), Idaho, Montana, and Washington for different styles of sedimentary rock-hosted cobalt deposits;Besshi-type VMS deposits, such as the Greens Creek (Alaska) deposit and the Ducktown (Tennessee) waste and tailings; andKnown five-element vein districts in Arizona and New Mexico, as well as in the Yukon-Tanana terrane of Alaska; and hydrothermal deposits associated with ultramafic rocks along the west coast, in Alaska, and in the Appalachian Mountains.

Distribution of uranium in the Bisbee district, Cochise County, Arizona

USGS Publications Warehouse

Wallace, Stewart R.

1956-01-01

The Bisbee district has been an important source of copper for many years, and substantial amounts of lead and zinc ore and minor amounts of manganese ore have been mined during certain periods. The copper deposits occur both as low-grade disseminated ore in the Sacramento Hill stock and as massive sulfide (and secondary oxide and carbonate) replacement bodies in Paleozoic limestones that are intruded by the stock and related igneous bodies. The lead-zinc production has come almost entirely from limestone replacement bodies. The disseminated ore exhibits no anomalous radioactivity, and samples from the Lavender pit contain from 0.002 to less than 0.001 percent equivalent uranium. The limestone replacement ores are distinctly radioactive and stoping areas can be readily distinguished from from unmineralized ground on the basis of radioactivity alone. The equivalent uranium content of the copper replacement ores ranges from 0.002 to 0.014 percent and averages about 0.005 percent; the lead-zinc replacement ores average more than 0.007 percent equivalent uranium. Most of the uranium in the copper ores of the district is retained in the smelter slag of a residual concentrate; the slag contains about 0.009 percent equivalent uranium. Uranium carried off each day by acid mine drainage is roughly equal to 1 percent of that being added to the slag dump. Although the total amount of uranium in the district is large, no minable concentrations of ore-grade material are known; samples of relatively high-grade material represent only small fractions of tons at any one locality.

Geochemical exploration for copper-nickel deposits in the cool-humid climate of northeastern Minnesota

USGS Publications Warehouse

Miller, W.R.; Ficklin, W.H.; McHugh, J.B.

1992-01-01

Water was used as a medium for geochemical exploration to detect copper-nickel mineralization along the basal zone of the Duluth Complex. Ni2+ is the most important pathfinder for the detection of the mineralized rocks, followed by Cu2+ and SO42- and to a lesser extent Mg2+ and SiO2. A normalized sum plot using these species defines the mineralization more consistently than a single-element plot, mainly because the absence of one variable does not significantly influence the normalized sum value. A hydrogeochemical survey was conducted in an area of known copper-nickel mineralization in the cool-humid climate of northeastern Minnesota. The area is covered with glacial drift, and wetlands are abundant. Modeling of the chemistry of waters indicates that the waters are oxidizing and have a pH of 7 or less. The most important pathfinder species in the waters, Cu2+, Ni2+, and SO42-, are derived from the simple weathering of sulfide minerals and are mobile in the waters in this environment. Plots of Cu and Ni concentrations in soils show that Cu followed by Ni are the most useful indicator elements for delineating copper-nickel mineralization. The ability of soils and water to delineate the mineralization supports the use of both media for geochemical exploration in this cool-humid environment. In the wetlands, abundant water is available and soils are scarce or absent; where soils are abundant, waters are generally scarce or absent. The use of both media is recommended for geochemical exploration in this environment. ?? 1992.

Summary of the mineralogy of the Colorado Plateau uranium ores

USGS Publications Warehouse

Weeks, Alice D.; Coleman, Robert Griffin; Thompson, Mary E.

1956-01-01

In the Colorado Plateau uranium has been produced chiefly from very shallow mines in carnotite ores (oxidized vanadiferous uranium ores) until recent deeper mining penetrated black unoxidized ores in water-saturated rocks and extensive exploration has discovered many deposits of low to nonvanadiferous ores. The uranium ores include a wide range from highly vanadiferous and from as much as one percent to a trace of copper, and contain a small amount of iron and traces of lead, zinc, molybdenum, cobalt, nickel, silver, manganese, and other metals. Recent investigation indicates that the carnotite ores have been derived by progressive oxidation of primary (unoxidized) black ores that contain low-valent uranium and vanadium oxides and silicates. The uranium minerals, uraninite and coffinite, are associated with coalified wood or other carbonaceous material. The vanadium minerals, chiefly montroseite, roscoelite, and other vanadium silicates, occur in the interstices of the sandstone and in siltstone and clay pellets as well as associated with fossil wood. Calcite, dolomite, barite and minor amounts of sulfides, arsenides, and selenides occur in the unoxidized ore. Partially oxidized vanadiferous ore is blue black, purplish brown, or greenish black in contrast to the black or dark gray unoxidized ore. Vanadium combines with uranium to form rauvite. The excess vanadium is present in corvusite, fernandinite, melanovanadite and many other quadrivalent and quinquevalent vanadium minerals as well as in vanadium silicates. Pyrite and part or all of the calcite are replaced by iron oxides and gypsum. In oxidized vanadiferous uranium ores the uranium is fixed in the relatively insoluble minerals carnotite and tyuyamunite, and the excess vanadium commonly combines with one or more of the following: calcium, sodium, potassium, magnesium, aluminum, iron, copper, manganese, or barium, or rarely it forms the hydrated pentoxide. The relatively stable vanadium silicates are little affected by oxidation. The unoxidized nonvanadiferous ores contain uraninite and coffinite in close association with coalified wood and iron and copper sulfides, and traces of many other sulfides, arsenides and selenides. The oxidized nonvanadiferous ores differ from the vanadiferous ores because, in the absence of vanadium to complex the uranium, a great variety of secondary yellow and greenish-yellow uranyl minerals are formed. The uranyl sulfates and carbonates are more common than the oxides, phosphates, arsenates, and silicates. Because the sulfates and carbonates are much less stable that carnotite, the oxidized nonvanadiferous ores occure only as halos around cores of unoxidized ore and do not form large oxidized deposits close to the surface of the ground as carnotite ores. Oxidation has taken place since the lowering of the water table in the present erosion cycle. Because of local structures and the highly lenticular character of the fluviatile host rocks perched water tables and water-saturated lenses of sandstone are common high above the regional water table. Unoxidized ore has been preserved in these water-saturated rocks and the boundary between oxidized and unoxidized ore is very irregular.

The Nokomis Cu-Ni-PGE Deposit, Duluth Complex: A sulfide-bearing, crystal-laden magmatic slurry

NASA Astrophysics Data System (ADS)

Peterson, D. M.

2009-12-01

Duluth Metals Limited’s Nokomis deposit is the most recently discovered Cu-Ni-PGE deposit in the 1.1 Ga. Duluth Complex, Minnesota. The deposit was discovered utilizing a genetic ore deposit model that identified and back-tracked channelized magma flow within the basal zone of the South Kawishiwi intrusion (SKI). The model led to exploratory drilling in 2006, deposit discovery and initial resource estimation in 2007, and significant resource expansion in 2008, all in a period of 18 months. The deposit’s updated 2008 NI 43-101 compliant Resource Estimate, based on 108 holes drilled by Duluth Metals and 52 historic drill holes on and off the property, contains 449 million tonnes of Indicated Resources grading 0.624% copper, 0.199% nickel, and 0.600 grams per tonne of total precious metals (TPM = Platinum+Palladium+Gold), and an additional 284 million tonnes of Inferred Resources grading 0.627% copper, 0.194% nickel, and 0.718 grams per tonne of TPM. The combined Indicated and Inferred Resources contain approximately 10 billion lbs Cu, 3.1 billion lbs Ni, 165 million lbs Co, 4 million ounces Pt, 9 million ounces Pd, and 2 million ounces of Au. Within these NI 43-101 resources are large tonnages of higher grade material, and the company has commenced an internal research program to identify the geologic controls on the formation nickel-rich and PGE-rich mineralization in the SKI, as well as copper-PGE rich mineralization in the footwall Archean rocks. To date, Duluth Metals has drilled more than 500,000 Ft. (~155,000 m) of core in 155 holes into the deposit, and has only drilled about half of the property. The ore deposit model was developed in cooperation with researchers from the Natural Resources Research Institute of the University of Minnesota, Duluth. As well, research and collaboration with faculty and students at Johns Hopkins University on the Ferrar Dolerites of the Antarctic Dry Valleys has played a key role in developing the magmatic model for the deposit. A fundamental aspect of the ever-developing ore deposit model is an understanding of the initial conditions of the magmatic system - its crystallinity, sulfur capacity, geochemistry, and geometry - and how the sulfur saturated SKI magma lived, worked, and died. Such understanding includes the realization that the magma was a crystal-liquid (silicate and sulfide liquids) slurry and the identification of magma channelways and sub-channels and their associated thermal anomalies. In addition, the SKI magmas locally melted the footwall granitoid rocks, and such melts have been incorporated into the sulfide-bearing troctolitic melts of the SKI. In the end, hard work (>16,000 outcrops mapped, ~20,000 geochemical analyses completed, and >155,000 meters of core drilled) and intellectual geologic thought has been used to identify one of the world’s largest resources of Cu-Ni-PGEs.

Zinc, copper, and lead in mid-ocean ridge basalts and the source rock control on Zn/Pb in ocean-ridge hydrothermal deposits

USGS Publications Warehouse

Doe, B.R.

1994-01-01

The contents of Zn, Cu, and Pb in mid-ocean ridge basalts (MORB) and the MORB source-rock control on Zn/Pb in ocean-ridge hydrothermal deposits are examined. The values of Zn, Cu, and Pb for submarine mid-ocean ridge basalts (MORB) are, respectively (in ppm): average MORB-75, 75, and 0.7; West Valley, Juan de Fuca Ridge (JFR)-87, 64, and 0.5; southern JFR-120 and 0.5; and 21??N, East Pacific Rise (EPR)-73, 78, and 0.5. Values of Zn/Pb range from about 100-240 and Cu/ Pb from 100-156. In this study, Zn is found to correlate positively with TiO2 + FeO (mean square of weighted deviates, MSWD, of 1.6 for JFR basalt), and inversely with Mg number (MSWD of 3.5). Therefore, contrary to statements in the literature that Zn should be compatible in MORB, Zn is a mildly incompatible element and must be enriched in the glass phase relative to olivine as Zn does not fit into the other major phenocryst phase, plagioclase. In the source of MORB, Zn likely is most enriched in oxides: spinel, magnetite, and titanomagnetite. Copper generally does not correlate well with other elements in most MORB data examined. When differentiation is dominated by olivine, Cu has a tendency to behave incompatibly (e.g., at Mg numbers > 70), but, overall, Cu shows some tendency towards being a compatible element, particularly along the Mid-Atlantic Ridge, a behavior presumably due to separation of sulfides in which Cu (but not Zn) is markedly enriched. Copper thus may be in dispersed sulfides in the source of MORB. Ocean ridges provide important data on source-rock controls for sulfide deposits because, in sediment-starved ridges, much is known about the possible source rocks and mineralization is presently occurring. In contrast to Zn/Pb ~5 in continental hot Cl-rich brines, Zn/Pb in the hottest sediment-starved ridge black smoker hydrothermal fluids at 21 ??N, EPR is about 110, similar to local MORB (145), but Cu/Pb is closer to 30, possibly due to subsurface deposition of Cu. At the JFR, the best value of Zn/Pb in the hydrothermal fluids is about 175, again similar to local MORB (240), but Cu is very low in the fluids that are at temperatures less than 300??C. The large MORB-like Zn/Pb in the hottest black-smoker fluids suggests a source-rock control for the metals that prohibits significant galena in the black-smoker deposits of sediment-starved ridges. In contrast, exhalative deposits on sediment-swamped ridges have significant galena; its presence is suggestive of Pb derivation from sediments, an origin supported by Pb isotope studies of LeHuray and colleagues in 1988. ?? 1994.

Genesis of the Permian Kemozibayi sulfide-bearing mafic-ultramafic intrusion in Altay, NW China: Evidence from zircon geochronology, Hf and O isotopes and mineral chemistry

NASA Astrophysics Data System (ADS)

Tang, Dongmei; Qin, Kezhang; Xue, Shengchao; Mao, Yajing; Evans, Noreen J.; Niu, Yanjie; Chen, Junlu

2017-11-01

The recently discovered Kemozibayi mafic-ultramafic intrusion and its associated magmatic Cu-Ni sulfide deposits are located at the southern margin of the Chinese Altai Mountain, Central Asian Orogenic Belt in north Xinjiang, NW China. The intrusion is composed of olivine websterite, norite, gabbro and diorite. Disseminated and net-textured Ni-Cu sulfide ores are hosted in the center of the gabbro. In this work, new zircon U-Pb ages, Hf-O isotopic and sulfide S isotopic data, and whole rock and mineral chemical analyses are combined in order to elucidate the characteristics of the mantle source, nature of subduction processes, degree of crustal contamination, geodynamic setting of bimodal magmatism in the region, and the metallogenic potential of economic Cu-Ni sulfide deposit at depth. SIMS zircon U-Pb dating of the gabbro yields Permian ages (278.3 ± 1.9 Ma), coeval with the Kalatongke Cu-Ni deposit and with Cu-Ni deposits in the Eastern Tianshan and Beishan areas. Several lines of evidence (positive εHf(t) from + 7.1 to + 13.3, Al2O3, TiO2 and SiO2 contents in clinopyroxene from olivine websterite, high whole rock TiO2 contents) suggest that the primary magma of the Kemozibayi intrusion was a calc-alkaline basaltic magma derived from depleted mantle, and that the degree of partial melting in the magma source was high. The evolution of the Kemozibayi mafic-ultramafic complex was strongly controlled by fractional crystallization and the crystallization sequence was olivine websterite, norite, and then gabbro. This is evidenced by whole rock Fe2O3 contents that are positively correlated with MgO and negatively correlated with Al2O3, CaO and Na2O, similar LREE enrichment and negative Nb, Ta, Hf anomalies in chondrite and primitive mantle-normalized patterns, and a decrease in total REE and trace elements contents and magnetite content from gabbro through to norite and olivine websterite. Varied and low εHf(t) (+ 7.1 to + 13.3) and high δ18O values (+ 6.4‰ to + 7.2‰) in zircon, high La/Ba, and Rb/Y ratios, and low Nb/La ratios in whole rock samples, suggest 5-10% contamination by subduction related fluid and 10-15% contribution from an upper crustal component. The clinopyroxene TiO2 and Alz values (percentage of tetrahedral sites occupied by Al) in the Kemozibayi intrusion show characteristics of rift cumulate rocks, but minor arc cumulate features, indicating that the mantle source might have experienced a lower degree of subduction metasomatism. A high degree of partial melting of the depleted mantle and subducted oceanic sediments with related fluid metasomatism and crustal contamination in the Kemozibayi mafic-ultramafic intrusion are appropriate for the formation of an economic copper and nickel sulfide deposit. Crustal contamination, crustal S addition and early fractionation of olivine and sulfide induced S saturation and the formation of immiscible sulfide in the Kemozibayi intrusion. With no obvious olivine and Ni-rich sulfide co-crystallization, the Cu grade in the present orebody is higher than the Ni grade, and the proportion of mafic rocks is high in the Kemozibayi mafic-ultramafic complex. Cumulatively, these features suggest that the mafic-ultramafic intrusion underwent early olivine and Ni sulfide segregation, and that deeper or extended portions of the present intrusive body may host Ni mineralization.

Presentation on mechanisms and applications of chalcopyrite and pyrite bioleaching in biohydrometallurgy - a presentation.

PubMed

Tao, Huang; Dongwei, Li

2014-12-01

This review outlines classic and current research, scientific documents and research achievements in bioleaching, particularly in respect of the bioleaching of chalcopyrite and pyrite. The diversity and commonality of the microbial leaching process can be easily studied through comparing the bioleaching mechanism and the application of these two metal sulfides. The crystal, electronic and surface structures of chalcopyrite and pyrite are summarized in detail in this paper. It determines the specific and complicated interaction pathways, kinetics of the atmospheric/aqueous oxidation, and the control process of bioleaching of the minerals as the precondition. Bioleaching of metal sulfides is performed by a diverse group of microorganisms and microbial communities. The species of the bacteria which have a significant effect on leaching ores are miraculously diverse. The newly identified acidophilic microorganisms with unique characteristics for efficient bioleaching of sulfidic minerals are increasing sharply. The cell-to-cell communication mechanisms, which are still implicit, elusive and intangible at present day, have gradually become a research hotspot. The different mineralogy characteristics and the acid solubility of the metal sulfides (e.g., chalcopyrite and pyrite) cause two different dissolution pathways, the thiosulfate and the polysulfide pathways. The bioleaching mechanisms are categorized by contact (an electrostatic attachment) and noncontact (planktonic) process, with emphasis on the produce of extracellular polymeric substances and formation of biofilm on the surface of the metal sulfides in this paper. The division of the direct and indirect effect are not adopted due to the redox chain, the reduction of the ferric iron and oxidation of the ferrous iron. The molecular oxygen is reduced by the electrons extracted from the specific metal sulfide, via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner membrane. The passivation of the mineral surface can obviously hinder the dissolution of metal sulfides during the bioleaching process, which is significantly affected by the kinetic model, microenvironment on the surface of ore and the leach conditions, such as temperature, pH and E h . The new development of mechanism research, enhanced and intensified technologies on the bioleaching of chalcopyrite and pyrite, are conducted and summarized from the different branches of natural science. Some are depicted and explained based on molecular level in this paper. Catalyst and catalytic mechanisms in bioleaching and biooxidation for this two sulfide minerals have been concluded and applied for several decades, the continuous emergence of the new material and technology are also gradually applied into the biohydrometallurgy. The industrial applications of the bioleaching on chalcopyrite and pyrite are totally based on the understanding of the interaction mechanism between microbes and minerals, the optimization of ore leaching conditions and the development of new material and the leaching equipment. It is not incredible and unimaginable to take a different bioleaching process and diagram to deal with the two sulfuric metals, which is vital to succeed in elevating the leaching rate of copper.

Ore grade decrease as life cycle impact indicator for metal scarcity: the case of copper.

PubMed

Vieira, Marisa D M; Goedkoop, Mark J; Storm, Per; Huijbregts, Mark A J

2012-12-04

In the life cycle assessment (LCA) of products, the increasing scarcity of metal resources is currently addressed in a preliminary way. Here, we propose a new method on the basis of global ore grade information to assess the importance of the extraction of metal resources in the life cycle of products. It is shown how characterization factors, reflecting the decrease in ore grade due to an increase in metal extraction, can be derived from cumulative ore grade-tonnage relationships. CFs were derived for three different types of copper deposits (porphyry, sediment-hosted, and volcanogenic massive sulfide). We tested the influence of the CF model (marginal vs average), mathematical distribution (loglogistic vs loglinear), and reserve estimate (ultimate reserve vs reserve base). For the marginal CFs, the statistical distribution choice and the estimate of the copper reserves introduce a difference of a factor of 1.0-5.0 and a factor of 1.2-1.7, respectively. For the average CFs, the differences are larger for these two choices, i.e. respectively a factor of 5.7-43 and a factor of 2.1-3.8. Comparing the marginal CFs with the average CFs, the differences are higher (a factor 1.7-94). This paper demonstrates that cumulative grade-tonnage relationships for metal extraction can be used in LCA to assess the relative importance of metal extractions.

Geology and geochemistry of epithermal precious metal vein systems in the intra-oceanic arcs of Palau and Yap, western Pacific

USGS Publications Warehouse

Rytuba, J.J.; Miller, W.R.

1990-01-01

The Palau and Yap arcs are part of an intra-oceanic island-arc-trench system which separates the Pacific and Philippine plates in the western Pacific Ocean. The 350-km-long Palau arc consists of over 200 islands while the 400-km-long Yap arc located to the north has only four major islands exposed. Four of the largest islands in Palau are composed primarily of early Eocene to mid-Miocene volcanic rocks and the four islands comprising Yap contain only Miocene volcanic rocks. Basalt and basaltic andesites of the Babelthuap Formation are the oldest volcanic rocks in Palau and are characterized by high MgO, Ni and Cr and low TiO2 and have a boninitic affinity. They form the central and southeastern parts of Babelthuap Island. Oligocene arc tholeiite flows having an age of 34-35.5 Ma comprise most of the three smaller volcanic islands in Palau and the western part of Babelthuap. The youngest volcanic rocks are dacitic intrusions having an age of 22.7-23.2 Ma. The Yap arc is unusual in that metamorphic rocks up to amphibolite grade form most of the islands. These are underlain by a melange composed of igneous and volcanic clasts as well as clasts from a dismembered copper-gold skarn deposit. Miocene volcanic rocks consisting of flows and volcaniclastic deposits overlie the melange and metamorphic complex. An epithermal precious-metal vein system hosted by flows and flow breccias of the Babelthuap Formation occurs in an area 1.5 km by 1 km on the southeast side of Babelthuap Island. Over 50 veins and mineralized breccias ranging up to 2 m in width and having a strike length up to 500 m contain from trace to 13.0 ppm gold. The veins consist of quartz with varying amounts of sulfides and iron oxides after sulfides and the mineralized breccias consist of brecciated country rock cemented by quartz and iron oxides after sulfides. The veins and mineralized breccias generally dip within 15?? of vertical and have two preferred orientations, north-northwest and north-northeast. Hydrothermal alteration of the host rocks consists of a widespread weak to moderately strong propylitic alteration and a more restricted sericitic alteration adjacent to the veins and shear zones. Sulfide minerals in the veins consist primarily of pyrite accompanied by lesser amounts of sphalerite, chalcopyrite, galena, acanthite, native silver, cerargyrite, and iodyrite in partly oxidized parts of the vein system. Gold is typically fine-grained, 1-20 microns, and occurs as native gold, electrum and gold-silver-telluride. Elements correlated with high gold concentrations include molybdenum, tellurium, bismuth, lead, silver, copper, zinc and arsenic. In Yap a similar vein system to that present in Palau is hosted by the Miocene Tomil Volcanics on the islands of Maap and Gagil Tamil. The quartz veins and quartz-cemented breccias contain up to 3.7 ppm gold and trace elements associated with the gold include tellurium, copper, silver and vanadium. Within the mineralized area an unusually iron-rich (3-20%), 4-m-thick, hot-spring deposit contains up to 1.04 ppm gold and high concentrations of tellurium, copper and vanadium. Hydrothermal eruption breccia beds are present within the deposit. The presence of the hot-spring deposit and banded and comb textures of the vein quartz suggest that the vein system presently exposed formed at a shallow level. The vein systems in Palau and Yap have similar textures, geochemical suites and alteration assemblages. Both vein systems formed late in the volcanic evolution of the intra-oceanic arc. Media tested for their effectiveness in geochemical exploration in the tropical, deeply weathered environment of Palau and Yap included stream sediments, heavy-mineral concentrates from stream sediments, and sediment from the mangrove coastal environment which is well developed around most of the islands of Yap and Palau. Geochemical surveys in both Yap and Palau of mangrove sediment show that adjacent to areas of gold mineralization, gold and tellu

Optimization Photodetectors from Zinc Sulfide Deposited on Porous Silicon with Different Doping Metals

NASA Astrophysics Data System (ADS)

Nayef, Uday Muhsin; Khalaf, Haider Amer

In this work, the structural properties of the zinc sulfide (ZnS) films have been investigated using X-ray diffraction (XRD) analysis which show an enhancement in the crystallite degree after doping with copper (Cu). Good matching between the ZnS and porous silicon (PS) structure was noted from the atomic force microscope (AFM) results. The reflectivity gave a clear observation of anti-reflected coating improvement for PS layer and more enhancements after the ZnS deposition. The optical properties show a blue shift in the bandgap for the ZnS deposited with higher substrate temperature and a red shift after doped with different elements. For ZnS/PS heterojunction, the electrical resistivity has been increased after PS layer formed and changed with the variation of the pore size and it was much higher after ZnS deposited on the PS. However, use of ZnS:Cu/PS photodetector showed much higher output current at the ultraviolet (UV) region compared to ZnS/PS. The ZnS:Cu/PS photodetector showed higher output current value than that of the ZnS/PS leading to improvement in the quantum efficiency of 42%.

Reactivity of metal oxide sorbents for removal of sulfur compounds from coal gases at high temperature and pressure

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

Kwon, K.C.; Crowe, E.R.; Gangwal, S.K.

1997-01-01

Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated to effectively remove hydrogen sulfide with various metal oxide sorbents at high temperatures and pressures. Metal oxide sorbents such as zinc titanate oxide, zinc ferrite oxide, copper oxide, manganese oxide and calcium oxide were found to be promising sorbents in comparison with other removal methods such as membrane separation and reactive membrane separation. The removal reaction of H{sub 2}S from coal gas mixtures with zinc titanate oxide sorbents was conducted in a batch reactor. The main objectives of this research are to formulate promising metal oxide sorbentsmore » for removal of hydrogen sulfide from coal gas mixtures, to compare reactivity of a formulated sorbent with a sorbent supplied by the Research Triangle Institute at high temperatures and pressures, and to determine effects of concentrations of moisture contained in coal gas mixtures on equilibrium absorption of H{sub 2}S into metal oxide sorbents. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders and calcining these powder mixtures.« less

Ferroplasma and relatives, recently discovered cell wall-lacking archaea making a living in extremely acid, heavy metal-rich environments.

PubMed

Golyshina, Olga V; Timmis, Kenneth N

2005-09-01

For several decades, the bacterium Acidithiobacillus (previously Thiobacillus) has been considered to be the principal acidophilic sulfur- and iron-oxidizing microbe inhabiting acidic environments rich in ores of iron and other heavy metals, responsible for the metal solubilization and leaching from such ores, and has become the paradigm of such microbes. However, during the last few years, new studies of a number of acidic environments, particularly mining waste waters, acidic pools, etc., in diverse geographical locations have revealed the presence of new cell wall-lacking archaea related to the recently described, acidophilic, ferrous-iron oxidizing Ferroplasma acidiphilum. These mesophilic and moderately thermophilic microbes, representing the family Ferroplasmaceae, were numerically significant members of the microbial consortia of the habitats studied, are able to mobilize metals from sulfide ores, e.g. pyrite, arsenopyrite and copper-containing sulfides, and are more acid-resistant than iron and sulfur oxidizing bacteria exhibiting similar eco-physiological properties. Ferroplasma cell membranes contain novel caldarchaetidylglycerol tetraether lipids, which have extremely low proton permeabilities, as a result of the bulky isoprenoid core, and which are probably a major contributor to the extreme acid tolerance of these cell wall-less microbes. Surprisingly, several intracellular enzymes, including an ATP-dependent DNA ligase have pH optima close to that of the external environment rather than of the cytoplasm. Ferroplasma spp. are probably the major players in the biogeochemical cycling of sulfur and sulfide metals in highly acidic environments, and may have considerable potential for biotechnological applications such as biomining and biocatalysis under extreme conditions.

Volunteer revegetation of waste rock surfaces at the Bingham Canyon Mine, Utah.

PubMed

Borden, Richard K; Black, Rick

2005-01-01

Voluntary recolonization of sulfide-bearing waste rock dumps by native vegetation is inhibited by the harsh chemical and physical conditions. The success of volunteer vegetation on the waste rock surfaces at the Bingham Canyon (Utah) porphyry copper deposit is most strongly dependent on the soil pH and salinity, and to a lesser extent on physical characteristics such as compaction and distance from seed source. Vegetation cover and richness both decline below a paste pH of about 6 and above a paste conductivity of about 0.7 dS/m (for a 1:1 soil to water mixture). No significant vegetation establishment occurs below a soil pH of about 4.5. Young sulfide-bearing waste rock surfaces at Bingham Canyon have high salinity, but as reactive pyrite is depleted and salts are flushed from the soil, the salinity eventually declines, allowing volunteer native vegetation to become established on surfaces with a circumneutral pH. Under natural conditions, the pH of older acidic weathered surfaces will recover very slowly, but it can be rapidly raised by adding relatively small amounts of limestone because there are few intact reactive sulfides. For uncompacted waste rock surfaces with favorable chemical conditions, less than 90% gravel content, and that are located near a native seed source, the arithmetic mean volunteer vegetation cover was 56 +/- 24% and the mean species richness was 17 +/- 5. These data indicate that with adequate surface preparation and limestone addition, direct planting of older, acidic, but low salinity waste rock surfaces can greatly accelerate natural revegetation.

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

Hatakeyama, Hiroto; Wu, Sherry Y.; Lyons, Yasmin A.

Even though hyperthermia is a promising treatment for cancer, the relationship between specific temperatures and clinical benefits and predictors of sensitivity of cancer to hyperthermia is poorly understood. Ovarian and uterine tumors have diverse hyperthermia sensitivities. Integrative analyses of the specific gene signatures and the differences in response to hyperthermia between hyperthermia-sensitive and -resistant cancer cells identified CTGF as a key regulator of sensitivity. CTGF silencing sensitized resistant cells to hyperthermia. CTGF small interfering RNA (siRNA) treatment also sensitized resistant cancers to localized hyperthermia induced by copper sulfide nanoparticles and near-infrared laser in orthotopic ovarian cancer models. Lastly, CTGF silencingmore » aggravated energy stress induced by hyperthermia and enhanced apoptosis of hyperthermia-resistant cancers.« less

Corrosion sensor

DOEpatents

Glass, Robert S.; Clarke, Jr., Willis L.; Ciarlo, Dino R.

1994-01-01

A corrosion sensor array incorporating individual elements for measuring various elements and ions, such as chloride, sulfide, copper, hydrogen (pH), etc. and elements for evaluating the instantaneous corrosion properties of structural materials. The exact combination and number of elements measured or monitored would depend upon the environmental conditions and materials used which are subject to corrosive effects. Such a corrosion monitoring system embedded in or mounted on a structure exposed to the environment would serve as an early warning system for the onset of severe corrosion problems for the structure, thus providing a safety factor as well as economic factors. The sensor array is accessed to an electronics/computational system, which provides a means for data collection and analysis.

Corrosion sensor

DOEpatents

Glass, R.S.; Clarke, W.L. Jr.; Ciarlo, D.R.

1994-04-26

A corrosion sensor array is described incorporating individual elements for measuring various elements and ions, such as chloride, sulfide, copper, hydrogen (pH), etc. and elements for evaluating the instantaneous corrosion properties of structural materials. The exact combination and number of elements measured or monitored would depend upon the environmental conditions and materials used which are subject to corrosive effects. Such a corrosion monitoring system embedded in or mounted on a structure exposed to the environment would serve as an early warning system for the onset of severe corrosion problems for the structure, thus providing a safety factor as well as economic factors. The sensor array is accessed to an electronics/computational system, which provides a means for data collection and analysis. 7 figures.

Method for monitoring environmental and corrosion

DOEpatents

Glass, Robert S.; Clarke, Jr., Willis L.; Ciarlo, Dino R.

1995-01-01

A corrosion sensor array incorporating individual elements for measuring various elements and ions, such as chloride, sulfide, copper, hydrogen (pH), etc. and elements for evaluating the instantaneous corrosion properties of structural materials. The exact combination and number of elements measured or monitored would depend upon the environmental conditions and materials used which are subject to corrosive effects. Such a corrosion monitoring system embedded in or mounted on a structure exposed to the environment would serve as an early warning system for the onset of severe corrosion problems for the structure, thus providing a safety factor as well as economic factors. The sensor array is accessed to an electronics/computational system, which provides a means for data collection and analysis.

Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

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

Just, J.; Lützenkirchen-Hecht, D.; Müller, O.

The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

DOE PAGES

Just, J.; Lützenkirchen-Hecht, D.; Müller, O.; ...

2017-12-12

The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

Studies of the mechanisms of turbine fuel instability

NASA Technical Reports Server (NTRS)

Daniel, S. R.

1983-01-01

The formation of insoluble deposits in a Jet A, a Diesel, and a model fuel (1/10 v/v tetralin/dodecane) was studied. Experiments were conducted using glass containers at 394 K with an air/fuel ratio of 14/1. The effects of addition of ppm levels of various compounds on deposit formation were evaluated. Nitrogen heterocycles were shown to produce a basicity dependent acceleration of deposition. Thiols and thiophene were shown to increase deposition while sulfides and disulfides act as inhibitors. Copper metal and its salts also promote deposition. Results of various instrumental analyses of deposits and development of a high performance liquid chromatographic method for monitoring deposit precursors are discussed.

Undiscovered locatable mineral resources in the Bay Resource Management Plan Area, Southwestern Alaska: A probabilistic assessment

USGS Publications Warehouse

Schmidt, J.M.; Light, T.D.; Drew, L.J.; Wilson, Frederic H.; Miller, M.L.; Saltus, R.W.

2007-01-01

The Bay Resource Management Plan (RMP) area in southwestern Alaska, north and northeast of Bristol Bay contains significant potential for undiscovered locatable mineral resources of base and precious metals, in addition to metallic mineral deposits that are already known. A quantitative probabilistic assessment has identified 24 tracts of land that are permissive for 17 mineral deposit model types likely to be explored for within the next 15 years in this region. Commodities we discuss in this report that have potential to occur in the Bay RMP area are Ag, Au, Cr, Cu, Fe, Hg, Mo, Pb, Sn, W, Zn, and platinum-group elements. Geoscience data for the region are sufficient to make quantitative estimates of the number of undiscovered deposits only for porphyry copper, epithermal vein, copper skarn, iron skarn, hot-spring mercury, placer gold, and placer platinum-deposit models. A description of a group of shallow- to intermediate-level intrusion-related gold deposits is combined with grade and tonnage data from 13 deposits of this type to provide a quantitative estimate of undiscovered deposits of this new type. We estimate that significant resources of Ag, Au, Cu, Fe, Hg, Mo, Pb, and Pt occur in the Bay Resource Management Plan area in these deposit types. At the 10th percentile probability level, the Bay RMP area is estimated to contain 10,067 metric tons silver, 1,485 metric tons gold, 12.66 million metric tons copper, 560 million metric tons iron, 8,100 metric tons mercury, 500,000 metric tons molybdenum, 150 metric tons lead, and 17 metric tons of platinum in undiscovered deposits of the eight quantified deposit types. At the 90th percentile probability level, the Bay RMP area is estimated to contain 89 metric tons silver, 14 metric tons gold, 911,215 metric tons copper, 330,000 metric tons iron, 1 metric ton mercury, 8,600 metric tons molybdenum and 1 metric ton platinum in undiscovered deposits of the eight deposit types. Other commodities, which may occur in the Bay RMP area, include Cr, Sn, W, Zn, and other platinum-group elements such as Ir, Os, and Pd. We define 13 permissive tracts for 9 additional deposit model types. These are: Besshi- and Cyprus, and Kuroko-volcanogenic massive sulfides, hot spring gold, low sulfide gold veins, Mississippi-Valley Pb-Zn, tin greisen, zinc skarn and Alaskan-type zoned ultramafic platinum-group element deposits. Resources in undiscovered deposits of these nine types have not been quantified, and would be in addition to those in known deposits and the undiscovered resources listed above. Additional mineral resources also may occur in the Bay RMP area in deposit types, which were not considered here.

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 reports on high Ag content reaching 49 wt.% Ag in bornite and 1.8 wt.% Ag in chalcocite occurring due to Ag substitution in Cu-minerals without modification of their crystallographic structure (Salamon 1979; Banaś et al 2007; Kucha 2007; Piestrzyński 2007, Pieczonka 2011). Acknowledgements. This work was supported by the National Science Centre research grant (No 2011/03/N/ST10/04619). References: Kucha H and Mayer W (2007) Geochemistry. [In:] Piestrzyński A (Ed) Monografia KGHM Polska Miedź SA., pp 197-207 (In Polish) Pieczonka J (2011) Factors controlling distribution of ore minerals within copper deposit, Fore-Sudetic Monocline, SW Poland. 195 pp (In Polish) Piestrzyński A (2007) Ore minerals. [In:] Piestrzyński A (Ed) Monografia KGHM Polska Miedź SA., pp 167-197 (in Polish) Salamon W (1979) Occurrence of the Ag and Mo in the Zechstein sediments of the Fore-Sudetic Monocline. Prace Mineralogiczne, PAN 62, pp 1-52 (In Polish)

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.

The Alaska Mineral Resource Assessment Program; background information to accompany geologic and mineral-resource maps of the Cordova and Middleton Island quadrangles, southern Alaska

USGS Publications Warehouse

Winkler, Gary R.; Plafker, George; Goldfarb, R.J.; Case, J.E.

1992-01-01

report summarizes recent results of integrated geological, geochemical, and geophysical field and laboratory studies conducted by the U.S. Geological Survey in the Cordova and Middleton Island 1?x3 ? quadrangles of coastal southern Alaska. Published open-file reports and maps accompanied by descriptive and interpretative texts, tables, diagrams, and pertinent references provide background information for a mineral-resource assessment of the two quadrangles. Mines in the Cordova and Middleton Island quadrangles produced copper and byproduct gold and silver in the first three decades of the 20th century. The quadrangles may contain potentially significant undiscovered resources of precious and base metals (gold, silver, copper, zinc, and lead) in veins and massive sulfide deposits hosted by Cretaceous and Paleogene sedimentary and volcanic rocks. Resources of manganese also may be present in the Paleogene rocks; uranium resources may be present in Eocene granitic rocks; and placer gold may be present in beach sands near the mouth of the Copper River, in alluvial sands within the canyons of the Copper River, and in smaller alluvial deposits underlain by rocks of the Valdez Group. Significant coal resources are present in the Bering River area, but difficult access and structural complexities have discouraged development. Investigation of numerous oil and gas seeps near Katalla in the eastern part of the area led to the discovery of a small, shallow field from which oil was produced between 1902 and 1933. The field has been inactive since, and subsequent exploration and drilling onshore near Katalla in the 1960's and offshore near Middleton Island on the outer continental shelf in the 1970's and 1980's was not successful.

Synthesis, structure and characterization of two new copper(I)-thioarsenates (III) constructed by the [AsS{sub 3}]{sup 3-} and CuS{sub x} units

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

Yao, Hua-Gang; Ji, Min; Ji, Shou-Hua

2013-02-15

Two new copper(I)-thioarsenates(III), CsCu{sub 2}AsS{sub 3}(1) and KCu{sub 4}AsS{sub 4}(2), have been synthesized solvothermally in the presence of copper powder. Compound 1 is built up of trigonal AsS{sub 3} pyramid, tetrahedral CuAsS{sub 3} and CuS{sub 3} moieties forming 4-membered, 5-membered and 6-membered rings. The fusion of these rings produces layered anions [Cu{sub 2}AsS{sub 3}]{sup -}, and cesium cations are located between metal-sulfide layers. The structure of 2 consists of infinite [Cu{sub 2}S{sub 2}]{sup 2-} chain and layered [Cu{sub 6}As{sub 2}S{sub 6}] linked to form a three-dimensional anionic framework, [Cu{sub 4}AsS{sub 4}]{sup -}, and containing channels in which the potassium cationsmore » reside. - Graphical abstract: Qne layered CsCu{sub 2}AsS{sub 3} and one framework KCu{sub 4}AsS{sub 4} possessing noncondensed [AsS{sub 3}]{sup 3-} unit have been synthesized solvothermally. The optical band gaps of the two compounds are 2.3 and 1.8 eV, respectively. Highlights: Black-Right-Pointing-Pointer We obtained two new copper(I)-thioarsenate(III), CsCu{sub 2}AsS{sub 3} and KCu{sub 4}AsS{sub 4}. Black-Right-Pointing-Pointer Both compounds possess noncondensed [AsS{sub 3}]{sup 3-} unit and represent new structure types. Black-Right-Pointing-Pointer The optical band gaps of the two compounds are 2.3 eV and 1.8 eV, respectively.« less

Fabrication of mesoporous iron (Fe) doped copper sulfide (CuS) nanocomposite in the presence of a cationic surfactant via mild hydrothermal method for supercapacitors

NASA Astrophysics Data System (ADS)

Brown, J. William; Ramesh, P. S.; Geetha, D.

2018-02-01

We report fabrication of mesoporous Fe doped CuS nanocomposites with uniform mesoporous spherical structures via a mild hydrothermal method employing copper nitrate trihydrate (Cu (NO3).3H2O), Thiourea (Tu,Sc(NH2)2 and Iron tri nitrate (Fe(No3)3) as initial materials with cationic surfactant cetyltrimethylamoniame bromide (CTAB) as stabilizer/size controller and Ethylene glycol as solvent at 130 °C temperature. The products were characterized by XRD, SEM/EDX, TEM, FTIR and UV analysis. X-ray diffraction (XRD) spectra confirmed the Fe doped CuS nanocomposites which are crystalline in nature. EDX and XRD pattern confirmed that the product is hexagonal CuS phase. Fe doped spherical structure of CuS with grain size of 21 nm was confirmed by XRD pattern. Fe doping was identified by energy dispersive spectrometry (EDS). The Fourier-transform infrared (FTIR) spectroscopy results revealed the occurrence of active functional groups required for the reduction of copper ions. Studies showed that after a definite time relining on the chosen copper source, the obtained Fe-CuS nanocomposite shows a tendency towards self-assembly and creating mesoporous like nano and submicro structures by TEM/SAED. The achievable mechanism of producing this nanocomposite was primarily discussed. The electrochemical study confirms the pseudocapacitive nature of the CuS and Fe-CuS electrodes. The CuS and Fe-CuS electrode shows a specific capacitance of about 328.26 and 516.39 Fg-1 at a scan rate of 5 mVs-1. As the electrode in a supercapacitor, the mesoporous nanostructured Fe-CuS shows excellent capacitance characteristics.

iron phase control during pressure leaching at elevated temperature

NASA Astrophysics Data System (ADS)

Fleuriault, Camille

Iron is a common contaminant encountered in most metal recovery operations, and particularly hydrometallurgical processes. For example, the Hematite Process uses autoclaves to precipitate iron oxide out of the leaching solution, while other metals are solubilized for further hydrometallurgical processing. In some cases, Basic Iron Sulfate (BIS) forms in place of hematite. The presence of BIS is unwanted in the autoclave discharge because it diminishes recovery and causes environmental matters. The focus of this master thesis is on the various iron phases forming during the pressure oxidation of sulfates. Artificial leaching solutions were produced from CuSO4, FeSO4 and H2SO4 in an attempt to recreate the matrix composition and conditions used for copper sulfides autoclaving. The following factors were investigated in order to determine which conditions hinder the formation of BIS: initial free acidity (5 -- 98 g/L), initial copper concentration (12.7 -- 63.5 g/L), initial iron concentration (16.7 -- 30.7 g/L) and initial iron oxidation state. There were three solid species formed in the autoclave: hematite, BIS and hydronium jarosite. The results show that free acid is the main factor influencing the composition of the residue. At an initial concentration of 22.3 g/L iron and no copper added, the upper limit for iron oxide formation is 41 g/L H2SO4. The increase of BIS content in the residue is not gradual and occurs over a change of a few grams per liter around the aforementioned limit. Increasing copper sulfate concentration in the solution hinders the formation of BIS. At 63.5g/L copper, the upper free acidity limit is increased to 61g/L. This effect seems to be related to the buffering action of copper sulfate, decreasing the overall acid concentration and thus extending the stability range of hematite. The effect of varying iron concentration on the precipitate chemistry is unclear. At high iron levels, the only noticeable effect was the inhibition of jarosite. The results were reported within a Cu-Fe-S ternary system and modeled. The modeling confirmed the experimental observations with the exception that increasing iron concentrations seem to promote BIS stability.

Chronic toxicity of copper to five benthic invertebrates in laboratory-formulated sediment: sensitivity comparison and preliminary risk assessment.

PubMed

Roman, Yblin E; De Schamphelaere, Karel A C; Nguyen, Lien T H; Janssen, Colin R

2007-11-15

Five benthic organisms commonly used for sediment toxicity testing were chronically (28 to 35 days) exposed to copper in standard laboratory-formulated sediment (following Organization for Economic Cooperation and Development guidelines) and lethal and sub-lethal toxicities were evaluated. Sub-lethal endpoints considered were reproduction and biomass production for Lumbriculus variegatus, growth and reproduction for Tubifex tubifex, growth and emergence for Chironomus riparius, and growth for Gammarus pulex and Hyalella azteca. Expressed on whole-sediment basis the observed lethal sensitivity ranking (from most to least sensitive) was: G. pulex>L. variegatus>H. azteca=C. riparius=T. tubifex, with median chronic lethal concentrations (LC50) between 151 and 327 mg/kg dry wt. The sub-lethal sensitivity ranking (from most to least sensitive, with the most sensitive endpoint between parentheses): C. riparius (emergence)>T. tubifex (reproduction)=L. variegatus (reproduction)>G. pulex (growth)>H. azteca (growth), with median effective concentrations (EC50) between 59.2 and 194 mg/kg dry wt. No observed effect concentrations (NOEC) or 10% effective concentrations (EC10) for the five benthic invertebrates were used to perform a preliminary risk assessment for copper in freshwater sediment by means of (a) the "assessment factor approach" or (b) the statistical extrapolation approach (species sensitivity distribution). Depending on the data (NOEC or EC10) and the methodology used, we calculated a Predicted No Effect Concentration (PNEC) for sediment between 3.3 and 47.1 mg Cu/dry wt. This range is similar to the range of natural (geochemical) background concentrations of copper in sediments in Europe, i.e. 90% of sediments have a concentration between 5 and 49 mg Cu/kg dry wt. A detailed analysis of the outcome of this preliminary exercise highlighted that multiple issues need to be explored for achieving a scientifically more sound risk assessment and for the development of robust sediment quality criteria for copper, including (i) the use of the assessment factor approach vs. the statistical extrapolation approach, (ii) the importance of bioavailability modifying factors (e.g., organic carbon, acid volatile sulfide), and (iii) the influence of prevailing geochemical (bioavailable) background concentrations on the copper sensitivity of local benthic biota.

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 techniques. From these results, a deeper understanding of the interplay between the numerous annealing variables was achieved and improved annealing processes were developed.

Plasmonic fluorescent CdSe/Cu2S hybrid nanocrystals for multichannel imaging and cancer directed photo-thermal therapy

NASA Astrophysics Data System (ADS)

Sheikh Mohamed, M.; Poulose, Aby Cheruvathoor; Veeranarayanan, Srivani; Romero Aburto, Rebecca; Mitcham, Trevor; Suzuki, Yuko; Sakamoto, Yasushi; Ajayan, Pulickel M.; Bouchard, Richard R.; Yoshida, Yasuhiko; Maekawa, Toru; Sakthi Kumar, D.

2016-04-01

A simple, crude Jatropha curcas (JC) oil-based synthesis approach, devoid of any toxic phosphine and pyrophoric ligands, to produce size and shape tuned CdSe QDs and a further copper sulfide (Cu2S) encasing is presented. The QDs exhibited excellent photoluminescent properties with narrow band gap emission. Furthermore, the Cu2S shell rendered additional cytocompatibility and stability to the hybrid nanomaterial, which are major factors for translational and clinical applications of QDs. The nanocomposites were PEGylated and folate conjugated to augment their cytoamiability and enhance their specificity towards cancer cells. The nanohybrids possess potentials for visible, near infrared (NIR), photoacoustic (PA) and computed tomography (μCT) imaging. The diverse functionality of the composite was derived from the multi-channel imaging abilities and thermal competence on NIR laser irradiation to specifically actuate the photo-thermal ablation of brain cancer cells.A simple, crude Jatropha curcas (JC) oil-based synthesis approach, devoid of any toxic phosphine and pyrophoric ligands, to produce size and shape tuned CdSe QDs and a further copper sulfide (Cu2S) encasing is presented. The QDs exhibited excellent photoluminescent properties with narrow band gap emission. Furthermore, the Cu2S shell rendered additional cytocompatibility and stability to the hybrid nanomaterial, which are major factors for translational and clinical applications of QDs. The nanocomposites were PEGylated and folate conjugated to augment their cytoamiability and enhance their specificity towards cancer cells. The nanohybrids possess potentials for visible, near infrared (NIR), photoacoustic (PA) and computed tomography (μCT) imaging. The diverse functionality of the composite was derived from the multi-channel imaging abilities and thermal competence on NIR laser irradiation to specifically actuate the photo-thermal ablation of brain cancer cells. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05225d

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.

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.

Geologic map of the Dusar area, Herat Province, Afghanistan; Modified from the 1973 original map compilations of V.I. Tarasenko and others

USGS Publications Warehouse

Tucker, Robert D.; Stettner, Will R.; Masonic, Linda M.; Bogdanow, Anya K.

2017-10-24

The geologic maps and cross sections presented in this report are redrafted and modified versions of the Geologic map and map of useful minerals of the Dusar area (scale 1:50,000) and Geologic sketch map of the Dusar and Namak-sory ore occurrences (scale 1:10,000), located in the Herat Province, Afghanistan. The original maps and cross sections are contained in unpublished Soviet report no. 0290 (Tarasenko and others, 1973) prepared in cooperation with the Ministry of Mines and Industries of the Royal Government of Afghanistan, in Kabul during 1973 under contract no. 50728. The redrafted maps and cross sections (modified from Tarasenko and others, 1973) illustrate the geological structure and mineral occurrences of the Dusar copper-gold-silver-lead-zinc prospect area of western Afghanistan, located within the Dusar-Shaida copper and tin area of interest (AOI), Herat Province, Afghanistan.Mineralization in the Dusar area is hosted within Early Jurassic to Early Cretaceous stratified volcanic and sedimentary rocks associated with numerous diabase and gabbro-diabase intrusive bodies and is generally near a major northeast-trending system of faults and quartz veins. Host rocks consist of quartz keratophyre and quartz-feldspar porphyry, with layers of schist, phyllite, and quartz-chlorite and chlorite-sericite slate; and limestone and shale, with schist and carbonate-chlorite and chlorite slate. Known mineralization includes an extensive quartz vein system, shown on the map as the “northern occurrence,” as well as the Dusar and Namak-sory gossan zones, interpreted to have formed from remnant pyrite mineralization. The veins of the northern occurrence and their altered host rocks are known to contain anomalous to economic concentrations of precious and base metals, with concentrations locally in excess of 2 parts per million gold, 100 parts per million silver, 5 percent copper, and 1 percent lead. These veins occur in swarms, and are hosted along structures that are approximately concordant with the plane of the metamorphic fabric. The veins consist mostly of quartz, with minor carbonate and sulfide minerals, and display weak alteration halos along their margins. The gossans are locally anomalous in these metals, but their size and extent makes them attractive exploration targets for potential massive sulfide mineralization.The Dusar gossan zone is a massive, ochreous, and siliceous limonitic rock, approximately 2,200 meters long, 30 to 250 meters wide, and 2.0 to 7.2 meters thick. Drilling below the Dusar gossan intersected a siliceous, sericitic, and limonitic rock underlain by quartz keratophyre with abundant disseminated pyrite. Mineralized sections grade 0.06 weight percent copper and up to 0.05 weight percent zinc. The Namak-sory gossan zone contains a similar deposit with anomalous concentrations of copper, zinc, and gold.The redrafted maps and cross sections reproduce the topology of rock units, contacts, and faults of the original Soviet maps and cross sections, and include minor modifications based on examination of the originals and observations made during two brief field visits by USGS staff in August, 2010, and June, 2013.

Selenium

USGS Publications Warehouse

Stillings, Lisa L.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Selenium (Se) was discovered in 1817 in pyrite from copper mines in Sweden. It is a trace element in Earth’s crust, with an abundance of three to seven orders of magnitude less than the major rock-forming elements. Commercial use of selenium began in the United States in 1910, when it was used as a pigment for paints, ceramic glazes, and red glass. Since that time, it has had many other economic uses—notably, in the 1930s and 1940s, when it was used in rectifiers (which change alternating current to direct current), and in the 1960s, when it began to be used in the liner of photocopier drums. In the 21st century, other compounds have replaced selenium in these older products; modern uses for selenium include energy-efficient windows that limit heat transfer and thin-film photovoltaic cells that convert solar energy into electricity.In Earth’s crust, selenium is found as selenide minerals, selenate and selenite salts, and as substitution for sulfur in sulfide minerals. It is the sulfide minerals, most commonly those in porphyry copper deposits, that provide the bulk of the selenium produced for the international commodity market. Selenium is obtained as a byproduct of copper refining and recovered from the anode slimes generated in electrolytic production of copper. Because of this, the countries that have the largest resources and (or) reserves of copper also have the largest resources and (or) reserves of selenium.Because selenium occurs naturally in Earth’s crust, its presence in air, water, and soil results from both geologic reactions and human activity. Selenium is found concentrated naturally in soils that overlie bedrock with high selenium concentrations. Selenium mining, processing, use in industrial and agricultural applications, and disposal may all contribute selenium to the environment. A well-known case of selenium contamination from agricultural practices was discovered in 1983 in the Kesterson National Wildlife Refuge in California. There, waters draining from agricultural fields created wetlands with high concentrations of dissolved selenium in the water. The selenium was taken up by aquatic wildlife and caused massive numbers of embryonic deformities and deaths.Regulatory agencies have since worked to safeguard ecological and human health by creating environmental exposure guidelines based upon selenium concentrations in water and in fish tissue. Any attempt to regulate selenium concentrations requires a delicate balance because selenium occurs naturally and is also a vital nutrient for the health of wildlife, domestic stock, and humans. Selenium is commonly added as a vitamin to animal feed, and in some regions of the United States and the world, it is added as an amendment to soils for uptake by agricultural crops.The important role of selenium in economic products, energy supply, agriculture, and health will continue for well into the future. The challenge to society is to balance the benefits of selenium use with the environmental consequences of its extraction. Increased understanding of the elemental cycle of selenium in the earth may lead to new (or unconventional) sources of selenium, the discovery of new methods of extraction, and new technologies for minimizing the transfer of selenium from rock to biota, so to protect environmental and human health.

Stable isotopic constraints on fluid-rock interaction and Cu-PGE-S redistribution in the Sonju Lake intrusion, Minnesota

USGS Publications Warehouse

Park, Y.-R.; Ripley, E.M.; Miller, J.D.; Li, C.; Mariga, J.; Shafer, P.

2004-01-01

The Sonju Lake intrusion, part of the 1.1 Ga Midcontinent rift-related Beaver Bay Complex, is a 1,200-m-thick, strongly differentiated, layered sequence of mafic cumulates located in northeastern Minnesota. Basal melatroctolite and dunite layers are overlain by troctolite, gabbro, Fe-Ti oxide-rich gabbro, apatite diorite, and monzodiorite. Stratigraphic intervals rich in Pt + Pd, Cu, and S occur over ???500 m in the Fe-Ti oxide-rich gabbro and apatite diorite units. Peak concentrations show offsets that are similar to those found in other tholeiitic layered intrusions. Concentrations of Pd in excess of 100 ppb are confined to the lowermost 25 m of the interval. Copper shows a sharp increase to 630 ppm above the Pd-rich interval. Sulfur contents are low (<375 ppm) in the Cu-rich interval, but they increase to values as high as 3,150 ppm above in the apatite diorite. Disseminated sulfides in the intrusion have ??34S values that range from -2.2 to 3 per mil Vienna-Canyon Diablo Troilite (V-CDT) and suggest that contamination by country rock sulfur was not an important process in the formation of the metal-rich interval. ??18O values of plagioclase from the intrusion range from 5.6 to 12.0 per mil (V-SMOW) and indicate that a relatively low-18O fluid (??18O ???3-5 ???) interacted with the rocks of the intrusion at temperatures less than ???275??C. Clinopyroxene and Fe-Ti oxides (ilmenite with minor amounts of titanomagnetite) show much more restricted ranges in ??18O values (4.6-5.7 and 5.5-6.7 per mil, respectively) and attest to the kinetic control of the oxygen isotope exchange process. The externally derived fluid that interacted with rocks now enriched in platinum group elements (PGE) + Cu- and Fe-sulfide minerals locally liberated sulfur and replaced chalcopyrite and pyrite with goethite. In the Cu-rich zone, goethite that replaces chalcopyrite may contain up to 8.5 weight percent Cu. It is evident that hydrothermal alteration resulted in a decoupling of copper and sulfur, with sulfur being transferred out of the Cu-rich interval. Interaction between rocks in the PGE-Cu-S interval of the Sonju Lake intrusion and an externally derived fluid at low temperatures modified what appears to have been a primary stratigraphic metal-sulfur zonation. The effects of hydrothermal alteration on PGE and base-metal sulfide mobility and redistribution must be understood before models of primary zonation processes can be meaningfully applied. ?? 2004 by Economic Geology.

Gold deposits of the Carolina Slate Belt, southeastern United States--Age and origin of the major gold producers

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

2012-01-01

Gold- and iron sulfide-bearing deposits of the southeastern United States have distinctive mineralogical and geochemical features that provide a basis for constructing models of ore genesis for exploration and assessment of gold resources. The largest (historic) deposits, in approximate million ounces of gold (Moz Au), include those in the Haile (~ 4.2 Moz Au), Ridgeway (~1.5 Moz Au), Brewer (~0.25 Moz Au), and Barite Hill (0.6 Moz Au) mines. Host rocks are Late Proterozoic to early Paleozoic (~553 million years old) metaigneous and metasedimentary rocks of the Carolina Slate Belt that share a geologic affinity with the classic Avalonian tectonic zone. The inferred syngenetic and epithermal-subvolcanic quartz-porphyry settings occur stratigraphically between sequences of metavolcanic rocks of the Persimmon Fork and Uwharrie Formations and overlying volcanic and epiclastic rocks of the Tillery and Richtex Formations (and regional equivalents). The Carolina Slate Belt is highly prospective for many types of gold ore hosted within quartz-sericite-pyrite altered volcanic rocks, juvenile metasedimentary rocks, and in associated shear zones. For example, sheared and deformed auriferous volcanogenic massive sulfide deposits at Barite Hill, South Carolina, and in the Gold Hill trend, North Carolina, are hosted primarily by laminated mudstone and felsic volcanic to volcaniclastic rocks. The high-sulfidation epithermal style of gold mineralization at Brewer and low-sulfidation gold ores of the Champion pit at Haile occur in breccias associated with subvolcanic quartz porphyry and within crystal-rich tuffs, ash flows, and subvolcanic rhyolite. The Ridgeway and Haile deposits are primarily epithermal replacements and feeder zones within (now) metamorphosed crystal-rich tuffs, volcaniclastic sediments, and siltstones originally deposited in a marine volcanic-arc basinal setting. Recent discoveries in the region include (1) extensions of known deposits, such as at Haile where drilling has identified an extensive gold-rich feeder system; and (2) newly discovered prospects like the porphyry-style gold-copper-molybdenum occurrence reported at Deep River, N.C. Gold ores at Ridgeway and Haile represent the low-sulfidation, disseminated, shallow subaqueous tuffaceous equivalents of intrusion-related high-sulfidation ores such as those at Brewer. Haile also has mineralogical features that support a stockwork disseminated model of pyrite-gold-sericite mineralization in which a significant amount of ore was deposited in sediments at or near the surface. The potential is high for gold-rich ore at depth in the funnel-shaped feeder zones that likely underlie such surface variants of high sulfidation–low sulfidation epithermal systems and for new discoveries of similar deposits in areas undercover. Exploration strategies for large-scale gold-mineralizing systems applied to rocks of the Carolina Slate Belt, and by extension, the Carolinian-Avalonian tectonic zone of North America, benefit from applying subvolcanic and basinal epithermal models for gold mineralization.

The Explorer XVI Micrometeoroid Satellite Description and Preliminary Results for the Period December 16, 1962 Through January 13, 1963

NASA Technical Reports Server (NTRS)

Hastings, E. C., Jr.

1963-01-01

Explorer XVI (1962 Beta Chi l) data that have been analyzed for the period between December 16, 1962 (launch date), and January 13, 1963, indicate that the orbit achieved was close to the predicted orbit. Ten punctures of annealed 0.001-inch-thick beryllium-copper have been used to determine a puncture rate of 0.035 per square foot per day in this material. One puncture of a 0.002-inch-thick sample has also occurred in this period. A tentative evaluation of the puncture rate for the 0.001-inch beryllium-copper in terms of the rate for an equivalent thickness of aluminum has been attempted, and the result has been compared with two different puncture rate estimates. The three micrometeoroid impact detecting systems are operating. Counting rates for the high- and low-sensitivity systems were close to anticipated values near the end of one week. Two of the 0.001-inch-steel-covered grid detectors have been punctured, but none of the 0.003- or 0.006-inch-steel-covered grid detectors have indicated punctures. One of the cadmium sulfide cells indicates three punctures of the 0.00025-inch Mylar cover. None of the 0.002- or 0.003-inch-copper-wire cards have indicated a break in the period covered. Telemetry temperatures were initially higher than expected although they remained well within operating limits. Sensor temperatures have remained within the expected bounds.

Weathering of PGE sulfides and Pt-Fe alloys in the Freetown Layered Complex, Sierra Leone

NASA Astrophysics Data System (ADS)

Bowles, John F. W.; Suárez, Saioa; Prichard, Hazel M.; Fisher, Peter C.

2017-12-01

Fresh and weathered rocks and saprolite from Horizon B of the Freetown Layered Complex contain platinum-group minerals (PGM). The PGM in the fresh rocks are 1-7 μm across, including cooperite (PtS), isoferroplatinum (Pt3Fe), minor tetraferroplatinum (PtFe), tulameenite (Pt2FeCu), Os-bearing laurite (RuS2), and other base metal-sulfide (BMS)-bearing PGM. The weathered rocks contain fewer of those PGM but a high proportion of disordered Cu-(±Pd)-bearing Pt-Fe alloys. The saprolite hosts scarce, smaller (1-3 μm) ordered PtFe and disordered PtFe3. The Pt-Fe alloys became increasingly Fe rich as weathering proceeded. Pt-Fe oxides appeared during weathering. Copper sulfides associated with the primary PGM and cooperite (with <3% Pd) were destroyed to provide the minor Cu and Pd found in some of the disordered Pt-Fe alloys. Platinum- and Pd-bearing saprolites have retained the original rock fabric and, to a depth of about 2 m, surround residual rocks that show progressive weathering (corestones). Ground water passing through the saprolite has transported Pt and Pd (and probably Au) in solution down slope into saprolite over unmineralized rocks. Transport is marked by changes in the Pt/Pd ratio indicating that the metals have moved independently. Palladium is present in marginally higher concentrations in the deeper saprolite than in the corestones suggesting some retention of Pd in the deeper saprolite. Platinum and Pd are less concentrated in the upper saprolite than the deeper saprolite indicating surface leaching. Alteration occurred over a long period in an organic and microbial rich environment that may have contributed to the leaching and transport of PGE.

Noble metal abundances in komatiite suites from Alexo, Ontario and Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Brügmann, G. E.; Arndt, N. T.; Hofmann, A. W.; Tobschall, H. J.

1987-08-01

The distribution of the chalcophile and siderophile metals Cu, Ni, Au, Pd, Ir, Os and Ru in an Archaean komatiite flow from Alexo, Ontario and in a Phanerozoic komatiitic suite of Gorgona Island, Colombia, provides new information about the geochemical behaviour of these elements. Copper, Au and Pd behave as incompatible elements during the crystallization of these ultramafic magmas. In contrast, Ni, Ir, Os and Ru concentrations systematically decrease with decreasing MgO contents, a pattern characteristic of compatible elements. These trends are most probably controlled by olivine crystallization, which implies that Ir, Os and Ru are compatible in olivine. Calculated partition coefficients for Ir, Os and Ru between olivine and the melt are about 1.8. Compared to primitive mantle, parental komatiitic liquids are enriched in (incompatible) Cu, Au and Pd and depleted in (compatible) Ir, Os and Ru. Within both Archaean and Phanerozoic komatiites, noble metal ratios such as Au/Pd, Ir/Os, Os/Ru and Ru/Ir and ratios of lithophile and siderophile elements such as Ti/Pd, Ti/Au are constant and similar to primitive mantle values. This implies that Au and Pd are moderately incompatible elements and that there has been no significant fractionation of siderophile and lithophile elements since the Archaean. Platinum-group element abundances of normal MORB are highly variable and always much lower than in komatiites, because MORB magma is saturated with sulfur and a variable but minor amount of sulfide segregated during mantle melting or during the ascent of magma to the surface. Sulfide deposits associated with komatiites display similar chalcophile element patterns to those of komatiites. Noble metal ratios such as Pd/Ir, Au/Ir, Pd/Os and Pd/Ru can be used to determine the composition of the host komatiite at the time of sulfide segregation.

Mechanistic study of the rubber-brass adhesion interphase

NASA Astrophysics Data System (ADS)

Ashirgade, Akshay

Brass-plated steel tire cords form an essential strengthening component of a radial automobile tire. Adhesion between rubber compound and brass-plated steel tire cord is crucial in governing the overall performance of tires. The rubber-brass interfacial adhesion is influenced by the chemical composition and thickness of the interfacial layer. It has been shown that the interfacial layer consists mainly of sulfides and oxides of copper and zinc. This thesis discusses the effect of changes in the chemical composition and the structure of the interfacial layers due to addition of adhesion promoter resins. Grazing incidence X-Ray Diffraction (GIXRD) experiments were run on sulfidized polished brass coupons previously bonded to six experimental rubber compounds. It was confirmed that heat and humidity conditions lead to physical and chemical changes of the rubber-steel tire cord interfacial layer, closely related to the degree of rubber-brass adhesion. Morphological transformation of the interfacial layer led to loss of adhesion after aging. The adhesion promoter resins inhibit unfavorable morphological changes in the interfacial layer thus stabilizing it during aging and prolonging failure. Tire cord adhesion tests illustrated that the one-component resins improved adhesion after aging using a rubber compound with lower cobalt loading. Based on the acquired diffraction profiles, these resins were also found to impede crystallization of the sulfide layer after aging leading to improved adhesion. Secondary Ion Mass Spectrometry (SIMS) depth profiles, SEM micrographs and AFM images strongly corroborated the findings from GIXRD. FTIR was utilized in a novel way to understand the degradation mechanism due to aging. A model for rubber and interfacial layer degradation is proposed to illustrate the effect of aging and the one-component resins. This interfacial analysis adds valuable new information to our understanding of the complex nature of the rubber-brass bonding mechanism.

Method for monitoring environmental and corrosion

DOEpatents

Glass, R.S.; Clarke, W.L. Jr.; Ciarlo, D.R.

1995-08-01

A corrosion sensor array is described incorporating individual elements for measuring various elements and ions, such as chloride, sulfide, copper, hydrogen (pH), etc. and elements for evaluating the instantaneous corrosion properties of structural materials. The exact combination and number of elements measured or monitored would depend upon the environmental conditions and materials used which are subject to corrosive effects. Such a corrosion monitoring system embedded in or mounted on a structure exposed to the environment would serve as an early warning system for the onset of severe corrosion problems for the structure, thus providing a safety factor as well as economic factors. The sensor array is accessed to an electronics/computational system, which provides a means for data collection and analysis. 7 figs.

Positive electrode current collector for liquid metal cells

DOEpatents

Shimotake, Hiroshi; Bartholme, Louis G.

1984-01-01

A current collector for the positive electrode of an electrochemical cell with a positive electrode including a sulfide. The cell also has a negative electrode and a molten salt electrolyte including halides of a metal selected from the alkali metals and the alkaline earth metals in contact with both the positive and negative electrodes. The current collector has a base metal of copper, silver, gold, aluminum or alloys thereof with a coating thereon of iron, nickel, chromium or alloys thereof. The current collector when subjected to cell voltage forms a sulfur-containing compound on the surface thereby substantially protecting the current collector from further attack by sulfur ions during cell operation. Both electroless and electrolytic processes may be used to deposit coatings.

The mineral resource potential of the Wadi Habawnah and Najran quadrangles, sheets 17/44A and 17/44C, Kingdom of Saudi Arabia

USGS Publications Warehouse

Fenton, Michael D.

1983-01-01

The metallic resource potential of the Wadi Habawnah and Najran quadrangles in the southern Precambrian Arabian Shield has been determined primarily by reconnaissance rock geochemistry, limited wadi-sediment and colluvium geochemistry, and gossanous and ferruginous outcrop geochemistry. These surveys were guided by geological information acquired during previous reconnaissance mapping. Locally anomalous areas in alkalic and calc-alkalic granitic terrane are possible sources of niobium-zirconiumthorium-fluorite, tin-tungsten, and copper-molybdenum, although the potential of these areas does not appear to be outstanding. The reconnaissance geochemistry of the layered volcanic terrane and the geochemistry of gossanous and ferruginous outcrops indicate that the potential for stratiform base metal sulfide deposits is low.

Role of CTGF in sensitivity to hyperthermia in ovarian and uterine cancers

DOE PAGES

Hatakeyama, Hiroto; Wu, Sherry Y.; Lyons, Yasmin A.; ...

2016-11-01

Even though hyperthermia is a promising treatment for cancer, the relationship between specific temperatures and clinical benefits and predictors of sensitivity of cancer to hyperthermia is poorly understood. Ovarian and uterine tumors have diverse hyperthermia sensitivities. Integrative analyses of the specific gene signatures and the differences in response to hyperthermia between hyperthermia-sensitive and -resistant cancer cells identified CTGF as a key regulator of sensitivity. CTGF silencing sensitized resistant cells to hyperthermia. CTGF small interfering RNA (siRNA) treatment also sensitized resistant cancers to localized hyperthermia induced by copper sulfide nanoparticles and near-infrared laser in orthotopic ovarian cancer models. Lastly, CTGF silencingmore » aggravated energy stress induced by hyperthermia and enhanced apoptosis of hyperthermia-resistant cancers.« less

Process for production of synthesis gas with reduced sulfur content

DOEpatents

Najjar, Mitri S.; Corbeels, Roger J.; Kokturk, Uygur

1989-01-01

A process for the partial oxidation of a sulfur- and silicate-containing carbonaceous fuel to produce a synthesis gas with reduced sulfur content which comprises partially oxidizing said fuel at a temperature in the range of 1800.degree.-2200.degree. F. in the presence of a temperature moderator, an oxygen-containing gas and a sulfur capture additive which comprises an iron-containing compound portion and a sodium-containing compound portion to produce a synthesis gas comprising H.sub.2 and CO with a reduced sulfur content and a molten slag which comprises (i) a sulfur-containing sodium-iron silicate phase and (ii) a sodium-iron sulfide phase. The sulfur capture additive may optionally comprise a copper-containing compound portion.

[Ultraviolet-visible spectrometry analysis of insoluble xanthate heavy metal complexes].

PubMed

Qiu, Bo; Liu, Jin-Feng; Liu, Yao-Chi; Yang, Zhao-Guang; Li, Hai-Pu

2014-11-01

A ultraviolet-visible spectrometry method of determining insoluble xanthate heavy metal complexes in flotation wastewater was the first time to be put forward. In this work, the changes of ultraviolet-visible spectra of xanthate solution after the addition of various heavy metal ions were investigated firstly. It was found that Pb2+ and Cu2+ can form insoluble complexes with xanthate, while Fe2+, Zn2+ and Mn2+ have little effect on the ultraviolet absorption of xanthate solution. Then the removal efficiencies of filter membrane with different pore sizes were compared, and the 0.22 μm membrane was found to be effective to separate copper xanthate or lead xanthate from the filtrate. Furthermore, the results of the study on the reaction of sodium sulfide and insoluble xanthate heavy metal complexes showed that S(2-) can release the xanthate ion quantitatively from insoluble complexes to solution. Based on the above research, it was concluded that the amount of insoluble xanthate heavy metal complexes in water samples can be obtained through the increase of free xanthate in the filtrate after the addition of sodium sulfide. Finally, the feasibility of this method was verified by the application to the analysis of flotation wastewater from three ore-dressing plants in the Thirty-six Coves in Chenzhou.

Analysis study of multispectral data, ERTS-A, from an area in West Pakistan

NASA Technical Reports Server (NTRS)

Schmidt, R. G. (Principal Investigator)

1973-01-01

The author has identified the following significant results. Geomorphic features related to a known porphyry copper deposit at Saindak, western Chagai District, Pakistan, are easily distinguished on ERTS-1 images. No new prospecting sites were recognized on the basis of the images alone, but new information from the images was used in conjunction with known geology to evaluate two previously known speculative areas and to suggest one additional one. The study showed that Saindak-type deposits are less likely in some extensive areas of the Chagai District than formerly believed. The Saindak deposit is in an area of relatively soft folded sedimentary and volcanic rocks. The deposit is characterized by a linear zone of easily eroded sulfide-rich rock surrounded by a resistant rim of hornfels and propylitically altered rock. Both 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. During field mapping, patches of strong red and yellow hue related to the mineral natrojarosite were noted in the central valley. Attempts to detect a color anomaly using simple false color composites were not successful.

Scientific communications: Re-Os sulfide (bornite, chalcopyrite, and pyrite) systematics of the carbonate-hosted copper deposits at ruby creek, southern brooks range, Alaska

USGS Publications Warehouse

Selby, D.; Kelley, K.D.; Hitzman, M.W.; Zieg, J.

2009-01-01

New Re-Os data for chalcopyrite, bornite, and pyrite from the carbonate-hosted Cu deposit at Ruby Creek (Bornite), Alaska, show extremely high Re abundances (hundreds of ppb, low ppm) and contain essentially no common Os. The Re-Os data provide the first absolute ages of ore formation for the carbonate-hosted Ruby Creek Cu-(Co) deposit and demonstrate that the Re-Os systematics of pyrite, chalcopyrite, and bornite are unaffected by greenschist metamorphism. The Re-Os data show that the main phase of Cu mineralization pre dominantly occurred at 384 ?? 4.2 Ma, with an earlier phase possibly at ???400 Ma. The Re-Os data are consistent with the observed paragenetic sequence and coincide with zircon U-Pb ages from igneous rocks within the Ambler metallogenic belt, some of which are spatially and genetically associated with regional volcanogenic massive sulfide deposits. The latter may suggest a temporal link between regional magmatism and hydrothermal mineralization in the Ambler district. The utility of bornite and chalcopyrite, in addition to pyrite, contributes to a new understanding of Re-Os geochronology and permits a refinement of the genetic model for the Ruby Creek deposit. ?? 2009 Society of Economices Geologists, Inc.

Hydrocarbon-fuel/combustion-chamber-liner materials compatibility

NASA Technical Reports Server (NTRS)

Homer, G. David

1991-01-01

The results of dynamic tests using methane and NASA-Z copper test specimen under conditions that simulate those expected in the cooling channels of a regeneratively cooled LOX/hydrocarbon booster engine operating at chamber pressures up to 3000 psi are presented. Methane with less than 0.5 ppm sulfur contamination has little or no effect on cooling channel performance. At higher sulfur concentrations, severe corrosion of the NASA-Z copper alloy occurs and the cuprous sulfide Cu2S, thus formed impedes mass flow rate and heat transfer efficiency. Therefore, it is recommended that the methane specification for this end use set the allowable sulfur content at 0.5 ppm (max). Bulk high purity liquid methane that meets this low sulfur requirement is currently available from only one producer. Pricing, availability, and quality assurance are discussed in detail. Additionally, it was found that dilute sodium cyanide solutions effectively refurbish sulfur corroded cooling channels in only 2 to 5 minutes by completely dissolving all the Cu2S. Sulfur corroded/sodium cyanide refurbished channels are highly roughened and the increased surface roughness leads to significant improvements in heat transfer efficiency with an attendant loss in mass flow rate. Both the sulfur corrosion and refurbishment effects are discussed in detail.

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

PubMed

Bose, Riya; Bera, Ashok; Parida, Manas R; Adhikari, Aniruddha; Shaheen, Basamat S; Alarousu, Erkki; Sun, Jingya; Wu, Tom; Bakr, Osman M; Mohammed, Omar F

2016-07-13

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions. Here, we precisely map the collective surface charge carrier dynamics of copper indium gallium selenide NCs as a function of the surface trap states before and after surface passivation in real space and time using S-UEM. The time-resolved snapshots clearly demonstrate that the density of the trap states is significantly reduced after zinc sulfide (ZnS) shelling. Furthermore, the removal of trap states and elongation of carrier lifetime are confirmed by the increased photocurrent of the self-biased photodetector fabricated using the shelled NCs.

Preliminary report on the Apex and Paymaster mines, Washington County, Utah

USGS Publications Warehouse

Kinkel, Arthur R.

1951-01-01

The Apex and Paymaster mines in the Tutsagubet mining district, 25 miles southwest of St. George, Utah, are at an elevation of about 5,000 feet in the Beaver Dam Mountains. The ore was deposited in a steeply dipping fault zone which cuts a thick series of gently dipping limestones of Pennsylvanian age with minor interbedded shales and sandstones. The ore now consists primarily of copper oxides, but is reported to contain small quantities of lead and sine oxides. Complete oxidation extends to the 1,400 level of the Apex mine, the deepest level in this mine. Lead oxides are reported to have been more plentiful in the workings near surface, but the stoped area is now caved to the 1,330 level. The ore bodies probably formed largely as a filling in the fault fissure, and in crushed zones along the fault, with only minor replacement extending for short distances along the bedding. The sulfides oxidized essentially in place and migration of the oxidized copper ores is believed to be limited to a few feet. Additional exploration below the known ore shoots in the Apex and Paymaster mines and along the fissure between the two mines may disclose new ore bodies.

Deposition of ultra thin CuInS₂ absorber layers by ALD for thin film solar cells at low temperature (down to 150 °C).

PubMed

Schneider, Nathanaelle; Bouttemy, Muriel; Genevée, Pascal; Lincot, Daniel; Donsanti, Frédérique

2015-02-06

Two new processes for the atomic layer deposition of copper indium sulfide (CuInS₂) based on the use of two different sets of precursors are reported. Metal chloride precursors (CuCl, InCl₃) in combination with H2S imply relatively high deposition temperature (Tdep = 380 °C), and due to exchange reactions, CuInS₂ stoechiometry was only achieved by depositing In₂S3 layers on a CuxS film. However, the use of acac- metal precursors (Cu(acac)₂, In(acac)₃) allows the direct deposition of CuInS₂ at temperature as low as 150 °C, involving in situ copper-reduction, exchange reaction and diffusion processes. The morphology, crystallographic structure, chemical composition and optical band gap of thin films were investigated using scanning electronic microscope, x-ray diffraction under grazing incidence conditions, x-ray fluorescence, energy dispersive spectrometry, secondary ion mass spectrometry, x-ray photoelectron spectroscopy and UV-vis spectroscopy. Films were implemented as ultra-thin absorbers in a typical CIS-solar cell architecture and allowed conversion efficiencies up to 2.8%.

Digestive kinetics determines bioavailability of pollutants. Final report, 1 July 1993--30 September 1998

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

Mayer, L.M.

1998-09-30

The bioavailability of sedimentary contaminants to animals in harbor sediments was addressed by studying the mechanisms by which animals solubilize contaminants during feeding and digestion. Digestive physiology work on many different animal species revealed patterns of enzymes, surfactants and dissolved organic matter that correlate with feeding mode, phyletic position, and diet. Incubation of digestive fluids to dissolve contaminants from polluted sediments was developed to provide numerical estimates of bioavailability, and showed that much higher fractions of total contaminant loading are available than predicted by currently established, aqueous equilibrium approaches. The kinetics of reactions are slow enough that variations in feedingmore » rates will influence overall bioavailability. Experimental manipulations showed mechanisms of bioavailability. Dissolved amino acids, in the form of enzyme proteins and hydrolyzed food, are responsible for solubilization of metals such as copper. At high levels, copper can inactivate digestive enzymes. Metals in sedimentary sulfide minerals were largely impervious to digestive fluid attack. Surfactants are responsible for most solubilization of polycyclic aromatic hydrocarbons (PAH), though other agents also appear to play a role. Bioavailability of both metals and PAH can be limited by saturating the digestive agents responsible for their dissolution.« less

Confirmation of Incorporation of Cu and Se Ions in Applied p- and n-Type-Doped Sb2S3 by Photoemission Spectroscopy

NASA Astrophysics Data System (ADS)

Validžić, Ivana Lj; Popović, Maja; Lojpur, Vesna; Bundaleski, Nenad; Rakočević, Zlatko

2018-04-01

The effect of incorporating copper (Cu) and selenium (Se) ions into stibnite (Sb2S3) lattice was investigated using x-ray photoelectron spectroscopy (XPS). The incorporation of Cu and Se ions was verified by comparing the XPS spectra of the undoped (amorphous Sb2S3), doped ( p and n-doped) and pure Se and Cu-acetate powders. The main photoelectron Cu 2p1/2 (951.8 eV) and Cu 2p3/2 (932.1 eV) lines derived from the Cu-doped and Cu-acetate powder samples were clearly observed, whereas in the undoped sample, none of the characteristic lines of Cu were detected. The Se Auger line (138.6 eV), the only line of Se which does not coincide with the lines of Sb and S, was successfully detected in an Se-doped XPS sample and the spectrum of pure Se, while Se in the undoped sample was not found. Further, the XPS measurements revealed the relative amounts of Cu and Se in antimony sulfide, as well as the oxidation state of copper incorporated into the matrix.

Platinum mineralization in the Kapalagulu Intrusion, western Tanzania

NASA Astrophysics Data System (ADS)

Wilhelmij, Harry R.; Cabri, Louis J.

2016-03-01

Low-grade copper and nickel mineralization was found near the eastern shore of Lake Tanganyika at Kungwe Bay in the early part of the twentieth century. The mineralization occurs in harzburgite at the base of a layered gabbro complex known as the Kapalagulu Intrusion, emplaced between the Paleoproterozoic Ubendian basement and overlying Neoproterozoic Itiaso Group metasediments. Several mining and exploration companies continued the geophysical and drilling exploration for base metals throughout the last century culminating in the discovery of high-grade platinum-group element (PGE) mineralization associated with chromitite and sulfide-bearing harzburgite within the southeastern extension of the Kapalagulu Intrusion (known as the Lubalisi Zone) that is covered by a layer of nickel-rich laterite regolith. The poorly layered southeastern harzburgite forms part of the >1500 m-thick Lower Ultramafic Sequence and resembles a dike-like body that flares upwards into a succession of well-layered gabbroic rocks of the Upper Mafic Sequence. No PGE mineralization has been found in the layered gabbro; all the mineralization is associated with the chromite- and sulfide-rich harzburgite of the Lower Ultramafic Sequence and the laterite regolith overlying the mineralized harzburgite. The Lubalisi Zone harzburgite is underlain by basal dunite and overlain by an interval of layered harzburgite and troctolite and this ultramafic sequence is folded into a syncline that plunges towards the northwest that has been modified by major dolerite-filled faults orientated subparallel to the fold axial surface. Extensive deep drilling in the Lubalisi Zone of the Kapalagulu Intrusion shows that the folded harzburgite can be subdivided into a lower feldspathic harzburgite, a harzburgite containing chromitite seams and intervals of sulfide and chromite mineralization known as the Main Chromite Sulfide Succession (MCSS), an overlying sulfide-rich harzburgite, and an upper feldspathic harzburgite. Impersistent, stratiform PGE mineralized horizons occur within the MCSS harzburgite from which drill core samples were taken for platinum-group mineral (PGM) characterization from two drill holes. Where the PGE reefs reach the surface there is residual PGE mineralization within the laterite regolith from which drill core samples were taken from various laterite lithological units for PGM characterization. As the harzburgite PGE reefs contain significant concentrations of both sulfide and chromite (including chromitite seams) they resemble the PGE-rich chromitite seams of the Bushveld Complex rather than the PGE-bearing Main Sulfide Zone of the Great Dyke and Main Sulfide Layer of the Munni Munni Complex. The dominant Pd PGM in three PGE reef samples varies, ranging ( n = 164, relative wt%) from bismuthides (63 %), bismuthtellurides (19 %), and tellurides (6 %), to tellurides (39 %), bismuthtellurides (24 %), stannides (14 %), and alloys (13 %), and to antimon-arsenides (33 %), stannides (21 %), bismuthides (17 %), tellurides (13 %), and alloys (10 %). From 13.5 % to 21.0 % of the total Pd occurs as a solid solution in pentlandite. The three samples have similar Pt PGM modal distributions ( n = 172, relative wt%); the dominant Pt mineral is sperrylite (79, 58, and 47 %) followed by tellurides (15, 17, 21 %), alloys (2, 1, 1 %), and sulfides (2, 1, 0 %). Comparison of Pd/Pt ratios from assays to those calculated from minerals show that the data for the Pt and Pd PGM are very robust, confirming the concentration methodology and characterization. Study of samples from a shallow drill hole penetrating the laterite regolith shows that the primary Pd mineralization has not survived oxidation, is mainly dispersed, but some was reconstituted to form secondary minerals: cabriite, unnamed tellurides, a selenide, a Pd-Te-Hg mineral, alloys and Pd-bearing secondary sulfides (millerite and heazlewoodite). The primary Pt minerals are more resistant to oxidation and dissolution, especially sperrylite and isoferroplatinum, but it is likely that other Pt alloys (tetraferroplatinum and tulameenite) are of secondary origin after dissolution of Pt tellurides.

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 to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially in the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity in this site.« less

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 element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially at the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity at this site.

Origin and evolution of mineralizing fluids and exploration of the Cerro Quema Au-Cu deposit (Azuero Peninsula, Panama) from a fluid inclusion and stable isotope perspective

USGS Publications Warehouse

Corral, Isaac; Cardellach, Esteve; Corbella, Merce; Canals, Angels; Griera, Albert; Gomez-Gras, David; Johnson, Craig A.

2017-01-01

Cerro Quema is a high sulfidation epithermal Au-Cu deposit with a measured, indicated and inferred resource of 35.98 Mt. @ 0.77 g/t Au containing 893,600 oz. Au (including 183,930 oz. Au equiv. of Cu ore). It is characterized by a large hydrothermal alteration zone which is interpreted to represent the lithocap of a porphyry system. The innermost zone of the lithocap is constituted by vuggy quartz with advanced argillic alteration locally developed on its margin, enclosed by a well-developed zone of argillic alteration, grading to an external halo of propylitic alteration. The mineralization occurs in the form of disseminations and microveinlets of pyrite, chalcopyrite, enargite, tennantite, and trace sphalerite, crosscut by quartz, barite, pyrite, chalcopyrite, sphalerite and galena veins.Microthermometric analyses of two phase (L + V) secondary fluid inclusions in igneous quartz phenocrysts in vuggy quartz and advanced argillically altered samples indicate low temperature (140–216 °C) and low salinity (0.5–4.8 wt% NaCl eq.) fluids, with hotter and more saline fluids identified in the east half of the deposit (Cerro Quema area).Stable isotope analyses (S, O, H) were performed on mineralization and alteration minerals, including pyrite, chalcopyrite, enargite, alunite, barite, kaolinite, dickite and vuggy quartz. The range of δ34S of sulfides is from − 4.8 to − 12.7‰, whereas δ34S of sulfates range from 14.1 to 17.4‰. The estimated δ34SΣS of the hydrothermal fluid is − 0.5‰. Within the advanced argillic altered zone the δ34S values of sulfides and sulfates are interpreted to reflect isotopic equilibrium at temperatures of ~ 240 °C. The δ18O values of vuggy quartz range from 9.0 to 17.5‰, and the δ18O values estimated for the vuggy quartz-forming fluid range from − 2.3 to 3.0‰, indicating that it precipitated from mixing of magmatic fluids with surficial fluids. The δ18O of kaolinite ranges from 12.7 to 18.1‰ and δD from − 103.3 to − 35.2‰, whereas the δ18O of dickite varies between 12.7 and 16.3‰ and δD from − 44 to − 30. Based on δ18O and δD, two types of kaolinite/dickite can be distinguished, a supergene type and a hypogene type. Combined, the analytical data indicate that the Cerro Quema deposit formed from magmatic-hydrothermal fluids derived from a porphyry copper-like intrusion located at depth likely towards the east of the deposit. The combination of stable isotope geochemistry and fluid inclusion analysis may provide useful exploration vectors for porphyry copper targets in the high sulfidation/lithocap environment.

CONSTRUCTED WETLAND TREATMENT SYSTEMS FOR WATER QUALITY IMPROVEMENT

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

Nelson, E.

2010-07-19

The Savannah River National Laboratory implemented a constructed wetland treatment system (CWTS) in 2000 to treat industrial discharge and stormwater from the Laboratory area. The industrial discharge volume is 3,030 m{sup 3} per day with elevated toxicity and metals (copper, zinc and mercury). The CWTS was identified as the best treatment option based on performance, capital and continuing cost, and schedule. A key factor for this natural system approach was the long-term binding capacity of heavy metals (especially copper, lead, and zinc) in the organic matter and sediments. The design required that the wetland treat the average daily discharge volumemore » and be able to handle 83,280 m{sup 3} of stormwater runoff in a 24 hour period. The design allowed all water flow within the system to be driven entirely by gravity. The CWTS for A-01 outfall is composed of eight one-acre wetland cells connected in pairs and planted with giant bulrush to provide continuous organic matter input to the system. The retention basin was designed to hold stormwater flow and to allow controlled discharge to the wetland. The system became operational in October of 2000 and is the first wetland treatment system permitted by South Carolina DHEC for removal of metals. Because of the exceptional performance of the A-01 CWTS, the same strategy was used to improve water quality of the H-02 outfall that receives discharge and stormwater from the Tritium Area of SRS. The primary contaminants in this outfall were also copper and zinc. The design for this second system required that the wetland treat the average discharge volume of 415 m{sup 3} per day, and be able to handle 9,690 m{sup 3} of stormwater runoff in a 24 hour period. This allowed the building of a system much smaller than the A-01 CWTS. The system became operational in July 2007. Metal removal has been excellent since water flow through the treatment systems began, and performance improved with the maturation of the vegetation during the first season of growth of each system. Sediment samples after the first and third years of operation indicated that copper was being bound in the sediments very rapidly after entering the treatment system. The design of the system encourages low redox and sulfide production in the sediments. The objective is to stabilize metals, including mercury, as sulfide compounds in the sediments. Costs for maintenance and operation of the systems are minimal, consisting primarily of ensuring that the pipes are not clogged and that water is flowing through the system. The treatment cost per thousand gallons is many times less than conventional wastewater treatment facilities. Life expectancy and function of the biological system is based on the life of the engineering aspects and not the wetland ecology.« less

Studies of the synthesis and deposition of Cu3BiS 3 for use in photovoltaic devices

NASA Astrophysics Data System (ADS)

Epstein, Joshua A.

As the world's climate continues to change, alternative energy is being adopted more and more. Solar energy is one extremely promising candidate to supplement our ever increasing energy needs. In order for it to be a viable solution, more efficient and less expensive solar panels must be made. While silicon solar panels are the current market leader their high manufacturing energy input and cost warrant looking into alternatives. Many thin film solar materials are being investigated such as CdTe, CIGS and CZTS, but all come with their own drawbacks. With a near ideal band gap, low toxicity and earth abundant elemental make up copper bismuth sulfide, Cu3BiS3, is a promising candidate for use in future photovoltaic devices. The research presented here details multiple methods to synthesize and deposit this material with an effort to keep the methods low cost, energy efficient and environmentally friendly. Multiple low temperature solvothermal routes to synthesizing copper bismuth sulfide, CBS, have been developed. The resulting powders have been verified as pure Cu3BiS3 via XRD peak matching. The precursor reactants tested for use were copper and bismuth nitrates, acetates, chlorides and hydroxides. L-cystine, L-cysteine, thiourea and CS2 have all been tested for use as sulfur sources. Seven of these combinations produced pure CBS powders. Two custom built benchtop reactors have been designed and fabricated with the aim of studying the possibility of a continuous flow reactor as a way to utilize these precipitation chemistries for making thin films of CBS. Heat and liquid flow simulations were performed in COMSOL multiphysics to assist in the reactor design process. The second reactor was designed to promote uniform liquid flow across the fluorine doped, tin oxide coated, FTO, glass. This reactor was also built with a temperature gradient transverse to the liquid flow so that the optimal temperature for the deposition of CBS could be evaluated. This reactor was also used to evaluate the deposition of CdS, an n-type semiconductor often used in thin film solar panels, onto FTO glass. CBS thin films were also prepared via electrodeposition and thermal treatment. The solution used was a mixture of copper nitrate, sodium sulfite and sodium citrate tribasic dihydrate dissolved in DI H2O and bismuth nitrate dissolved in ethylene glycol. To get the best coating it was found that the electrodeposition should be done at 1.2 V and last 5 minutes. Thermal treatment carried out in a 450°C tube furnace for 90 min in forming gas (95% N2 with 5% H2) along with sulfur vapor was proved best. No further treatment was required to obtain phase pure CBS coatings. This was verified with XRD peak analysis. Optical absorption, microstructural, and photoconductivity data are reported for CBS materials made using the above techniques.

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 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

Fluid inclusion studies in quartz veinlets in the porphyry copper deposit at Sungun, East-Azarbaidjan, Iran

NASA Astrophysics Data System (ADS)

Calagari, Ali Asghar

2004-05-01

The porphyry copper deposit (PCD) at Sungun is located in East Azarbaidjan, in the NW of Iran.The Sungun porphyries occur as stocks and dikes ranging in composition from quartz monzodiorite through quartz monzonite and granodiorite to granite. The stocks are divided into two groups (1) Porphyry Stocks I and (2) Porphyry Stock II. Porphyry Stock II, hosting the copper ore, experienced intense hydro-fracturing leading to the formation of stockwork-type and anastomozing veinlets and micro-veinlets of quartz, sulfides, carbonates, and sulfates. Three distinct types of hydrothermal alteration and sulfide mineralization are recognized at Sungun (1) hypogene, (2) contact metasomatic (skarn), and (3) supergene. Four types of hypogene alteration are developed at Sungun, potassic, propylitic, potassic-phyllic, and phyllic. Four types of inclusion are common at Sungun based upon their phase content (1) mono-phase vapor, (2) vapor-rich 2-phase, (3) liquid-rich 2-phase, and (4) multi-phase solid. Halite is the principal solid phase. The distribution pattern, shape, and phase contents of fluid inclusions in quartz veinlets at Sungun are analogous to those from Bingham and Globe-Miami in western USA. The fluid inclusion data at Sungun showed that the liquid-vapor homogenization temperature [ TH(L-V)] values for liquid-rich 2-phase, vapor-rich 2-phase, and halite-bearing inclusions vary from 160 to 580 °C, from 200 to 600 °C, and from 160 to 580 °C, respectively. The ascending unboiled fluid at the onset of the phyllic alteration episode had temperatures ˜580 °C and was moderately saline (˜15 wt%). With the gradual decrease in temperature, the salinity of this fluid gradually decreased, so that its salinity at temperatures of ˜370 and <270 °C were ˜7 and <2 wt%, respectively. Multiple boiling events occurred in Porphyry Stock II during phyllic alteration. With each boiling event the salinity of the residual fluid increased substantially. The first boiling event occurred at temperatures 540-560 °C, and increased the salinity of the residual fluid up to ˜50 wt%. At temperatures >350 °C the residual fluid remained undersaturated (with respect to NaCl) however, at temperatures <350 °C they became saturated. The minimum internal pressures calculated for the inclusions having Ts(NaCl)≈ TH(L-V) showed that they were developed under the maximum hydrostatic pressure head of ˜1500 m during the boiling events.

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 stoichiometric kesterite CZTS. The ~2 nm nanocrystals synthesized at 150 °C exhibit quantum confinement, with a band gap of 1.67 eV. Larger nanocrystals have the expected bulk CZTS band gap of 1.5 eV. Several micron thick films deposited by drop casting colloidal dispersions of ~40 nm CZTS nanocrystals were crack-free, while those cast using 5 nm nanocrystals had micron-scale cracks. We showed the applicability of these nanocrystal coatings for thin film solar cells by demonstrating a CZTS thin film solar cell using coatings annealed in a sulfur atmosphere. We conducted a systematic study of the factors controlling crystal growth and microstructure development during sulfidation annealing of films cast from colloidal dispersions of CZTS nanocrystals. The film microstructure is controlled by concurrent normal and abnormal grain growth. At 600 °C to 800 °C and low sulfur pressures (50 Torr), abnormal CZTS grains up to 10 microm in size grow on the surface of the CZTS nanocrystal film via transport of material from the nanocrystals to the abnormal grains. Meanwhile, the nanocrystals coarsen, sinter, and undergo normal grain growth. The driving force for abnormal grain growth is the reduction in total energy associated with the high surface area nanocrystals. The eventual coarsening of the CZTS nanocrystals reduces the driving force for abnormal crystal growth. Increasing the sulfur pressure by an order of magnitude to 500 Torr accelerates both normal and abnormal crystal growth though sufficient acceleration of the former eventually reduces the latter by reducing the driving force for abnormal grain growth. For example, at high temperatures (700-800 oC) and sulfur pressures (500 Torr) normal grains quickly grow to ~500 nm which significantly reduces abnormal grain growth. The use of soda lime glass as the substrate, instead of quartz, accelerates normal grain growth. Normal grains grow to ~500 nm at lower temperatures and sulfur pressures (i.e., 600 °C and 50 Torr) than those required to grow the same size grains on quartz (700 °C and 500 Torr). Moreover, carbon is removed by volatilization from films where normal crystal growth is fast. There are significant differences in the chemistry and in the thermodynamics involved during selenization and sulfidation of CZTS colloidal nanocrystal coatings to form CZTSSe or CZTS thin films, respectively. To understand these differences, the roles of vapor pressure, annealing temperature, and heating rate in the formation of different microstructures of CZTSSe films were investigated. Selenization produced a bi-layer microstructure where a large CZTSSe-crystal layer grew on top of a nanocrystalline carbon-rich bottom layer. Differences in the chemistry of carbon and selenium and that of carbon and sulfur account for this segregation of carbon during selenization. For example, CSe 2 and CS2, both volatile species, may form as a result of chalcogen interactions with carbon during annealing. Unlike CS2, however, CSe2 may readily polymerize at room temperature and one atmosphere. Carbon segregation may be occurring only during selenization due to the formation of a Cu-Se polymer [i.e., (CSe 2-x)] within the nanocrystal film. The (CSe2-x) inhibits sintering of nanocrystals in the bottom layer. Additionally, a fast heating rate results in temperature variations that lead to transient condensation of selenium on the film. This is observed only during selenization because the equilibrium vapor pressure of selenium is lower than that of sulfur. The presence of liquid selenium during sintering accelerates coarsening and densification of the normal crystal layer (no abnormal crystal layer) by liquid phase sintering. Carbon segregation does not occur where liquid selenium was present.

Geology and porphyry copper-type alteration-mineralization of igneous rocks at the Christmas Mine, Gila County, Arizona

USGS Publications Warehouse

Koski, Randolph A.

1979-01-01

The Christmas copper deposit, located in southern Gila County, Arizona, is part of the major porphyry copper province of southwestern North America. Although Christmas is known for skarn deposits in Paleozoic carbonate rocks, ore-grade porphyry-type copper mineralization also occurs in a composite granodioritic intrusive complex and adjacent mafic volcanic country rocks. This study considers the nature, distribution, and genesis of alteration-mineralization in the igneous rock environment at Christmas. At the southeast end of the Dripping Spring Mountains, the Pennsylvanian Naco Limestone is unconformably overlain by the Cretaceous Williamson Canyon Volcanics, a westward-thinning sequence of basaltic volcanic breccia and lava flows, and subordinate clastic sedimentary rocks. Paleozoic and Mesozoic strata are intruded by Laramide-age dikes, sills, and small stocks of hornblende andesite porphyry and hornblende rhyodacite porphyry, and the mineralized Christmas intrusive complex. Rocks of the elongate Christmas stock, intruded along an east-northeast-trending fracture zone, are grouped into early, veined quartz diorite (Dark Phase), biotite granodiorite porphyry (Light Phase), and granodiorite; and late, unveined dacite porphyry and granodiorite porphyry. Biotite rhyodacite porphyry dikes extending east and west from the vicinity of the stock are probably coeval with biotite granodiorite porphyry. Accumulated normal displacement of approximately 1 km along the northwest-trending Christmas-Joker fault system has juxtaposed contrasting levels (lower, intrusive-carbonate rock environment and upper, intrusive-volcanic rock environment) within the porphyry copper system. K-Ar age determinations and whole-rock chemical analyses of the major intrusive rock types indicate that Laramide calc-alkaline magmatism and ore deposition at Christmas evolved over an extended period from within the Late Cretaceous (~75-80 m.y. ago) to early Paleocene (~63-61 m.y. ago). The sequence of igneous rocks is progressively more alkaline and silicic from basalt to granodiorite. Early (Stage I) chalcopyrite-bornite (-molybdenite) mineralization and genetically related K-silicate alteration are centered on the Christmas stock. K-silicate alteration is manifested by pervasive hornblende-destructive biotitization in the stock, biotitization of basaltic volcanic wall rocks, and a continuous stockwork of K-feldspar veinlets and quartz-K-feldspar veins in the stock and quartz-sulfide veins in volcanic rocks. Younger (Stage II) pyrite-chalcopyrite mineralization and quartz-sericite-chlorite alteration occur in a zone overlapping with but largely peripheral to the zone of Stage I stockwork veins. Within the Christmas intrusive complex, K-silicate-altered rocks in the central stock are flanked east and west by zones of fracture-controlled quartz-sericite alteration and strong pyritization. In volcanic rocks quartz-chlorite-pyrite-chalcopyrite veins are superimposed on earlier biotitization and crosscut Stage I quartz-sulfide veins. Beyond the zones of quartz-sericite alteration, biotite rhyodacite porphyry dikes contain the propylitic alteration assemblage epidote-chlorite-albite-sphene. Chemical analyses indicate the following changes during pervasive alteration of igneous rocks: (1) addition of Si, K, H, S, and Cu, and loss of Fe 3+ and Ca during intense biotitization of basalt; (2) loss of Na and Ca, increase of Fe3+/Fe2+, and strong H-metasomatism during sericitization of quartz diorite; and (3) increase in Ca, Na, and Fe3+/Fe2+, and loss of K during intense propylitization of biotite rhyodacite porphyry dikes. Thorough biotitization of biotite granodiorite porphyry in the Christmas stock was largely an isochemical process. Fluid-inclusion petrography reveals that Stage I veins are characterized by low to moderate populations of moderate-salinity and gas-rich inclusions, and sparse but ubiquitous halite-bearing inclusions. Moderate-salinity an

Assessing the Influence of Copper-Nickel-Bearing Bedrock on Baseline Water Quality in Filson Creek Watershed, Northeast Minnesota

NASA Astrophysics Data System (ADS)

Runkel, R. L.; Jones, P. M.; Elliott, S. M.; Woodruff, L. G.

2017-12-01

Mining sulfide-bearing copper (Cu), nickel (Ni), and platinum-group-elements (PGE) deposits in the Duluth Complex of northeast Minnesota could have detrimental effects on surrounding water resources and associated ecosystems. A study was conducted to 1) assess copper, nickel, and other metal concentrations in surface water, bedrock, streambed sediments, and soils in watersheds where the basal part of the Duluth Complex is exposed or near the land surface; and 2) determine if these concentrations, and metal-bearing deposits, are currently influencing regional water quality in areas of potential base-metal mining. One of the watersheds that was assessed was the Filson Creek watershed, where shallow Cu-Ni-PGE deposits are present. Field water-quality, streambed sediments, soils, bedrock, and streamflow data set were collected in Filson Creek and it's watershed in 2014 and 2015. Surface-water samples were analyzed for 12 trace metals (dissolved and total concentrations), 14 inorganic constituents (dissolved concentrations), alkalinity, 18 O /16O and 2H/1H isotopes, and total and dissolved organic carbon. Background total Cu and Ni concentrations in the creek in 2014 and 2015 ranged from 1.2 to 10.8 micrograms per liter (µg/L), and 1.7 to 8.4 µg/L, respectively. The concentrations of copper, nickel, and other trace metals in surface waters and streambed sediments reflects the geochemistry of underlying rock types and glacially transported unconsolidated material, establishing baseline conditions prior to any mining. Dissolved and total organic carbon (DOC and TOC) concentrations in surface waters are very high compared to most surface waters in Minnesota, ranging from 21.3 to 43.2 milligrams per liter (mg/L), and 22.4 and 53.5 mg/L. Synoptic water-quality and flow data from a tracer test conducted over a stream segment of Filson Creek above a shallow Cu-Ni-PGE deposit (Spruce Road Deposit) was used with the 2014-15 water-quality and synthetic flow data to calibrate the reactive transport model. Results from transport modeling suggest that the high DOC content exert control on copper and other trace metal transport.

Coarse muscovite veins and alteration deep in the Yerington batholith, Nevada: insights into fluid exsolution in the roots of porphyry copper systems

NASA Astrophysics Data System (ADS)

Runyon, Simone E.; Steele-MacInnis, Matthew; Seedorff, Eric; Lecumberri-Sanchez, Pilar; Mazdab, Frank K.

2017-04-01

Veins and pervasive wall-rock alteration composed of coarse muscovite±quartz±pyrite are documented for the first time in a porphyritic granite at Luhr Hill in the Yerington District, Nevada. Coarse muscovite at Luhr Hill occurs at paleodepths of 6-7 km in the roots of a porphyry copper system and crops out on the scale of tens to hundreds of meters, surrounded by rock that is unaltered or variably altered to sodic-calcic assemblages. Coarse muscovite veins exhibit a consistent orientation, subvertical and N-S striking, which structurally restores to subhorizontal at the time of formation. Along strike, coarse muscovite veins swell from distal, millimeter-thick muscovite-only veinlets to proximal, centimeter-thick quartz-sulfide-bearing muscovite veins. Crosscutting relationships between coarse muscovite veins, pegmatite dikes, and sodic-calcic veins indicate that muscovite veins are late-stage magmatic-hydrothermal features predating final solidification of the Luhr Hill porphyritic granite. Fluid inclusions in the muscovite-quartz veins are high-density aqueous inclusions of 3-9 wt% NaCl eq. and <1 mol% CO2 that homogenize between 150 and 200 °C, similar to fluid inclusions from greisen veins in Sn-W-Mo vein systems. Our results indicate that muscovite-forming fluids at Luhr Hill were mildly acidic, of low to moderate salinity and sulfur content and low CO2 content, and that muscovite in deep veins and alteration differs in texture, composition, and process of formation from sericite at shallower levels of the hydrothermal system. Although the definition of greisen is controversial, we suggest that coarse muscovite alteration is more similar to alteration in greisen-type Sn-W-Mo districts worldwide than to sericitic alteration at higher levels of porphyry copper systems. The fluids that form coarse muscovite veins and alteration in the roots of porphyry copper systems are distinct from fluids that formed copper ore or widespread, shallower, acidic alteration. We propose that this style of veins and alteration at Luhr Hill represents degassing of moderate volumes of overpressured hydrothermal fluid during late crystallization of deep levels of the Yerington batholith.

Understanding Copper Isotope Behavior in the High Temperature Magmatic-Hydrothermal Porphyry Environment

NASA Astrophysics Data System (ADS)

Gregory, Melissa J.; Mathur, Ryan

2017-11-01

Copper stable isotope geochemistry has the potential to constrain aspects of ore deposit formation once variations in the isotopic data can be related to the physiochemical conditions during metal deposition. This study presents Cu isotope ratios for samples from the Pebble porphyry Cu-Au-Mo deposit in Alaska. The δ65Cu values for hypogene copper sulfides range from -2.09‰ to 1.11‰ and show linear correlations with the δ18O isotope ratios calculated for the fluid in equilibrium with the hydrothermal alteration minerals in each sample. Samples with sodic-potassic, potassic, and illite alteration display a negative linear correlation between the Cu and O isotope results. This suggests that fractionation of Cu isotopes between the fluid and precipitating chalcopyrite is positive as the hydrothermal fluid is evolving from magmatic to mixed magmatic-meteoric compositions. Samples with advanced argillic alteration display a weak positive linear correlation between Cu and O isotope results consistent with small negative fluid-chalcopyrite Cu isotope fractionation during fluid evolution. The hydrothermal fluids that formed sodic-potassic, potassic, and illite alteration likely transported Cu as CuHS0. Hydrothermal fluids that resulted in advanced argillic alteration likely transport Cu as CuCl2-. The pH conditions also control Cu isotope fractionation, consistent with previous experimental work. Larger fractionation factors were found between fluids and chalcopyrite precipitating under neutral conditions contrasting with small fractionation factors calculated between fluids and chalcopyrite precipitating under acidic conditions. Therefore, this study proposes that hydrothermal fluid compositions and pH conditions are related to Cu isotope variations in high temperature magmatic-hydrothermal deposits.

The octahaem MccA is a haem c-copper sulfite reductase.

PubMed

Hermann, Bianca; Kern, Melanie; La Pietra, Luigi; Simon, Jörg; Einsle, Oliver

2015-04-30

The six-electron reduction of sulfite to sulfide is the pivot point of the biogeochemical cycle of the element sulfur. The octahaem cytochrome c MccA (also known as SirA) catalyses this reaction for dissimilatory sulfite utilization by various bacteria. It is distinct from known sulfite reductases because it has a substantially higher catalytic activity and a relatively low reactivity towards nitrite. The mechanistic reasons for the increased efficiency of MccA remain to be elucidated. Here we show that anoxically purified MccA exhibited a 2- to 5.5-fold higher specific sulfite reductase activity than the enzyme isolated under oxic conditions. We determined the three-dimensional structure of MccA to 2.2 Å resolution by single-wavelength anomalous dispersion. We find a homotrimer with an unprecedented fold and haem arrangement, as well as a haem bound to a CX15CH motif. The heterobimetallic active-site haem 2 has a Cu(I) ion juxtaposed to a haem c at a Fe-Cu distance of 4.4 Å. While the combination of metals is reminiscent of respiratory haem-copper oxidases, the oxidation-labile Cu(I) centre of MccA did not seem to undergo a redox transition during catalysis. Intact MccA tightly bound SO2 at haem 2, a dehydration product of the substrate sulfite that was partially turned over due to photoreduction by X-ray irradiation, yielding the reaction intermediate SO. Our data show the biometal copper in a new context and function and provide a chemical rationale for the comparatively high catalytic activity of MccA.

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

DOE PAGES

Hassan, Asra; Zhang, Xiaoyi; Liu, Xiaohan; ...

2017-08-28

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopantmore » oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.« less

Deformation, geochemistry, and origin of massive sulfide deposits, Gossan lead district, Virginia.

USGS Publications Warehouse

Gair, J.E.; Slack, J.F.

1984-01-01

Lenses and layers of massive sulphides comprise a discontinuous horizon in the late Proterozoic metasedimentary Ashe formation. The folded and brecciated sulphides include pyrrhotite, minor chalcopyrite, sphalerite and pyrite, and rare arsenopyrite and galena. The deposits were mined for supergene copper, later for gossan iron, and finally for sulphur. The Ashe formation is interpreted to be marine turbidites, and contains lenses of mafic rocks of probable tholeiitic basalt parentage. Mineralogically and chemically distinctive rocks - for the Ashe formation - are interbedded with the sulphides and may represent metamorphosed alteration zones and/or mixed chemical and clastic sediments. The sulphide deposits are interpreted as syngenetic sediments, modified by deformation during metamorphism. Their deposition occurred in a deep, elongate marine basin overlying a crustal rift zone.-G.J.N.

Depositing of CuS nanocrystals upon the graphene scaffold and their photocatalytic activities

NASA Astrophysics Data System (ADS)

Wang, Yongbin; Zhang, Lixin; Jiu, Hongfang; Li, Na; Sun, Yixin

2014-06-01

A series of copper sulfide nanocrystals/graphene nanocomposites (CuS/GR) with different weight ratios of GR were fabricated via a one-step hydrothermal approach by using dimethylsulfoxide (DMSO) as the source of sulfur and solvent. The as-prepared samples were studied by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (DRS), transmission scanning electron microscopy (TEM) and photoluminescence spectra (PL) are employed to determine the properties of the samples. The results show that the CuS nanocrystals with an average size of 16 nm almost overspread on the GR graphene scaffold. The samples exhibit excellent photocatalytic activities in degrading the methylene blue (MB) compared with pure CuS. This work shows that CuS/GR nanocomposites would be promising in dye wastewater treatment as Fenton-like reagents.

Heavy metal mining using microbes.

PubMed

Rawlings, Douglas E

2002-01-01

The use of acidiphilic, chemolithotrophic iron- and sulfur-oxidizing microbes in processes to recover metals from certain types of copper, uranium, and gold-bearing minerals or mineral concentrates is now well established. During these processes insoluble metal sulfides are oxidized to soluble metal sulfates. Mineral decomposition is believed to be mostly due to chemical attack by ferric iron, with the main role of the microorganisms being to reoxidize the resultant ferrous iron back to ferric iron. Currently operating industrial biomining processes have used bacteria that grow optimally from ambient to 50 degrees C, but thermophilic microbes have been isolated that have the potential to enable mineral biooxidation to be carried out at temperatures of 80 degrees C or higher. The development of higher-temperature processes will extend the variety of minerals that can be commercially processed.

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

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

Hassan, Asra; Zhang, Xiaoyi; Liu, Xiaohan

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopantmore » oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.« less

Chemical Bath Deposited Zinc Sulfide Buffer Layers for Copper Indium Gallium Sulfur-selenide Solar Cells and Device Analysis

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

Kundu, Sambhu N.; Olsen, Larry C.

2005-01-03

Cd free CIGSS thin film solar cell structures with a MgF2/TCO/CGD-ZnS/CIGSS/Mo/SLG structure have been fabricated using chemical bath deposited (CBD)-ZnS buffer layers and high quality CIGSS absorber layers supplied from Shell Solar Industries. The use of CBD-ZnS, which is a higher band gap materials than CdS, improved the quantum efficiency of fabricated cells at lower wavelengths, leading to an increase in short circuit current. The best cell to date yielded an active area (0.43 cm2) efficiency of 13.3%. This paper also presents a discussion of the issues relating to the use of the CBD-ZnS buffer materials for improving device performance.

Sediment quality in Burlington Harbor, Lake Champlain, U.S.A.

USGS Publications Warehouse

Lacey, E.M.; King, J.W.; Quinn, J.G.; Mecray, E.L.; Appleby, P.G.; Hunt, A.S.

2001-01-01

Surface samples and cores were collected in 1993 from the Burlington Harbor region of Lake Champlain. Sediment samples were analyzed for trace metals (cadmium, copper, lead, nickel, silver and zinc), simultaneously extracted metal/acid volatile sulfide (SEM-AVS), grain size, nutrients (carbon and nitrogen) and organic contaminants (polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs)). The concentrations of cadmium, copper, silver and zinc from the partial sediment digestion of the surface samples correlated well with each other (r2 > 0.60) indicating that either a common process, or group of processes determined the sediment concentrations of these metals. In an analysis of the spatial distribution of the trace metals and PAHs, high surficial concentrations were present in the southern portion of the Harbor. The trace metal trend was strengthened when the concentrations were normalized by grain size. A sewage treatment plant outfall discharge was present in the southeastern portion of the Harbor at the time of this study and is the major source of trace metal and PAH contamination. Evaluation of sediment cores provides a proxy record of historical trace metal and organic inputs. The peak accumulation rate for copper, cadmium, lead, and zinc was in the late 1960s and the peak silver accumulation rate was later. The greatest accumulation of trace metals occurred in the late 1960s after discharges from the STP began. Subsequent declines in trace metal concentrations may be attributed to increased water and air regulations. The potential toxicity of trace metals and organic contaminants was predicted by comparing contaminant concentrations to benchmark concentrations and potential trace metal bioavailability was predicted with SEM-AVS results. Surface sample results indicate lead, silver, ???PAHs and ???PCBs are potentially toxic and/or bioavailable. These predictions were supported by studies of biota in the Burlington Harbor watershed. There is a clear trend of decreasing PAH and trace metal contaminant concentrations with distance from the STP outfall.Surface samples and cores were collected in 1993 from the Burlington Harbor region of Lake Champlain. Sediment samples were analyzed for trace metals (cadmium, copper, lead, nickel, silver and zinc), simultaneously extracted metal/acid volatile sulfide (SEM-AVS), grain size, nutrients (carbon and nitrogen) and organic contaminants (polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs)). The concentrations of cadmium, copper, silver and zinc from the partial sediment digestion of the surface samples correlated well with each other (r2>0.60) indicating that either a common process, or group of processes determined the sediment concentrations of these metals. In an analysis of the spatial distribution of the trace metals and PAHs, high surficial concentrations were present in the southern portion of the Harbor. The trace metal trend was strengthened when the concentrations were normalized by grain size. A sewage treatment plant outfall discharge was present in the southeastern portion of the Harbor at the time of this study and is the major source of trace metal and PAH contamination. Evaluation of sediment cores provides a proxy record of historical trace metal and organic inputs. The peak accumulation rate for copper, cadmium, lead, and zinc was in the late 1960s and the peak silver accumulation rate was later. The greatest accumulation of trace metals occurred in the late 1960s after discharges from the STP began. Subsequent declines in trace metal concentrations may be attributed to increased water and air regulations. The potential toxicity of trace metals and organic contaminants was predicted by comparing contaminant concentrations to benchmark concentrations and potential trace metal bioavailability was predicted with SEM-AVS results. Surface sample results indicate lead, silver, ??PAHs and ??PCBs are potentially toxic and/or bi

Strata-bound Fe-Co-Cu-Au-Bi-Y-REE deposits of the Idaho Cobalt Belt: Multistage hydrothermal mineralization in a magmatic-related iron oxide copper-gold system

USGS Publications Warehouse

Slack, John F.

2012-01-01

Mineralogical and geochemical studies of strata-bound Fe-Co-Cu-Au-Bi-Y-rare-earth element (REE) deposits of the Idaho cobalt belt in east-central Idaho provide evidence of multistage epigenetic mineralization by magmatic-hydrothermal processes in an iron oxide copper-gold (IOCG) system. Deposits of the Idaho cobalt belt comprise three types: (1) strata-bound sulfide lenses in the Blackbird district, which are cobaltite and, less commonly, chalcopyrite rich with locally abundant gold, native bismuth, bismuthinite, xenotime, allanite, monazite, and the Be-rich silicate gadolinite-(Y), with sparse uraninite, stannite, and Bi tellurides, in a gangue of quartz, chlorite, biotite, muscovite, garnet, tourmaline, chloritoid, and/or siderite, with locally abundant fluorapatite or magnetite; (2) discordant tourmalinized breccias in the Blackbird district that in places have concentrations of cobaltite, chalcopyrite, gold, and xenotime; and (3) strata-bound magnetite-rich lenses in the Iron Creek area, which contain cobaltiferous pyrite and locally sparse chalcopyrite or xenotime. Most sulfide-rich deposits in the Blackbird district are enclosed by strata-bound lenses composed mainly of Cl-rich Fe biotite; some deposits have quartz-rich envelopes.Whole-rock analyses of 48 Co- and/or Cu-rich samples show high concentrations of Au (up to 26.8 ppm), Bi (up to 9.16 wt %), Y (up to 0.83 wt %), ∑REEs (up to 2.56 wt %), Ni (up to 6,780 ppm), and Be (up to 1,180 ppm), with locally elevated U (up to 124 ppm) and Sn (up to 133 ppm); Zn and Pb contents are uniformly low (≤821 and ≤61 ppm, respectively). Varimax factor analysis of bulk compositions of these samples reveals geochemically distinct element groupings that reflect statistical associations of monazite, allanite, and xenotime; biotite and gold; detrital minerals; chalcopyrite and sparse stannite; quartz; and cobaltite with sparse selenides and tellurides. Significantly, Cu is statistically separate from Co and As, consistent with the general lack of abundant chalcopyrite in cobaltite-rich samples.Paragenetic relations determined by scanning electron microscopy indicate that the earliest Y-REE-Be mineralization preceded deposition of Co, Cu, Au, and Bi. Allanite, xenotime, and gadolinite-(Y) commonly occur as intergrowths with and inclusions in cobaltite; the opposite texture is rare. Monazite, in contrast, forms a poikiloblastic matrix to cobaltite and thin rims on allanite and xenotime, reflecting a later metamorphic paragenesis. Allanite and xenotime also show evidence of late dissolution and reprecipitation, forming discordant rims on older anhedral allanite and xenotime and separate euhedral crystals of each mineral. Textural data suggest extensive deformation of the deposits by folding and shearing, and by pervasive recrystallization, all during Cretaceous metamorphism. Sensitive high resolution ion microprobe U-Pb geochronology by Aleinikoff et al. (2012) supports these paragenetic interpretations, documenting contemporaneous Mesoproterozoic growth of early xenotime and crystallization of megacrystic A-type granite on the northern border of the district. These ages are used together with mineralogical and geochemical data from the present study to support an epigenetic, IOCG model for Fe-Co-Cu-Au-Bi-Y-REE deposits of the Idaho cobalt belt. A sulfide facies variant of IOCG deposits is proposed for the Blackbird district, in which reducing hydrothermal conditions favored deposition of sulfide minerals over iron oxides. This new model includes Mesoproterozoic vein mineralization and related Fe-Cl metasomatism that formed the biotite-rich lenses, a predominantly felsic magmatic source for metals in the deposits, given their local abundance of Y, REEs, and Be, and a major sedimentary component in the hydrothermal fluids based on independent sulfur isotope and boron isotope data for sulfides and ore-related tourmaline, respectively.

An Example of Cyprus type Volcanogenic Massive Sulfide Deposit in the Southeast of Turkey

NASA Astrophysics Data System (ADS)

Kang, J.; Lee, I.; Donmez, C.; Yildirim, N.; Chang, S.

2013-12-01

Ortaklar mineral deposit of Gaziantep province in Turkey is located in the Southeast Anatolian orogenic belt which was developed as a result of closure of Neotethyan ocean, between Tauride (at north) and Arabian platform (at south), during upper Cretaceous-Miocene periods. Copper mineralization is in spilitic basalt and pillow lavas of Kocali complex. The complex includes oceanic fragments that represent serpentinite, mafic and ultramafic cumulates, isotropic gabbros, sheeted dyke complexes, spilitic basalt, pillow lavas, and radiolarian chert. The deposit is generally parallel to the thrust lines (E-W/30-60 North). Ore minerals occur in massive form and also as stockwork or disseminated forms at subsurface. Oxidized zone appears about 1 km in width at surface. The orebody is underlain and contacted with radiolarian chert. The samples mainly have been collected from open pit but also include some core samples. The samples were examined with unaided eyes and under microscope. In basalts, clino-pyroxenes subophitically enclose laths of plagioclases. Amygdales are filled with calcite in spilitic basalts and it is heavily chloritized and cut by calcite veins. In some parts of basalt, crystobalite is intergrowth with plagioclas. Globules between laths of plagioclase are also observed due to liquid immiscibility. Cherts have spherical radiolaria skeletons and their long thin spines. A lot of carbonate veinlets are developed as well. Few samples of cherts have radialfibrous quartz, known as chalcedonic quartz. Serpentinites in the study area are divided into two types on the basis of the existence of relics of the original minerals. One has relict crystals of olivine or pyroxene within the network of serpenitine and the other has no mineral remnants. Both types have opaque iron oxides with some brown stains among small blocks by numerous veinlets. Major ore minerals consist of chalcopyrite, pyrite, magnetite, and hematite. Minor ore minerals are composed of bornite, covellite, chalcocite, sphalerite, and Fe-oxide. Pyrite occurs as a typical cube shape or shows cataclastic texture. And intergrowth of chalcopyrite with magnetite and massive chalcopyrite are observed in the samples. Goethite and lepidocrocite occur in needle or lath shape in the samples from the iron cap as the secondary minerals. It is also shown that pyrite and chalcopyrite are replaced by anhedral bornite and chalcocite. Sulfide textures also indicate grain-coarsening and crystallization under hydrothermal conditions. Electron microprobe was used to identify several minerals and to find out the difference of trace elements such as Cr, Ni, Co, As, Zn, and Pb within mineral grains. Ortaklar copper deposit in Gaziantep resembles Cyprus type volcanogenic massive sulfide deposit based on ore mineralogy, mineral assemblages, textures, and host rock relationship. To investigate more detail characteristics of the deposit, trace elements and rare earth elements were analyzed using inductively coupled plasma mass spectrometer.

Chemometric and multivariate statistical analysis of time-of-flight secondary ion mass spectrometry spectra from complex Cu-Fe sulfides.

PubMed

Kalegowda, Yogesh; Harmer, Sarah L

2012-03-20

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra of mineral samples are complex, comprised of large mass ranges and many peaks. Consequently, characterization and classification analysis of these systems is challenging. In this study, different chemometric and statistical data evaluation methods, based on monolayer sensitive TOF-SIMS data, have been tested for the characterization and classification of copper-iron sulfide minerals (chalcopyrite, chalcocite, bornite, and pyrite) at different flotation pulp conditions (feed, conditioned feed, and Eh modified). The complex mass spectral data sets were analyzed using the following chemometric and statistical techniques: principal component analysis (PCA); principal component-discriminant functional analysis (PC-DFA); soft independent modeling of class analogy (SIMCA); and k-Nearest Neighbor (k-NN) classification. PCA was found to be an important first step in multivariate analysis, providing insight into both the relative grouping of samples and the elemental/molecular basis for those groupings. For samples exposed to oxidative conditions (at Eh ~430 mV), each technique (PCA, PC-DFA, SIMCA, and k-NN) was found to produce excellent classification. For samples at reductive conditions (at Eh ~ -200 mV SHE), k-NN and SIMCA produced the most accurate classification. Phase identification of particles that contain the same elements but a different crystal structure in a mixed multimetal mineral system has been achieved.

Interaction of CuS and sulfur in Li-S battery system

DOE PAGES

Sun, Ke; Su, Dong; Zhang, Qing; ...

2015-10-27

Lithium-Sulfur (Li-S) battery has been a subject of intensive research in recent years due to its potential to provide much higher energy density and lower cost than the current state of the art lithiumion battery technology. In this work, we have investigated Cupric Sulfide (CuS) as a capacitycontributing conductive additive to the sulfur electrode in a Li-S battery. Galvanostatic charge/discharge cycling has been used to compare the performance of both sulfur electrodes and S:CuS hybrid electrodes with various ratios. We found that the conductive CuS additive enhanced the utilization of the sulfur cathode under a 1C rate discharge. However, undermore » a C/10 discharge rate, S:CuS hybrid electrodes exhibited lower sulfur utilization in the first discharge and faster capacity decay in later cycles than a pure sulfur electrode due to the dissolution of CuS. The CuS dissolution is found to be the result of strong interaction between the soluble low order polysulfide Li 2S 3 and CuS. As a result, we identified the presence of conductive copper-containing sulfides at the cycled lithium anode surface, which may degrade the effectiveness of the passivation function of the solid-electrolyte-interphase (SEI) layer, accounting for the poor cycling performance of the S:CuS hybrid cells at low rate.« less

Removal of hydrogen sulfide and sulfur dioxide by carbons impregnated with triethylenediamine.

PubMed

Wu, Li-Chun; Chang, Tsu-Hua; Chung, Ying-Chien

2007-12-01

Activated carbon (AC) adsorption has long been considered to be a readily available technology for providing protection against exposure to acutely toxic gases. However, ACs without chemical impregnation have proven to be much less efficient than impregnated ACs in terms of gas removal. The impregnated ACs in current use are usually modified with metalloid impregnation agents (ASC-carbons; copper, chromium, or silver) to simultaneously enhance the chemical and physical properties of the ACs in removing specific poisonous gases. These metalloid agents, however, can cause acute poisoning to both humans and the environment, thereby necessitating the search for organic impregnation agents that present a much lower risk. The aim of the study reported here was to assess AC or ASC-carbon impregnated with triethylenediamine (TEDA) in terms of its adsorption capability for simulated hydrogen sulfide (H2S) and sulfur dioxide (SO2) gases. The investigation was undergone in a properly designed laboratory-scale and industrial fume hood evaluation. Using the system reported here, we obtained a significant adsorption: the removal capability for H2S and SO2 was 375 and 229 mg/g-C, respectively. BET measurements, element analysis, scanning electron microscopy, and energy dispersive spectrometry identified the removal mechanism for TEDA-impregnated AC to be both chemical and physical adsorption. Chemical adsorption and oxidation were the primary means by which TEDA-impregnated ASC-carbons removed the simulated gases.

Analysis study of multispectral data, ERTS-A, from an area in West Pakistan

NASA Technical Reports Server (NTRS)

Schmidt, R. G. (Principal Investigator)

1973-01-01

The author has identified the following significant results. 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 a resistant rim of hornfels and propylitically altered rock. Both 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. The investigation showed that a rim like that at Saindak does not form if regional metamorphism has increased the resistance of the country rock to erosion, as in the Pakistan-Iran border region northwest of Saindak.

Do constructed wetlands remove metals or increase metal bioavailability?

PubMed

Xu, Xiaoyu; Mills, Gary L

2018-07-15

The H-02 wetland was constructed to treat building process water and storm runoff water from the Tritium Processing Facility on the Department of Energy's Savannah River Site (Aiken, SC). Monthly monitoring of copper (Cu) and zinc (Zn) concentrations and water quality parameters in surface waters continued from 2014 to 2016. Metal speciation was modeled at each sampling occasion. Total Cu and Zn concentrations released to the effluent stream were below the NPDES limit, and the average removal efficiency was 65.9% for Cu and 71.1% for Zn. The metal-removal processes were found out to be seasonally regulated by sulfur cycling indicated by laboratory and model results. High temperature, adequate labile organic matter, and anaerobic conditions during the warm months (February to August) favored sulfate reduction that produced sulfide minerals to significantly remove metals. However, the dominant reaction in sulfur cycling shifted to sulfide oxidation during the cool months (September to next March). High concentrations of metal-organic complexes were observed, especially colloidal complexes of metal and fulvic acid (FA), demonstrating adsorption to organic matter became the primary process for metal removal. Meanwhile, the accumulation of metal-FA complexes in the wetland system will cause negative effects to the surrounding environment as they are biologically reactive, highly bioavailable, and can be easily taken up and transferred to ecosystems by trophic exchange. Copyright © 2018 Elsevier Ltd. All rights reserved.

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-diagenetic. Any loss of primitive features and development of incongruency are due to subsequent deformation and metamorphism to which the ores and their hosts were together subjected.

Structural and functional engineering of one-dimensional nanostructures for device applications

NASA Astrophysics Data System (ADS)

Singh, Krishna Veer

Fabrication of 1-D nanostructures has been an area of keen interest due to their application in nanodevices. Carbon nanotubes (CNTs) and semiconducting nanorods are 1-D nanostructures of great importance. There are various challenges related to structural and functional aspects of these materials, which need to be addressed for their adaptation in devices. To this end, two approaches have been developed: (1) structural engineering of the nanorods and (2) functionalization of CNTs for device applications. In first approach, a new technique to produce single crystal semiconducting nanorods was developed. Single crystalline structure of nanorods is essential to obtain reproducible performance. The novel synthesis technique 'template assisted sonoelectrochemical deposition' was utilized to develop 'copper sulfide' and 'copper indium sulfide' nanorods. The use of sonoelectrochemical method resulted in the best deposition rate as compared to stirring-assisted and regular electrochemical deposition, respectively. Observed increase in the bulk electrolyte temperature, high acoustic pressure and shock waves generated from the collapse of bubbles could explain improved mass transport and reaction rate, which results in the formation of single crystal nanorods. Nanorods in the range of 50-200nm in diameter were synthesized and electrically characterized as p-type semiconductors. Excellent structural and repeatable electrical properties of the various nanorods developed by this technique make it suitable for developing nanorods for device applications. In addition, detailed statistical analysis of the polycarbonate templates (50-200 nm nominal pore size) used in electrodeposition provided a better understanding of template's as well as nanorods' structure. In the second approach, we functionally engineered single walled carbon nanotubes (SWNTs) with peptide nucleic acid (PNA) to form functional conjugates for molecular electronics. SWNT-PNA-SWNT conjugates were synthesized using carbodiimide chemistry. Also in this work, the electric transport measurements of SWNT-PNA conjugates are reported for the first time. Corresponding analysis reveals that these conjugates exhibit diodic behaviour and in some devices negative differential resistance (NDR) was also observed. The unique electrical and structural properties of these conjugates make them a potential candidate for application in CNT based nanodevices. Hence, this work demonstrates novel techniques to functionally and structurally engineer 1-D nanomaterials for device applications.

Structural and optical properties of CuS thin films deposited by Thermal co-evaporation

NASA Astrophysics Data System (ADS)

Sahoo, A. K.; Mohanta, P.; Bhattacharyya, A. S.

2015-02-01

Copper sulfide (CuS) thin films with thickness 100, 150 and 200 nm have been deposited on glass substrates by thermal co-evaporation of Copper and Sulphur. The effect of CuS film thickness on the structural and optical properties have investigated and discussed. Structural and optical investigations of the films were carried out by X-ray diffraction, atomic force microscopy, high-resolution transmission electron microscopy and UV spectroscopy. XRD and selected area electron diffraction conforms that polycrystalline in nature with hexagonal crystal structure. AFM studies revealed a smooth surface morphology with root mean-square roughness values increases from 24 nm to 42 nm as the film thickness increase from 100 nm to 200 nm. AFM image showed that grain size increases with thickness of film increases and good agreement with the calculated from full width half maximum of the X-ray diffraction peak using Scherrer's formula and Williamson-Hall plot. The absorbance of the thin films were absorbed decreases with wavelength through UV-visible regions but showed a increasing in the near-infrared regions. The reflectance spectra also showed lower reflectance peak (25% to 32%) in visible region and high reflectance peak (49 % to 54 %) in near-infrared region. These high absorbance films made them for photo-thermal conversion of solar energy.

Thermodynamics for arsenic and antimony in copper matte converting; Computer simulation

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

Chaubal, P.C.; Nagamori, M.

1989-08-01

In this paper thermodynamic data for arsenic and antimony and their sulfide and oxide gases have been critically reviewed and compiled. The entropy values for AsS(g), SbS(g), and BiS(g) have been recalculated based on a statistical thermodynamic method. The standard heat of formation and entropy of As/sub 2/O/sub 3/(g) have been newly assessed. Copper matte converting has been mathematically described using the stepwise equilibrium simulation technique together with quadratic approximations of oxygen and magnetite solubilities in molten mattes. A differential equation for the volatilization of arsenic and antimony has been solved for successive reaction microsteps whereby the volatilization, slagging, andmore » alloying of the minor elements have been examined as functions of reaction time and other process variables. Only the first (slag-making) stage of converting is responsible for the elimination of arsenic and antimony by volatilization. Arsenic volatilizes mainly as AsS(g) and AsO(g), with As/sub 2/(g) also contributing when initial mattes are unusually rich in arsenic (above 0.5 pct arsenic). Antimony volatilizes chiefly as SbS(g), and the contributions of other gases such as SbO(g) and Sb(g) remain negligibly low. The results of the simulation compare favorably with industrial operating data.« less

Escondida Mine, Chile

NASA Technical Reports Server (NTRS)

2002-01-01

Full resolution visible and near-infrared image (1.4 MB) Full resolution shortwave infrared image (1.6 MB) This Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) image covers 30 by 23 km (full images 30 x 37 km) in the Atacama Desert, Chile, and was acquired on April 23, 2000. The Escondida copper, gold, and silver open-pit mine is at an elevation of 3050 m, and began operations in 1990. Current capacity is 127,000 tons/day of ore; in 1999 production totaled 827,000 tons of copper, 150,000 ounces of gold, and 3.53 million ounces of silver. Primary concentrate of the ore is done on-site; the concentrate is then sent to the coast for further processing through a 170 km long, 9-inch pipe. Escondida is related geologically to three porphyry bodies intruded along the Chilean West Fissure Fault System. A high grade supergene cap overlies primary sulfide ore. The top image is a conventional 3-2-1 (near infrared, red, green) RGB composite. The bottom image displays shortwave infrared bands 4-6-8 (1.65um, 2.205um, 2.33um) in RGB, and highlights the different rock types present on the surface, as well as the changes caused by mining. Image courtesy NASA/GSFC/MITI/ERSDAC/JAROS, and U.S./Japan ASTER Science Team

Effects of intrusions on grades and contents of gold and other metals in volcanogenic massive sulfide deposits

USGS Publications Warehouse

Singer, Donald A.; Berger, Vladimir; Mosier, Dan L.

2011-01-01

The reason some VMS deposits contain more gold or other metals than others might be due to the influence of intrusions. A new approach examining this possibility is based on examining the information about many VMS deposits to test statistically if those with associated intrusions have significantly different grades or amounts of metals. A set of 632 VMS deposits with reported grades, tonnages, and information about the observed presence or absence of subvolcanic or plutonic intrusive bodies emplaced at or after VMS mineralization is statistically analyzed.Deposits with syn-mineralization or post-mineralization intrusions nearby have higher tonnages than deposits without reported intrusions, but the differences are not statistically significant. When both kinds of intrusions are reported, VMS deposit sizes are significantly higher than in the deposits without any intrusions. Gold, silver, zinc, lead, and copper average grades are not significantly different in the VMS deposits with nearby intrusions compared to deposits without regardless of relative age of intrusive. Only zinc and copper contents are significantly higher in VMS deposits with both kinds of intrusive reported. These differences in overall metal content are due to significantly larger deposit sizes of VMS deposits where both intrusive kinds are observed and reported, rather than any difference in metal grades.

Interim Report on the Examination of Corrosion Damage in Homes Constructed With Imported Wallboard: Examination of Samples Received September 28, 2009.

PubMed

Pitchure, D J; Ricker, R E; Williams, M E; Claggett, S A

2010-01-01

Since many household systems are fabricated out of metallic materials, changes to the household environment that accelerate corrosion rates will increase the frequency of failures in these systems. Recently, it has been reported that homes constructed with imported wallboard have increased failure rates in appliances, air conditioner heat exchanger coils, and visible corrosion on electrical wiring and other metal components. At the request of the Consumer Product Safety Commission (CPSC), the National Institute of Standards and Technology (NIST) became involved through the Interagency Agreement CPSC-1-09-0023 to perform metallurgical analyses on samples and corrosion products removed from homes constructed using imported wallboard. This document reports on the analysis of the first group of samples received by NIST from CPSC. The samples received by NIST on September 28, 2009 consisted of copper tubing for supplying natural gas and two air conditioner heat exchanger coils. The examinations performed by NIST consisted of photography, metallurgical cross-sectioning, optical microscopy, scanning electron microscopy (SEM), and x-ray diffraction (XRD). Leak tests were also performed on the air conditioner heat exchanger coils. The objective of these examinations was to determine extent and nature of the corrosive attack, the chemical composition of the corrosion product, and the potential chemical reactions or environmental species responsible for accelerated corrosion. A thin black corrosion product was found on samples of the copper tubing. The XRD analysis of this layer indicated that this corrosion product was a copper sulfide phase and the diffraction peaks corresponded with those for the mineral digenite (Cu9S5). Corrosion products were also observed on other types of metals in the air conditioner coils where condensation would frequently wet the metals. The thickness of the corrosion product layer on a copper natural gas supply pipe with a wall thickness of 1.2 mm ± 0.2 mm was between 5 μm and 10 μm. These results indicate that a chemical compound that contains reduced sulfur, such as hydrogen sulfide (H2S), is present in the environment to which these samples were exposed. The literature indicates that these species strongly influence corrosion rates of most metals and alloys even at low concentrations. None of the samples examined were failed components, and no evidence of imminent failure was found on any of the samples examined. All of the corrosion damage observed to date is consistent with a general attack form of corrosion that will progress in a uniform and relatively predictable manner. No evidence of localized attack was found, but these forms of attack typically require an incubation period before they initiate. Therefore, the number of samples examined to date is too small to draw a conclusion on the relative probability of these forms of corrosion being able to cause or not cause failure. Samples from failed systems or from laboratory tests conducted over a wide range of metallurgical and environmental conditions will be required to assess the probability of these other forms of corrosion causing failure.

Interim Report on the Examination of Corrosion Damage in Homes Constructed With Imported Wallboard: Examination of Samples Received September 28, 2009

PubMed Central

Pitchure, D. J.; Ricker, R. E.; Williams, M. E.; Claggett, S. A.

2010-01-01

Since many household systems are fabricated out of metallic materials, changes to the household environment that accelerate corrosion rates will increase the frequency of failures in these systems. Recently, it has been reported that homes constructed with imported wallboard have increased failure rates in appliances, air conditioner heat exchanger coils, and visible corrosion on electrical wiring and other metal components. At the request of the Consumer Product Safety Commission (CPSC), the National Institute of Standards and Technology (NIST) became involved through the Interagency Agreement CPSC-1-09-0023 to perform metallurgical analyses on samples and corrosion products removed from homes constructed using imported wallboard. This document reports on the analysis of the first group of samples received by NIST from CPSC. The samples received by NIST on September 28, 2009 consisted of copper tubing for supplying natural gas and two air conditioner heat exchanger coils. The examinations performed by NIST consisted of photography, metallurgical cross-sectioning, optical microscopy, scanning electron microscopy (SEM), and x-ray diffraction (XRD). Leak tests were also performed on the air conditioner heat exchanger coils. The objective of these examinations was to determine extent and nature of the corrosive attack, the chemical composition of the corrosion product, and the potential chemical reactions or environmental species responsible for accelerated corrosion. A thin black corrosion product was found on samples of the copper tubing. The XRD analysis of this layer indicated that this corrosion product was a copper sulfide phase and the diffraction peaks corresponded with those for the mineral digenite (Cu9S5). Corrosion products were also observed on other types of metals in the air conditioner coils where condensation would frequently wet the metals. The thickness of the corrosion product layer on a copper natural gas supply pipe with a wall thickness of 1.2 mm ± 0.2 mm was between 5 μm and 10 μm. These results indicate that a chemical compound that contains reduced sulfur, such as hydrogen sulfide (H2S), is present in the environment to which these samples were exposed. The literature indicates that these species strongly influence corrosion rates of most metals and alloys even at low concentrations. None of the samples examined were failed components, and no evidence of imminent failure was found on any of the samples examined. All of the corrosion damage observed to date is consistent with a general attack form of corrosion that will progress in a uniform and relatively predictable manner. No evidence of localized attack was found, but these forms of attack typically require an incubation period before they initiate. Therefore, the number of samples examined to date is too small to draw a conclusion on the relative probability of these forms of corrosion being able to cause or not cause failure. Samples from failed systems or from laboratory tests conducted over a wide range of metallurgical and environmental conditions will be required to assess the probability of these other forms of corrosion causing failure. PMID:27134786

Radio-photothermal therapy mediated by a single compartment nanoplatform depletes tumor initiating cells and reduces lung metastasis in the orthotopic 4T1 breast tumor model

NASA Astrophysics Data System (ADS)

Zhou, Min; Zhao, Jun; Tian, Mei; Song, Shaoli; Zhang, Rui; Gupta, Sanjay; Tan, Dongfeng; Shen, Haifa; Ferrari, Mauro; Li, Chun

2015-11-01

Tumor Initiating Cells (TICs) are resistant to radiotherapy and chemotherapy, and are believed to be responsible for tumor recurrence and metastasis. Combination therapies can overcome the limitation of conventional cancer treatments, and have demonstrated promising application in the clinic. Here, we show that dual modality radiotherapy (RT) and photothermal therapy (PTT) mediated by a single compartment nanosystem copper-64-labeled copper sulfide nanoparticles ([64Cu]CuS NPs) could suppress breast tumor metastasis through eradication of TICs. Positron electron tomography (PET) imaging and biodistribution studies showed that more than 90% of [64Cu]CuS NPs was retained in subcutaneously grown BT474 breast tumor 24 h after intratumoral (i.t.) injection, indicating the NPs are suitable for the combination therapy. Combined RT/PTT therapy resulted in significant tumor growth delay in the subcutaneous BT474 breast cancer model. Moreover, RT/PTT treatment significantly prolonged the survival of mice bearing orthotopic 4T1 breast tumors compared to no treatment, RT alone, or PTT alone. The RT/PTT combination therapy significantly reduced the number of tumor nodules in the lung and the formation of tumor mammospheres from treated 4T1 tumors. No obvious side effects of the CuS NPs were noted in the treated mice in a pilot toxicity study. Taken together, our data support the feasibility of a therapeutic approach for the suppression of tumor metastasis through localized RT/PTT therapy.Tumor Initiating Cells (TICs) are resistant to radiotherapy and chemotherapy, and are believed to be responsible for tumor recurrence and metastasis. Combination therapies can overcome the limitation of conventional cancer treatments, and have demonstrated promising application in the clinic. Here, we show that dual modality radiotherapy (RT) and photothermal therapy (PTT) mediated by a single compartment nanosystem copper-64-labeled copper sulfide nanoparticles ([64Cu]CuS NPs) could suppress breast tumor metastasis through eradication of TICs. Positron electron tomography (PET) imaging and biodistribution studies showed that more than 90% of [64Cu]CuS NPs was retained in subcutaneously grown BT474 breast tumor 24 h after intratumoral (i.t.) injection, indicating the NPs are suitable for the combination therapy. Combined RT/PTT therapy resulted in significant tumor growth delay in the subcutaneous BT474 breast cancer model. Moreover, RT/PTT treatment significantly prolonged the survival of mice bearing orthotopic 4T1 breast tumors compared to no treatment, RT alone, or PTT alone. The RT/PTT combination therapy significantly reduced the number of tumor nodules in the lung and the formation of tumor mammospheres from treated 4T1 tumors. No obvious side effects of the CuS NPs were noted in the treated mice in a pilot toxicity study. Taken together, our data support the feasibility of a therapeutic approach for the suppression of tumor metastasis through localized RT/PTT therapy. Electronic supplementary information (ESI) available: Details of methods used for radiolabeling efficiency and stability of 64Cu-labeled CuS NPs. See DOI: 10.1039/c5nr04587h

Evolution of ore deposits on terrestrial planets

NASA Astrophysics Data System (ADS)

Burns, R. G.

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Evolution of ore deposits on terrestrial planets

NASA Technical Reports Server (NTRS)

Burns, R. G.

1991-01-01

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Geologic map of the Strawberry Butte 7.5’ quadrangle, Meagher County, Montana

USGS Publications Warehouse

Reynolds, Mitchell W.; Brandt, Theodore R.

2017-06-19

The 7.5′ Strawberry Butte quadrangle in Meagher County, Montana near the southwest margin of the Little Belt Mountains, encompasses two sharply different geologic terranes.  The northern three-quarters of the quadrangle are underlain mainly by Paleoproterozoic granite gneiss, across which Middle Cambrian sedimentary rocks rest unconformably.  An ancestral valley of probable late Eocene age, eroded northwest across the granite gneiss terrane, is filled with Oligocene basalt and overlying Miocene and Oligocene sandstone, siltstone, tuffaceous siltstone, and conglomerate.  The southern quarter of the quadrangle is underlain principally by deformed Mesoproterozoic sedimentary rocks of the Newland Formation, which are intruded by Eocene biotite hornblende dacite dikes.  In this southern terrane, Tertiary strata are exposed only in a limited area near the southeast margin of the quadrangle.  The distinct terranes are juxtaposed along the Volcano Valley fault zone—a zone of recurrent crustal movement beginning possibly in Mesoproterozoic time and certainly established from Neoproterozoic–Early Cambrian to late Tertiary time.  Movement along the fault zone has included normal faulting, the southern terrane faulted down relative to the northern terrane, some reverse faulting as the southern terrane later moved up against the northern terrane, and lateral movement during which the southern terrane likely moved west relative to the northern terrane.  Near the eastern margin of the quadrangle, the Newland Formation is locally the host of stratabound sulfide mineralization adjacent to the fault zone; west along the fault zone across the remainder of the quadrangle are significant areas and bands of hematite and iron-silicate mineral concentrations related to apparent alteration of iron sulfides.  The map defines the distribution of a variety of surficial deposits, including the distribution of hematite-rich colluvium and iron-silicate boulders.  The southeast corner of the quadrangle is the site of active exploration and potential development for copper from the sulfide-bearing strata of the Newland Formation.

The coupled geochemistry of Au and As in pyrite from hydrothermal ore deposits

NASA Astrophysics Data System (ADS)

Deditius, Artur P.; Reich, Martin; Kesler, Stephen E.; Utsunomiya, Satoshi; Chryssoulis, Stephen L.; Walshe, John; Ewing, Rodney C.

2014-09-01

The ubiquity of Au-bearing arsenian pyrite in hydrothermal ore deposits suggests that the coupled geochemical behaviour of Au and As in this sulfide occurs under a wide range of physico-chemical conditions. Despite significant advances in the last 20 years, fundamental factors controlling Au and As ratios in pyrite from ore deposits remain poorly known. Here we explore these constraints using new and previously published EMPA, LA-ICP-MS, SIMS, and μ-PIXE analyses of As and Au in pyrite from Carlin-type Au, epithermal Au, porphyry Cu, Cu-Au, and orogenic Au deposits, volcanogenic massive sulfide (VHMS), Witwatersrand Au, iron oxide copper gold (IOCG), and coal deposits. Pyrite included in the data compilation formed under temperatures from ∼30 to ∼600 °C and in a wide variety of geological environments. The pyrite Au-As data form a wedge-shaped zone in compositional space, and the fact that most data points plot below the solid solubility limit defined by Reich et al. (2005) indicate that Au1+ is the dominant form of Au in arsenian pyrite and that Au-bearing ore fluids that deposit this sulfide are mostly undersaturated with respect to native Au. The analytical data also show that the solid solubility limit of Au in arsenian pyrite defined by an Au/As ratio of 0.02 is independent of the geochemical environment of pyrite formation and rather depends on the crystal-chemical properties of pyrite and post-depositional alteration. Compilation of Au-As concentrations and formation temperatures for pyrite indicates that Au and As solubility in pyrite is retrograde; Au and As contents decrease as a function of increasing temperature from ∼200 to ∼500 °C. Based on these results, two major Au-As trends for Au-bearing arsenian pyrite from ore deposits are defined. One trend is formed by pyrites from Carlin-type and orogenic Au deposits where compositions are largely controlled by fluid-rock interactions and/or can be highly perturbed by changes in temperature and alteration by hydrothermal fluids. The second trend consists of pyrites from porphyry Cu and epithermal Au deposits, which are characterised by compositions that preserve the Au/As signature of mineralizing magmatic-hydrothermal fluids, confirming the role of this sulfide in controlling metal ratios in ore systems.

In Vivo Tumor Vasculature Targeting of CuS@MSN Based Theranostic Nanomedicine.

PubMed

Chen, Feng; Hong, Hao; Goel, Shreya; Graves, Stephen A; Orbay, Hakan; Ehlerding, Emily B; Shi, Sixiang; Theuer, Charles P; Nickles, Robert J; Cai, Weibo

2015-01-01

Actively targeted theranostic nanomedicine may be the key for future personalized cancer management. Although numerous types of theranostic nanoparticles have been developed in the past decade for cancer treatment, challenges still exist in the engineering of biocompatible theranostic nanoparticles with highly specific in vivo tumor targeting capabilities. Here, we report the design, synthesis, surface engineering, and in vivo active vasculature targeting of a new category of theranostic nanoparticle for future cancer management. Water-soluble photothermally sensitive copper sulfide nanoparticles were encapsulated in biocompatible mesoporous silica shells, followed by multistep surface engineering to form the final theranostic nanoparticles. Systematic in vitro targeting, an in vivo long-term toxicity study, photothermal ablation evaluation, in vivo vasculature targeted imaging, biodistribution and histology studies were performed to fully explore the potential of as-developed new theranostic nanoparticles.

GRANITE FIORDS WILDERNESS STUDY AREA, ALASKA.

USGS Publications Warehouse

Berg, Henry C.; Pittman, Tom L.

1984-01-01

Mineral surveys of the Granite Fiords Wilderness study area revealed areas with probable and substantiated mineral-resource potential. In the northeastern sector, areas of probable and substantiated resource potential for gold, sivler, and base metals in small, locally high grade vein and disseminated deposits occur in recrystallized Mesozoic volcanic, sedimentary, and intrusive rocks. In the central part, areas of probable resource potential for gold, silver, copper, and zinc in disseminated and locally massive sulfide deposits occur in undated pelitic paragneiss roof pendants. A molybdenite-bearing quartz vein has been prospected in western Granite Fiords, and molybdenum also occurs along with other metals in veins in the northeastern sector and in geochemical samples collected from areas where there is probable resource potential for low-grade porphyry molybdenum deposits in several Cenozoic plutons. No energy resource potential was identified in the course of this study.

Mineral potential for nickel, copper, platinum group elements(PGE), and chromium deposits hosted in ultramafic rocks in the Islamic Republic of Mauritania (phase V, deliverable 67): Chapter G in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Taylor, Cliff D.; Marsh, Erin; Anderson, Eric D.

2015-01-01

PRISM-I summary documents mention the presence of mafic-ultramafic igneous intrusive rocks in several areas of Mauritania and a number of chromium (Cr) and copper-nickel (Cu-Ni (±Co, Au)) occurrences associated with them. Permissive geologic settings generally include greenstone belts of any age, layered mafic-ultramafic and unlayered gabbro-anorthosite intrusive complexes in cratonic settings, ophiolite complexes, flood basalt provinces, and fluid-rich shear zones cutting accumulations of mafic-ultramafic rocks. Regions of Mauritania having these characteristics that are discussed in PRISM-I texts include the Mesoarchean greenstone belts of the TasiastTijirit terrane in the southwestern Rgueïbat Shield, two separate layered ultramafic complexes in the Amsaga Complex west of Atar, serpentinized metadunites in Mesoarchean rocks of the Rgueïbat Shield in the Zednes map sheet, several lateritized annular mafic-ultramafic complexes in the Paleoproterozoic northwestern portion of the Rgueïbat Shield, and the serpentinized ophiolitic segments of the Gorgol Noir Complex in the axial portion of the southern Mauritanides. Bureau de Recherches Géologiques et Minières (BRGM) work in the “Extreme Sud” zone also suggests that small copper occurrences associated with the extensive Jurassic microgabbroic intrusive rocks in the Taoudeni Basin of southeastern Mauritania could have potential for magmatic Cu-Ni (PGE, Co, Au) sulfide mineralization. Similarly, Jurassic mafic intrusive rocks in the northeastern Taoudeni Basin may be permissive. Known magmatic Cu-Ni deposits of these types in Mauritania are few in number and some uncertainty exists as to the nature of several of the more important ones.

Permissive tracts for iron oxide copper-gold deposits in Mauritania (phase V, deliverable 78 ): Chapter M1 in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Fernette, Gregory; Horton, John D.

2012-01-01

This report contains the USGS results of the PRISM-II Mauritania Minerals Project and is presented in cooperation with the Ministry of Petroleum, Energy, and Mines of the Islamic Republic of Mauritania. The Report is composed of separate chapters consisting of multidisciplinary interpretive reports with accompanying plates on the geology, structure, geochronology, geophysics, hydrogeology, geochemistry, remote sensing (Landsat TM and ASTER), and SRTM and ASTER digital elevation models of Mauritania. The syntheses of these multidisciplinary data formed the basis for additional chapters containing interpretive reports on 12 different commodities and deposit types known to occur in Mauritania, accompanied by countrywide mineral resource potential maps of each commodity/deposit type. The commodities and deposit types represented include: (1) Ni, Cu, PGE, and Cr deposits hosted in ultramafic rocks; (2) orogenic, Carlin-like, and epithermal gold deposits; (3) polymetallic Pb-Zn-Cu vein deposits; (4) sediment-hosted Pb-Zn-Ag deposits of the SEDEX and Mississippi Valley-type; (5) sediment-hosted copper deposits; ( 6) volcanogenic massive sulfide deposits; (7) iron oxide copper-gold deposits; (8) uranium deposits; (9) Algoma-, Superior-, and oolitic-type iron deposits; (10) shoreline Ti-Zr placer deposits; (11) incompatible element deposits hosted in pegmatites, alkaline rocks, and carbonatites, and; (12) industrial mineral deposits. Additional chapters include the Mauritanian National Mineral Deposits Database are accompanied by an explanatory text and the Mauritania Minerals Project GIS that contains all of the interpretive layers created by USGS scientists. Raw data not in the public domain may be obtained from the Ministry of Petroleum, Energy, and Mines in Nouakchott, Mauritania.

Permissive tracts for nickel, copper, platinum group elements (PGE), and chromium deposits of Mauritania (phase V, deliverable 66): Chapter G1 in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Taylor, Cliff D.; Horton, John D.

2012-01-01

This report contains the USGS results of the PRISM-II Mauritania Minerals Project and is presented in cooperation with the Ministry of Petroleum, Energy, and Mines of the Islamic Republic of Mauritania. The Report is composed of separate chapters consisting of multidisciplinary interpretive reports with accompanying plates on the geology, structure, geochronology, geophysics, hydrogeology, geochemistry, remote sensing (Landsat TM and ASTER), and SRTM and ASTER digital elevation models of Mauritania. The syntheses of these multidisciplinary data formed the basis for additional chapters containing interpretive reports on 12 different commodities and deposit types known to occur in Mauritania, accompanied by countrywide mineral resource potential maps of each commodity/deposit type. The commodities and deposit types represented include: (1) Ni, Cu, PGE, and Cr deposits hosted in ultramafic rocks; (2) orogenic, Carlin-like, and epithermal gold deposits; (3) polymetallic Pb-Zn-Cu vein deposits; (4) sediment-hosted Pb-Zn-Ag deposits of the SEDEX and Mississippi Valley-type; (5) sediment-hosted copper deposits; ( 6) volcanogenic massive sulfide deposits; (7) iron oxide copper-gold deposits; (8) uranium deposits; (9) Algoma-, Superior-, and oolitic-type iron deposits; (10) shoreline Ti-Zr placer deposits; (11) incompatible element deposits hosted in pegmatites, alkaline rocks, and carbonatites, and; (12) industrial mineral deposits. Additional chapters include the Mauritanian National Mineral Deposits Database are accompanied by an explanatory text and the Mauritania Minerals Project GIS that contains all of the interpretive layers created by USGS scientists. Raw data not in the public domain may be obtained from the Ministry of Petroleum, Energy, and Mines in Nouakchott, Mauritania.

Modeling pore corrosion in normally open gold- plated copper connectors.

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

Battaile, Corbett Chandler; Moffat, Harry K.; Sun, Amy Cha-Tien

2008-09-01

The goal of this study is to model the electrical response of gold plated copper electrical contacts exposed to a mixed flowing gas stream consisting of air containing 10 ppb H{sub 2}S at 30 C and a relative humidity of 70%. This environment accelerates the attack normally observed in a light industrial environment (essentially a simplified version of the Battelle Class 2 environment). Corrosion rates were quantified by measuring the corrosion site density, size distribution, and the macroscopic electrical resistance of the aged surface as a function of exposure time. A pore corrosion numerical model was used to predict bothmore » the growth of copper sulfide corrosion product which blooms through defects in the gold layer and the resulting electrical contact resistance of the aged surface. Assumptions about the distribution of defects in the noble metal plating and the mechanism for how corrosion blooms affect electrical contact resistance were needed to complete the numerical model. Comparisons are made to the experimentally observed number density of corrosion sites, the size distribution of corrosion product blooms, and the cumulative probability distribution of the electrical contact resistance. Experimentally, the bloom site density increases as a function of time, whereas the bloom size distribution remains relatively independent of time. These two effects are included in the numerical model by adding a corrosion initiation probability proportional to the surface area along with a probability for bloom-growth extinction proportional to the corrosion product bloom volume. The cumulative probability distribution of electrical resistance becomes skewed as exposure time increases. While the electrical contact resistance increases as a function of time for a fraction of the bloom population, the median value remains relatively unchanged. In order to model this behavior, the resistance calculated for large blooms has been weighted more heavily.« less

Mining legacy across a wetland landscape: high mercury in Upper Peninsula (Michigan) rivers, lakes, and fish.

PubMed

Kerfoot, W Charles; Urban, Noel R; McDonald, Cory P; Zhang, Huanxin; Rossmann, Ronald; Perlinger, Judith A; Khan, Tanvir; Hendricks, Ashley; Priyadarshini, Mugdha; Bolstad, Morgan

2018-04-25

A geographic enigma is that present-day atmospheric deposition of mercury in the Upper Peninsula of Michigan is low (48%) and that regional industrial emissions have declined substantially (ca. 81% reduction) relative to downstate. Mercury levels should be declining. However, state (MDEQ) surveys of rivers and lakes revealed elevated total mercury (THg) in Upper Peninsula waters and sediment relative to downstate. Moreover, Western Upper Peninsula (WUP) fish possess higher methyl mercury (MeHg) levels than Northern Lower Peninsula (NLP) fish. A contributing explanation for elevated THg loading is that a century ago the Upper Peninsula was a major industrial region, centered on mining. Many regional ores (silver, copper, zinc, massive sulfides) contain mercury in part per million concentrations. Copper smelters and iron furnace-taconite operations broadcast mercury almost continuously for 140 years, whereas mills discharged tailings and old mine shafts leaked contaminated water. We show that mercury emissions from copper and iron operations were substantial (60-650 kg per year) and dispersed over relatively large areas. Moreover, lake sediments in the vicinity of mining operations have higher THg concentrations. Sediment profiles from the Keweenaw Waterway show that THg accumulation increased 50- to 400-fold above modern-day atmospheric deposition levels during active mining and smelting operations, with lingering MeHg effects. High MeHg concentrations are geographically correlated with low pH and dissolved organic carbon (DOC), a consequence of biogeochemical cycling in wetlands, characteristic of the Upper Peninsula. DOC can mobilize metals and elevate MeHg concentrations. We argue that mercury loading from mining is historically superimposed upon strong regional wetland effects, producing a combined elevation of both THg and MeHg in the Western Upper Peninsula.

Monzonitoid magmatism of the copper-porphyritic Lazurnoe deposit (South Primor'e): U-Pb and K-Ar geochronology and peculiarities of ore-bearing magma genesis by the data of isotopic-geochemical studies

NASA Astrophysics Data System (ADS)

Sakhno, V. G.; Kovalenko, S. V.; Alenicheva, A. A.

2011-05-01

Magmatic rocks from the copper-porphyritic Lazurnoe deposit (Central Primor'e) have been studied. It has been found that rocks from the Lazurnyi massif are referred to gabbro-monzodiorites, monzodiorites, and monzo-granodiorites formed during two magmatic phases of different ages. The earlier phase is represented by gabbro-monzodiorites and diorites of the North Stock, and the later one, by gabbro-monzodiorites and monzo-grano-diorites of the South Stock. On the basis of isotopic dating by the U-Pb (SHRIMP) method for zircon and by the K-Ar method for hornblendes and biotites, the age of magmatic rocks is determined at 110 ± 4 for the earlier phase and at 103.5 ± 1.5 for the later one. Examination of the isotopic composition for Nd, Sr, Pb, Hf, δ18O, and REE spectra has shown that melts of the first phase are contaminated with crustal rocks and they are typical for a high degree of secondary alterations. Potassiumfeldspar, biotite, propylitic alterations, and sulfidization are manifested in these rocks. The rocks of the later stage of magmatism are characteristic for a primitive composition of isotopes and the absence of secondary alterations. They carry the features of adakite specifics that allows us to consider them derivatives of mantle generation under high fluid pressure. The intrusion of fluid-saturated melts of the second phase into the magmatic source of the first phase caused both an alteration pattern of rocks and copper-porphyritic mineralization. Isotopes of sulfur and oxygen allow us to consider the ore component to be of magmatic origin.

Copper Nanowires: A Substitute for Noble Metals to Enhance Photocatalytic H2 Generation.

PubMed

Xiao, Shuning; Liu, Peijue; Zhu, Wei; Li, Guisheng; Zhang, Dieqing; Li, Hexing

2015-08-12

Microwave-assisted hydrothermal approach was developed as a general strategy to decorate copper nanowires (CuNWs) with nanorods (NRs) or nanoparticles (NPs) of metal oxides, metal sulfides, and metal organic frameworks (MOFs). The microwave irradiation induced local "super hot" dots generated on the CuNWs surface, which initiated the adsorption and chemical reactions of the metal ions, accompanied by the growth and assembly of NPs building blocks along the metal nanowires' surfaces. This solution-processed approach enables the NRs (NPs) @CuNWs hybrid structure to exhibit three unique characteristics: (1) high coverage density of NRs (NPs) per NWs with the morphology of NRs (NPs) directly growing from the CuNWs core, (2) intimate contact between CuNWs and NRs (NPs), and (3) flexible choices of material composition. Such hybrid structures also increased light absorption by light scattering. In general, the TiO2/CuNWs showed excellent photocatalytic activity for H2 generation. The corresponding hydrogen production rate is 5104 μmol h(-1) g(-1) with an apparent quantum yield (AQY) of 17.2%, a remarkably high AQY among the noble-metal free TiO2 photocatalysts. Such performance may be associated with the favorable geometry of the hybrid system, which is characterized by a large contact area between the photoactive materials (TiO2) and the H2 evolution cocatalyst (Cu), the fast and short diffusion paths of photogenerated electrons transferring from the TiO2 to the CuNWs. This study not only shows a possibility for the utilization of low cost copper nanowires as a substitute for noble metals in enhanced solar photocatalytic H2 generation but also exhibits a general strategy for fabricating other highly active H2 production photocatalysts by a facile microwave-assisted solution approach.

Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

USGS Publications Warehouse

Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

2016-01-01

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition of copper or was cotransported with copper, and (2) sulfur isotope analysis may be useful in evaluating southeast Missouri iron deposits for copper and possibly for gold.

One-pot synthesis of silica-hybridized Ag{sub 2}S–CuS nanocomposites with tunable nonlinear optical properties

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

Ann Mary, K.A.; Unnikrishnan, N.V., E-mail: nvu100@yahoo.com; Philip, Reji

2015-10-15

Highlights: • Silica modified QDs of CuS and Ag{sub 2}S is developed at room temperature. • Formation of Ag{sub 2}S/CuS nanocomposites is confirmed from XRD and FFT of HRTEM images. • The concentration dependent growth of silica modified QDs is discussed. • Nonlinear absorption observed in ns excitations is dominated by SA and ESA. • Tuning of optical limiting efficiency is achieved with relative Ag{sub 2}S content. - Abstract: In the present work we report a simple, facile route developed for preparing silica hybridized copper sulfide and silver sulfide quantum dots at room temperature. By adjusting the concentration of themore » precursors, Ag{sub 2}S can form Ag{sub 2}S–CuS nanocomposites which are self regulated in one pot. Their crystalline, structural and optical properties have been investigated in detail, and the optical limiting nature is studied from fluence-dependent transmittance measurements employing short (5 ns) laser pulses at 532 nm. Ag{sub 2}S nanoparticles are found to have large third order nonlinear optical coefficients with a relatively lower optical limiting threshold of 1.7 J cm{sup −2}, while the nonlinearity of the nanocomposites is found to lie in between that of Ag{sub 2}S and CuS nanoparticles. These results suggest pathways for designing good quality optical limiters with tunable optical limiting efficiencies by varying the constituent nanocrystal compositions.« less

Metallogeny of precious and base metal mineralization in the Murchison Greenstone Belt, South Africa: indications from U-Pb and Pb-Pb geochronology

NASA Astrophysics Data System (ADS)

Jaguin, J.; Poujol, M.; Boulvais, P.; Robb, L. J.; Paquette, J. L.

2012-10-01

The 3.09 to 2.97 Ga Murchison Greenstone Belt is an important metallotect in the northern Kaapvaal Craton (South Africa), hosting several precious and base metal deposits. Central to the metallotect is the Antimony Line, striking ENE for over 35 km, which hosts a series of structurally controlled Sb-Au deposits. To the north of the Antimony Line, hosted within felsic volcanic rocks, is the Copper-Zinc Line where a series of small, ca. 2.97 Ga Cu-Zn volcanogenic massive sulfide (VMS)-type deposits occur. New data are provided for the Malati Pump gold mine, located at the eastern end of the Antimony Line. Crystallizations of a granodiorite in the Malati Pump Mine and of the Baderoukwe granodiorite are dated at 2,964 ± 7 and 2,970 ± 7 Ma, respectively (zircon U-Pb), while pyrite associated with gold mineralization yielded a Pb-Pb age of 2,967 ± 48 Ma. Therefore, granodiorite emplacement, sulfide mineral deposition and gold mineralization all happened at ca. 2.97 Ga. It is, thus, suggested that the major styles of orogenic Au-Sb and the Cu-Zn VMS mineralization in the Murchison Greenstone Belt are contemporaneous and that the formation of meso- to epithermal Au-Sb mineralization at fairly shallow levels was accompanied by submarine extrusion of felsic volcanic rocks to form associated Cu-Zn VMS mineralization.

Undocumented water column sink for cadmium in open ocean oxygen-deficient zones

PubMed Central

Janssen, David J.; Conway, Tim M.; John, Seth G.; Christian, James R.; Kramer, Dennis I.; Pedersen, Tom F.; Cullen, Jay T.

2014-01-01

Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals. PMID:24778239

Undocumented water column sink for cadmium in open ocean oxygen-deficient zones.

PubMed

Janssen, David J; Conway, Tim M; John, Seth G; Christian, James R; Kramer, Dennis I; Pedersen, Tom F; Cullen, Jay T

2014-05-13

Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals.

Effects of spatial and temporal variation of acid-volatile sulfide on the bioavailability of copper and zinc in freshwater sediments

USGS Publications Warehouse

Besser, John M.; Ingersoll, Christopher G.; Giesty, John P.

1996-01-01

Variation in concentrations of acid-volatile sulfide (AVS) in sediments from the upper Clark Fork River of Montana, USA, was associated with differences in bioaccumulation of Cu and Zn and growth of larvae of the midge, Chironomus tentans. Growth of midge larvae was significantly greater and bioaccumulation of Cu was significantly less in surface sections (0–3 cm depth) of sediment cores, which had greater concentrations of AVS and lesser ratios of simultaneously extracted metals to AVS (SEM:AVS ratios) than in subsurface sediments (6–9 cm). Concentrations of AVS were significantly less in sediments incubated with oxic overlying water for 9 weeks than in the same sediments incubated under anoxic conditions. Bioaccumulation of Cu differed significantly between incubation treatments, corresponding to differences in concentrations of AVS and SEM:AVS ratios, although midge growth did not. Bioaccumulation of Zn did not differ significantly between depth strata of sediment cores or between incubation treatments. When results from the two sets of bioassays were combined, bioaccumulation of Cu and Zn, but not growth, was significantly correlated with SEM:AVS ratios and other estimates of bioavailable metal fractions in sediments. Growth of midge larvae was significantly correlated with bioaccumulation of Zn, but not Cu, suggesting that Zn was the greater contributor to the toxicity of these sediments. Assessments of the toxicity of metal-contaminated freshwater sediments should consider the effects of spatial and temporal variation in AVS concentrations on metal bioavailability.

Functionalization of cotton fiber by partial etherification and self-assembly of polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework.

PubMed

Lange, Laura E; Obendorf, S Kay

2015-02-25

A combination of a Keggin-type polyoxometalate (POM), [CuPW11O39](5-), with a Cu3(BTC)2 metal-organic framework (MOF-199/HKUST-1; where BTC is benzene-1,3,5-tricarboxylate), was successfully self-assembled on a cellulose substrate (cotton) with a room-temperature process. Cotton fibers were functionalized by partial etherification. Cu3(BTC)2 metal-organic framework and polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework were self-assembled on the carboxymethylate ion sites initiated with copper nitrate using ethanol and water as solvents. Octahedral crystals were observed on both MOF-cotton and POM-MOF-cotton; both contained copper while the POM-MOF-cotton also contained tungsten. Occupancy of POM in MOF cages was calculated to be about 13%. Moisture content remained at 3 to 4 wt % similar to that of untreated cotton. Reactivity to both hydrogen sulfide and methyl parathion was higher for POM-MOF-cotton due to the Keggin polyoxometalate and the extra-framework cations Cu(2+) ions compensating the charges of the encapsulated Keggins. The POM-MOF material was found to effectively remove 0.089 mg of methyl parathion per mg of MOF from a hexane solution while MOF-cotton removed only 0.054 mg of methyl parathion per mg of MOF.

A theoretical study on the geometry and spectroscopic properties of ground-state and local minima isomers of (CuS)n=2-6 clusters

NASA Astrophysics Data System (ADS)

Luque-Ceballos, Jonathan C.; Posada-Borbón, Alvaro; Herrera-Urbina, Ronaldo; Aceves, R.; Juárez-Sánchez, J. Octavio; Posada-Amarillas, Alvaro

2018-03-01

Spectroscopic properties of gas-phase copper sulfide clusters (CuS)n (n = 2-6) are calculated using Density Functional Theory (DFT) and time-dependent (TD) DFT approaches. The energy landscape of the potential energy surface is explored through a basin-hopping DFT methodology. Ground-state and low-lying isomer structures are obtained. The global search was performed at the B3PW91/SDD level of theory. Normal modes are calculated to validate the existence of optimal cluster structures. Energetic properties are obtained for the ground-state and isomer clusters and their relative energies are evaluated for probing isomerization. This is a few tenths of an eV, except for (CuS)2 cluster, which presents energy differences of ∼1 eV. Notable differences in the infrared spectra exist between the ground-state and first isomer structures, even for the (CuS)5 cluster, which has in both configurations a core copper pyramid. TDDFT provides the simulated absorption spectrum, presenting a theoretical description of optical absorption bands in terms of electronic excitations in the UV and visible regions. Results exhibit a significant dependence of the calculated UV/vis spectra on clusters size and shape regarding the ground state structures. Optical absorption is strong in the UV region, and weak or forbidden in the visible region of the spectrum.

Construction of Hierarchical CuO/Cu₂O@NiCo₂S₄ Nanowire Arrays on Copper Foam for High Performance Supercapacitor Electrodes.

PubMed

Zhou, Luoxiao; He, Ying; Jia, Congpu; Pavlinek, Vladimir; Saha, Petr; Cheng, Qilin

2017-09-15

Hierarchical copper oxide @ ternary nickel cobalt sulfide (CuO/Cu₂O@NiCo₂S₄) core-shell nanowire arrays on Cu foam have been successfully constructed by a facile two-step strategy. Vertically aligned CuO/Cu₂O nanowire arrays are firstly grown on Cu foam by one-step thermal oxidation of Cu foam, followed by electrodeposition of NiCo₂S₄ nanosheets on the surface of CuO/Cu₂O nanowires to form the CuO/Cu₂O@NiCo₂S₄ core-shell nanostructures. Structural and morphological characterizations indicate that the average thickness of the NiCo₂S₄ nanosheets is ~20 nm and the diameter of CuO/Cu₂O core is ~50 nm. Electrochemical properties of the hierarchical composites as integrated binder-free electrodes for supercapacitor were evaluated by various electrochemical methods. The hierarchical composite electrodes could achieve ultrahigh specific capacitance of 3.186 F cm -2 at 10 mA cm -2 , good rate capability (82.06% capacitance retention at the current density from 2 to 50 mA cm -2 ) and excellent cycling stability, with capacitance retention of 96.73% after 2000 cycles at 10 mA cm -2 . These results demonstrate the significance of optimized design and fabrication of electrode materials with more sufficient electrolyte-electrode interface, robust structural integrity and fast ion/electron transfer.

Identification of geostructures of continental crust, particularly as they relate to mineral-resource evaluation

NASA Technical Reports Server (NTRS)

Gryc, G. (Principal Investigator); Lathram, E. H.

1972-01-01

The authors have identified the following significant results. As a precursor to the ERTS-1 investigation, the spatial relationship of geostructures seen on Nimbus IDCS photographs to the distribution of mineralized areas in Alaska and western Canada was analyzed to determine the possible metallogenic significance of the geostructures. In Canada, mercury and porphyry molybdenum deposits are closely associated with strong northwest-trending fault systems; the development of mineralized regions seems related to major crustal zones or fractures trending southwestward across the Cordillera from the Precambrian shield. In Alaska, comparison of the northeast- and northwest-trending set of possible crustal structures shown on the Nimbus photo, with the distribution of known mineral deposits suggests a similar relationship. The mineralized region of massive sulfides in Prince William Sound and upper Copper River areas and of porphyry coppers in the Nabesna area forms a broad northeast-trending belt possibly related to the Minto Arch on the Shield. The belt of metalliferous deposits in the western Alaska Range follows a comparable northeast trend. Mercury deposits, suggested by many to be fault-controlled, together with most tin and tungsten deposits, occupy a northeast-trending belt between the Bristol Bay-Mackenzie Bay linear and extensions of a linear along the lower Yukon River. This belt intersects the northwest-trending Canadian belt of similar deposits in the Fairbanks area.

Geochemical evidence for a brooks range mineral belt, Alaska

USGS Publications Warehouse

Marsh, S.P.; Cathrall, J.B.

1981-01-01

Geochemical studies in the central Brooks Range, Alaska, delineate a regional, structurally controlled mineral belt in east-west-trending metamorphic rocks and adjacent metasedimentary rocks. The mineral belt extends eastward from the Ambler River quadrangle to the Chandalar and Philip Smith quadrangles, Alaska, from 147?? to 156??W. longitude, a distance of more than 375 km, and spans a width from 67?? to 69??N. latitude, a distance of more than 222 km. Within this belt are several occurrences of copper and molybdenum mineralization associated with meta-igneous, metasedimentary, and metavolcanic rocks; the geochemical study delineates target areas for additional occurrences. A total of 4677 stream-sediment and 2286 panned-concentrate samples were collected in the central Brooks Range, Alaska, from 1975 to 1979. The -80 mesh ( 2.86) nonmagnetic fraction of the panned concentrates from stream sediment were analyzed by semiquantitative spectrographic methods. Two geochemical suites were recognized in this investigation; a base-metal suite of copper-lead-zinc and a molybdenum suite of molybdenum-tin-tungsten. These suites suggest several types of mineralization within the metamorphic belt. Anomalies in molybdenum with associated Cu and W suggest a potential porphyry molybdenum system associated with meta-igneous rocks. This regional study indicates that areas of metaigneous rocks in the central metamorphic belt are target areas for potential mineralized porphyry systems and that areas of metavolcanic rocks are target areas for potential massive sulfide mineralization. ?? 1981.

Control of accidental releases of hydrogen selenide in vented storage cabinets

NASA Astrophysics Data System (ADS)

Fthenakis, V. M.; Moskowitz, P. D.; Sproull, R. D.

1988-07-01

Highly toxic hydrogen selenide and hydrogen sulfide gases are used in the production of copper-indium-diselenide photovoltaic cells by reactive sputtering. In the event of an accident, these gases may be released to the atmosphere and pose hazards to public and occupational safety and health. This paper outlines an approach for designing systems for the control of these releases given the uncertainty in release conditions and lack of data on the chemical systems involved. Accidental releases of these gases in storage cabinets can be controlled by either a venturi and packed-bed scrubber and carbon adsorption bed, or containment scrubbing equipment followed by carbon adsorption. These systems can effectively reduce toxic gas emissions to levels needed to protect public health. The costs of these controls (˜0.012/Wp) are samll in comparison with current (˜6/Wp) and projected (˜I/Wp) production costs.

Effects of the capping ligands, linkers and oxide surface on the electron injection mechanism of copper sulfide quantum dot-sensitized solar cells.

PubMed

Suárez, Javier Amaya; Plata, Jose J; Márquez, Antonio M; Sanz, Javier Fdez

2017-06-07

Quantum dot-sensitized solar cells, QDSCs, are a clean and effective alternative to fossil fuels to reduce CO 2 emissions. However, the different components that constitute the QDSCs and the difficulty of isolating experimentally their effects on the performance of the whole system slow down the development of more efficient devices. In this work, DFT calculations are combined with a bottom-up approach to differentiate the effect of each component on the electronic structure and absorption spectra. First, Cu 2 S QDs were built including a U parameter to effectively describe the localization of electrons. The effect of capping agents is addressed using ligands with different electron-donating/withdrawing groups. The role of linkers and their adsorption on the oxide surface are also examined. Finally, we propose a main indirect electron injection mechanism based on the position of the peaks of the spectra.