A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite.

PubMed

Li, Y; Kawashima, N; Li, J; Chandra, A P; Gerson, A R

2013-09-01

Most investigators regard CuFeS2 as having the formal oxidation states of Cu(+)Fe(3+)(S(2-))2. However, the spectroscopic characterisation of chalcopyrite is clearly influenced by the considerable degree of covalency between S and both Fe and Cu. The poor cleavage of CuFeS2 results in conchoidal surfaces. Reconstruction of the fractured surfaces to form, from what was previously bulk S(2-), a mixture of surface S(2-), S2(2) and S(n)(2-) (or metal deficient sulfide) takes place. Oxidation of chalcopyrite in air (i.e. 0.2 atm of O2 equilibrated with atmospheric water vapour) results in a Fe(III)-O-OH surface layer on top of a Cu rich sulfide layer overlying the bulk chalcopyrite with the formation of Cu(II) and Fe(III) sulfate, and Cu(I)-O on prolonged oxidation. Cu2O and Cu2S-like species have also been proposed to form on exposure of chalcopyrite to air. S2(2-), S(n)(2-) and S(0) form on the chalcopyrite surface upon aqueous leaching. The latter two of these species along with a jarosite-like species are frequently proposed to result in surface leaching passivation. However, some investigators have reported the formation of S(0) sufficiently porous to allow ion transportation to and from the chalcopyrite surface. Moreover, under some conditions both S(n)(2-) and S(0) were observed to increase in surface concentration for the duration of the leach with no resulting passivation. The effect of a number of oxidants, e.g. O2, H2O2, Cu(2+), Cr(6+) and Fe(3+), has been examined. However, this is often accompanied by poor control of leach parameters, principally pH and E(h). Nevertheless, there is general agreement in the literature that chalcopyrite leaching is significantly affected by solution redox potential with an optimum E(h) range suggesting the participation of leach steps that involve both oxidation and reduction. Three kinetic models have generally been suggested by researchers to be applicable: diffusion, chemical reaction and a mixed model containing diffusion and chemical components which occur at different stages of leaching. Passivation effects, due to surface diffusion rate control, may be affected by leach conditions such as pH or E(h). However, only initial conditions are generally described and these parameters are not controlled in most studies. However, at fixed pH, E(h) and temperature, it appears most likely that leaching in sulfuric acid media in the presence of added Fe(3+) is surface reaction rate controlled with some initial period, depending on leach conditions, where the leach rate is surface layer diffusion controlled. Although bioleaching of some copper ores has been adopted by industry, bioleaching has yet to be applied to predominantly chalcopyrite ores due to the slow resulting leach rates. Mixed microbial strains usually yield higher leach rates, as compared to single strains, as different bacterial strains are able to adapt to the changing leach conditions throughout the leach process. As for chemical leaching, passivation is also observed on bioleaching with jarosite being likely to be the main contributor. In summary, whilst much has been observed at the macro-scale regarding the chalcopyrite leach process it is clear that interpretation of these phenomena is hampered by lack of understanding at the molecular or atomic scale. Three primary questions that require elucidation, before the overall mechanism can be understood are: 1. How does the surface of chalcopyrite interact with solution or air borne oxidants? 2. How does the nature of these oxidants affect the surface products formed? 3. What determines whether the surface formed will be passivating or not? These can only realistically be tackled by the application of near atomic-scale analytical approaches, which may include quantum chemical modelling, PEEM/SPEM, TEM, AFM etc. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Free Energy Defect Model for the Cu-In-Ga-Se Tetrahedral Lattice

NASA Astrophysics Data System (ADS)

Stanbery, B. J.

2003-03-01

The most efficient thin-film photovoltaic converters of solar insolation to electrical power have recently achieved conversion efficiencies exceeding 19%, and are based on light absorbing layers containing the binary alloy (CuInSe_2)_1-X(CuGaSe_2)X of the α phases of these ternary chalcopyrite compounds. A statistical quantum mechanical model of the thermodynamic equilibrium defect structure of the tetrahedral lattice of copper, indium, and selenium with composition in the domain between that of the stoichiometric CuIn_1-XGa_XSe2 alloy and the β phase Cu(In_1-XGa_X)_3Se5 composition is presented. Compositions more copper-deficient than the latter have been reported experimentally to result in a breakdown of the tetrahedral coordination characteristic of the chalcopyrite lattice. These computations are based on a cluster expansion algorithm that minimizes the total free energy of the system using the Gibbs-Duhem equation to compute quasichemical reaction equilibria between the neutral clusters, and explicitly incorporates Fermi-Dirac statistics to determine their ionization equilibria and consequent carrier concentrations in the conduction and valence bands. The results are consistent with recent experimental evidence that the stoichiometric CuIn_1-XGa_XSe2 composition segregates in equilibrium into a two-phase mixture of a copper-deficient quaternary Cu_1-γIn_1-XGa_XSe2 composition and the binary Cu_2-δSe compound. The model predicts that the hole majority carrier (p-type) can only be achieved in the equilibrium single-phase chalcopyrite lattice with compositions that correspond to Cu_1-γIn_1-XGa_XSe_2+ɛ with γ and ɛ >0. This predicted requirement for selenium enrichment compared to the stoichiometric CuIn_1-XGa_XSe2 alloy composition for the dominance of holes over electrons as the majority carrier type is consistent with experimental evidence, and is explained in terms of a transition of the dominant lattice defect from the selenium vacancy in the stoichiometric case to the copper vacancy defect in the selenium-enriched lattice. This result is of particular importance since all CuIn_1-XGa_XSe2 thin-film solar cells utilize p-type absorber films.

Development of Proxies for Vent Fluid Trace Metal Concentrations and pH through Study of Sulfide Chimney Linings

NASA Astrophysics Data System (ADS)

Evans, G. N.; Tivey, M. K.; Seewald, J.; Rouxel, O. J.; Monteleone, B.

2016-12-01

Analyses of trace elements (Ag, As, Co, Mn, and Zn) hosted in the chalcopyrite linings of `black smoker' chimneys using secondary ion mass spectrometry (SIMS) have been combined with data for trace metal concentrations in corresponding vent fluids to investigate fluid-mineral partitioning of trace elements. Goals of this research include development of proxies for fluid chemistry based on mineral trace element content. The use of SIMS allows for the measurement of trace elements below the detection limits of electron microprobe and at the necessary spatial resolution (20 microns) to examine fine-grained and mixed-mineral samples. Results indicate that the chalcopyrite linings of many `black smoker' chimneys are homogeneous with respect to Ag, Mn, Co, and Zn. Minerals picked from samples exhibiting homogeneity with respect to specific elements were dissolved and analyzed by solution inductively coupled plasma mass spectrometry (ICP-MS) for use as working standards. Results also document a strong correlation between the Ag content of chalcopyrite and the Ag:Cu ratio of the corresponding hydrothermal fluid. This supports systematic partitioning of Ag into chalcopyrite as a substitute for Cu, providing a proxy for fluid Ag concentration. Additionally, the Ag content of chalcopyrite correlates with fluid pH, particularly at pH>3, and thus represents an effective proxy for fluid pH. Application of these proxies to chimney samples provides an opportunity to better identify hydrothermal conditions even when fluids have not been sampled, or not fully analyzed.

Mineralogy, chemical composition and structure of the MIR Mound, TAG Hydrothermal Field

NASA Astrophysics Data System (ADS)

Stepanova, T. V.; Krasnov, S. G.; Cherkashev, G. A.

The study of samples collected from the surface of the MIR mound (TAG Hydrothermal Field) by video-controlled hydraulic grab allowed identification of a number of mineralogical types. These include pyrite-chalcopyrite (Py-Cp), bornite-chalcopyrite-opaline (Bn-Cp-Op) and sphalerite-opaline (Sp-Op) sulfide chimneys, massive sulfides composed of pyrite (Py), chalcopyrite-pyrite (Cp-Py), marcasite-pyrite-opaline (Mc-Py-Op), sphalerite-pyrite-opaline (Sp-Py-Op) and sphalerite-chalcopyrite-pyrite-opaline (Sp-Cp-Py-Op), as well as siliceous and Fe-Mn oxide hydrothermal deposits. Most of the minor elements (Ag, Au, Cd, Ga, Hg, Sb and Pb) are associated with Zn-rich massive sulfides, Co Bi, Pb, and As with Ferich ones, while Cu-rich sulfides are depleted of trace metals. Cu-enriched assemblages are concentrated in the northern part, Zn-enriched in the center, and siliceous rocks in the south of the MIR mound. According to paragenetic relations, the development of the mound started with the formation of quartz (originally opaline) rocks and dendritic assemblages of melnikovite-pyrite, followed by deposition of chalcopyrite and recrystallization of primary pyrite, subsequent generation of sphalerite-rich assemblages and final deposition of opaline rocks. The late renewal of hydrothermal activity led to local formation of Cu-rich chimneys enriched in Au, Ag, Hg and Pb probably due to their remobilization from inner parts of the deposit.

A High-Yield Synthesis of Chalcopyrite CuIn S 2 Nanoparticles with Exceptional Size Control

DOE PAGES

Sun, Chivin; Gardner, Joseph S.; Shurdha, Endrit; ...

2009-01-01

We repormore » t high-yield and efficient size-controlled syntheses of Chalcopyrite CuIn S 2 nanoparticles by decomposing molecular single source precursors (SSPs) via microwave irradiation in the presence of 1,2-ethanedithiol at reaction temperatures as low as 100 ° C and times as short as 30 minutes. The nanoparticles sizes were 1.8 nm to 10.8 nm as reaction temperatures were varied from 100 ° C to 200 ° C with the bandgaps from 2.71 eV to 1.28 eV with good size control and high yields (64%–95%). The resulting nanoparticles were analyzed by XRD, UV-Vis, ICP-OES, XPS, SEM, EDS, and HRTEM. Titration studies by 1 H NMR using SSP 1 with 1,2-ethanedithiol and benzyl mercaptan were conducted to elucidate the formation of Chalcopyrite CuIn S 2 nanoparticles.« less

Textures and compositions of cobalt pentlandite and cobaltian mackinawite from the Madan-Kudan copper deposit, Khetri Copper Belt, Rajasthan, India

NASA Astrophysics Data System (ADS)

Baidya, Abu Saeed; Sen, Atlanta; Pal, Dipak C.

2018-06-01

The Khetri Copper Belt (KCB), a part of the Proterozoic Delhi-Aravalli fold belt in western India, hosts several Cu deposits, which are known to contain considerable Au, Ag, Co and Ni. Although many Co-bearing phases have been reported from the KCB and adjacent areas, detailed textural and geochemical data are either unavailable or scant except for mackinawite. In this study, we describe the textures and compositions (determined by EPMA) of two very rare Co-rich phases, namely cobaltian mackinawite (containing up to 12.68 wt.% Co, 1.90 wt.% Ni and 2.52 wt.% Cu) and cobalt-pentlandite (containing up to 49.30 wt.% Co and 10.19 wt.% Ni), identified based on composition, from the Madan-Kudan deposit. To the best of our knowledge, neither cobalt-pentlandite nor such highly Co-rich mackinawite have previously been reported from this area. The common sulphide minerals viz. chalcopyrite, pyrrhotite and rare pyrite occur in chalcopyrite-pyrrhotite ± pyrite-magnetite-chlorite-blue amphibole (Cl-rich hastingsite-pargasite-sadanagaite) ± marialitic scapolite ± allanite ± uraninite veins in amphibole-bearing feldspathic quartzite and garnetiferous chlorite schist. Cobaltian mackinawite is invariably associated with chalcopyrite and occurs as exsolution and inclusion within chalcopyrite or outside, but at the contact of chalcopyrite. On the other hand, cobalt-pentlandite is invariably associated with pyrrhotite and shows similar textural relation with pyrrhotite as that of mackinawite with chalcopyrite. Mineralogically diverse undeformed sulphide veins comprising Cl-rich amphibole and locally Cl-rich marialitic scapolite suggests epigenetic hydrothermal mineralization involving Cl-rich saline fluid in the Madan-Kudan deposit. Transport of metals, derived from a mafic source rock with high intrinsic Ni:Co ratio, by Cl-rich fluid can suitably explain the high Co:Ni ratio of the studied ore minerals. Presence of such highly Co-rich phases and other circumstantial evidences, enumerated in this work, are consistent with variants of Fe oxide (-Cu-Au) (IOCG) style mineralization, at least for some stages of mineralization in the Madan-Kudan deposit.

Indium-bearing sulfides from the Hämmerlein skarn deposit, Erzgebirge, Germany: evidence for late-stage diffusion of indium into sphalerite

NASA Astrophysics Data System (ADS)

Bauer, Matthias E.; Seifert, Thomas; Burisch, Mathias; Krause, Joachim; Richter, Nancy; Gutzmer, Jens

2017-12-01

At the Hämmerlein skarn deposit, located in the western Erzgebirge (Germany), a major cassiterite-dominated Sn mineralization stage is spatially associated with a younger Zn-Cu-In sulfide mineralization stage. In this contribution, we provide the first detailed description of the Zn-Cu-In sulfide mineralization stage, based on field geological observations combined with detailed petrographic studies and electron probe microanalysis data. Indium-rich sulfide mineralization occurs as irregular, semi-massive lenses or as infill of short, discontinuous veinlets that crosscut the cassiterite-bearing skarn assemblage. Indium- and Cu-rich sphalerite and roquesite are found to be closely associated with In-bearing chalcopyrite. The highest In concentrations in sphalerite occur at the rims and along cracks of sphalerite grains. The distribution resembles diffusion profiles, suggesting that the In enrichment is due to an hydrothermal overprint that postdates the initial formation of both sphalerite and chalcopyrite. Textural relations illustrate that the diffusion fronts in sphalerite grains are thicker where they are in contact to anhedral masses of hematite and magnetite. Our observations suggest that In enrichment in sphalerite at the Hämmerlein skarn deposit is due to the decomposition of In-bearing chalcopyrite. The resultant release of Fe led to the formation of hematite and magnetite, whereas Cu and In were incorporated into sphalerite along grain boundaries and micro fractures. Incorporation into the sphalerite lattice took place by coupled substitution of Cu+ + In3+ ↔ 2Zn2+, suggesting that the concurrent availability of Cu and In may be an essential factor to enrich In in sphalerite in hydrothermal ore-forming environments.

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.

Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites.

PubMed

Miglio, Anna; Heinrich, Christophe P; Tremel, Wolfgang; Hautier, Geoffroy; Zeier, Wolfgang G

2017-09-01

Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu 2 ZnGeS 4- x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlying bonding interactions at the band edges can help design properties of these quaternary chalcopyrites for photovoltaic and thermoelectric applications.

Experimental indication for band gap widening of chalcopyrite solar cell absorbers after potassium fluoride treatment

NASA Astrophysics Data System (ADS)

Pistor, P.; Greiner, D.; Kaufmann, C. A.; Brunken, S.; Gorgoi, M.; Steigert, A.; Calvet, W.; Lauermann, I.; Klenk, R.; Unold, T.; Lux-Steiner, M.-C.

2014-08-01

The implementation of potassium fluoride treatments as a doping and surface modification procedure in chalcopyrite absorber preparation has recently gained much interest since it led to new record efficiencies for this kind of solar cells. In the present work, Cu(In,Ga)Se2 absorbers have been evaporated on alkali containing Mo/soda-lime glass substrates. We report on compositional and electronic changes of the Cu(In,Ga)Se2 absorber surface as a result of a post deposition treatment with KF (KF PDT). In particular, by comparing standard X-ray photoelectron spectroscopy and synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES), we are able to confirm a strong Cu depletion in the absorbers after the KF PDT which is limited to the very near surface region. As a result of the Cu depletion, we find a change of the valence band structure and a shift of the valence band onset by approximately 0.4 eV to lower binding energies which is tentatively explained by a band gap widening as expected for Cu deficient compounds. The KF PDT increased the open circuit voltage by 60-70 mV compared to the untreated absorbers, while the fill factor deteriorated.

Electrochemical and spectroscopic study of interfacial interactions between chalcopyrite and typical flotation process reagents

NASA Astrophysics Data System (ADS)

Urbano, Gustavo; Lázaro, Isabel; Rodríguez, Israel; Reyes, Juan Luis; Larios, Roxana; Cruz, Roel

2016-02-01

Comparative voltammetry and differential double-layer capacitance studies were performed to evaluate interfacial interactions between chalcopyrite (CuFeS2) and n-isopropyl xanthate (X) in the presence of ammonium bisulfite/39wt% SO2 and caustic starch at different pH values. Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, contact angle measurements, and microflotation tests were used to establish the type and extent of xanthate adsorption as well as the species involved under different mineral surface conditions in this study. The results demonstrate that the species that favor a greater hydrophobicity of chalcopyrite are primarily CuX and S0, whereas oxides and hydroxides of Cu and Fe as well as an excess of starch decrease the hydrophobicity. A conditioning of the mineral surface with ammonium bisulfite/39wt% SO2 at pH 6 promotes the activation of surface and enhances the xanthate adsorption. However, this effect is diminished at pH ≥ 8, when an excess of starch is added during the preconditioning step.

Optimization of Cu-Zn Massive Sulphide Flotation by Selective Reagents

NASA Astrophysics Data System (ADS)

Soltani, F.; Koleini, S. M. J.; Abdollahy, M.

2014-10-01

Selective floatation of base metal sulphide minerals can be achieved by using selective reagents. Sequential floatation of chalcopyrite-sphalerite from Taknar (Iran) massive sulphide ore with 3.5 % Zn and 1.26 % Cu was studied. D-optimal design of response surface methodology was used. Four mixed collector types (Aer238 + SIPX, Aero3477 + SIPX, TC1000 + SIPX and X231 + SIPX), two depressant systems (CuCN-ZnSO4 and dextrin-ZnSO4), pH and ZnSO4 dosage were considered as operational factors in the first stage of flotation. Different conditions of pH, CuSO4 dosage and SIPX dosage were studied for sphalerite flotation from first stage tailings. Aero238 + SIPX induced better selectivity for chalcopyrite against pyrite and sphalerite. Dextrin-ZnSO4 was as effective as CuCN-ZnSO4 in sphalerite-pyrite depression. Under optimum conditions, Cu recovery, Zn recovery and pyrite content in Cu concentrate were 88.99, 33.49 and 1.34 % by using Aero238 + SIPX as mixed collector, CuCN-ZnSO4 as depressant system, at ZnSO4 dosage of 200 g/t and pH 10.54. When CuCN was used at the first stage, CuSO4 consumption increased and Zn recovery decreased during the second stage. Maximum Zn recovery was 72.19 % by using 343.66 g/t of CuSO4, 22.22 g/t of SIPX and pH 9.99 at the second stage.

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.

Surface modifications of chalcopyrite CuInS2 thin films for photochatodes in photoelectrochemical water splitting under sunlight irradiation

NASA Astrophysics Data System (ADS)

Gunawan; Haris, A.; Widiyandari, H.; Septina, W.; Ikeda, S.

2017-02-01

Copper chalcopyrite semiconductors include a wide range of compounds that are of interest for photoelectrochemical water splitting which enables them to be used as photochatodes for H2 generation. Among them, CuInS2 is one of the most important materials due to its optimum band gap energy for sunlight absorption. In the present study, we investigated the application of CuInS2 fabricated by electrodeposition as photochatodes for water splitting. Thin film of CuInS2 chalcopyrite was formed on Mo-coated glass substrate by stacked electrodeposition of copper and indium followed by sulfurization under H2S flow. The films worked as a H2 liberation electrode under cathodic polarization from a solution containing Na2SO4 after loading Pt deposits on the film. Introduction of an n-type CdS layer by chemical bath deposition on the CuInS2 surface before the Pt loading resulted appreciable improvements of H2 liberation efficiency and a higher photocurrent onset potential. Moreover, the use of In2S3 layer as an alternative n-type layer to the CdS significantly improved the H2 liberation performance: the CuInS2 film modified with In2S3 and Pt deposits worked as an efficient photocathode for photoelectrochemical water splitting.

Bioleaching of chalcopyrite and bornite by moderately thermophilic bacteria: an emphasis on their interactions

NASA Astrophysics Data System (ADS)

Zhao, Hong-bo; Wang, Jun; Gan, Xiao-wen; Qin, Wen-qing; Hu, Ming-hao; Qiu, Guan-zhou

2015-08-01

Interactions between chalcopyrite and bornite during bioleaching by moderately thermophilic bacteria were investigated mainly by X-ray diffraction, scanning electron microscopy, and electrochemical measurements performed in conjunction with bioleaching experiments. The results showed that a synergistic effect existed between chalcopyrite and bornite during bioleaching by both Acidithiobacillus caldus and Leptospirillum ferriphilum and that extremely high copper extraction could be achieved when chalcopyrite and bornite coexisted in a bioleaching system. Bornite dissolved preferentially because of its lower corrosion potential, and its dissolution was accelerated by the galvanic current during the initial stage of bioleaching. The galvanic current and optimum redox potential of 390-480 mV vs. Ag/AgCl promoted the reduction of chalcopyrite to chalcocite (Cu2S), thus accelerating its dissolution.

A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

NASA Technical Reports Server (NTRS)

Banger, K. K.; Cowen, J.; Harris, J.; McClarnon, R.; Hehemann, D. G.; Duraj, S. A.; Scheiman, D.; Hepp, A. F.

2002-01-01

The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

Experimental indication for band gap widening of chalcopyrite solar cell absorbers after potassium fluoride treatment

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

Pistor, P., E-mail: paul.pistor@physik.uni-halle.de; Greiner, D.; Kaufmann, C. A.

2014-08-11

The implementation of potassium fluoride treatments as a doping and surface modification procedure in chalcopyrite absorber preparation has recently gained much interest since it led to new record efficiencies for this kind of solar cells. In the present work, Cu(In,Ga)Se{sub 2} absorbers have been evaporated on alkali containing Mo/soda-lime glass substrates. We report on compositional and electronic changes of the Cu(In,Ga)Se{sub 2} absorber surface as a result of a post deposition treatment with KF (KF PDT). In particular, by comparing standard X-ray photoelectron spectroscopy and synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES), we are able to confirm a strong Cu depletionmore » in the absorbers after the KF PDT which is limited to the very near surface region. As a result of the Cu depletion, we find a change of the valence band structure and a shift of the valence band onset by approximately 0.4 eV to lower binding energies which is tentatively explained by a band gap widening as expected for Cu deficient compounds. The KF PDT increased the open circuit voltage by 60–70 mV compared to the untreated absorbers, while the fill factor deteriorated.« less

Microwave heating synthesis and formation mechanism of chalcopyrite structured CuInS{sub 2} nanorods in deep eutectic solvent

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

Zhang, Jianjun, E-mail: zhangjianjun7110@163.com; Chen, Jun; Li, Qiang

2015-03-15

Graphical abstract: Chalcopyrite structured CuInS{sub 2} nanorods were synthesized by an environmentally friendly microwave heating method in deep eutectic solvent. Results show that microwave heating time plays an important role in the formation of CuInS{sub 2} nanostructure phase. The SEM results indicated that the obtained CuInS{sub 2} nanostructures display rod-like morphology with diameters of about 40 nm and lengths of about 400 nm. The UV–vis spectrum results indicated that the CuInS{sub 2} nanorods exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1100 nm. The possible growth mechanism of CuInS{sub 2} nanorods was discussed. -more » Abstract: Chalcopyrite structured CuInS{sub 2} nanorods were synthesized by an environmentally friendly microwave heating method in deep eutectic solvent. The as-synthesized CuInS{sub 2} nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. The results indicated that the obtained CuInS{sub 2} nanostructures display rod-like morphology with diameters of about 40 nm and lengths of about 400 nm. The influences of microwave heating time on the formation of CuInS{sub 2} phase were discussed. Ultraviolet–visible (UV–vis) and photoluminescence (PL) spectra were utilized to investigate the optical properties of CuInS{sub 2} nanorods. The results showed that the as-synthesized CuInS{sub 2} nanorods exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1100 nm. PL spectrum of the as-synthesized CuInS{sub 2} nanorods displays an emission peak centered at 580 nm under excitation wavelength of 366 nm at room temperature. The possible growth mechanism of CuInS{sub 2} nanorods was discussed.« less

Generalized stacking fault energies, cleavage energies, ionicity and brittleness of Cu(Al/Ga/In)Se2 and CuGa(S/Se/Te)2

NASA Astrophysics Data System (ADS)

Xue, H. T.; Tang, F. L.; Gruhn, T.; Lu, W. J.; Wan, F. C.; Rui, Z. Y.; Feng, Y. D.

2014-04-01

We calculate the generalized stacking fault (GSF) energies and cleavage energies γcl of the chalcopyrite compounds CuAlSe2, CuGaSe2, CuInSe2, CuGaS2 and CuGaTe2 using first principles. From the GSF energies, we obtain the unstable stacking fault energies γus and intrinsic stacking fault energies γisf. By analyzing γus and γisf, we find that the \\langle \\bar{{1}}\\,1\\,0\\rangle (1 1 2) direction is the easiest slip direction for these five compounds. Also, for CuInSe2, it is most possible to undergo a dislocation-nucleation-induced plastic deformation along the \\langle \\bar{{1}}\\,1\\,0\\rangle (1 1 2) slip direction. We show that the (1 1 2) plane is the preferable plane for fracture in the five compounds by comparing γcl of the (0 0 1) and (1 1 2) planes. It is also found that both γus and γcl decrease as the cationic or anionic radius increases in these chalcopyrites, i.e. along the sequences CuAlSe2 → CuGaSe2 → CuInSe2 and CuGaS2 → CuGaSe2 → CuGaTe2. Based on the values of the ratio γcl/γus, we discuss the brittle-ductile properties of these compounds. All of the compounds can be considered as brittle materials. In addition, a strong relationship between γcl/γus and the total proportion of ionic bonding in these compounds is found.

Recovery of Copper from Cyanidation Tailing by Flotation

NASA Astrophysics Data System (ADS)

Qiu, Tingsheng; Huang, Xiong; Yang, Xiuli

2016-02-01

In this work, sodium hypochlorite, hydrogen peroxide, sodium metabisulfite and copper sulfate as activators were investigated to lessen the depression effect of cyanide for deep-depressing chalcopyrite. The experimental results indicate that the copper recovery exceeded 94%, 84% and 97% at the dosage: sodium hypochlorite 3 mL/L, hydrogen peroxide 2 mL/L, sodium metabisulfite 2 × 10-3 mol/L and copper sulfate 1.67 × 10-4 mol/L, respectively. According to the results of zeta potential and Fourier transform infrared spectrum, it is suggested that chalcopyrite was depressed because of the chemical adsorption of cyanide on the chalcopyrite surfaces. Sodium hypochlorite, hydrogen peroxide and sodium metabisulfite can destroy Cu-C bond on the deep-depressing chalcopyrite surface by chemical reaction. Copper sulfate can activate deep-depressing chalcopyrite by copper ion adsorption.

Geochemistry and geochronology of carbonate-hosted base metal deposits in the southern Brooks Range, Alaska: temporal association with VMS deposits and metallogenic implications

USGS Publications Warehouse

Kelly, Karen; Slack, John; Selby, David

2009-01-01

The Brooks Range contains enormous accumulations of zinc and copper, either as VMS or sediment-hosted deposits. The Ruby Creek and Omar deposits are Cu-Co stratabound deposits associated with dolomitic breccias. Numerous volcanogenic Cu-Zn (+/-Ag, Au) deposits are situated ~20 km north of the Ruby Creek deposit. The carbonate-hosted deposits consist of chalcopyrite and bornite that fill open spaces, replace the matrix of the breccias, and occur in later cross-cutting veins. Cobaltiferous pyrite, chalcocite, minor tennantite-tetrahedrite, galena, and sphalerite are also present. At Ruby Creek, phases such as carrollite, renierite, and germanite occur rarely. The deposits have undergone post-depositional metamorphism (Ruby Creek, low greenschist facies; Omar, blueschist facies). The unusual geochemical signature includes Cu-Co +/- Ag, As, Au, Bi, Ge, Hg, Sb, and U with sporadic high Re concentrations (up to 2.7 ppm). New Re-Os data were obtained for chalcopyrite, bornite, and pyrite from the Ruby Creek deposit (analyses of sulfides from Omar are in progress). The data 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 Ruby Creek 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 occurred at 384 +/-4.2 Ma, which coincides with zircon U-Pb ages from igneous rocks that are spatially and genetically associated with VMS deposits. This suggests a temporal link between regional magmatism and hydrothermal mineralization.

Study on Gold and base metal occurrence in Uluwai Prospect, Western Latimojong Mountain, South Sulawesi

NASA Astrophysics Data System (ADS)

Maulana, Adi; Jaya, Asri; Imai, Akira

2018-02-01

Uluwai Prospect is located in the northern part of South Arm of Sulawesi along the eastern part of the Kalosi Fold Belt and Latimojong Mountain. The area is generally characterized by moderate to rugged topography area with elevation in the range of 700 to 1400 m above sea level in the mountainous complex called Latimojong Mountain Complex. The mineralization is characterized by a relatively simple sulphide ore mineral assemblage consists of pyrite, sphalerite and chalcopyrite. Samples were collected in areas showing abundant sulphide minerals where younger faults cut the bedding and foliation of country rocks. A number of silicified zones have been observed, as well as float material containing disseminated pyrite, chalcopyrite, and sphalerite with hematite, goethite and limonite. Some alteration types have been observed including sericitization, albitization, carbonatization and silisification. The samples collected indicated that the mineralisation is contained within metasedimentary (sandstone to mudstone) and greenschist. Geochemical analyses from 16 samples including 5 stream sediment samples indicated that the most promising mineralization occur in the prospect area are copper (Cu) and zinc (Zn). This is also supported by the abundance of chalcopyrite and sphalerite in some highly altered samples. Assaying of the collected samples revealed most of samples contain relatively low gold (Au) concentration. However, two samples contain 0.007 and 0.01 ppm of Au. In the mineralized area, Zn concentrations are up to 134 ppm, Cu up to 120 ppm and Pb up to 18 ppm and As up to 70 ppm. There is no clear relationship that exists between Au and the base metals except that one of the samples with highest Au values tend to have high Zn and As. This unclear pattern also shown by Cu, Pb and Zn. Base metal concentration in stream sediment samples show a relatively stable pattern than in rock samples. Arsenic tends to be elevated in base metal rich samples. Sb and Mo are relatively low in all sample type. However, Mo values will be high in the samples which contain highest Cu and Zn.

Thermodynamic assessment of Ag–Cu–In

DOE PAGES

Muzzillo, Christopher P.; Anderson, Tim

2018-01-16

The Ag-Cu-In thermodynamic material system is of interest for brazing alloys and chalcopyrite thin-film photovoltaics. To advance these applications, Ag-Cu-In was assessed and a Calphad model was developed. Binary Ag-Cu and Cu-In parameters were taken from previous assessments, while Ag-In was re-assessed. Structure-based models were employed for ..beta..-bcc(A2)-Ag 3In, ..gamma..-Ag 9In 4, and AgIn 2 to obtain good fit to enthalpy, phase boundary, and invariant reaction data for Ag-In. Ternary Ag-Cu-In parameters were optimized to achieve excellent fit to activity, enthalpy, and extensive phase equilibrium data. Relative to the previous Ag-Cu-In assessment, fit was improved while fewer parameters were used.

Thermodynamic assessment of Ag–Cu–In

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

Muzzillo, Christopher P.; Anderson, Tim

The Ag-Cu-In thermodynamic material system is of interest for brazing alloys and chalcopyrite thin-film photovoltaics. To advance these applications, Ag-Cu-In was assessed and a Calphad model was developed. Binary Ag-Cu and Cu-In parameters were taken from previous assessments, while Ag-In was re-assessed. Structure-based models were employed for ..beta..-bcc(A2)-Ag 3In, ..gamma..-Ag 9In 4, and AgIn 2 to obtain good fit to enthalpy, phase boundary, and invariant reaction data for Ag-In. Ternary Ag-Cu-In parameters were optimized to achieve excellent fit to activity, enthalpy, and extensive phase equilibrium data. Relative to the previous Ag-Cu-In assessment, fit was improved while fewer parameters were used.

Saline-water bioleaching of chalcopyrite with thermophilic, iron(II)- and sulfur-oxidizing microorganisms.

PubMed

Watling, Helen R; Collinson, David M; Corbett, Melissa K; Shiers, Denis W; Kaksonen, Anna H; Watkin, Elizabeth L J

2016-09-01

The application of thermoacidophiles for chalcopyrite (CuFeS2) bioleaching in hot, acidic, saline solution was investigated as a possible process route for rapid Cu extraction. The study comprised a discussion of protective mechanisms employed for the survival and/or adaptation of thermoacidophiles to osmotic stress, a compilation of chloride tolerances for three genera of thermoacidophiles applied in bioleaching and an experimental study of the activities of three species in a saline bioleaching system. The data showed that the oxidation rates of iron(II) and reduced inorganic sulfur compounds (tetrathionate) were reduced in the presence of chloride levels well below chloride concentrations in seawater, limiting the applicability of these microorganisms in the bioleaching of CuFeS2 in saline water. Copyright © 2016. Published by Elsevier Masson SAS.

Les minéralisations Cu_(Ni_Bi_U_Au_Ag) d'Ifri (district du Haut Seksaoua, Maroc) : apport de l'étude texturale au débat syngenèse versus épigenèseThe Cu_(Ni_Bi_U_Au_Ag) mineralization of Ifri ('Haut Seksaoua' district, Morocco): contribution of a textural study to the discussion syngenetic versus epigenetic

NASA Astrophysics Data System (ADS)

Barbanson, Luc; Chauvet, Alain; Gaouzi, Aziz; Badra, Lakhifi; Mechiche, Mohamed; Touray, Jean Claude; Oukarou, Saı̈d

2003-11-01

The Cu ore of Ifri is a chalcopyrite stockwork hosted by Cambrian formations and was until now interpreted as a syngenetic massive sulphide deposit. Textural studies highlight two generations of pyrite early (Py I) and late (Py II) with respect to the regional deformation. The chalcopyrite stockwork overprinted Py II, outlining the epigenetic nature of the Cu mineralization. Regarding the origin of Cu-depositing fluids, the presence in the stockwork paragenesis of an U, W, Sn association and preliminary Pb/Pb dating of a brannerite belonging to this association suggest a contribution of the Tichka granite. To cite this article: L. Barbanson et al., C. R. Geoscience 335 (2003).

Synthesis and structures of metal chalcogenide precursors

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

1990-01-01

The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

Correlating Cu-sulfide and Au mineralization in the Ertsberg-Grasberg District using LA-ICP-MS and HRXCT

NASA Astrophysics Data System (ADS)

Wright, K. A.; Miller, N. R.; Ketcham, R. A.; Kyle, R.

2016-12-01

The Ertsberg-Grasberg district in Papua, Indonesia, hosts to two of the largest intrusion-related Cu-Au deposits in the world: the Ertsberg East Skarn system and the Grasberg Intrusive Complex. Cu mineralization within the Grasberg porphyry and Ertsberg skarn systems primarily consists of bornite and chalcopyrite, with minor digenite and idiate. Native Au is commonly found in association with Cu mineralization where Au occurs as inclusions within or immediately proximal to primary Cu-sulfide minerals. At hydrothermal-ore forming temperatures, approximately 400° to 700° C, bornite and chalcopyrite can host up to 1800 ppm Au within the Cu-sulfide lattice. Upon retrograde cooling of the hydrothermal system, the ability of bornite and chalcopyrite to host Au decreases significantly to about 10 ppm, indicating that the Au could be expulsed from the sulfide lattice. Given the close association of native Au and Cu-sulfide concentrations, it is possible that native gold grains form as the Au emerges from the Cu-sulfides. Constraining the genetic and spatio-temporal relationship between Cu-sulfide and Au mineralization within these deposits is of significant interest with regard to the geometallurgical processing of the ore, and to future exploration. This study seeks to evaluate this relationship using High Resolution X-ray Computed Tomography (HRXCT) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Previous HRXCT studies on Ertsberg-Grasberg ore samples have identified numerous occurrences of native Au grains at the edges of Cu-sulfide masses. HRXCT data are used here to construct 3D Voronoi regions of potential Au "diffusional drainage" from within the Cu-sulfides, where the expectation is a positive correlation between Au grain size and modified Voronoi polyhedron volume, defined as the volume of sulfide closer to that grain than any other via a connected path through sulfide. LA-ICP-MS data are used to determine variations in Au contents of Cu-sulfide minerals using 2D transects away from Au inclusions in 3D contact with Cu-sulfide minerals.

High-Temperature Formation Phases and Crystal Structure of Hot-Pressed Thermoelectric CuGaTe2 with Chalcopyrite-Type Structure

NASA Astrophysics Data System (ADS)

Fujii, Yosuke; Kosuga, Atsuko

2017-11-01

Polycrystalline CuGaTe2 with a chalcopyrite-type structure consolidated by hot-pressing is a potential candidate as a medium-temperature thermoelectric (TE) material. However, its high-temperature formation phases have rarely been reported to date. Here, we investigated the temperature-dependent formation phases and crystal structure at 300-800 K of hot-pressed CuGaTe2. From synchrotron x-ray diffraction data and crystal structure analysis of the heating and cooling processes, it was clarified that a certain amount of impurity phases, such as Te and CuTe, precipitated from the CuGaTe2 matrix when the temperature was increased (to 500-650 K). This is the temperature range where CuGaTe2 has been reported to show high TE performance. After CuGaTe2 was heated to 800 K, such impurity phases remained, even when cooled to room temperature. They also affected the tetragonal distortion and the x-coordinate of Te in the CuGaTe2 matrix, probably due to deficiencies of Cu and Te in the matrix. Our results reveal detailed information on the formation phases of CuGaTe2 at high temperature and thus provide insight for evaluation of its high-temperature stability and transport properties.

High-Temperature Formation Phases and Crystal Structure of Hot-Pressed Thermoelectric CuGaTe2 with Chalcopyrite-Type Structure

NASA Astrophysics Data System (ADS)

Fujii, Yosuke; Kosuga, Atsuko

2018-06-01

Polycrystalline CuGaTe2 with a chalcopyrite-type structure consolidated by hot-pressing is a potential candidate as a medium-temperature thermoelectric (TE) material. However, its high-temperature formation phases have rarely been reported to date. Here, we investigated the temperature-dependent formation phases and crystal structure at 300-800 K of hot-pressed CuGaTe2. From synchrotron x-ray diffraction data and crystal structure analysis of the heating and cooling processes, it was clarified that a certain amount of impurity phases, such as Te and CuTe, precipitated from the CuGaTe2 matrix when the temperature was increased (to 500-650 K). This is the temperature range where CuGaTe2 has been reported to show high TE performance. After CuGaTe2 was heated to 800 K, such impurity phases remained, even when cooled to room temperature. They also affected the tetragonal distortion and the x-coordinate of Te in the CuGaTe2 matrix, probably due to deficiencies of Cu and Te in the matrix. Our results reveal detailed information on the formation phases of CuGaTe2 at high temperature and thus provide insight for evaluation of its high-temperature stability and transport properties.

The effect of processing on the properties of CuInS2 nanomaterials synthesized by simple hot injection route

NASA Astrophysics Data System (ADS)

Chen, Qin-Miao; Zhou, Fang-Fang; Yuan, Hong-Chun; Chen, Jin; Ni, Yi; Zhu, Xi-Fang; Dou, Xiao-Ming

2017-07-01

Chalcopyrite and wurtzite CuInS2 (CIS) nanomaterials were synthesized from Cu2+, In3+, thiourea with or without triethanolamine (TEA) by simple hot injection method at low temperature. The effect of synthesis duration on the various properties of the synthesized CIS nanomaterials was studied. It shows that for chalcopyrite CIS, the optimal synthesis duration is 60 min and the synthesized nanomaterial is in spherical shape with diameter of about 90 nm. However, for the wurtzite CIS, the optimal synthesis duration should reach 150 min and the synthesized nanomaterial looks like nanoplate with thicknesses of ˜10 nm and diameters near 100 nm. The photovoltaic characteristics of two types of nanomaterials are quite different. This study may contribute to the synthesis of CIS nanomaterials at low temperatures.

Catalytic effect of light illumination on bioleaching of chalcopyrite.

PubMed

Zhou, Shuang; Gan, Min; Zhu, Jianyu; Li, Qian; Jie, Shiqi; Yang, Baojun; Liu, Xueduan

2015-04-01

The influence of visible light exposure on chalcopyrite bioleaching was investigated using Acidithiobacillus ferrooxidans. The results indicated, in both shake-flasks and aerated reactors with 8500-lux light, the dissolved Cu was 91.80% and 23.71% higher, respectively, than that in the controls without light. The catalytic effect was found to increase bioleaching to a certain limit, then plateaued as the initial chalcopyrite concentration increased from 2% to 4.5%. Thus a balanced mineral concentration is highly amenable to bioleaching via offering increased available active sites for light adsorption while eschewing mineral aggregation and screening effects. Using semiconducting chalcopyrite, the light facilitated the reduction of Fe(3+) to Fe(2+) as metabolic substrates for A.ferrooxidans, leading to better biomass, lower pH and redox potential, which are conducive to chalcopyrite leaching. The light exposure on iron redox cycling was further confirmed by chemical leaching tests using Fe(3+), which exhibited higher Fe(2+) levels in the light-induced system. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Radiative transitions in highly doped and compensated chalcopyrites and kesterites: The case of Cu2ZnSnS4

NASA Astrophysics Data System (ADS)

Teixeira, J. P.; Sousa, R. A.; Sousa, M. G.; da Cunha, A. F.; Fernandes, P. A.; Salomé, P. M. P.; Leitão, J. P.

2014-12-01

The theoretical models of radiative recombinations in both CuIn1 -xGaxSe2 chalcopyrite and Cu2ZnSnS4 kesterite, and related compounds, were revised. For heavily doped materials, electrons are free or bound to large donor agglomerates which hinders the involvement of single donors in the radiative recombination channels. In this work, we investigated the temperature and excitation power dependencies of the photoluminescence of Cu2ZnSnS4-based solar cells in which the absorber layer was grown through sulphurization of multiperiod structures of precursor layers. For both samples the luminescence is dominated by an asymmetric band with peak energy at ˜1.22 eV, which is influenced by fluctuating potentials in both conduction and valence bands. A value of ˜60 meV was estimated for the root-mean-square depth of the tails in the conduction band. The radiative transitions involve the recombination of electrons captured by localized states in tails of the conduction band with holes localized in neighboring acceptors that follow the fluctuations in the valence band. The same acceptor level with an ionization energy of ˜280 meV was identified in both absorber layers. The influence of fluctuating potentials in the electrical performance of the solar cells was discussed.

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

Detection of microstructural defects in chalcopyrite Cu(In,Ga)Se2 solar cells by spectrally-filtered electroluminescence

NASA Astrophysics Data System (ADS)

Skvarenina, L.; Gajdos, A.; Macku, R.; Skarvada, P.

2017-12-01

The aim of this research is to detect and localize microstructural defects by using an electrically excited light emission from a forward/reverse-bias stressed pn-junction in thin-film Cu(In; Ga)Se2 solar cells with metal wrap through architecture. A different origin of the local light emission from intrinsic/extrinsic imperfections in these chalcopyrite-based solar cells can be distinguished by a spectrally-filtered electroluminescence mapping. After a light emission mapping and localization of the defects in a macro scale is performed a micro scale exploration of the solar cell surface by a scanning electron microscope which follows the particular defects obtained by an electroluminescence. In particular, these macroscopic/microscopic examinations are performed independently, then the searching of the corresponding defects in the micro scale is rather difficult due to a diffused light emission obtained from the macro scale localization. Some of the defects accompanied by a highly intense light emission very often lead to a strong local overheating. Therefore, the lock-in infrared thermography is also performed along with an electroluminescence mapping.

The effects of Na on high pressure phases of CuIn(0.5)Ga(0.5)Se(2) from ab initio calculation.

PubMed

Pluengphon, P; Bovornratanaraks, T; Vannarat, S; Pinsook, U

2012-03-07

The effects of Na atoms on high pressure structural phase transitions of CuIn(0.5)Ga(0.5)Se(2) (CIGS) were studied by an ab initio method using density functional theory. At ambient pressure, CIGS is known to have chalcopyrite (I42d) structure. The high pressure phase transitions of CIGS were proposed to be the same as the order in the CuInSe(2) phase transitions which are I42d → Fm3m → Cmcm structures. By using the mixture atoms method, the Na concentration in CIGS was studied at 0.1, 1.0 and 6.25%. The positive mixing enthalpy of Na at In/Ga sites (Na(InGa)) is higher than that of Na at Cu sites (Na(Cu)). It confirmed previous studies that Na preferably substitutes on the Cu sites more than the (In, Ga) sites. From the energy-volume curves, we found that the effect of the Na substitutes is to reduce the hardness of CIGS under high pressure. The most significant effects occur at 6.25% Na. We also found that the electronic density of states of CIGS near the valence band maximum is increased noticeably in the chalcopyrite phase. The band gap is close in the cubic and orthorhombic phases. Also, the Na(Cu)-Se bond length in the chalcopyrite phase is significantly reduced at 6.25% Na, compared with the pure Cu-Se bond length. Consequently, the energy band gap in this phase is wider than in pure CIGS, and the gap increased at the rate of 31 meV GPa(-1) under pressure. The Na has a small effect on the transition pressure. The path of transformation from the cubic to orthorhombic phase was derived. The Cu-Se plane in the cubic phase displaced relatively parallel to the (In, Ga)-Se plane by 18% in order to transform to the Cmcm phase. The enthalpy barrier is 0.020 eV/atom, which is equivalent to a thermal energy of 248 K. We predicted that Fm3m and Cmcm can coexist in some pressure range.

Ionic liquids for metal extraction from chalcopyrite: solid, liquid and gas phase studies.

PubMed

Kuzmina, O; Symianakis, E; Godfrey, D; Albrecht, T; Welton, T

2017-08-16

We studied leaching of Cu and Fe from naturally occurring chalcopyrite ore using aqueous solutions of ionic liquids (ILs) based on imidazolium and ethylammonium cations and hydrogensulfate, nitrate, acetate or dicyanamide anions. Liquid, solid and gas phases of the leaching systems were characterised. We have shown that nonoxidative leaching is greatly dependant not only on temperature and pH, but on the anion species of the IL. Solutions of 1-butylimidazolium hydrogen sulfate exhibited the best leaching performance among hydrogen sulphate ILs. We have suggested that the formation of an oxide layer in some ILs may be responsible for a reduced leaching ability. The analysis of the gas phase showed the production of CO 2 and CS 2 in all leached samples. Our results suggested that the CS 2 produced upon leaching could be responsible for decreasing the sulfur, but not oxide, layer on the surface of chalcopyrite samples and therefore more efficient leaching. This is the first study, to our knowledge, to provide a systematic comparison of the leaching performance of ILs composed of different anions and cations and without added oxidants.

Numerical study of the electronic structure, elastic and optical properties of defect quaternary semiconductor CuGaSnSe4

NASA Astrophysics Data System (ADS)

Shen, Kesheng; Lu, Hai; Zhang, Xianzhou; Jiao, Zhaoyong

2018-06-01

The electronic structure, elastic and optical properties of the defect quaternary semiconductor CuGaSnSe4 in I 4 bar structure are systematically investigated using first-principles calculations. We summarize and discuss some of the studies on CuGaSnSe4 in partially ordered chalcopyrite structure and find that there are three atomic arrangements so far, but it is still uncertain which is the most stable. Through detailed simulation and comparison with the corresponding literature, we get three models and predict that M1 model should be the most stable. The band structure and optical properties of compound CuGaSnSe4, including dielectric constant, refractive index and absorption spectrum, are drawn for a more intuitive understanding. The elastic constants are also calculated, which not only prove that CuGaSnSe4 in I 4 bar structure is stable naturally but also help solve the problem of no data to accurately predict axial thermal expansion coefficients. The calculated values of the zero frequency dielectric constant and refractive index are comparable to those of the corresponding chalcopyrite structure but slightly larger.

Characterization of Primary Carrier Transport Properties of the Light-Harvesting Chalcopyrite Semiconductors CuIn(S 1–xSe x) 2

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

Frick, Jessica J.; Kushwaha, Satya K.; Cava, Robert J.

We report the carrier transport properties of CuIn(S 1-xSe x) 2 (0 ≤ x ≤ 1), a promising chalcopyrite semiconductor series for solar water splitting. A low concentration Mg dopant is used to decrease the carrier resistivity through facilitating bulk p-type transport at ambient temperature. Temperature-dependent resistivity measurements reveal a four-order magnitude decrease in bulk electrical resistivity (from 10 3 to 10 –1 Ohm cm) for 1% Mg-doped CuIn(S 1–xSe x) 2 as x increases from 0 to 1. Hall effect measurements at room temperature reveal p-type majority carrier concentrations that vary from 10 15 to 10 18 cm –3more » and mobilities of approximately 1–10 cm 2 V –1 s –1. These results provide insights into the fundamental carrier transport properties of CuIn(S 1–xSe x) 2 and will be of value in optimizing these materials further for photoelectrochemistry applications.« less

Characterization of Primary Carrier Transport Properties of the Light-Harvesting Chalcopyrite Semiconductors CuIn(S 1–xSe x) 2

DOE PAGES

Frick, Jessica J.; Kushwaha, Satya K.; Cava, Robert J.; ...

2017-07-27

We report the carrier transport properties of CuIn(S 1-xSe x) 2 (0 ≤ x ≤ 1), a promising chalcopyrite semiconductor series for solar water splitting. A low concentration Mg dopant is used to decrease the carrier resistivity through facilitating bulk p-type transport at ambient temperature. Temperature-dependent resistivity measurements reveal a four-order magnitude decrease in bulk electrical resistivity (from 10 3 to 10 –1 Ohm cm) for 1% Mg-doped CuIn(S 1–xSe x) 2 as x increases from 0 to 1. Hall effect measurements at room temperature reveal p-type majority carrier concentrations that vary from 10 15 to 10 18 cm –3more » and mobilities of approximately 1–10 cm 2 V –1 s –1. These results provide insights into the fundamental carrier transport properties of CuIn(S 1–xSe x) 2 and will be of value in optimizing these materials further for photoelectrochemistry applications.« less

Effects of solvents on the synthesis of CuInSe2 nanoparticles for thin film solar cells.

PubMed

Lee, Jaehyeong; Lee, Soo-Ho; Hahn, Jae-Sub; Sun, Ho-Jung; Park, Gyungse; Shim, Joongpyo

2014-12-01

Chalcopyrite CuInSe2 (CIS) nanoparticles were synthesized in oleic acid, 1-octadecene, oleyl amine and tetraethylene glycol at temperature above 200 degrees C. Depending on the solvent used and reaction temperature, the obtained nanoparticles had different shapes, sizes, chemical compositions, and crystal and thermal properties. CIS powders synthesized in oleic acid, 1-octadecene and oleyl amine above 200 degrees C exhibited chalcopyrite structure. On the other hand, powders prepared in tetraethylene glycol contained a mixture of CIS and CuSe compounds. The CIS powder obtained in oleyl amine had a high thermal stability over 500 degrees C. CIS thin films prepared from nanoparticles were heat-treated in order to observe changes in their property. After 10 min heat-treatment at 500 degrees C, their crystal structure and chemical composition were slightly changed, and their band gap energies were ca. 1.01 eV except in the case of powders prepared in tetraethylene glycol.

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.

Melt and metallic solution crystal growth of CuInSe 2

NASA Astrophysics Data System (ADS)

Baldus, A.; Benz, K. W.

1993-05-01

In this paper the fabrication of CuInSe 2 chalcopyrite single crystals by the vertical Bridgman technique using non-stoichiometric In 2Se 3-rich congruent composition and a novel ampoule design is describe. Furthermore the growth of CuInSe 2 crystals by the travelling heater method (THM) using an In solvent was investigated. The elemental composition of as-grown CuInSe 2 semiconducting compounds and their electrical properties are discussed and correlated with predictions made by an intrinsic chemistry model.

Structural, optical, electron paramagnetic, thermal and dielectric characterization of chalcopyrite.

PubMed

Prameena, B; Anbalagan, G; Gunasekaran, S; Ramkumaar, G R; Gowtham, B

2014-03-25

Chalcopyrite (CuFeS2) a variety of pyrite minerals was investigated through spectroscopic techniques and thermal analysis. The morphology and elemental analysis of the chalcopyrite have been done by high resolution SEM with EDAX. The lattice parameters were from the powder diffraction data (a=5.3003±0.0089 Å, c=10.3679±0.0289 Å; the volume of the unit cell=291.266 Å(3) with space group I42d (122)). The thermal decomposition behavior of chalcopyrite was studied by means of thermogravimetric analysis at three different heating rates 10, 15 and 20 °C/min. The values of effective activation energy (Ea), pre-exponential factor (ln A) for thermal decomposition have been measured at three different heating rates by employing Kissinger, Kim-Park and Flynn-Wall methods. Dielectric studies at different temperatures have also been carried out and it was found that both dielectric constant and dielectric loss decreases with the increase of frequency. Copyright © 2013 Elsevier B.V. All rights reserved.

Selective depression mechanism of ferric chromium lignin sulfonate for chalcopyrite-galena flotation separation

NASA Astrophysics Data System (ADS)

Yu, Jin-sheng; Liu, Run-qing; Wang, Li; Sun, Wei; Peng, Hong; Hu, Yue-hua

2018-05-01

Selective recovery of chalcopyrite-galena ore by flotation remains a challenging issue. The development of highly efficient, low-cost, and environmentally friendly depressants for this flotation is necessary because most of available reagents (e.g., K2Cr2O4) are expensive and adversely affect the environment. In this study, ferric chromium lignin sulfonate (FCLS), which is a waste-product from the paper and pulp industry, was introduced as a selective depressant for galena with butyl xanthate (BX) as a collector. Results show that the residue recovery of Pb in Cu concentrate was substantially reduced to 4.73% using FCLS compared with 10.71% using the common depressant K2Cr2O4. The underlying mechanisms were revealed using zeta-potential measurements and X-ray photoelectron spectroscopy (XPS). Zeta-potential measurements revealed that FCLS was more efficiently absorbed onto galena than onto chalcopyrite. XPS measurements further suggested that FCLS enhanced the surface oxidation of galena but prevented that of chalcopyrite. Thus, FCLS could be a potential candidate as a depressant for chalcopyrite-galena flotation because of its low cost and its lack of detrimental effects on the environment.

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

Bourlier, Yoan; Cristini Robbe, Odile; Laboratoire de Physique des Lasers, Atomes et Molécules

Highlights: • CuIn{sub (1−x)}Ga{sub x}S{sub 2} thin films were prepared by sol–gel process. • Evolution of lattice parameters is characteristic of a solid solution. • Optical band gap was found to be linearly dependent on the gallium rate. - Abstract: In this paper, we report the elaboration of Cu(In,Ga)S{sub 2} chalcopyrite thin films via a sol–gel process. To reach this aim, solutions containing copper, indium and gallium complexes were prepared. These solutions were thereafter spin-coated onto the soda lime glass substrates and calcined, leading to metallic oxides thin films. Expected chalcopyrite films were finally obtained by sulfurization of oxides layersmore » using a sulfur atmosphere at 500 °C. The rate of gallium incorporation was studied both at the solutions synthesis step and at the thin films sulfurization process. Elemental and X-ray diffraction (XRD) analyses have shown the efficiency of monoethanolamine used as a complexing agent for the preparation of CuIn{sub (1−x)}Ga{sub x}S{sub 2} thin layers. Moreover, the replacement of diethanolamine by monoethanolamine has permitted the substitution of indium by isovalent gallium from x = 0 to x = 0.4 and prevented the precipitation of copper derivatives. XRD analyses of sulfurized thin films CuIn{sub (1−x)}Ga{sub x}S{sub 2,} clearly indicated that the increasing rate of gallium induced a shift of XRD peaks, revealing an evolution of the lattice parameter in the chalcopyrite structure. These results were confirmed by Raman analyses. Moreover, the optical band gap was also found to be linearly dependent upon the gallium rate incorporated within the thin films: it varies from 1.47 eV for x = 0 to 1.63 eV for x = 0.4.« less

Platinum-group element concentrations in pyrite from the Main Sulfide Zone of the Great Dyke of Zimbabwe

NASA Astrophysics Data System (ADS)

Piña, R.; Gervilla, F.; Barnes, S.-J.; Oberthür, T.; Lunar, R.

2016-10-01

The Main Sulfide Zone (MSZ) of the Great Dyke of Zimbabwe hosts the world's second largest resource of platinum-group elements (PGE) after the Bushveld Complex in South Africa. The sulfide assemblage of the MSZ comprises pyrrhotite, pentlandite, chalcopyrite, and minor pyrite. Recently, several studies have observed in a number of Ni-Cu-PGE ore deposits that pyrite may host significant amounts of PGE, particularly Pt and Rh. In this study, we have determined PGE and other trace element contents in pyrite from the Hartley, Ngezi, Unki, and Mimosa mines of the Great Dyke by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Based on the textures and PGE contents, two types of pyrite can be differentiated. Py1 occurs as individual euhedral or subhedral grains or clusters of crystals mostly within chalcopyrite and pentlandite, in some cases in the form of symplectitic intergrowths, and is PGE rich (up to 99 ppm Pt and 61 ppm Rh; 1.7 to 47.1 ppm Ru, 0.1 to 7.8 ppm Os, and 1.2 to 20.2 ppm Ir). Py2 occurs as small individual euhedral or subhedral crystals within pyrrhotite, pentlandite, and less frequently within chalcopyrite and silicates and has low PGE contents (<0.11 ppm Pt, <0.34 ppm Rh, <2.5 ppm Ru, <0.37 ppm Ir, and <0.40 ppm Os). Py1 contains higher Os, Ir, Ru, Rh, and Pt contents than the associated pyrrhotite, pentlandite, and chalcopyrite, whereas Py2 has similar PGE contents as coexisting pyrrhotite and pentlandite. Based on the textural relationships, two different origins are attributed for each pyrite type. Py1 intergrowth with pentlandite and chalcopyrite is inferred to have formed by late, low temperature (<300 °C) decomposition of residual Ni-rich monosulfide solid solution, whereas Py2 is suggested to have formed by replacement of pyrrhotite and pentlandite caused by late magmatic/hydrothermal fluids.

Pressure-Induced Structural Transition and Enhancement of Energy Gap of CuAlO2

NASA Astrophysics Data System (ADS)

Nakanishi, Akitaka

2011-02-01

By using first-principles calculations, we studied the stable crystal structures and energy gaps of CuAlO2 under high pressure. Our simulation shows that CuAlO2 transforms from a delafossite structure to a leaning delafossite structure. The critical pressure of the transition was determined to be 60 GPa. The energy gap of CuAlO2 increases through the structural transition due to the enhanced covalency of Cu 3d and O 2p states. We found that a chalcopyrite structure does not appear as a stable structure under high pressure.

Self-organized antireflection CuIn(S,Se)2 nano-protrusions on flexible substrates by ion erosion based on CuInS2 nanocrystal precursor inks

NASA Astrophysics Data System (ADS)

Yen, Yu-Ting; Wang, Yi-Chung; Chen, Chia-Wei; Tsai, Hung-Wei; Chen, Yu-Ze; Hu, Fan; Chueh, Yu-Lun

2015-11-01

In this work, an approach to achieve surface nano-protrusions on a chalcopyrite CuIn(S,Se)2 thin film was demonstrated. Home-made CuInS2 nanocrystals with average diameter of 20 nm were prepared and characterized. By applying ion erosion process on the CuIn(S,Se)2 film, large-area self-aligned nano-protrusions can be formed. Interestingly, the process can be applied on flexible substrate where the CuIn(S,Se)2 film remains intact with no visible cracking after several bending tests. In addition, reflectance spectra reveal the extraordinary anti-reflectance characteristics of nano-protrusions on the CuIn(S,Se)2 film with the incident light from 350 to 2000 nm. A 36-cm2 CuIn(S,Se)2 film with nano-protrusions on flexible molybdenum foil substrate has been demonstrated, which demonstrated the feasibility of developing low cost with a high optical absorption CuIn(S,Se)2 flexible thin film.

Sulfide enrichment at an oceanic crust-mantle transition zone: Kane Megamullion (23°N, MAR)

NASA Astrophysics Data System (ADS)

Ciazela, Jakub; Koepke, Juergen; Dick, Henry J. B.; Botcharnikov, Roman; Muszynski, Andrzej; Lazarov, Marina; Schuth, Stephan; Pieterek, Bartosz; Kuhn, Thomas

2018-06-01

The Kane Megamullion oceanic core complex located along the Mid-Atlantic Ridge (23°30‧N, 45°20‧W) exposes lower crust and upper mantle directly on the ocean floor. We studied chalcophile elements and sulfides in the ultramafic and mafic rocks of the crust-mantle transition and the mantle underneath. We determined mineralogical and elemental composition and the Cu isotope composition of the respective sulfides along with the mineralogical and elemental composition of the respective serpentines. The rocks of the crust-mantle transition zone (i.e., plagioclase harzburgite, peridotite-gabbro contacts, and dunite) overlaid by troctolites are by one order of magnitude enriched in several chalcophile elements with respect to the spinel harzburgites of the mantle beneath. Whereas the range of Cu concentrations in spinel harzburgites is 7-69 ppm, the Cu concentrations are highly elevated in plagioclase harzburgites with a range of 90-209 ppm. The zones of the peridotite-gabbro contacts are even more enriched, exhibiting up to 305 ppm Cu and highly elevated concentrations of As, Zn, Ga, Sb and Tl. High Cu concentrations show pronounced correlation with bulk S concentrations at the crust-mantle transition zone implying an enrichment process in this horizon of the oceanic lithosphere. We interpret this enrichment as related to melt-mantle reaction, which is extensive in crust-mantle transition zones. In spite of the ubiquitous serpentinization of primary rocks, we found magmatic chalcopyrites [CuFeS2] as inclusions in plagioclase as well as associated with pentlandite [(Fe,Ni)9S8] and pyrrhotite [Fe1-xS] in polysulfide grains. These chalcopyrites show a primary magmatic δ65Cu signature ranging from -0.04 to +0.29 ‰. Other chalcopyrites have been dissolved during serpentinization. Due to the low temperature (<300 °C) of circulating fluids chalcophile metals from primary sulfides have not been mobilized and transported away but have been trapped in smaller secondary sulfides and hydroxides. Combined with the Cu deposits documented in the crust-mantle transition zones of various ophiolite complexes, our results indicate that the metal enrichment, increased sulfide modes, and potentially formation of small sulfide deposits could be expected globally along the petrological Moho.

The structure of reconstructed chalcopyrite surfaces

NASA Astrophysics Data System (ADS)

Thinius, Sascha; Islam, Mazharul M.; Bredow, Thomas

2018-03-01

Chalcopyrite (CuFeS2) surfaces are of major interest for copper exploitation in aqueous solution, called leaching. Since leaching is a surface process knowledge of the surface structure, bonding pattern and oxidation states is important for improving the efficiency. At present such information is not available from experimental studies. Therefore a detailed computational study of chalcopyrite surfaces is performed. The structures of low-index stoichiometric chalcopyrite surfaces {hkl} h, k, l ∈ {0, 1, 2} have been studied with density functional theory (DFT) and global optimization strategies. We have applied ab initio molecular dynamics (MD) in combination with simulated annealing (SA) in order to explore possible reconstructions via a minima hopping (MH) algorithm. In almost all cases reconstruction involving substantial rearrangement has occurred accompanied by reduction of the surface energy. The analysis of the change in the coordination sphere and migration during reconstruction reveals that S-S dimers are formed on the surface. Further it was observed that metal atoms near the surface move toward the bulk forming metal alloys passivated by sulfur. The obtained surface energies of reconstructed surfaces are in the range of 0.53-0.95 J/m2.

Simulation of Bioleaching Heat Effects for Enhancement of Copper Recovery from Sarcheshmeh Chalcopyrite

NASA Astrophysics Data System (ADS)

Mahmoudian, Ali Reza; Sadrnezhaad, S. K.; Manafi, Zahra

2014-08-01

A heat-transfer model was formulated to determine the distribution of temperature within a bioheap of chalcopyrite of Sarcheshmeh copper mine. Bioleaching employs mixed mesophilic and thermophilic microbes for Cu extraction. Thermophiles are better than mesophiles to dissolve CuFeS2. The solution irrigation and aeration rates were taken into account as the main operational factors. The model was validated by comparing the temperature profiles of test columns with those of bioheap. The model was used to find the optimal ratio of irrigation to aeration. It was found that when the solution was fed at a flow rate of 5 kg/m2 h and air was blown at a flow rate of 7.5 kg/m2 h, the transition from a mesophilic to thermophilic state inside the heap was possible. In this situation, the maximum temperature rise inside the heap was about 332 K (59 °C) after 60 days.

Pressure leaching of chalcopyrite concentrate

NASA Astrophysics Data System (ADS)

Aleksei, Kritskii; Kirill, Karimov; Stanislav, Naboichenko

2018-05-01

The results of chalcopyrite concentrate processing using low-temperature and high-temperature sulfuric acid pressure leaching are presented. A material of the following composition was used, 21.5 Cu, 0.1 Zn, 0.05 Pb, 0.04 Ni, 26.59 S, 24.52 Fe, 16.28 SiO2 (in wt.%). The influence of technological parameters on the degree of copper and iron extraction into the leach solution was studied in the wide range of values. The following conditions were suggested as the optimal for the high-temperature pressure leaching: t = 190 °C, PO2 = 0.5 MPa, CH2SO4 = 15 g/L, L:S = 6:1. At the mentioned parameters, it is possible to extract at least 98% Cu from concentrate into the leaching solution during 100 minutes. The following conditions were suggested as optimal for the low-temperature pressure leaching: t = 105 °C, PO2 = 1.3-1.5 MPa, CH2SO4 = 90 g/L, L:S = 10:1. At the mentioned parameters, it is possible to extract up to 83% Cu from the concentrate into the leach solution during 300-360 minutes.

Impact of Molecular Hydrogen on Chalcopyrite Bioleaching by the Extremely Thermoacidophilic Archaeon Metallosphaera sedula▿

PubMed Central

Auernik, Kathryne S.; Kelly, Robert M.

2010-01-01

Hydrogen served as a competitive inorganic energy source, impacting the CuFeS2 bioleaching efficiency of the extremely thermoacidophilic archaeon Metallosphaera sedula. Open reading frames encoding key terminal oxidase and electron transport chain components were triggered by CuFeS2. Evidence of heterotrophic metabolism was noted after extended periods of bioleaching, presumably related to cell lysis. PMID:20190092

Geologic setting, sedimentary architecture, and paragenesis of the Mesoproterozoic sediment-hosted Sheep Creek Cu-Co-Ag deposit, Helena embayment, Montana

USGS Publications Warehouse

Graham, Garth; Hitzman, Murray W.; Zieg, Jerry

2012-01-01

The northern margin of the Helena Embayment contains extensive syngenetic to diagenetic massive pyrite horizons that extend over 25 km along the Volcano Valley-Buttress fault zone and extend up to 8 km basinward (south) within the Mesoproterozoic Newland Formation. The Sheep Creek Cu-Co deposit occurs within a structural block along a bend in the fault system, where replacement-style chalcopyrite mineralization is spatially associated mostly with the two stratigraphically lowest massive pyrite zones. These mineralized pyritic horizons are intercalated with debris flows derived from synsedimentary movement along the Volcano Valley-Buttress fault zone. Cominco American Inc. delineated a geologic resource of 4.5 Mt at 2.5% Cu and 0.1% Co in the upper sulfide zone and 4 Mt at 4% Cu within the lower sulfide zone. More recently, Tintina Resources Inc. has delineated an inferred resource of 8.48 Mt at 2.96% Cu, 0.12% Co, and 16.4 g/t Ag in the upper sulfide zone. The more intact upper sulfide zone displays significant thickness variations along strike thought to represent formation in at least three separate subbasins. The largest accumulation of mineralized sulfide in the upper zone occurs as an N-S–trending body that thickens southward from the generally E trending Volcano Valley Fault and probably occupies a paleograben controlled by normal faults in the hanging wall of the Volcano Valley Fault. Early microcrystalline to framboidal pyrite was accompanied by abundant and local barite deposition in the upper and lower sulfide zones, respectively. The sulfide bodies underwent intense (lower sulfide zone) to localized (upper sulfide zone) recrystallization and overprinting by coarser-grained pyrite and minor marcasite that is intergrown with and replaces dolomite. Silicification and paragenetically late chalcopyrite, along with minor tennantite in the upper sulfide zone, replaces fine-grained pyrite, barite, and carbonate. The restriction of chalcopyrite to inferred synsedimentary E- and northerly trending faults and absence of definitive zonation with respect to the Laramide Volcano Valley Fault in the lower sulfide zone suggest a diagenetic age related to basin development for the Sheep Creek Cu-Co-Ag deposit.

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.

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

USGS Publications Warehouse

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

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite. ?? Springer-Verlag 2006.

Doping effect on the thermoelectric properties of chalcopyrite CuGaTe2

NASA Astrophysics Data System (ADS)

Sharma, Sonu; Singh, Birender; Kumar, Pradeep

2018-05-01

In the present work, we have investigated the thermoelectric properties of CuGaTe2 by combining the first principle calculations with Boltzmann transport theory. CuGaTe2 is found to be a potential thermoelectric material with Seebeck coefficient 275µVK-1 at 200K. The thermoelectric properties of the compound can be further improved by doping it with p as well as n-type charge carriers. The heavily p-doped and lightly n-doped, CuGaTe2 provides power factor comparable to that of state-of-art Bi2Te3.

Structural and optical properties of (Ag,Cu)(In,Ga)Se{sub 2} polycrystalline thin film alloys

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

Boyle, J. H.; Shafarman, W. N.; Birkmire, R. W.

2014-06-14

The structural and optical properties of pentenary alloy (Ag,Cu)(In,Ga)Se{sub 2} polycrystalline thin films were characterized over the entire compositional range at a fixed (Cu + Ag)/(In + Ga) ratio. Films deposited at 550 °C on bare and molybdenum coated soda-lime glass by elemental co-evaporation in a single-stage process with constant incident fluxes exhibit single phase chalcopyrite structure, corresponding to 122 spacegroup (I-42d) over the entire compositional space. Unit cell refinement of the diffraction patterns show that increasing Ag substitution for Cu, the refined a{sub o} lattice constant, (Ag,Cu)-Se bond length, and anion displacement increase in accordance with the theoretical model proposed by Jaffe, Wei, andmore » Zunger. However, the refined c{sub o} lattice constant and (In,Ga)-Se bond length deviated from theoretical expectations for films with mid-range Ag and Ga compositions and are attributed to influences from crystallographic bond chain ordering or cation electronegativity. The optical band gap, derived from transmission and reflection measurements, widened with increasing Ag and Ga content, due to influences from anion displacement and cation electronegativity, as expected from theoretical considerations for pseudo-binary chalcopyrite compounds.« less

CuInS2 Films Deposited by Aerosol-Assisted Chemical Vapor Deposition Using Ternary Single-Source Precursors

NASA Technical Reports Server (NTRS)

Jin, Michael; Banger, Kal; Harris, Jerry; Hepp, Aloysius

2003-01-01

Polycrystalline CuInS2 films were deposited by aerosol-assisted chemical vapor deposition using both solid and liquid ternary single-source precursors (SSPs) which were prepared in-house. Films with either (112) or (204/220) preferred orientation, had a chalcopyrite structure, and (112)-oriented films contained more copper than (204/220)-oriented films. The preferred orientation of the film is likely related to the decomposition and reaction kinetics associated with the molecular structure of the precursors at the substrate. Interestingly, the (204/220)-oriented films were always In-rich and were accompanied by a secondary phase. From the results of post-growth annealing, etching experiments, and Raman spectroscopic data, the secondary phase was identified as an In-rich compound. On the contrary, (112)-oriented films were always obtained with a minimal amount of the secondary phase, and had a maximum grain size of about 0.5 micron. Electrical and optical properties of all the films grown were characterized. They all showed p-type conduction with an electrical resistivity between 0.1 and 30 Omega-cm, and an optical band gap of approximately 1.46 eV +/- 0.02, as deposited. The material properties of deposited films revealed this methodology of using SSPs for fabricating chalcopyrite-based solar cells to be highly promising.

Optimization of staged bioleaching of low-grade chalcopyrite ore in the presence and absence of chloride in the irrigating lixiviant: ANFIS simulation.

PubMed

Vakylabad, Ali Behrad; Schaffie, Mahin; Naseri, Ali; Ranjbar, Mohammad; Manafi, Zahra

2016-07-01

In this investigation, copper was bioleached from a low-grade chalcopyrite ore using a chloride-containing lixiviant. In this regard, firstly, the composition of the bacterial culture media was designed to control the cost in commercial application. The bacterial culture used in this process was acclimated to the presence of chloride in the lixiviant. Practically speaking, the modified culture helped the bio-heap-leaching system operate in the chloridic media. Compared to the copper recovery from the low-grade chalcopyrite by bioleaching in the absence of chloride, bioleaching in the presence of chloride resulted in improved copper recovery. The composition of the lixiviant used in this study was a modification with respect to the basal salts in 9 K medium to optimize the leaching process. When leaching the ore in columns, 76.81 % Cu (based on solid residues of bioleaching operation) was recovered by staged leaching with lixiviant containing 34.22 mM NaCl. The quantitative findings were supported by SEM/EDS observations, X-ray elemental mapping, and mineralogical analysis of the ore before and after leaching. Finally, Adaptive neuro-fuzzy inference system (ANFIS) was used to simulate the operational parameters affecting the bioleaching operation in chloride-sulfate system.

Subsurface deposition of Cu-rich massive sulphide underneath a Palaeoproterozoic seafloor hydrothermal system—the Red Bore prospect, Western Australia

NASA Astrophysics Data System (ADS)

Agangi, Andrea; Reddy, S. M.; Plavsa, D.; Vieru, C.; Selvaraja, V.; LaFlamme, C.; Jeon, H.; Martin, L.; Nozaki, T.; Takaya, Y.; Suzuki, K.

2018-02-01

The Proterozoic Bryah and Yerrida basins of Western Australia contain important base and precious metal deposits. Here we present microtextural data, trace element and S isotope analyses of massive sulphide mineralisation hosted in Palaeoproterozoic subvolcanic rocks (dolerite) recently discovered at Red Bore. The small-scale high-grade mineralisation, which extends from the sub-surface to at least 95 m down-hole, is dominated by massive chalcopyrite and contains minor pyrite and Bi-Te-(Se) phases. Massive sulphide mineralisation is surrounded by discontinuous brecciated massive magnetite, and a narrow (< 2 m) alteration halo, which suggests very focussed fluid flow. Laser ablation ICP-MS analyses indicate that chalcopyrite contains up to 10 ppm Au and in excess of 100 ppm Ag. Sulphur isotope analyses of pyrite and chalcopyrite indicate a narrow range of δ34SVCD (- 0.2 to + 4.6 ‰), and no significant mass-independent fractionation (- 0.1 < Δ33S < + 0.05 ‰). Re-Os isotope analyses yield scattered values, which suggests secondary remobilisation. Despite the geographical proximity and the common Cu-Au-Ag association, the mineralisation at Red Bore has significant differences with massive sulphide mineralisation at neighbouring DeGrussa, as well as other massive sulphide deposits around the world. These differences include the geometry, sub-volcanic host rocks, extreme Cu enrichment and narrow δ34S ranges. Although a possible explanation for some of these characteristics is leaching of S and metals from the surrounding volcanic rocks, we favour formation as a result of the release of a magmatic fluid phase along very focussed pathways, and we propose that mixing of this fluid with circulating sea water contributed to sea floor mineralisation similar to neighbouring VHMS deposits. Our data are permissive of a genetic association of Red Bore mineralisation with VHMS deposits nearby, thus suggesting a direct connection between magmatism and mineralising fluids responsible for VHMS deposition at surface. Therefore, the Red Bore mineralisation may represent the magmatic roots of a VHMS system.

Chalcogen Polymers for Completely Solution-Processed Inorganic Photovoltaics

NASA Astrophysics Data System (ADS)

Martin, Trevor R.

Chalcopyrite materials such as CuInSxSe2-x (CISSe), the gallium alloy variant CuInxGa1-xSySe2-y (CIGSSe), and the earth-abundant kesterite material Cu2ZnSnS xSe4-x (CZTSSe) possess a range of properties that are ideally suited for thin-film photovoltaics (PV) applications. Although these materials are beginning to see some commercial success, they are manufactured using complicated and expensive techniques such as high temperature processing, vacuum deposition methods, and vapor-phase reactions. These production methods require an exorbitantly large capital investment to create new manufacturing facilities, which severely hampers the widespread and rapid deployment of these emerging solar energy technologies. This work has focused on developing novel chalcogen polymers to synthesize nanoparticles and produce thin-films for printed photovoltaics applications. This new method provides a pathway towards using chalcogen copolymers to produce these materials via a completely solution-processed, low-temperature fabrication procedure. This technique constitutes one of the first viable means to produce low-bandgap chalcogenides without additional vapor-phase or high-temperature reactions. Therefore, this process can potentially be implemented to rapidly and cheaply manufacture printed chalcopyrite and kesterite photovoltaics.

Cu-In Halide Perovskite Solar Absorbers.

PubMed

Zhao, Xin-Gang; Yang, Dongwen; Sun, Yuanhui; Li, Tianshu; Zhang, Lijun; Yu, Liping; Zunger, Alex

2017-05-17

The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in ns 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu(d)/Se(p) → Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6 , Rb 2 [AgIn]Br 6 , and Cs 2 [AgIn]Br 6 , having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar absorbers.

Metal mobilisation in hydrothermal sediments at the TAG Hydrothermal Field (MAR, 26°N)

NASA Astrophysics Data System (ADS)

Dutrieux, A. M.; Lichtschlag, A.; Martins, S.; Barriga, F. J.; Petersen, S.; Murton, B. J.

2017-12-01

Metalliferous sediments in the vicinity of hydrothermal systems are enriched in base metals, but few studies have addressed their potential as mineral resources. These metalliferous sediments have been accumulated by different processes and reflect modifications of the primary mineral deposits by: oxidation of the chimney materials, in situ precipitation of low-temperature minerals and mass wasting. To understand the post-formation processes in metalliferous sediments, we investigated sub-seafloor metal mobilisation in different geological environments. This presentation focuses on the TAG Hydrothermal Field (Mid-Atlantic Ridge, 26°N) and explores sediment and pore water compositions using ICP-MS and ICP-OES. We use reactive transport modelling to interpret the degree of metal remobilisation and to identify the most important geochemical reactions in the different sediments. The pore water concentrations measured in sediments above inactive sulphide mounds present constant major elements composition that indicates this environment is dominated by complete exchange with seawater. The sediments, that are mainly composed of hematite and goethite formed during the oxidation of sulphides, have low Cu concentrations (< 0.1%) and the main part of their primary Cu and Zn content has likely been mobilized. Cu concentrations increase at the edges of the mounds (up to wt. 20%) or in distal depositionary channels (up to wt.10%) where sulphide minerals (e.g. pyrite, chalcopyrite and sphalerite) are still present in the sediments and capped by more recent sediment slumping. In the depositionary channels, pore waters show metal concentrations affected by diagenesis and redox-sensitive metals are released at depth (e.g. Mn2+ and Cu2+). The leaching of the primary sulphides (e.g. deprecated grains of chalcopyrite), and metal mobilisation lead to an enrichment of Cu and Zn at shallower depth. Here, some stratigraphic horizons scavenge metallic cations back into solid phases and form Mn-oxide crusts between 30 and 60 cm, in which Cu concentrations also increase. Our results demonstrate that metal mobilisation differs depending on the geological environment and their related accumulation processes, causing the absence of Cu on the top of inactive hydrothermal mounds but enriched in more distal sediment basins.

Hydrometallurgical Extraction of Zinc and Copper A 57Fe-Mössbauer and XRD Approach

NASA Astrophysics Data System (ADS)

Mulaba-Bafubiandi, A. F.; Waanders, F. B.

2005-02-01

The most commonly used route in the hydrometallurgical extraction of zinc and copper from a sulphide ore is the concentrate roast leach electro winning process. In the present investigation a zinc copper ore from the Maranda mine, located in the Murchison Greenstone Belt, South Africa, containing sphalerite (ZnS) and chalcopyrite (CuFeS2), was studied. The 57Fe-Mössbauer spectrum of the concentrate yielded pyrite, chalcopyrite and clinochlore, consistent with XRD data. Optimal roasting conditions were found to be 900°C for 3 h and the calcine produced contained according to X-ray diffractometry equal amounts of franklinite (ZnFe2O4) and zinc oxide (ZnO) and half the amount of willemite (Zn2SiO4). The Mössbauer spectrum showed predominantly franklinite (59%), hematite (6%) and other Zn- or Cu-depleted ferrites (35%). The latter could not be detected by XRD analyses as peak overlapping with other species occurred. Leaching was done with HCl, H2SO4 and HNO3, to determine which process would result in maximum recovery of Zn and Cu. More than 80% of both were recovered by using either one of the three techniques. From the residue of the leaching, the Fe-compounds were precipitated and <1% of the Zn and Cu was not recovered.

Chalcopyrite dissolution: Scanning photoelectron microscopy examination of the evolution of sulfur species with and without added iron or pyrite

NASA Astrophysics Data System (ADS)

Li, Yubiao; Qian, Gujie; Brown, Paul L.; Gerson, Andrea R.

2017-09-01

Dissolution and oxidation of sulfide minerals play key roles in both acid and metalliferous rock drainage and supergene enrichment. Surface speciation heterogeneity, critical to understanding mechanisms of mineral sulfide dissolution, has to date largely not been considered. To this end synchrotron scanning photoelectron microscopy (SPEM) was employed to examine freshly fractured and partially dissolved chalcopyrite (CuFeS2) surfaces (pH 1.0 HClO4 solution, redox potential 650 mV relative to a standard hydrogen electrode, 75 °C). S2- (bulk), S22- and Sn2- were found to be present on all samples at varying concentrations. Oxidation was observed to take place heterogeneously at the sub-micron scale. As compared to chalcopyrite partially dissolved for 5 days, extended dissolution to 10 days did not show appreciably enhanced oxidation of surface species; however surface roughness increased markedly due to the growth/overlap of oxidised sulfur species. On addition of 4 mM iron both S0 and SO42- were observed but not SO32-, indicating that the greater Fe3+ activity/concentration promotes heterogeneous sulfur oxidation. On contact of pyrite (FeS2) with chalcopyrite, significantly greater chalcopyrite surface oxidation was observed than for the other systems examined, with S0, SO32- and SO42- being identified heterogeneously across the surface. It is proposed that chalcopyrite oxidative dissolution is enhanced by increasing its cathodic area, e.g. contacting with pyrite, while increased Fe3+ activity/concentration also contributes to increased dissolution rates. The high degree of surface heterogeneity of these surface products indicates that these surfaces are not passivated by their formation. These results suggest that chalcopyrite dissolution will be accelerated when in contact with pyrite at solution redox potential intermediate between the rest potentials of chalcopyrite and pyrite (560 mV and 660 mV, respectively) and/or iron rich acidic waters with resulting enhanced formation of secondary sulfur containing species and release of copper and iron. This in turn suggests accelerated supergene formation and enhanced metalliferous drainage under these conditions.

Polymorph engineering of CuMO2 (M = Al, Ga, Sc, Y) semiconductors for solar energy applications: from delafossite to wurtzite.

PubMed

Scanlon, David O; Walsh, Aron

2015-12-01

The cuprous oxide based ternary delafossite semiconductors have been well studied in the context of p-type transparent conducting oxides. CuAlO2, CuGaO2 and CuInO2 represent a homologous series where the electronic properties can be tuned over a large range. The optical transparency of these materials has been associated with dipole forbidden transitions, which are related to the linear O-Cu-O coordination motif. The recent demonstration that these materials can be synthesized in tetrahedral structures (wurtzite analogues of the chalcopyrite lattice) opens up a new vista of applications. We investigate the underlying structure-property relationships (for Group 3 and 13 metals), from the perspective of first-principles materials modelling, towards developing earth-abundant photoactive metal oxides. All materials studied possess indirect fundamental band gaps ranging from 1 to 2 eV, which are smaller than their delafossite counterparts, although in all cases the difference between direct and indirect band gaps is less than 0.03 eV.

Involvement of magmatic fluids at the Laloki and Federal Flag massive sulfide Cu-Zn-Au-Ag deposits, Astrolabe mineral district, Papua New Guinea: sulfur isotope evidence

NASA Astrophysics Data System (ADS)

Noku, Shadrach K.; Espi, Joseph O.; Matsueda, Hiroharu

2015-01-01

We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu-Zn-Au-Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite-marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from -4.5 to +7.0 ‰ ( n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of -1.9 to +4.7 ‰ ( n = 16). The mineralizing stage these correspond to had moderately saline (5.9-8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of -36.1 to -33.8 ‰ ( n = 2), which suggest an organic source for S. Pyrite-marcasite and chalcopyrite from Federal Flag show δ34S values of -2.4 to -1.9 ‰ ( n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic-hydrothermal fluids. The very narrow range and near-zero δ34S values (-1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.

Rapid thermal processing for production of chalcopyrite thin films for solar cells: Design, analysis, and experimental implementation

NASA Astrophysics Data System (ADS)

Lovelett, Robert J.

The direct conversion of solar energy to electricity, or photovoltaic energy conversion, has a number of environmental, social, and economic advantages over conventional electricity generation from fossil fuels. Currently, the most commonly-used material for photovoltaics is crystalline silicon, which is now produced at large scale and silicon-based devices have achieved power conversion efficiencies over 25% However, alternative materials, such as inorganic thin films, offer a number of advantages including the potential for lower manufacturing costs, higher theoretical efficiencies, and better performance in the field. One of these materials is the chalcopyrite Cu(InGa)(SeS) 2, which has demonstrated module efficiencies over 17% and cell efficiencies over 22%. Cu(InGa)(SeS)2 is now in the early stages of commercialization using a precursor reaction process referred to as a "selenization/sulfization" reaction. The precursor reaction process is promising because it has demonstrated high efficiency along with the large area (approximately 1 m2) uniformity that is required for modules. However, some challenges remain that limit the growth of the chalcopyrite solar cell industry including: slow reactions that limit process throughput, a limited understanding of complex reaction kinetics and transport phenomena that affect the through-film composition, and the use of highly toxic H2Se in the reaction process. In this work, I approach each of these challenges. First, to improve process throughput, I designed and implemented a rapid thermal processing (RTP) reactor, whereby the samples are heated by a 1000 W quartz-halogen lamp that is capable of fast temperature ramps and high temperature dwells. With the reactor in place, however, achieving effective temperature control in the thin film material system is complicated by two intrinsic process characteristics: (i) the temperature of the Cu(InGa)(SeS)2 film cannot be measured directly, which leaves the system without complete state feedback; and (ii), the process is significantly nonlinear due to the dominance of radiative heat transfer at high temperatures. Therefore, I developed a novel control system using a first principles-based observer and a specialized temperature controller. Next, to understand the complex kinetics governing the selenization/sulfization processes, a stochastic model of solid state reaction kinetics was developed and applied to the system. The model is capable of predicting several important phenomena observed experimentally, including steep through-film gradients in gallium mole fraction. Furthermore, the model is mathematically general and can be useful for understanding a number of solid state reaction systems. Finally, the RTP system was then used to produce and characterize chalcopyrite films using two general methods: (i) single stage and multi stage reactions in H2Se and H2S, and (ii), reaction of a selenium "capped" precursor in H2S, where selenium was deposited on the precursor by thermal evaporation and the use of toxic H2Se was avoided. It was found that the processing conditions could be used to control material properties including relative sulfur incorporation, crystallinity, and through-film gallium and sulfur profiles. Films produced using the selenium-capped precursor reaction process were used to fabricate solar cell devices using a Mo/Cu(InGa)(SeS)2/CdS/ZnO/ITO substrate device structure, and the devices were tested by measuring the current-voltage characteristic under standard conditions. Devices with approximately 10% efficiency were obtained over a range of compositions and the best device obtained in this work had an efficiency of 12.7%.

Synthesis and Characterization of Chalcopyrite (CuInS2 and CuhInSe2) Colloidal Nanoparticles for Optoelectronic Applications via Low-Temperature Pyrolysis of Single-Source Precursors

NASA Technical Reports Server (NTRS)

Castro, S. L.; Bailey, S. G.; Raffaelle, R. P.; Banger, K. K.; Fahey, Stephen; Hepp, A. F.

2003-01-01

Nanocrystalline (or quantum dot) materials hold potential as components of next-generation photovoltaic (PV) devices. The inclusion of quantum dots in PV devices has been proposed as a means to improve the efficiency of photon conversion (quantum dot solar cell), enable low-cost deposition of thin-films, provide sites for exciton dissociation, and pathways for electron transport. Quantum dots are also expected to be more resistant to degradation from electron, proton, and alpha particle radiation than the corresponding bulk material, a requirement for use in space solar sells. Chalcopyrite nanocrystals can be produced by low-temperature thermal decomposition of single-source precursors such as (PR3)2CuIn(ER')4 (R = Ph, R' = Et, E = S; R = R' = Ph, E = Se). Single-source precursors are molecules which contain all the necessary elements for synthesis of a desired material. Thermal decomposition of the precursor results in the formation of material with the correct stoichiometry as a nanocrystalline powder or a thin film, often at significantly lower temperatures than those typically employed for thin-film deposition by multi-source evaporation techniques, typically less than 500 C. We show that CuInSz and CuInSe2 nanocrystals can be synthesized from the precursors at temperatures as low as 250 C. The nanocrystals are characterized by optical spectroscopy, X-ray diffraction, and electron microscopy.

Spray Chemical Vapor Deposition of CulnS2 Thin Films for Application in Solar Cell Devices

NASA Technical Reports Server (NTRS)

Hollingsworth, Jennifer A.; Buhro, William E.; Hepp, Aloysius F.; Jenkins. Philip P.; Stan, Mark A.

1998-01-01

Chalcopyrite CuInS2 is a direct band gap semiconductor (1.5 eV) that has potential applications in photovoltaic thin film and photoelectrochemical devices. We have successfully employed spray chemical vapor deposition using the previously known, single-source, metalorganic precursor, (Ph3P)2CuIn(SEt)4, to deposit CuInS2 thin films. Stoichiometric, polycrystalline films were deposited onto fused silica over a range of temperatures (300-400 C). Morphology was observed to vary with temperature: spheroidal features were obtained at lower temperatures and angular features at 400 C. At even higher temperatures (500 C), a Cu-deficient phase, CuIn5S8, was obtained as a single phase. The CuInS2 films were determined to have a direct band gap of ca. 1.4 eV.

Elastic, vibration and thermodynamic properties of Cu1‑x Ag x InTe2 (x = 0, 0.25, 0.5, 0.75 and 1) chalcopyrite compounds via first principles

NASA Astrophysics Data System (ADS)

Zhong, Yuhan; Wang, Peida; Mei, Huayue; Jia, Zhenyuan; Cheng, Nanpu

2018-06-01

CuInTe2 chalcopyrite compound is widely used in the fields of optoelectronics and pyroelectricity, and doping atoms can further improve the physical properties of the CuInTe2 compound. For all we know, this is the first time that the elastic behaviors and lattice dynamical properties of Ag-doped CuInTe2 compounds with the tetragonal system are determined theoretically. The elastic, lattice dynamical and thermal properties of Cu1‑x Ag x InTe2 (x = 0, 0.25, 0.5, 0.75 and 1) compounds have been investigated by using density functional theory. The obtained elastic constants of Cu1‑x Ag x InTe2 compounds indicate that these compounds are mechanically stable and elastic anisotropic. The anisotropy of the {001} plane is more obvious than those of the {100} and {010} planes. Additionally, with increasing Ag doping concentrations, the bulk and shear moduli of Cu1‑x Ag x InTe2 compounds decrease and their toughness improves. The phonon spectra and density of states reveal that Cu (or Ag) atoms in Cu1‑x Ag x InTe2 compounds form chemical bonds with Te atoms, and Cu-Te bonds are gradually replaced by Ag-Te bonds with increasing Ag doping concentration. Vibration modes of Cu1‑x Ag x InTe2 compounds at the {{Γ }} point in the Brillouin zone show that each Cu1‑x Ag x InTe2 (x = 0 and 1) crystal includes five irreducible representations (A1, A2, B1, B2 and E). As for Cu1‑x Ag x InTe2 (x = 0.25, 0.5 and 0.75) compounds, each crystal has three irreducible representations (A, B and E). The atomic displacements of several typical phonon modes in CuInTe2 crystals have been analyzed to deepen the understanding of lattice vibrations in Cu1‑x AgxInTe2 compounds. With increasing Ag doping concentration, the Debye temperatures of Cu1‑x Ag x InTe2 compounds decrease, while their heat capacities increase.

Characteristics of the Late Devonian Tsagaan Suvarga Cu-Mo deposit, Southern Mongolia

NASA Astrophysics Data System (ADS)

Tungalag, Naidansuren; Jargalan, Sereenen; Khashgerel, Bat-Erdene; Mijiddorj, Chuluunbaatar; Kavalieris, Imants

2018-05-01

The Late Devonian Tsagaan Suvarga deposit (255 Mt at 0.55% Cu, 0.02% Mo) is located on the NW margin of the Tsagaan Suvarga Complex (TSC), which extends ENE over 15 × 10 km and comprises mainly medium-grained equigranular hornblende-biotite quartz monzonite and monzodiorite. Distinct mineralized intrusions are inferred from distribution of Cu-Mo mineralization but are not clearly discernible. The Tsagaan Suvarga Complex is a window within Carboniferous volcanic and sedimentary rocks, and wall rocks to the TSC are not known or exposed in the nearby district. Whole-rock analyses and Sr-Nd isotopes, 87Sr/86Sr0 = 0.7027 to 0.7038 (n = 12) and ɛNd0 = + 4.26 to + 2.77 (n = 12), show that the granitoids are subduction-related I-type, high K-calc-alkaline to shoshonitic series and derived from a mantle source. They exhibit fractionated light rare earth elements, without depleted Eu and depleted middle heavy rare earth elements and Y, typical of oxidized, fertile porphyry magmatic suites. Early porphyry-style quartz veins include A- and B-type. Molybdenite occurs in monomineralic veins (1-5 mm) or A veins. Copper mineralization occurs mainly as chalcopyrite and subordinate bornite, disseminated and associated with quartz-muscovite veins. Pyrite (vol%) content is less than chalcopyrite and bornite combined. Deep oxidation to about 50 m depth has formed zones of malachite and covellite in late fractures. The most important alteration is actinolite-biotite-chlorite-magnetite replacing hornblende and primary biotite. Quartz-K-feldspar alteration is minor. Late albite replaces primary K-feldspar and enhances sodic rims on plagioclase crystals. Quartz-muscovite (or sericitic alteration) overprints actinolite-biotite and porphyry-type quartz veins. Field observations and petrographic studies suggest that the bulk of the chalcopyrite-bornite mineralization at the Tsagaan Suvarga formed together with coarse muscovite alteration.

Polymorph engineering of CuMO2 (M = Al, Ga, Sc, Y) semiconductors for solar energy applications: from delafossite to wurtzite

PubMed Central

Scanlon, David O.; Walsh, Aron

2015-01-01

The cuprous oxide based ternary delafossite semiconductors have been well studied in the context of p-type transparent conducting oxides. CuAlO2, CuGaO2 and CuInO2 represent a homologous series where the electronic properties can be tuned over a large range. The optical transparency of these materials has been associated with dipole forbidden transitions, which are related to the linear O—Cu—O coordination motif. The recent demonstration that these materials can be synthesized in tetrahedral structures (wurtzite analogues of the chalcopyrite lattice) opens up a new vista of applications. We investigate the underlying structure–property relationships (for Group 3 and 13 metals), from the perspective of first-principles materials modelling, towards developing earth-abundant photoactive metal oxides. All materials studied possess indirect fundamental band gaps ranging from 1 to 2 eV, which are smaller than their delafossite counterparts, although in all cases the difference between direct and indirect band gaps is less than 0.03 eV. PMID:26634726

Geochemical element mobility during the hydrothermal alteration in the Tepeoba porphyry Cu-Mo-Au deposits at Balikesir, NW Turkey

NASA Astrophysics Data System (ADS)

Abdelnasser, Amr; Kiran Yildirim, Demet; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Tepeoba porphyry Cu-Mo-Au deposit represents one of the important copper source and mineral deposits in the Anatolian tectonic belt at Balikesir province, NW Turkey. It considered as a vein-type deposit locally associated with intense hydrothermal alteration within the brecciation, quartz stockwork veining, and brittle fracture zones in the main host rock that represented by hornfels, as well as generally related to the shallow intermediate to silicic intrusive Eybek pluton. Based on the field and geologic relationships and types of ore mineral assemblages and the accompanied alteration types, there are two mineralization zones; hypogene (primary) and oxidation/supergene zones are observed associated with three alteration zones; potassic, phyllic, and propylitic zones related to this porphyry deposit. The phyllic and propylitic alterations locally surrounded the potassic alteration. The ore minerals related to the hypogene zone represented by mostly chalcopyrite, Molybdenite, and pyrite with subordinate amount of marcasite, enargite, and gold. On the other hand they include mainly cuprite with chalcopyrite, pyrite and gold as well as hematite and goethite at the oxidation/supergene zone. This study deals with the quantitative calculations of the mass/volume changes (gains and losses) of the major and trace elements during the different episodes of alteration in this porphyry deposit. These mass balance data reveal that the potassic alteration zone that the main Cu- and Mo-enriched zone, has enrichment of K, Si, Fe, and Mg, and depletion of Na referring to replacement of plagioclase and amphibole by K-feldspar, sericite and biotite. While the propylitic alteration that is the main Mo- and Au-enriched zone is accompanied with K and Na depletion with enrichment of Si, Fe, Mg, and Ca forming chlorite, epidote, carbonate and pyrite. On the other hand the phyllic alteration that occurred in the outer part around the potassic alteration, characterized by less amount of Cu and Mo mineralization having addition of Si and K with removal of Fe, Mg, Ca, and Na. Keywords: Mass balance calculation; Tepeoba porphyry Cu-Mo-Au deposits; Balikesir; Turkey

Characteristics and 40Ar/39Ar geochronology of the Erdenet Cu-Mo deposit, Mongolia

USGS Publications Warehouse

Kavalieris, Imants; Khashgerel, Bat-Erdene; Morgan, Leah; Undrakhtamir, Alexander; Borohul, Adiya

2017-01-01

The Early to Middle Triassic Erdenet porphyry Cu-Mo deposit, in northern Mongolia, developed in a continent-continent arc collision zone, within the Central Asian orogenic belt. The porphyry system is related to multiple intrusions of crystal-crowded biotite granodiorite porphyry, which formed a composite stock about 900 m in diameter, with multiple porphyritic microgranodiorite dikes. Wall rocks are Late Permian to Early Triassic, medium-grained granodiorite, with similar whole-rock geochemistry, mineralogy, and composition to the granodiorite porphyry. Whole-rock analysis of the granodiorite porphyry and wall rocks shows that these rocks cannot be discriminated, but both have depleted middle heavy rare earth elements and Y, typical of fertile porphyry magmatic suites.At the current pit level (1,250 m elev), early porphyry-style quartz veins (A and B type) are locally infilled by pyrite-chalcopyrite, with subordinate bornite, but most of the chalcopyrite occurs in D veins that constitute more than 50% of the Cu grade (~0.5 wt % Cu). The 0.3 wt % Cu shell resembles a molar tooth, enveloping the granodiorite porphyry, with deeper roots extending down the wal-rock contacts. Molybdenite occurs in monomineralic veins, and in finely laminated to massive quartz-molybdenite veins.The most important alteration is quartz-muscovite, which occurs as relatively coarse (100–500 μm) alteration selvages (1–5 cm) that envelop D veins. The D veins cut illite ± kaolinite-smectite (or intermediate argillic) alteration. Intermediate argillic alteration, together with abundant pink anhydrite (commonly hydrated to gypsum), extends from at least 1,300- to 900-m elevation in the deepest drill holes, and has overprinted early potassic alteration, or relatively unaltered red granodiorite. Meter-wide zones of kaolinite cut the anhydrite-gypsum at all levels. There is an abrupt transition outward from the intermediate argillic alteration to chlorite-epidote (propylitic) alteration, at 50 to 200 m from the granodiorite porphyry contact, although D veins (and chalcopyrite) extend outward to the propylitic zone.The Erdenet porphyry system, was overprinted by advanced argillic alteration, which outcrops 2 km northwest of the pit, and forms a lithocap that extends over 10 × 2.5 km. It is characterized by residual quartz, andalusite, Na-Ca and K-alunite, diaspore, pyrophyllite, zunyite, topaz, dickite, and kaolinite. The upper part of the porphyry Cu-Mo deposit (removed by mining), comprised a bornite-chalcocite enriched zone up to 300 m thick with an average grade of 0.7 wt % Cu and up to 5 wt % Cu locally. Based on hypogene bornite-chalcocite mineral textures and high-sulfidation state mineralogy, the enriched zone is inferred to be of hypogene origin, but modified by supergene processes. Consequently, it may be related to formation of the lithocap.Previous Re-Os dates of 240.4 and 240.7 ± 0.8 Ma for molybdenite in quartz veins are comparable to new 40Ar/39Ar dates of 239.7 ± 1.6 and 240 ± 2 Ma for muscovite that envelops D veins. One 40Ar/39Ar date on K-alunite from the lithocap of 223.5 ± 1.9 Ma suggests that it may be about 16 m.y. younger than Erdenet, but this result needs to be verified by further dating.

New crystal structures in hexagonal CuInS2 nanocrystals

NASA Astrophysics Data System (ADS)

Shen, Xiao; Hernández-Pagan, Emil A.; Zhou, Wu; Puzyrev, Yevgeniy S.; Idrobo, Juan C.; MacDonald, Janet E.; Pennycook, Stephen J.; Pantelides, Sokrates T.

2013-03-01

CuInS2 is one of the best candidate materials for solar energy harvesting. Its nanocrystals with a hexagonal lattice structure that is different from the bulk chalcopyrite phase have been synthesized by many groups. The structure of these CuInS2 nanocrystals has been previously identified as the wurtzite structure in which the copper and indium atoms randomly occupy the cation sites. Using first-principles total energy and electronic structure calculations based on density functional theory, UV-vis absorption spectroscopy, X-ray diffraction, and atomic resolution Z-contrast images obtained in an aberration-corrected scanning transmission electron microscope, we show that CuInS2 nanocrystals do not form random wurtzite structure. Instead, the CuInS2 nanocrystals consist of several wurtzite- related crystal structures with ordered cation sublattices, some of which are reported for the first time here. This work is supported by the NSF TN-SCORE (JEM), by NSF (WZ), by ORNL's Shared Research Equipment User Program (JCI) sponsored by DOE BES, by DOE BES Materials Sciences and Engineering Division (SJP, STP), and used resources of the National Energy Research Scientific Computing Center, supported by the DOE Office of Science under Contract No. DE-AC02-05CH11231.

Large magnetoresistance in Heusler-alloy-based epitaxial magnetic junctions with semiconducting Cu(In{sub 0.8}Ga{sub 0.2})Se{sub 2} spacer

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

Kasai, S.; Center for Emergent Matter Science, RIKEN, 2-1 Hirosawa, Wako 351-0198; Takahashi, Y. K.

2016-07-18

We investigated the structure and magneto-transport properties of magnetic junctions using a Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5}) Heusler alloy as ferromagnetic electrodes and a Cu(In{sub 0.8}Ga{sub 0.2})Se{sub 2} (CIGS) semiconductor as spacers. Owing to the semiconducting nature of the CIGS spacer, large magnetoresistance (MR) ratios of 40% at room temperature and 100% at 8 K were obtained for low resistance-area product (RA) values between 0.3 and 3 Ω μm{sup 2}. Transmission electron microscopy observations confirmed the fully epitaxial growth of the chalcopyrite CIGS layer, and the temperature dependence of RA indicated that the large MR was due to spin dependent tunneling.

Biomining with bacteriophage: selectivity of displayed peptides for naturally occurring sphalerite and chalcopyrite.

PubMed

Curtis, Susan B; Hewitt, Jeff; Macgillivray, Ross T A; Dunbar, W Scott

2009-02-01

During mineral processing, concentrates of sulfide minerals of economic interest are formed by froth flotation of fine ore particles. The method works well but recovery and selectivity can be poor for ores with complex mineralogy. There is considerable interest in methods that improve the selectivity of this process while avoiding the high costs of using flotation chemicals. Here we show the first application of phage biotechnology to the processing of economically important minerals in ore slurries. A random heptapeptide library was screened for peptide sequences that bind selectively to the minerals sphalerite (ZnS) and chalcopyrite (CuFeS2). After several rounds of enrichment, cloned phage containing the surface peptide loops KPLLMGS and QPKGPKQ bound specifically to sphalerite. Phage containing the peptide loop TPTTYKV bound to both sphalerite and chalcopyrite. By using an enzyme-linked immunosorbant assay (ELISA), the phage was characterized as strong binders compared to wild-type phage. Specificity of binding was confirmed by immunochemical visualization of phage bound to mineral particles but not to silica (a waste mineral) or pyrite. The current study focused primarily on the isolation of ZnS-specific phage that could be utilized in the separation of sphalerite from silica. At mining sites where sphalerite and chalcopyrite are not found together in natural ores, the separation of sphalerite from silica would be an appropriate enrichment step. At mining sites where sphalerite and chalcopyrite do occur together, more specific phage would be required. This bacteriophage has the potential to be used in a more selective method of mineral separation and to be the basis for advanced methods of mineral processing.

Optimization of vertical and lateral distances between target and substrate in deposition process of CuGaSe 2 thin films using one-step sputtering

DOE PAGES

Park, Jae -Cheol; Al-Jassim, Mowafak; Kim, Tae -Won

2017-02-01

Here, copper gallium selenide (CGS) thin films were fabricated using a combinatorial one-step sputtering process without an additional selenization process. The sample libraries as a function of vertical and lateral distance from the sputtering target were synthesized on a single soda-lime glass substrate at the substrate temperature of 500 °C employing a stoichiometric CGS single target. As we increased the vertical distance between the target and substrate, the CGS thin films had more stable and uniform characteristics in structural and chemical properties. Under the optimized conditions of the vertical distance (150 mm), the CGS thin films showed densely packed grainsmore » and large grain sizes up to 1 μm in scale with decreasing lateral distances. The composition ratio of Ga/[Cu+Ga] and Se/[Cu+Ga] showed 0.50 and 0.93, respectively, in nearly the same composition as the sputtering target. X-ray diffraction and Raman spectroscopy revealed that the CGS thin films had a pure chalcopyrite phase without any secondary phases such as Cu–Se or ordered vacancy compounds, respectively. In addition, we found that the optical bandgap energies of the CGS thin films are shifted from 1.650 to 1.664 eV with decreasing lateral distance, showing a near-stoichiometric region with chalcopyrite characteristics.« less

Proposed suitable electron reflector layer materials for thin-film CuIn1-xGaxSe2 solar cells

NASA Astrophysics Data System (ADS)

Sharbati, Samaneh; Gharibshahian, Iman; Orouji, Ali A.

2018-01-01

This paper investigates the electrical properties of electron reflector layer to survey materials as an electron reflector (ER) for chalcopyrite CuInGaSe solar cells. The purpose is optimizing the conduction-band and valence-band offsets at ER layer/CIGS junction that can effectively reduce the electron recombination near the back contact. In this work, an initial device model based on an experimental solar cell is established, then the properties of a solar cell with electron reflector layer are physically analyzed. The electron reflector layer numerically applied to baseline model of thin-film CIGS cell fabricated by ZSW (efficiency = 20.3%). The improvement of efficiency is achievable by electron reflector layer materials with Eg > 1.3 eV and -0.3 < Δχ < 0.7, depends on bandgap. Our simulations examine various electron reflector layer materials and conclude the most suitable electron reflector layer for this real CIGS solar cells. ZnSnP2, CdSiAs2, GaAs, CdTe, Cu2ZnSnS4, InP, CuO, Pb10Ag3Sb11S28, CuIn5S8, SnS, PbCuSbS3, Cu3AsS4 as well as CuIn1-xGaxSe (x > 0.5) are efficient electron reflector layer materials, so the potential improvement in efficiency obtained relative gain of 5%.

Hydrothermal Evolution of the Giant Cenozoic Kadjaran porphyry Cu-Mo deposit, Tethyan metallogenic belt, Armenia, Lesser Caucasus: mineral paragenetic, cathodoluminescence and fluid inclusion constraints

NASA Astrophysics Data System (ADS)

Hovakimyan, Samvel; Moritz, Robert; Tayan, Rodrik; Rezeau, Hervé

2016-04-01

The Lesser Caucasus belongs to the Central segment of the Tethyan metallogenic belt and it is a key area to understand the metallogenic evolution between the Western & Central parts of the Tethyan belt and its extension into Iran. Zangezur is the most important mineral district in the southernmost Lesser Caucasus. It is a component of the South Armenian block, and it was generated during the convergence and collision of the southern margin of the Eurasian plate and the northern margin of the Arabian plate, and terranes of Gondwana origin (Moritz et al., in press). The Zangezur ore district consists of the Tertiary Meghri-Ordubad composite pluton, which is characterized by a long-lasting Eocene to Pliocene magmatic, tectonic and metallogenic evolution. It hosts major porphyries Cu-Mo and epithermal Au - polymetallic deposits and occurrences, including the giant world class Kadjaran porphyry Cu-Mo deposit (2244 Mt reserves, 0.3% Cu, 0.05% Mo and 0.02 g/t Au). The Kadjaran deposit is hosted by a monzonite intrusion (31.83±0.02Ma; Moritz et al., in press). Detailed field studies of the porphyry stockwork and veins of the different mineralization stages, their crosscutting and displacement relationships and the age relationship between different paragenetic mineral associations were the criteria for distinction of the main stages of porphyry mineralization at the Kadjaran deposit. The economic stages being: quartz- molybdenite, quartz-molybdenite-chalcopyrite, and quartz-chalcopyrite. The main paragenetic association of the Kadjaran porphyry deposit includes pyrite, molybdenite, chalcopyrite, bornite, chalcocite, pyrrhotite, covellite, sphalerite, and galena. Recent field observations in the Kadjaran open pit revealed the presence of epithermal veins with late vuggy silica and advanced argillic alteration in the north-eastern and eastern parts of the deposit. They are distributed as separate veins and have also been recognized in re-opened porphyry veins and in stockwork. One of them is the east-west-oriented 6th vein zone in the northern part of the deposit, which contains quartz-molybdenite veins and late quartz-galena-sphalerite veins. This is interpreted as a telescoping between porphyry and epithermal environments. It is supported by microscopic studies of mineral paragenesis, which reveal the presence of enargite and tennantite-tetrahedrite, luzonite, sphalerite, and galena, generally in a gangue of quartz, followed by a late carbonate and gypsum stage. On-going fluid inclusion studies are being carried out on quartz samples from the different mineralization stages. Five types of fluid inclusions were distinguished according to their nature, bubble size, and daughter mineral content: vapor-rich, aqueous-carbonic, brine, polyphase brine and liquid-rich inclusions. Cathodoluminescence images from the porphyry veins reveal four generations of quartz. Molybdenite and chalcopyrite are associated with two different dark luminescent quartz generations, which contain typical brine, aqueous-carbonic and vapour-rich H2O fluid inclusions, with some of them coexisting locally as boiling assemblages. Epithermal veins are mainly characterized by liquid-rich H2O fluid inclusions. Microthermometric studies of fluid inclusions reveal a major difference in homogenisation temperatures between the early quartz-molybdenite- chalcopyrite stage (Thtotal between 3600 and 4250C) and the late quartz-galena-sphalerite vein stage (Thtotal 300-2700C), which is attributed to the transition from a porphyry to an epithermal environment in the Kadjaran deposit.

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.

Geochemistry of the Patricia Zn-Pb-Ag Deposit (paguanta, NE Chile)

NASA Astrophysics Data System (ADS)

Chinchilla Benavides, D.; Merinero Palomares, R.; Piña García, R.; Ortega Menor, L.; Lunar Hernández, R.

2013-12-01

The Patricia Zn-Pb-Ag ore deposit is located within the Paguanta mining project, situated at the northern end of the Andean Oligocene Porphyry Copper Belt of Chile. The sulfide mineralization occurs as W-E oriented veins hosted in volcanic rocks, mainly andesite (pyroclastic, ash and lavas), of Upper Cretaceous to Middle Tertiary age. The ore mineralogy (obtained by EMPA analyses) comprises in order of abundance, pyrite, sphalerite (5.5 - 10.89 wt % Fe, 9.8-19 % molar FeS and 0.52 wt % Cd), galena, arsenopyrite, chalcopyrite and Ag-bearing sulfosalts. The veins show a zoned and banded internal structure with pyrite at the edges and sphalerite in the center. The Ag occurs mostly as Ag-Cu-Sb sulfosalts, in order of abundance: series freibergite - argentotennantite -polybasite and stephanite. Other minor Ag phases such as argentite, pyrargirite and diaphorite were also identified. These Ag phases are typically associated with the base-metal sulfides. Freibergite occurs filling voids within sphalerite, chalcopyrite and at the contact between sphalerite and galena. Polybasite, stephanite, pyrargirite and argentite are mostly in close association with freibergite. In the case of diaphorite, it commonly occurs filling voids between galena crystals or as inclusions within galena. Some minor Ag-bearing sulfosalts are also identified between pyrite crystals. The alteration minerals are dominated by chlorite, illite and kaolinite. The gangue minerals consist of quartz and carbonates identified by XRD as kutnahorite. We obtained linear correlation statistically significant only for Ag, As Au, Cd, Cu, Pb, Sb and Zn and therefore we generated an enhanced scatter plot matrix of these elements. Bulk rock analyses (ICP/MS and XRF) of drill cores show that Ag is strongly and positively correlated with Pb and As, moderately with Cd, Sb, Au and Zn and weakly with Cu, while Au is moderately and positively correlated with Ag, As, Cd, Sb and Zn and weakly with Cu and Pb. These results are consistent with bulk rock analyses of selected and mineralized samples were similar correlations have been obtained. Ag positive correlations indicate that the formation of Ag-bearing minerals is mainly associated with galena, arsenopyrite and sphalerite occurrence. Au positive correlations indicate that this element occurs in close relationship with Ag-bearing minerals, arsenopyrite and sphalerite. The weak correlation between Cu and Ag and Au indicate that the formation of chalcopyrite is not related with the main stages of Ag-Au mineralization. The main conclusion of this study is that geochemical analyses along drill cores that cut mineralization confirm that the occurrence of Ag and Au in the Paguanta deposit is associated with the formation of galena, arsenopyrite and sphalerite. This study also confirm previous conclusions suggesting that the Patricia Pb-Zn-Ag ore deposit probably represents an example of epithermal mineralization of intermediate sulfidation state, with periods of lower sulfidation state during sphalerite deposition.

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

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

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. In this work, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We demonstratemore » the modeling approach with the example of chalcopyrite Cu(InGa)(SeS){sub 2} thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS){sub 2} thin films arises and persists. We believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

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

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. Here, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We also demonstrate themore » modeling approach with the example of chalcopyrite Cu(InGa)(SeS) 2 thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS) 2 thin films arises and persists. Finally, we believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

DOE PAGES

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.; ...

2016-04-01

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. Here, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We also demonstrate themore » modeling approach with the example of chalcopyrite Cu(InGa)(SeS) 2 thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS) 2 thin films arises and persists. Finally, we believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

Non-injection synthesis of monodisperse Cu-Fe-S nanocrystals and their size dependent properties.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Żukrowski, Jan; Zabost, Damian; Kotwica, Kamil; Malinowska, Karolina; Ostrowski, Andrzej; Wielgus, Ireneusz; Lisowski, Wojciech; Sobczak, Janusz W; Przybylski, Marek; Pron, Adam

2016-06-01

It is demonstrated that ternary Cu-Fe-S nanocrystals differing in composition (from Cu-rich to Fe-rich), structure (chalcopyrite or high bornite) and size can be obtained from a mixture of CuCl, FeCl3, thiourea and oleic acid (OA) in oleylamine (OLA) using the heating up procedure. This new preparation method yields the smallest Cu-Fe-S nanocrystals ever reported to date (1.5 nm for the high bornite structure and 2.7 nm for the chalcopyrite structure). A comparative study of nanocrystals of the same composition (Cu1.6Fe1.0S2.0) but different in size (2.7 nm and 9.3 nm) revealed a pronounced quantum confinement effect, confirmed by three different techniques: UV-vis spectroscopy, cyclic voltammetry and Mössbauer spectroscopy. The optical band gap increased from 0.60 eV in the bulk material to 0.69 eV in the nanocrystals of 9.3 nm size and to 1.39 eV in nanocrystals of 2.7 nm size. The same trend was observed in the electrochemical band gaps, derived from cyclic voltammetry studies (band gaps of 0.74 eV and 1.54 eV). The quantum effect was also manifested in Mössbauer spectroscopy by an abrupt change in the spectrum from a quadrupole doublet to a Zeeman sextet below 10 K, which could be interpreted in terms of the well defined energy states in these nanoparticles, resulting from quantum confinement. The Mössbauer spectroscopic data confirmed, in addition to the results of XPS spectroscopy, the co-existence of Fe(iii) and Fe(ii) in the synthesized nanocrystals. The organic shell composition was investigated by NMR (after dissolution of the inorganic core) and IR spectroscopy. Both methods identified oleylamine (OLA) and 1-octadecene (ODE) as surfacial ligands, the latter being formed in situ via an elimination-hydrogenation reaction occurring between OLA and the nanocrystal surface.

Current scenario of chalcopyrite bioleaching: a review on the recent advances to its heap-leach technology.

PubMed

Panda, Sandeep; Akcil, Ata; Pradhan, Nilotpala; Deveci, Haci

2015-11-01

Chalcopyrite is the primary copper mineral used for production of copper metal. Today, as a result of rapid industrialization, there has been enormous demand to profitably process the low grade chalcopyrite and "dirty" concentrates through bioleaching. In the current scenario, heap bioleaching is the most advanced and preferred eco-friendly technology for processing of low grade, uneconomic/difficult-to-enrich ores for copper extraction. This paper reviews the current status of chalcopyrite bioleaching. Advanced information with the attempts made for understanding the diversity of bioleaching microorganisms; role of OMICs based research for future applications to industrial sectors and chemical/microbial aspects of chalcopyrite bioleaching is discussed. Additionally, the current progress made to overcome the problems of passivation as seen in chalcopyrite bioleaching systems have been conversed. Furthermore, advances in the designing of heap bioleaching plant along with microbial and environmental factors of importance have been reviewed with conclusions into the future prospects of chalcopyrite bioleaching. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chalcopyrite—bearer of a precious, non-precious metal

USGS Publications Warehouse

Kimball, Bryn E.

2013-01-01

The mineral chalcopyrite (CuFeS2) is the world's most abundant source of copper, a metal component in virtually every piece of electrical equipment. It is the main copper mineral in several different ore deposit types, the most important of which are porphyry deposits. Chalcopyrite is unstable at the Earth's surface, so it weathers from sulphide outcrops and mine waste piles, contributing acid and dissolved copper to what is known as acid rock drainage. If not prevented, dissolved copper from chalcopyrite weathering will be transported downstream, potentially harming ecosystems along the way. Pristine areas are becoming targets for future copper supply as we strive to meet ever-increasing demands for copper by developed and developing nations. Additionally, our uses for copper are expanding to include technology such as solar energy production. This has lead to the processing of increasingly lower grade ores, which is possible, in part, due to advances in bio-leaching (i.e. metal extraction catalysed by micro-organisms). Although copper is plentiful, it is still a nonrenewable resource. Future copper supply promises to fall short of demand and the volatility of the copper market may continue if we do not prioritize copper use and improve copper recycling and ore extraction efficiency.

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.

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.

Hydrothermal synthesis of a photovoltaic material based on CuIn0.5Ga0.5Se2

NASA Astrophysics Data System (ADS)

Castellanos Báez, Y. T.; Fuquen Peña, D. A.; Gómez-Cuaspud, J. A.; Vera-López, E.; Pineda-Triana, Y.

2017-12-01

The present work report, the synthesis and characterization of the CuIn0.5Ga0.5Se2 system (abbreviated CIGS), by the implementation of a hydrothermal route, in order to obtain a solid with appropriate properties in terms of surface, morphological and texture properties for potential applications in the design of photovoltaic cells. The synthesis was carried out using the corresponding stoichiometric quantities (Cu:In:Ga:Se 1:0.5:0.5:2), which were mixed in a Teflon vessel under stirring conditions. The homogeneous solution was treated in a steel autoclave at 300°C for 72 hours at the end of which the resulting material was characterized by X-Ray Diffraction (XRD) and Rietveld refinement. The results of the structural characterization allowed to confirm the obtaining of a chalcopyrite type structure, with a I-42 d (122) structure and cell parameters a=0.570, b=0.570, c=1.140nm, α=90, β=90, γ=90° oriented along (1 0 4) facet, detecting the presence of a secondary phases, related with CuInSe and CuIn metallic selenides, derived from synthesis process. The structural refinement allowing to validate the obtaining of a nanometric crystalline material (10-20nm) for potential applications in field of photovoltaic technology.

Preparation and characterization of CuInS2 absorber layers by sol-gel method for solar cell applications

NASA Astrophysics Data System (ADS)

Amerioun, M. H.; Ghazi, M. E.; Izadifard, M.; Bahramian, B.

2016-04-01

CuInSe2 , CuInS2 ( CIS2 and CuInGaS2 alloys and their compounds with band gaps between 1.05 and 1.7eV are absorbance materials based on chalcopyrite, in which, because of their suitable direct band gap, high absorbance coefficient and short carrier diffusion are used as absorbance layers in solar cells. In this work, the effects of decrease in p H and thickness variation on characteristics of the CIS2 absorber layers, grown by spin coating on glass substrates, are investigated. Furthermore by using thiourea as a sulphur source in solvent, the sulfurization of layers was done easier than other sulfurization methods. Due to the difficulty in dissolving thiourea in the considered solvent that leads to a fast deposition during the dissolving process, precise conditions are employed in order to prepare the solution. In fact, this procedure can facilitate the sulfurization process of CuIn layers. The results obtained from this investigation indicate reductions in absorbance and band gap in the visible region of the spectrum as a result of decrease in p H. Finally, conductivity of layers is studied by the current vs. voltage curve that represents reduction of electrical resistance with decrease and increase in p H and thickness, respectively.

Bioleaching of two different types of chalcopyrite by Acidithiobacillus ferrooxidans

NASA Astrophysics Data System (ADS)

Dong, Ying-bo; Lin, Hai; Fu, Kai-bin; Xu, Xiao-fang; Zhou, Shan-shan

2013-02-01

Two different types of chalcopyrite (pyritic chalcopyrite and porphyry chalcopyrite) were bioleached with Acidithiobacillus ferrooxidans ATF6. The bioleaching of the pyritic chalcopyrite and porphyry chalcopyrite is quite different. The copper extraction reaches 46.96% for the pyritic chalcopyrite after 48-d leaching, but it is only 14.50% for the porphyry chalcopyrite. Proper amounts of initial ferrous ions can improve the efficiency of copper extraction for the two different types of chalcopyrite. The optimum dosage of ferrous ions for the pyritic chalcopyrite and porphyry chalcopyrite is different. The adsorption of ATF6 on the pyritic chalcopyrite and porphyry chalcopyrite was also studied in this paper. It is found that ATF6 is selectively adsorbed by the two different types of chalcopyrite; the higher adsorption onto the pyritic chalcopyrite than the porphyry chalcopyrite leads to the higher copper dissolution rate of the pyritic chalcopyrite. In addition, the zeta-potential of chalcopyrite before and after bioleaching further confirms that ATF6 is more easily adsorbed onto the pyritic chalcopyrite.

Improved Single-Source Precursors for Solar-Cell Absorbers

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Harris, Jerry; Hepp, Aloysius

2007-01-01

Improved single-source precursor compounds have been invented for use in spray chemical vapor deposition (spray CVD) of chalcopyrite semiconductor absorber layers of thin-film cells. A "single-source precursor compound" is a single molecular compound that contains all the required elements, which when used under the spray CVD conditions, thermally decomposes to form CuIn(x)Ga(1-x)S(y)Se(2-y).

Influence of carrier concentration on the performance of CIAS solar cell

NASA Astrophysics Data System (ADS)

Patel, Kinjal; Ray, Jaymin

2018-05-01

Photovoltaic research has moved beyond the use of single crystalline materials such as Group IV elemental Si and Group III-V compounds like GaAs to much more complex compounds of the Group I-III-VI2 with chalcopyrite structure. The ternary ABC2 chalcopyrites (A=Cu; B=In, Ga or Al; C= S, Se or Te) form a large group of semiconducting materials with diverse structural and electrical properties. These materials are attractive for thin film photovoltaic application for a number of reasons. The bandgap of CuInSe2 is relatively low, 1.04 eV, but it can be adjusted to better match the solar spectrum either by substituting part of In by Ga or part of Se by S. Most reported and popular Cu(In,Ga)Se2 (CIGS) is one of its derivative. Efficiency of the CIGS devices with Eg >1.3 eV is reduced by the degradation of the electronic properties of the absorber leading to losses in the fill-factor and the open-circuit voltage. Alternatively, the performance can be improved by the addition of Al to form CuInAlSe2 (CIAS) absorber layers with an increase in the bandgap energy, which matches closely with the solar spectrum. In the present work an effort was made in the direction of improving the conversion efficiency by studying the influence of carrier concentration. SCAPS simulation program is used to simulate the CIAS structure numerically. The obtained results intended the significant variation in the values of conversion efficiency. Variation in the efficiency can be considered because of the relation optical absorption and carrier concentration. Observed highest efficiency is 10 %, which can be further improved by considering actual parameters of the device as well as the operating condition.

Characterization and device performance of (AgCu)(InGa)Se2 absorber layers

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

Hanket, Gregory; Boyle, Jonathan H.; Shafarman, William N.

The study of (AgCu)(InGa)Se2 absorber layers is of interest in that Ag-chalcopyrites exhibit both wider bandgaps and lower melting points than their Cu counterparts. (AgCu)(InGa)Se2 absorber layers were deposited over the composition range 0 < Ag/(Ag+Cu) < 1 and 0.3 < Ga/(In+Ga) < 1.0 using a variety of elemental co-evaporation processes. Films were found to be singlephase over the entire composition range, in contrast to prior studies. Devices with Ga content 0.3 < Ga/(In+Ga) <0.5 tolerated Ag incorporation up to Ag/(Ag+Cu) = 0.5 without appreciable performance loss. Ag-containing films with Ga/(In+Ga) = 0.8 showed improved device characteristics over Cu-only controlmore » samples, in particular a 30-40% increase in short-circuit current. An absorber layer with composition Ag/(Ag+Cu) = 0.75 and Ga/(In+Ga) = 0.8 yielded a device with VOC = 890 mV, JSC = 20.5mA/cm2, fill factor = 71.3%, and η = 13.0%.« less

Arsenic-enriched Cu-Ni-PGE Mineralization in Wetlegs, Duluth Complex, St. Louis County, Minnesota, USA

NASA Astrophysics Data System (ADS)

Raič, Sara; Mogessie, Aberra; Benkó, Zsolt; Molnár, Ferenc; Hauck, Steven; Severson, Mark

2014-05-01

The magmatic sulfide ore deposit Wetlegs is found within the troctolitic Partridge River Intrusion (PRI) of the 1.1 Ga Duluth Complex. It is of great interest, due to its highly mineralized zones containing Cu-Ni-Fe-Sulfides, platinum-group minerals (PGM) and arsenic-enriched ores. Sulfides appear as disseminated patches of primary pyrrhotite, chalcopyrite, Co-rich pentlandite and cubanite within a plagioclase, olivine and pyroxene matrix. Ores associated with hydrous silicate phases are secondary chalcopyrite, arsenic-enriched minerals, PGMs like sperrylite, stibiopalladinite and other precious minerals such as clausthalite, parkerite and electrum. Based on textural relationships, mineral compositions and sulfur isotopic studies, a paragenetic sequence of ore genesis in Wetlegs could be reconstructed starting with the formation of composite sulfides such as pyrrhotite, chalcopyrite, Co-enriched pentlandite and cubanite (at increased sulfur fugacity), defined as the Sulfide Stage. The Arsenide Stage is characterized by increased arsenic fugacity and a strong drop in sulfur fugacity with the following succession of precipitated minerals: 1) Monoarsenides (nickeline) found as remnants in diarsenides. 2) Diarsenides comprising members of the rammelsbergite - safflorite - loellingite solid-solution series (RSLss) and minerals of the rammelsbergite - loellingite solid-solutions series (RLss). Their crystallization temperature is between 550 and 625°C, estimated with solvus lines postulated by ROSEBOOM (1963) and GERVILLA & RØNSBO (1992) in the system CoAs2 - NiAs2 - FeAs2. This is subsequently followed by an Arsenide/Sulfide Stage which marks the formation of sulfarsenides of the cobaltite - gersdorffite solid-solution series at increased sulfur fugacity (drop in arsenic fugacity). Sulfarsenides display a clear cobalt trend from core to rim, and formed around 650°C with a decrease in temperature to ~ 500°C, documented by cobalt enriched rims, based on the solvus lines form HEM & MAKOVICKY (2004) and HEM (2006) in the system CoAsS - NiAsS - FeAsS. The presence of arsenides, sulfarsenides and graphite in footwall rocks may suggest the metasedimentary Virginia Formation as a potential source of As, Sb, and C. These elements were remobilized by hydrothermal fluids and introduced in the crystallizing magma to form arsenic-enriched Cu-Ni-PGE mineralization within the basal ultramafic rocks. δ34S of sulfides from representative samples of Wetlegs vary between 2.04 and 22.80 ‰. This suggests the involvement of crustal materials in addition to the magmatic source of sulfur in the Cu-Ni-PGE mineralization, as documented in previous studies (MOGESSIE & STUMPFL, 1992). We acknowledge financial support by the Austrian Research Fund (P23157-N21) to A. Mogessie GERVILLA, F. & RØNSBO, J. (1992): Neues Jahrb. Mineral., Monatsh. 13, pp. 193-206. HEM, S. R. (2006): Chem. Geol. 225, pp. 291-303. HEM. S. R. & MAKOVICKY, E. (2004): Canadian Mineralogist, v. 42, pp. 63-86. MOGESSIE, A. & STUMPLF, E. F. (1992): Australian Journal of Earth Sciences, v. 39, pp. 315-325. ROSEBOOM, E. H. (1963): American Mineralogist, v. 48, pp. 271-299.

Structural, mineralogical and geochemical constraints on the atypical komatiite-hosted Turret deposit in the Agnew-Mt. White district, Western Australia

NASA Astrophysics Data System (ADS)

Voute, F.; Thébaud, N.

2015-08-01

In the Norseman-Wiluna belt, Yilgarn Craton, the Agnew-Mt. White district is the host of many gold deposits. Located in the hinge of the regional Lawlers anticline, the Turret gold deposit is structurally controlled by the Table Hill shear zone that transects the Agnew Ultramafic unit. Geochemistry, coupled with petrographic data, allowed the delineation of the paragenetic sequence associated with gold mineralisation and include (1) a pervasive talc-carbonate alteration assemblage, (2) a pre-mineralisation stage associated with pervasive arsenopyrite + chalcopyrite + pyrrhotite + pyrite alteration, followed by (3) a late deformation event along a dilatational segment of the main Table Hill shear zone, leading to the formation of a breccia hosting a Cu-Bi-Mo-Au (± Ag ± Zn ± Te ± W) metal assemblage. The presence of Au-Ag-Cu alloys, native bismuth, chalcopyrite and other Bi-Te-S phases in the mineralisation stage suggest that gold may have been scavenged from the hydrothermal fluids by composite Bi-Te-Cu-Au-Ag-S liquids or melts. Using this mineral paragenetic sequence, together with mineralogical re-equilibration textures observed, we show that the gold deposition at Turret occurred over a temperature range approximately between c. 350 and 270 °C. This temperature range, together with the structural control and typical mesothermal alteration pattern including carbonate-chlorite alteration, shows that the Turret deposit shares common characteristics with the orogenic gold deposit class. However, the metal association of Cu, Au, Bi, and Mo, the quartz-poor, and high copper-sulphide content (up to 15 %) are characteristics that depart from the typical orogenic gold deposit mineralogy. Through comparison with similar deposits in the Yilgarn Craton and worldwide, we propose that the Turret deposit represents an example of a porphyry-derived Au-Cu-Bi-Mo deposit.

Thermoelectricity Generation and Electron-Magnon Scattering in a Natural Chalcopyrite Mineral from a Deep-Sea Hydrothermal Vent.

PubMed

Ang, Ran; Khan, Atta Ullah; Tsujii, Naohito; Takai, Ken; Nakamura, Ryuhei; Mori, Takao

2015-10-26

Current high-performance thermoelectric materials require elaborate doping and synthesis procedures, particularly in regard to the artificial structure, and the underlying thermoelectric mechanisms are still poorly understood. Here, we report that a natural chalcopyrite mineral, Cu1+x Fe1-x S2 , obtained from a deep-sea hydrothermal vent can directly generate thermoelectricity. The resistivity displayed an excellent semiconducting character, and a large thermoelectric power and high power factor were found in the low x region. Notably, electron-magnon scattering and a large effective mass was detected in this region, thus suggesting that the strong coupling of doped carriers and antiferromagnetic spins resulted in the natural enhancement of thermoelectric properties during mineralization reactions. The present findings demonstrate the feasibility of thermoelectric energy generation and electron/hole carrier modulation with natural materials that are abundant in the Earth's crust. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraction of Copper from Malanjkhand Low-Grade Ore by Bacillus stearothermophilus.

PubMed

Singh, Sradhanjali; Sukla, Lala Behari; Mishra, Baroda Kanta

2011-10-01

Thermophilic bacteria are actively prevalent in hot water springs. Their potential to grow and sustain at higher temperatures makes them exceptional compare to other microorganism. The present study was initiated to isolate, identify and determine the feasibility of extraction of copper using thermophilic heterotrophic bacterial strain. Bacillus stearothermophilus is a thermophilic heterotrophic bacterium isolated from hot water spring, Atri, Orissa, India. This bacterium was adapted to low-grade chalcopyrite ore and its efficiency to solubilize copper from Malanjkhand low-grade ore was determined. The low-grade copper ore contains 0.27% Cu, in which the major copper-bearing mineral is chalcopyrite associated with other minerals present as minor phase. Variation in parameters such as pulp-density and temperatures were studied. After 30 days of incubation, it was found that Bacillus stearothermophilus solubilize copper up to 81.25% at pH 6.8 at 60°C.

Thin Film CuInS2 Prepared by Spray Pyrolysis with Single-Source Precursors

NASA Technical Reports Server (NTRS)

Jin, Michael H.; Banger, Kulinder K.; Harris, Jerry D.; Cowen, Jonathan E.; Hepp, Aloysius F.; Lyons, Valerie (Technical Monitor)

2002-01-01

Both horizontal hot-wall and vertical cold-wall atmospheric chemical spray pyrolysis processes deposited near single-phase stoichiometric CuInS2 thin films. Single-source precursors developed for ternary chalcopyrite materials were used for this study, and a new liquid phase single-source precursor was tested with a vertical cold-wall reactor. The depositions were carried out under an argon atmosphere, and the substrate temperature was kept at 400 C. Columnar grain structure was obtained with vapor deposition, and the granular structure was obtained with (liquid) droplet deposition. Conductive films were deposited with planar electrical resistivities ranging from 1 to 30 Omega x cm.

The influence of different locations of sputter guns on the morphological and structural properties of Cu-In-Ga precursors and Cu(In,Ga)Se2 thin films

NASA Astrophysics Data System (ADS)

Wang, J.; Zhu, J.; He, Y. X.

2014-01-01

The influence of two different locations of sputter guns on the morphological and structural properties of Cu-In-Ga precursors and Cu(In,Ga)Se2 (CIGS) thin films was investigated. All the precursors contained cauliflower-like nodules, whereas smaller subnodules were observed on the background. All the precursors revealed apparent three-layered structures, and voids were observed at the CIGS/SLG interface of Sets 1 and 2 films rather than Set 3 film. EDS results indicated that all CIGS thin films were Cu-deficient. Based on the grazing incidence X-ray diffraction (GIXRD) patterns, as-selenized films showed peaks corresponding to the chalcopyrite-type CIGS structure. Depth-resolved Raman spectra showed the formation of a dominant CIGS phase inside the films for all the as-selenized samples investigated, and of an ordered vacancy compound (OVC) phase like Cu(In,Ga)3Se5 or Cu(In,Ga)2Se3.5 at the surface and/or CIGS/SLG interface region of Sets 2 and 3 films. No evidence was obtained on the presence of an OVC phase in Set 1 CIGS film, which may be speculated that long-time annealing is contributed to suppress the growth of OVC phases. The results of the present work suggest that the metallic precursors deposited with the upright-location sputter gun might be more appropriate to prepare CIGS thin films than those sputtered with the titled-location gun.

Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations

NASA Astrophysics Data System (ADS)

Varley, J. B.; Lordi, V.; Ogitsu, T.; Deangelis, A.; Horsley, K.; Gaillard, N.

2018-04-01

Understanding the impact of impurities in solar absorbers is critical to engineering high-performance in devices, particularly over extended periods of time. Here, we use hybrid functional calculations to explore the role of hydrogen interstitial (Hi) defects in the electronic properties of a number of attractive solar absorbers within the chalcopyrite and kesterite families to identify how this common impurity may influence device performance. Our results identify that Hi can inhibit the highly p-type conditions desirable for several higher-band gap absorbers and that H incorporation could detrimentally affect the open-circuit voltage (Voc) and limit device efficiencies. Additionally, we find that Hi can drive the Fermi level away from the valence band edge enough to lead to n-type conductivity in a number of chalcopyrite and kesterite absorbers, particularly those containing Ag rather than Cu. We find that these effects can lead to interfacial Fermi-level pinning that can qualitatively explain the observed performance in high-Ga content CIGSe solar cells that exhibit saturation in the Voc with increasing band gap. Our results suggest that compositional grading rather than bulk alloying, such as by creating In-rich surfaces, may be a better strategy to favorably engineering improved thin-film photovoltaics with larger-band gap absorbers.

Metallogeny of The Sierra de Guanajuato Range, Central México

NASA Astrophysics Data System (ADS)

Pedro F., Z. D.

2004-12-01

The Sierra de Guanajuato Range (SGR), trending N315° at Central México, is an orographic feature extending over a distance of 80 km. SGR comprises three well defined lithostratigraphic units: (1) a cretaceous basement including an arc-derived terrane named Guanajuato Arc (GA) made of gabbro, diorite and basaltic pillowed lava, and volcano-sedimentary rocks belonging to Arperos fore-arc basin which are geochemically anomalous in Au (0.15 ppm), Ag (3 ppm), Cu (40 ppm), Pb (50 ppm) and Zn (15 ppm); (2) Early Tertiary intrusive rocks, e.g., Comanja Granite which is affected by the presence of tourmalinized (schörl) aplito-pegmatite dykes mineralized with rare earths elements, and (3) Eocene redbeds (1,500-2000 m) and Oligocene-Miocene volcanics cover. The metallogeny of the SGR shows a multiple origin in time and space: volcano-sedimentary, granitic and volcanic, being possible to define three metallogenic epochs: cretaceous, paleocene and oligocene. Cretaceous epoch includes: (a) volcanogenic massive sulphide deposits (VMS) of bimodal-siliclastic type belonging to León-Guanajuato district; wallrock of VMS is made of felsic-internediate volcanics and black argillite; at Los Gavilanes deposit paragenesis is next: chalcopyrite > sphalerite > galena, pyrite > pyrrhotite > marcasite; grade is as follows: Au: .02-.07 g/t; Ag: 157-18.5 g/t; Cu: 2.24-0.81%, Pb: 4.16-0.03%; Zn: 10.35-3.02 %; (b) lens-shaped stratiform bodies of massive pyrite (i. ex., San Ignacio prospect; ˜ 4,000 ton) of exhalative-sedimentary origin with chalcopyrite and sphalerite microveins. Paleocene epoch includes both quartz-cordierite-sanidine veins and replacement bodies of hydrothermal metamorphic filliation (W +Se-Bi, Pb, Zn, Cu), and pyrometasomatic bodies [Cu, Pb, Zn (Ag), W] which genetically are linked to Comanja Granite emplacement. The wallrock at El Maguey mine (35,000 ton; 0.6% WO3) is made of hornfel and the vein (1.8-3.2m width) has a banding structure made of : \\{quartz & K-feldspar\\}, \\{(schörl) & specular hematite\\} and epidote alternating bands; ore minerals are scheelite and tetradymite. Oligocene epoch includes quartz-calcite-adulaire epithermal veins (Ag-Au) of geothermal-volcanic filliation. At Guanajuato mining District; ore minerals are: Au, electrum, acanthite, aguilarite, naumannite, polybasite, proustite, fischesserite (?); chalcopyrite, sphalerite and galena. Ore grade at Las Torres mine are: Ag 300 g/t, Au 2 g/t. At El Cubo mine because of the presence of rhyolitic domes gold grade reaches 100 g/t. Since Early Cretaceous Epoch, metallogenic concepts of heritage and permanence are valid in SG ore deposits.

Effect of Pressure on the Stability and Electronic Structure of ZnO0.5S0.5 and ZnO0.5Se0.5

NASA Astrophysics Data System (ADS)

Manotum, R.; Klinkla, R.; Phaisangittisakul, N.; Pinsook, U.; Bovornratanaraks, T.

2017-12-01

Structures and high-pressure phase transitions in ZnO0.5S0.5 and ZnO0.5Se0.5 have been investigated using density functional theory calculations. The previously proposed structures of ZnO0.5S0.5 and ZnO0.5Se0.5 which are chalcopyrite ( I\\bar{4}2d ), rocksalt ( Fm3m ), wurtzite ( P63 mc ) and CuAu-I ( P\\bar{4}m2 ) have been fully investigated. Stabilities of these materials have been systematically studied up to 40 GPa using various approaches. We have confirmed the stability of the chalcopyrite structure up to 30 GPa for which the CuAu-I structure has been previously proposed. However, our calculation revealed that CuAu-I is not a stable structure under 32 GPa and 33 GPa for both ZnO0.5S0.5 and ZnO0.5Se0.5, respectively, which could explain the failure in several attempts to fabricate these materials under such conditions. We have also examined the pressure-dependence of the bandgap and electronic structure up to 30 GPa. We can conclude from our PDOS analysis that the applied pressure does not change the atomic state characters of electronic states near the top of valence and the bottom of conduction bands, but mainly modifies the dominant Zn-3d atomic state of the deep Bloch state at -1 eV below Fermi level.

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

Detailed Visualization of Phase Evolution during Rapid Formation of Cu(InGa)Se2 Photovoltaic Absorber from Mo/CuGa/In/Se Precursors.

PubMed

Koo, Jaseok; Kim, Sammi; Cheon, Taehoon; Kim, Soo-Hyun; Kim, Woo Kyoung

2018-03-02

Amongst several processes which have been developed for the production of reliable chalcopyrite Cu(InGa)Se 2 photovoltaic absorbers, the 2-step metallization-selenization process is widely accepted as being suitable for industrial-scale application. Here we visualize the detailed thermal behavior and reaction pathways of constituent elements during commercially attractive rapid thermal processing of glass/Mo/CuGa/In/Se precursors on the basis of the results of systematic characterization of samples obtained from a series of quenching experiments with set-temperatures between 25 and 550 °C. It was confirmed that the Se layer crystallized and then melted between 250 and 350 °C, completely disappearing at 500 °C. The formation of CuInSe 2 and Cu(InGa)Se 2 was initiated at around 450 °C and 550 °C, respectively. It is suggested that pre-heat treatment to control crystallization of Se layer should be designed at 250-350 °C and Cu(InGa)Se 2 formation from CuGa/In/Se precursors can be completed within a timeframe of 6 min.

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

DOE PAGES

Mezher, Michelle; Mansfield, Lorelle M.; Horsley, Kimberly; ...

2017-08-14

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfacesmore » reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.« less

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

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

Mezher, Michelle; Mansfield, Lorelle M.; Horsley, Kimberly

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfacesmore » reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.« less

Microstructure and thermoelectric properties of CuInSe2/In2Se3 compound

NASA Astrophysics Data System (ADS)

Wang, Kang; Feng, Jing; Ge, Zhen-Hua; Qin, Peng; Yu, Jie

2018-01-01

CuInSe2 powders were synthesized by solvothermal method, and then the CuInSe2/In2Se3 bulk samples were fabricated by spark plasma sintering (SPS) technique. To investigate the phase composition, the powders were determined by X-ray diffraction (XRD). The microstructures of the powders and bulk samples were observed by scanning electron microscopy (SEM). The transportation of the electronic properties and thermal conductivity were measured at room temperature to 700 K. According to the results, the CuInSe2 powders appeared in flower-like patterns which ranged from 3 μm to 6 μm. CuInSe2 powders were synthesized at 180∘C with a chalcopyrite structure. The Seebeck coefficient increased significantly in composite thermoelectric materials up to 200μVṡK-1 at 623 K. The thermal conductivity of the sample significantly decreases from the room temperature to 700 K. The CuInSe2 bulk composite by solvothermal method achieves the highest ZT value of 0.187 at 700 K.

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Schoonen, Martin A.

2017-06-01

The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and exposure to dust containing the two metal sulfides may present a health burden.

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.

Spray Chemical Vapor Deposition of Single-Source Precursors for Chalcopyrite I-III-VI2 Thin-Film Materials

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Banger, Kulbinder K.; Jin, Michael H.-C.; Harris, Jerry D.; McNatt, Jeremiah S.; Dickman, John E.

2008-01-01

Thin-film solar cells on flexible, lightweight, space-qualified substrates provide an attractive approach to fabricating solar arrays with high mass-specific power. A polycrystalline chalcopyrite absorber layer is among the new generation of photovoltaic device technologies for thin film solar cells. At NASA Glenn Research Center we have focused on the development of new single-source precursors (SSPs) for deposition of semiconducting chalcopyrite materials onto lightweight, flexible substrates. We describe the syntheses and thermal modulation of SSPs via molecular engineering. Copper indium disulfide and related thin-film materials were deposited via aerosol-assisted chemical vapor deposition using SSPs. Processing and post-processing parameters were varied in order to modify morphology, stoichiometry, crystallography, electrical properties, and optical properties to optimize device quality. Growth at atmospheric pressure in a horizontal hotwall reactor at 395 C yielded the best device films. Placing the susceptor closer to the evaporation zone and flowing a more precursor-rich carrier gas through the reactor yielded shinier-, smoother-, and denser-looking films. Growth of (112)-oriented films yielded more Cu-rich films with fewer secondary phases than growth of (204)/(220)-oriented films. Post-deposition sulfur-vapor annealing enhanced stoichiometry and crystallinity of the films. Photoluminescence studies revealed four major emission bands and a broad band associated with deep defects. The highest device efficiency for an aerosol-assisted chemical vapor deposited cell was one percent.

Magmatic sulphides in Quaternary Ecuadorian arc magmas

NASA Astrophysics Data System (ADS)

Georgatou, Ariadni; Chiaradia, Massimo; Rezeau, Hervé; Wälle, Markus

2018-01-01

New petrographic and geochemical data on magmatic sulphide inclusions (MSIs) are presented and discussed for 15 Quaternary volcanic centers of the Ecuadorian frontal, main and back volcanic arc. MSIs occur mostly in Fe-Ti oxides (magnetite and/or magnetite-ilmenite pair) and to a lesser extent in silicate minerals (amphibole, plagioclase, and pyroxene). MSIs are present in all volcanic centers ranging in composition from basalt to dacite (SiO2 = 50-67 wt.%), indicating that sulphide saturation occurs at various stages of magmatic evolution and independently from the volcano location along the volcanic arc. MSIs also occur in dioritic, gabbroic and hornblenditic magmatic enclaves of the volcanic rocks. MSIs display variable sizes (1-30 μm) and shapes (globular, ellipsoidal, angular, irregular) and occur mostly as polymineralic inclusions composed of Fe-rich and Cu-poor (pyrrhotite) and Cu-rich (mostly chalcopyrite) phases. Aerial sulphide relative abundances range from 0.3 to 7 ppm in volcanic host rocks and from 13 to 24 ppm in magmatic enclaves. Electron microprobe analyses of MSIs indicate maximum metal contents of Cu = 65.7 wt.%, Fe = 65.2 wt.%, Ni = 10.1 wt.% for those hosted in the volcanic rocks and of Cu = 57.7 wt.%, Fe = 60.9 wt.%, Ni = 5.1 wt.%, for those hosted in magmatic enclaves. Relationships of the sulphide chemistry to the host whole rock chemistry show that with magmatic differentiation (e.g., increasing SiO2) the Cu and Ni content of sulphides decrease whereas the Fe and S contents increase. The opposite behavior is observed with the increase of Cu in the whole rock, because the latter is anti-correlated with the SiO2 whole rock content. Laser ablation ICP-MS analyses of MSIs returned maximum values of PGEs and noble metals of Pd = 30 ppm, Rh = 8.1 ppm, Ag = 92.8 ppm and Au = 0.6 ppm and Pd = 43 ppm, Rh = 22.6 ppm, Ag = 89 ppm and Au = 1 ppm for those hosted in volcanic rocks and magmatic enclaves, respectively. These PGE contents display a different range of values with respect to those in previously investigated magmatic sulphides. MSIs that are Cu- and PGE/Cu-rich are found in less evolved rocks (i.e., lower SiO2 contents) that also display a lower amount of sulphide inclusions. Cu-rich sulphide phases (chalcopyrite ± bornite) are mostly hosted by magnetite, whereas PGE-rich ones consist of a Cu-poor phase (pyrrhotite) hosted by plagioclase. However, no systematic changes in the chemistry of the host silicate mineral are observed in coincidence with the occurrence of MSIs. We use the results of our study to draw some implications on Cu (and other chalcophile elements) behavior during arc magmatic processes potentially associated with the formation of porphyry-type deposits.

Igneous and Ore-Forming Processes at the Roots of Giant - Ultra-Mafic Pluming System: the Seiland Igneous Comples, Norway

NASA Astrophysics Data System (ADS)

Larsen, R. B.; Iljina, M.; Schanke, M.

2012-12-01

SIP covers an area of 5500 km2 in N. Norway. 50 % of the volume comprises mafic layered or homogenous plg+px+Fe-Ti±ol gabbros. 25 % of the area comprises ultramafic intrusions, mostly peridotite and subsidiary pyroxenite and hornblendite. 25 % comprises calc-alkaline and alkaline plutons, respectively. Ultramafic plutons intersect gabbros and calc-alkaline plutons. Recent zircon U/Pb geochronology imply that SIP formed at 560-570 Ma, with mafic- and ultramafic rocks being emplaced in <4 Ma (Roberts et al., Geol. Mag, 2007). Geothermobarometry of contact metamorphic mineral assemblages, implies minimum depth of 20-30 kilometres. Accordingly, the Seiland province arguably provides a unique cross section through the deep-seated parts of a huge magmatic plumbing system. Sulphide Cu-Ni-(PGE) deposits are intimately associated with the ultramafic rock suite. One deposit from Stjernøy comprises sulphide dissiminations at the floor of a peridotitic pluton, another deposit occur at the floor of the Reinfjord ultramafic layered complex in the far West of SIP and the third deposit comprises vertical sulphide dykes in the interior of a hornblendite on the Øksfjord peninsula. Currently, only the Reinfjord deposit is studied in detail. The Reinfjord intrusions is layered and develops from olivine clinopyroxenites in the Lower Zone to wherlite in the Middle Zone to wehrlites and dunite in the Upper Zone. Earlier studies suggest parental melts with pyroxenitic compositions whereas the dunites and wherlites formed by fractional crystallization (Bennet et al., Bull. NGU, 405, 1-41). During our fieldwork we observed spectacular examples of cumulus structures, not previously reported, and including modally layered and modally graded dunite/wherlite, cross-bedding, slumping and mush-diapirs. Finally we saw an example of magma-replenishment where an olivine pyroxenitic magma was emplaced in to and mixed with the contemporary olivine/wherlite mushes!. The country rock gabbros were unconsolidated and were partially melted during emplacement of the hot peridotitic melts. Previous studies (Søyland Hansen, 1971, unpub. MSc thesis, NTNU) and our preliminary work document dissiminated Cu-Ni sulphides in a 10-20 metres thick and two km's long deposit at the lower contacts of the Reinfjord intrusion. Several analysis imply 0.15 wt% for both Ni and Cu. The sulphide assemblage iincludes pentlandite, chalcopyrite, pyrrhotite and minor pyrite. Pentlandite is partially bravoitised. Airborne and ground geophysics done as part of our study implied a bowled shaped conducter c. 100 metres below the surface. Exploratory drilling confirmed two layers of 7 and 9 metres, respectively with 0.3-0.4 wt% Ni and minor Cu. The 9 m's zone included 5 m's with 0.6 ppm PGE+Au. Ni is in pentlandite whereas Cu is in chalcopyrite, cubanite or native Cu that apparently exsolved from Chalcopyrite. All sulphide deposits at Reinfjord has only 0.3 to 0.7 wt% S. The source of S is currently unknown, but new sulphur isotope data will be reported at the AGU-meeting.

The Transfiguration continental red-bed Cu-Pb-Zn-Ag deposit, Quebec Appalachians, Canada

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Beaudoin, Georges; Taylor, Bruce E.

2009-04-01

The Transfiguration Cu-Pb-Zn-Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from -7.5‰ to -1.1‰ δ13C and from 14.7‰ to 21.3‰ δ18O. The negative δ13C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from -19‰ to 25‰ δ34S, as measured on mineral concentrates by a conventional SO2 technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ34S values, from -21‰ to 25‰. Negative and positive δ34S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ34S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised by the ponding of groundwater over the Taconian unconformity, recorded by calcrete and early pyrite formation via BSR in grey sandstone. Early pyrite contains up to 2 wt.% Pb, which is consistent with Pb fixation by sulphate-reducing bacteria. The second stage (II) is defined by the replacement of early pyrite by chalcopyrite, as well as by sulphide precipitation via either BSR or thermochemical sulphate reduction (TSR) in grey sandstone. This event resulted from the synsedimentary fault-controlled percolation and mixing of (1) an oxidising, sulphate-bearing cupriferous fluid migrating per descensum from the red-bed sequence and (2) a hydrocarbon-bearing fluid migrating per ascensum from the Cambro-Ordovician basement. Mixing between the two fluids led to sulphate reduction, causing Cu sulphide precipitation. The positive correlation between Cu and Fe3+/Fe2+ bulk rock values suggests that Fe acted as a redox agent during sulphate reduction. Stage II diagenetic fluid migration is tentatively attributed to the Late Silurian Salinic extensional event.

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)

Insight into the core-shell structures of Cu-In-S microspheres

NASA Astrophysics Data System (ADS)

Wochnik, Angela S.; Frank, Anna; Heinzl, Christoph; Häusler, Jonas; Schneider, Julian; Hoffmann, Ramona; Matich, Sonja; Scheu, Christina

2013-12-01

In this study we report about the inner and outer structure of CuInS2 microspheres which might be used e.g. in pastes for simple, low-cost solar cell preparation, as well as in electrodes for light-driven water splitting. The microspheres are synthesized via a mild, template-free solvothermal synthesis route and characterised by electron and focused ion beam microscopy, X-ray diffraction, inductively coupled plasma atomic emission and energy dispersive X-ray spectroscopy. The investigations of cross sections prepared by focused ion beam showed that the spheres consist of compact cores and flaky surface structures. Depending on the reaction time, the core possesses a stoichiometric or Cu-rich chemical composition surrounded by an In-rich shell. The flaky surface always comprises a stoichiometric composition in tetragonal chalcopyrite crystal structure, whereas the other areas additionally show minor contributions of CuS, and CuInS2 in hexagonal wurtzite structure. The presence of different phases can be beneficial for future applications since they offer different absorption behaviour in the visible range.

RBS-channeling study of radiation damage in Ar{sup +} implanted CuInSe{sub 2} crystals

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

Yakushev, Michael V., E-mail: michael.yakushev@strath.ac.uk; Ural Federal University, Ekaterinburg 620002; Institute of Solid State Chemistry of the Urals Branch of RAS, Ekaterinburg 620990

2016-09-15

Chalcopyrite solar cells are reported to have a high tolerance to irradiation by high energy electrons or ions, but the origin of this is not well understood. This work studies the evolution of damage in Ar{sup +}-bombarded CuInSe{sub 2} single crystal using Rutherford backscattering/channeling analysis. Ar{sup +} ions of 30 keV were implanted with doses in the range from 10{sup 12} to 3 × 10{sup 16} cm{sup −2} at room temperature. Implantation was found to create two layers of damage: (1) on the surface, caused by preferential sputtering of Se and Cu atoms; (2) at the layer of implanted Ar, possibly consisting of stackingmore » faults and dislocation loops. The damage in the second layer was estimated to be less than 2% of the theoretical prediction suggesting efficient healing of primary implantation defects.« less

Preparation of CuIn{sub x}Ga{sub 1{minus}x}Se{sub 2} thin films on Si substrates

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

Yamamoto, Yukio; Yamaguchi, Toshiyuki; Suzuki, Masayoshi

For fabricating efficient tandem solar cells, CuIn{sub x}Ga{sub 1{minus}x}Se{sub 2} thin films have been prepared on Si(100), Si(110) and Si(111) substrates in the temperature range (R.T.{approximately}400 C) by rf sputtering. From EPMA analysis, these sputtered thin films are found to be nearly stoichiometric over the whole substrate temperature range, irrespective of the azimuth plane of the Si substrate. XPS studies showed that the compositional depth profile in these thin films is uniform. X-ray diffraction analysis indicated that all the thin films had a chalcopyrite structure. CuIn{sub x}Ga{sub 1{minus}x}Se{sub 2} thin films were strongly oriented along the (112) plane with increasingmore » the substrate temperature, independent of the azimuth plane of the Si substrate, suggesting the larger grain growth.« less

Post-collisional magmatism and ore-forming systems in the Menderes massif: new constraints from the Miocene porphyry Mo-Cu Pınarbaşı system, Gediz-Kütahya, western Turkey

NASA Astrophysics Data System (ADS)

Delibaş, Okan; Moritz, Robert; Chiaradia, Massimo; Selby, David; Ulianov, Alexey; Revan, Mustafa Kemal

2017-12-01

The Pınarbaşı Mo-Cu prospect is hosted within the Pınarbaşı intrusion, which is exposed together with the NW-SE-trending Koyunoba, Eğrigöz, and Baklan plutons along the northeastern border of the Menderes massif. The Pınarbaşı intrusion predominantly comprises monzonite, porphyritic granite, and monzodiorite. All units of the Pınarbaşı intrusion have sharp intrusive contacts with each other. The principal mineralization style at the Pınarbaşı prospect is a porphyry-type Mo-Cu mineralization hosted predominantly by monzonite and porphyritic granite. The porphyry type Mo-Cu mineralization consists mostly of stockwork and NE- and EW-striking sub-vertical quartz veins. Stockwork-type quartz veins hosted by the upper parts of the porphyritic granite within the monzonite, are typically enriched in chalcopyrite, molybdenite, pyrite, and limonite. The late NE- and EW-striking normal faults cut the stockwork vein system and control the quartz-molybdenite-chalcopyrite-sphalerite-fahlore-galena veins, as well as molybdenite-hematite-bearing silicified zones. Lithogeochemical and whole-rock radiogenic isotope data (Sr, Nd and Pb) of the host rocks, together with Re-Os molybdenite ages (18.3 ± 0.1 Ma - 18.2 ± 0.1 Ma) reveal that the monzonitic and granitic rocks of the Pınarbaşı intrusion were derived from an enriched lithospheric mantle-lower crust during Oligo-Miocene post-collisional magmatism. The lithospheric mantle was metasomatised by fluids and subducted sediments, and the mantle-derived melts interacted with lower crust at 35-40 km depth. This mechanism explains the Mo and Cu enrichments of the Pınarbaşı intrusion during back-arc magmatism. We conclude that the melt of the Pınarbaşı intrusion could have rapidly ascended to mid-crustal levels, with only limited crustal assimilation along major trans-lithospheric faults as a result of thinning of the middle to upper crust during regional extension, and resulted in the development of porphyry-style mineralization during the early Miocene (˜18 Ma). The subsequent exhumation history of the Mo-Cu-bearing Pınarbaşı intrusion is attributed to regional-scale uplift, and further exhumation along detachment faults of the associated core complexes during the middle to late Miocene.

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.

Properties of CuInS₂ Nano-Particles on TiO₂ by Spray Pyrolysis for CuInS₂/TiO₂ Composite Solar Cell.

PubMed

Park, Gye-Choon; Li, Zhen-Yu; Yang, O-Bong

2017-04-01

In this letter, for the absorption layer of a CuInS₂/TiO₂ composite solar cell, I–III–VI2 chalcopyrite semiconductor CuInS₂ nano-particles were deposited by using spray pyrolysis method on TiO2 porous film. Their material characteristics including structural and optical properties of CuInS₂ nano-particles on TiO₂ nanorods were analyzed as a function of its composition ratios of Cu:In:S. Crystalline structure, surface morphology and crystalline size were also investigated by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), and High-Resolution TEM (HRTEM), respectively. On the other hand, optical property was characterized by an UV-Visible Spectrophotometer. As a result, it was found that the size of CuInS₂ nano-particles, which was formed at 300±5 °C, was smaller than 16 nm from HRTEM analyses, and it was identified that the CuInS₂ particle size was increased as increasing the heat-treatment temperature and time. However, as the size of CuInS₂ nano-particle becomes smaller, optical absorption edge of ternary compound film tends to move to the blue wavelength band. It turns out that the optical energy-band gap of the compound films was ranging from 1.48 eV to 1.53 eV.

Self-assembled synthesis of 3D Cu(In1 - xGax)Se2 nanoarrays by one-step electroless deposition into ordered AAO template

NASA Astrophysics Data System (ADS)

Zhang, Bin; Zhou, Tao; Zheng, Maojun; Xiong, Zuzhou; Zhu, Changqing; Li, Hong; Wang, Faze; Ma, Li; Shen, Wenzhong

2014-07-01

Quaternary nanostructured Cu(In1 - xGax)Se2 (CIGS) arrays were successfully fabricated via a novel and simple solution-based protocol on the electroless deposition method, using a flexible, highly ordered anodic aluminium oxide (AAO) substrate. This method does not require electric power, complicated sensitization processes, or complexing agents, but provides nearly 100% pore fill factor to AAO templates. The field emission scanning electron microscopy (FE-SEM) images show that we obtained uniformly three-dimensional nanostructured CIGS arrays, and we can tailor the diameter and wall thicknesses of the nanostructure by adjusting the pore diameter of the AAO and metal Mo layer. Their chemical composition was determined by energy-dispersive spectroscopy analysis, which is very close to the stoichiometric value. The Raman spectroscopy, x-ray diffraction (XRD) pattern, and transmission electron microscopy (TEM) further confirm the formation of nanostructured CIGS with prominent chalcopyrite structure. The nanostructured CIGS arrays can support the design of low-cost, highlight-trapping, and enhanced carrier collection nanostructured solar cells.

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.

Potassium-induced surface modification of Cu(In,Ga)Se2 thin films for high-efficiency solar cells.

PubMed

Chirilă, Adrian; Reinhard, Patrick; Pianezzi, Fabian; Bloesch, Patrick; Uhl, Alexander R; Fella, Carolin; Kranz, Lukas; Keller, Debora; Gretener, Christina; Hagendorfer, Harald; Jaeger, Dominik; Erni, Rolf; Nishiwaki, Shiro; Buecheler, Stephan; Tiwari, Ayodhya N

2013-12-01

Thin-film photovoltaic devices based on chalcopyrite Cu(In,Ga)Se2 (CIGS) absorber layers show excellent light-to-power conversion efficiencies exceeding 20%. This high performance level requires a small amount of alkaline metals incorporated into the CIGS layer, naturally provided by soda lime glass substrates used for processing of champion devices. The use of flexible substrates requires distinct incorporation of the alkaline metals, and so far mainly Na was believed to be the most favourable element, whereas other alkaline metals have resulted in significantly inferior device performance. Here we present a new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer. The described treatment leads to a significant depletion of Cu and Ga concentrations in the CIGS near-surface region and enables a significant thickness reduction of the CdS buffer layer without the commonly observed losses in photovoltaic parameters. Ion exchange processes, well known in other research areas, are proposed as underlying mechanisms responsible for the changes in chemical composition of the deposited CIGS layer and interface properties of the heterojunction.

Sulphur isotope constraints on formation conditions of the Luiswishi ore deposit, Democratic Republic of Congo (DRC)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Cailteux, J.; Kampunzu, A. B.; Milesi, J. P.; Fléhoc, C.

2005-07-01

Luiswishi is a Congo-type Neoproterozoic sediment-hosted stratiform Cu-Co ore deposit of the Central Africa Copperbelt, located northwest of Lubumbashi (DRC). The ores form two main Cu-Co orebodies hosted by the Mines Subgroup, one in the lower part of the Kamoto Formation and the other at the base of the Dolomitic Shales Formation. Sulphides occur essentially as early parallel layers of chalcopyrite and carrolite, and secondarily as late stockwork sulphides cross-cutting the bedding and the early sulphide generation. Both types of stratiform and stockwork chalcopyrite and carrolite were systematically analyzed for sulphur isotopes, along the lithostratigraphic succession of the Mine Series. The quite similar δ 34S values of stratiform sulphides and late stockwork sulphides suggest an in situ recrystallization or a slight remobilization of stockwork sulphides without attainment of isotopic equilibrium between different sulphide phases (chalcopyrite and carrolite). The distribution of δ 34S values (-14.4‰ to +17.5‰) combined with the lithology indicates a strong stratigraphic control of the sulphur isotope signature, supporting bacterial sulphate reduction during early diagenesis of the host sediments, in a shallow marine to lacustrine environment. Petrological features combined with sulphur isotopic data of sulphides at Luiswishi and previous results on nodules of anhydrite in the Mine Series indicate a dominant seawater/lacustrine origin for sulphates, precluding a possible hydrothermal participation. The high positive δ 34S values of sulphides in the lower orebody at Luiswishi, hosted in massive chloritic-dolomitic siltite (known as Grey R.A.T.), fine-grained stratified dolostone (D.Strat.) and silicified-stromatolitic dolomites alternating with chloritic-dolomitic silty beds (R.S.F.), suggest that they were probably deposited during a period of regression in a basin cut off from seawater. The variations of δ 34S values (i.e. the decrease of δ 34S values from the Kamoto Formation to the overlying Dolomitic Shales and then the slight increase from S.D.2d to S.D.3a and S.D.3b members) are in perfect agreement with the inferred lithological and transgressive-regressive evolution of the ore-hosting sedimentary rocks [Cailteux, J., 1994. Lithostratigraphy of the Neoproterozoic Shaba-type (Zaire) Roan Supergroup and metallogenesis of associated stratiform mineralization. In: Kampunzu A.B., Lubala, R.T. (Eds.), Neoproterozoic Belts of Zambia, Zaire and Namibia. Journal of African Earth Sciences 19, 279-301].

Analysis of future generation solar cells and materials

NASA Astrophysics Data System (ADS)

Yamaguchi, Masafumi; Zhu, Lin; Akiyama, Hidefumi; Kanemitsu, Yoshihiko; Tampo, Hitoshi; Shibata, Hajime; Lee, Kan-Hua; Araki, Kenji; Kojima, Nobuaki

2018-04-01

The efficiency potentials of future generation solar cells such as wide bandgap chalcopyrite, Cu2ZnSnS4 (CZTS), Cu2ZnSn(S,Se)4 (CZTSSe), multi quantum well (MQW) and quantum dot (QD) solar cells are discussed on the basis of external radiative efficiency (ERE), open-circuit voltage loss, fill factor loss, and nonradiative recombination losses. CZTS and CZTSSe solar cells have efficiency potentials of more than 20% owing to the improvement in ERE from about 0.001 to 1%. MQW and QD cells have efficiency potentials of 24.8%, and 25.8% owing to the improvement in ERE from around 0.01 to 0.1%, and 1%, respectively. In this paper, the effects of nonradiative recombination on the properties of future generation solar cells are discussed.

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.

First-principles study on alkali-metal effect of Li, Na, and K in CuInSe2 and CuGaSe2

NASA Astrophysics Data System (ADS)

Maeda, Tsuyoshi; Kawabata, Atsuhito; Wada, Takahiro

2015-08-01

The substitution energies and migration energies of the alkali metal atoms of Li, Na, and K in CuInSe2 (CIS) and CuGaSe2 (CGS) were investigated by first-principles calculations. The substitution energies of Li, Na, and K atoms in CIS and CGS were calculated for two different cationic atom positions of Cu and In/Ga in the chalcopyrite unit cell. In CIS and CGS, the substitution energies of NaCu are much lower than those of NaIn and NaGa. The substitution energies of the LiCu atoms in CIS and CGS are lower than those of NaCu, while the substitution energies of KCu atoms in CIS and CGS are much higher than those of NaCu. Therefore, it is difficult to form KCu in CIS and CGS. The migration energies of Li, Na, and K atoms in CIS and CGS are obtained by a combination of the linear and quadratic synchronous transit (LST/QST) methods and the nudged elastic band (NEB) method. The theoretical migration energies of a Na atom at the Cu site to the nearest Cu vacancy (NaCu → VCu) in CIS and CGS are much lower than those of (CuCu → VCu) in CIS and CGS. The mechanism underlying the alkali metal effect of Li, Na, and K in the CIGS film during the post-deposition treatment of LiF, NaF, and KF is discussed on the basis of the calculated substitution and migration energies.

Leaching of S, Cu, and Fe from disseminated Ni-(Fe)-(Cu) sulphide ore during serpentinization of dunite host rocks at Mount Keith, Agnew-Wiluna belt, Western Australia

NASA Astrophysics Data System (ADS)

Gole, Martin J.

2014-10-01

Komatiite-hosted disseminated Ni sulphide deposits in the Agnew-Wiluna greenstone belt occur both above and below the olivine isograd that was imposed on the greenstone sequence during the M2 metamorphic/deformation event. Deposits in the northern and central part of the belt and that are located below the isograd (Mount Keith, Honeymoon Well and West Jordan) have complex sulphide mineralogy and strongly zoned sulphide assemblages. These range from least-altered assemblages of pentlandite-pyrrhotite-chalcopyrite±pyrite to altered assemblages of pentlandite±chalcopyrite, pentlandite-heazlewoodite (or millerite), heazlewoodite (or millerite), and rarely to heazlewoodite-native Ni. Deposits to the south and that are above of the olivine isograd (Six Mile, Goliath North) are dominated by less complex magmatic assemblages with a lower proportion of weakly altered pentlandite±chalcopyrite assemblages. More altered assemblages are uncommon in these deposits and occur as isolated patches around the periphery of the deposits. The sulphide zonation is reflected by whole-rock reductions in S, Cu, Fe and Zn, whereas Ni, Pt and Pd and, with some exceptions, Co are conservative. The leaching of S, Cu, Fe and Zn from sulphide assemblages and the whole rock was initiated by highly reduced conditions that were produced during low fluid/rock ratio serpentinization. Consumption of H2O resulted in Cl, a component of the fluid, being concentrated sufficiently to stabilise iowaite as part of lizardite-rich assemblages. Once the rate of olivine hydration reactions declined and during and after expansion and associated fracturing of the ultramafic sequence allowed higher fluid access, a more fluid-dominated environment formed and new carbonate-bearing fluid gained access to varying extents to the ultramafic rock sequence. This drove Cl from iowaite (to form pyroaurite) and caused the sulphide assemblages to be altered from the original magmatic assemblages and compositions to those stable at the prevailing fO2 and fS2 conditions. Mass transfer was made possible via metal chloride complexes and H2S with fluids driven by deformation associated with the M2 metamorphism. Disseminated deposits in higher metamorphic grade terrains where olivine was stable during peak metamorphism did not undergo the metasomatism seen in the deposits in areas of lower metamorphic grade. Some minor leaching of S, Fe and Cu occurred around the periphery of the deposits during early, pre-M2 peak metamorphism, but once olivine stability was reached the driving force for the series of leaching reactions was exhausted. The effect of this process on the original magmatic sulphides is to induce significant variability in texture, mineralogy and bulk composition and to markedly reduce the Fe and S contents of the sulphide fraction (in extreme cases to zero for both elements), and to reduce the volume of the sulphide fraction per unit of Ni. These changes impact unfavourably on Ni sulphide recoveries and metallurgical characteristics of these Ni ores.

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.

Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite weathering at historic mine sites Špania Dolina-Piesky and Lubietová-Svätodušná, Slovakia

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

Bor,; #269; inová rAdková, AnežkA

The legacy of copper (Cu) mining at Špania Dolina-Piesky and Lubietová-Svätodušná (central Slovakia) is waste rock and soil, surface waters, and groundwaters contaminated with antimony (Sb), arsenic (As), Cu, and other metals. Copper ore is hosted in chalcopyrite (CuFeS2) and sulfosalt solid-solution tetrahedrite-tennantite {Cu6[Cu4(Fe,Zn)2]Sb4S13–Cu6[Cu4(Fe,Zn)2]As4S13} that show wide-spread oxidation characteristic by olive-green color secondary minerals. Tetrahedrite-tennantite can be a significant source of As and Sb contamination. Synchrotron-based μ-XRD, μ-XRF, and μ-XANES combined with electron microprobe analyses have been used to determine the mineralogy, chemical composition, element distribution, and Sb speciation in tetrahedrite-tennantite oxidation products in waste rock. Our results show thatmore » the mobility of Sb is limited by the formation of oxidation products such as tripuhyite and roméite group mineral containing 36.54 wt% Sb for samples where the primary mineral chemical composition is close to tetrahedrite end-member. Antimony K-edge μ-XANES spectra of these oxidation products indicate that the predominant Sb oxidation state is 5+. Arsenic and Cu are also hosted by amorphous phases containing 6.23 wt% Sb on average and these are intergrown with tripuhyite and roméite. Antimony in this environment is not very mobile, meaning it is not easily released from solid phases to water, especially compared to As, Cu, and S. For samples where the primary sulfosalt is close to tennantite composition, the oxidation products associated with tennantite relicts contain 2.43 wt% Sb and are amorphous. The variable solubility of the secondary minerals that have been identified is expected to influence mobility of Sb and As in near-surface environment.« less

Temperature induced CuInSe2 nanocrystal formation in the Cu2Se-In3Se2 multilayer thin films

NASA Astrophysics Data System (ADS)

Mohan, A.; Rajesh, S.

2017-04-01

The paper deals with the impact of annealing on Cu2Se-In3Se2 multilayer structure and discusses the quantum confinements. Thermal evaporation technique was used to prepare multilayer films over the glass substrates. The films were annealed at different temperatures (150 °C-350 °C) under vacuum atmosphere. The XRD pattern reveals that the films exhibit (112) peaks with CuInSe2 Chalcopyrite structure and upon annealing crystallinity improved. The grain size comes around 13-19 nm. The optical band gap value was found to be 2.21 to 2.09 eV and band gap splitting was observed for higher annealing temperatures. The increase in the band gap is related to quantum confinement effect. SEM image shows nano crystals spread over the entire surface for higher annealing temperatures. Optical absorption and PL spectra shows the blue shift during annealing. The HR-TEM shows the particle size in the nano range and which confirms the CuInSe2 nanocrystal formation. AFM image shows the rough surface with homogenous grains for the as deposited films and smooth surface for annealed films.

Geology, ore facies and sulfur isotopes geochemistry of the Nudeh Besshi-type volcanogenic massive sulfide deposit, southwest Sabzevar basin, Iran

NASA Astrophysics Data System (ADS)

Maghfouri, Sajjad; Rastad, Ebrahim; Mousivand, Fardin; Lin, Ye; Zaw, Khin

2016-08-01

The southwest Sabzevar basin is placed in the southwestern part of a crustal domain known as the Sabzevar zone, at the north of Central Iranian microcontinent. This basin hosts abundant mineral deposits; particularly of the Mn exhalative and Cu-Zn volcanogenic massive sulfide (VMS) types. The evolution of this basin is governed by the Neo-tethys oceanic crust subduction beneath the Central Iranian microcontinent and by the resulting continental arc (Sanandaj-Sirjan) and back-arc (Sabzevar-Naien). This evolution followed two major sequences: (I) Lower Late Cretaceous Volcano-Sedimentary Sequence (LLCVSS), which is indicated by fine-grained siliciclastic sediments, gray basic coarse-grained different pyroclastic rocks and bimodal volcanism. During this stage, tuff-hosted stratiform, exhalative Mn deposits (Nudeh, Benesbourd, Ferizy and Goft), oxide Cu deposits (Garab and Ferizy) and Cu-Zn VMS (Nudeh, Chun and Lala) deposits formed. (II) Upper Late Cretaceous Sedimentary Dominated Sequence (ULCSS), including pelagic limestone, marly tuff, silty limestone and marl with minor andesitic tuff rocks. The economically most important Mn (Zakeri and Cheshmeh-sefid) deposits of Sabzevar zone occur within the marly tuff of this sequence. The Nudeh Cu-Zn volcanogenic massive sulfide (VMS) deposit is situated in the LLCVSS. The host-rock of deposits consists of alkali olivine basalt flow and tuffaceous silty sandstone. Mineralization occurs as stratiform blanket-like and tabular orebodies. Based on ore body structure, mineralogy, and ore fabric, we recognize three different ore facies in the Nudeh deposit: (1) a stringer zone, consisting of a discordant mineralization of sulfides forming a stockwork of sulfide-bearing quartz veins cutting the footwall volcano-sedimentary rocks; (2) a massive ore, consisting of massive replacement pyrite, chalcopyrite, sphalerite and Friedrichite with magnetite; (3) bedded ore, with laminated to disseminated pyrite, and chalcopyrite. Chloritization, silicification, sericitization and epidotization are the main wall-rock alterations; alteration intensity increases towards the stringer zone. The δ34S composition of the sulfides ranges from -1.5‰ to +3.69‰ with a general increase of δ34S ratios of massive ore facies to stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones. Sulfur isotopes, along with sedimentological, textural, petrological, mineralogical, and geochemical evidences, suggest that this deposit should be classified as a Besshi-type VMS ore deposit.

Geology and mineralization of the Jabalat alkali-feldspar granite, northern Asir region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Al Tayyar, Jaffar; Jackson, Norman J.; Al-Yazidi, Saeed

The Jabalat post-tectonic granite pluton is composed of albite- and oligoclase-bearing, low-calcium, F-, Sn- and Rb-rich subsolvus granites. These granites display evidence of late-magmatic, granitophile- and metallic-element specialization, resulting ultimately in the development of post-magmatic, metalliferous hydrothermal systems characterized by a Mo sbnd Sn sbnd Cu sbnd Pb sbnd Zn sbnd Bi sbnd Ag sbnd F signature. Two main types of mineralization are present within the pluton and its environs: (1) weakly mineralized felsic and aplitic dikes and veins enhanced in Mo, Bi, Ag, Pb and Cu; and (2) pyrite—molybdenite—chalcopyrite-bearing quartz and quartz—feldspar veins rich in Mo, Sn, Bi, Cu, Zn and Ag. A satellite stock, 3 km north of the main intrusion, is composed of fine-grained, miarolitic, muscovite—albite—microcline (microperthite) granite. The flanks of this intrusion and adjacent dioritic rocks are greisenized and highly enriched in Sn, Bi and Ag. Quartz veins which transect the satellite stock contain molybdenite and stannite.

Ecofriendly and Nonvacuum Electrostatic Spray-Assisted Vapor Deposition of Cu(In,Ga)(S,Se)2 Thin Film Solar Cells.

PubMed

Hossain, Md Anower; Wang, Mingqing; Choy, Kwang-Leong

2015-10-14

Chalcopyrite Cu(In,Ga)(S,Se)2 (CIGSSe) thin films have been deposited by a novel, nonvacuum, and cost-effective electrostatic spray-assisted vapor deposition (ESAVD) method. The generation of a fine aerosol of precursor solution, and their controlled deposition onto a molybdenum substrate, results in adherent, dense, and uniform Cu(In,Ga)S2 (CIGS) films. This is an essential tool to keep the interfacial area of thin film solar cells to a minimum value for efficient charge separation as it helps to achieve the desired surface smoothness uniformity for subsequent cadmium sulfide and window layer deposition. This nonvacuum aerosol based approach for making the CIGSSe film uses environmentally benign precursor solution, and it is cheaper for producing solar cells than that of the vacuum-based thin film solar technology. An optimized CIGSSe thin film solar cell with a device configuration of molybdenum-coated soda-lime glass substrate/CIGSSe/CdS/i-ZnO/AZO shows the photovoltaic (j-V) characteristics of Voc=0.518 V, jsc=28.79 mA cm(-2), fill factor=64.02%, and a promising power conversion efficiency of η=9.55% under simulated AM 1.5 100 mW cm(-2) illuminations, without the use of an antireflection layer. This demonstrates the potential of ESAVD deposition as a promising alternative approach for making thin film CIGSSe solar cells at a lower cost.

Rechargeable solid state neutron detector and visible radiation indicator

DOEpatents

Stowe, Ashley C.; Wiggins, Brenden; Burger, Arnold

2017-05-23

A radiation detection device, including: a support structure; and a chalcopyrite crystal coupled to the support structure; wherein, when the chalcopyrite crystal is exposed to radiation, a visible spectrum of the chalcopyrite crystal changes from an initial color to a modified color. The visible spectrum of the chalcopyrite crystal is changed back from the modified color to the initial color by annealing the chalcopyrite crystal at an elevated temperature below a melting point of the chalcopyrite crystal over time. The chalcopyrite crystal is optionally a .sup.6LiInSe.sub.2 crystal. The radiation is comprised of neutrons that decrease the .sup.6Li concentration of the chalcopyrite crystal via a .sup.6Li(n,.alpha.) reaction. The initial color is yellow and the modified color is one of orange and red. The annealing temperature is between about 450 degrees C. and about 650 degrees C. and the annealing time is between about 12 hrs and about 36 hrs.

Slime coating of kaolinite on chalcopyrite in saline water flotation

NASA Astrophysics Data System (ADS)

Li, Zhi-li; Rao, Feng; Song, Shao-xian; Li, Yan-mei; Liu, Wen-biao

2018-05-01

In saline water flotation, the salinity can cause a distinguishable slime coating of clay minerals on chalcopyrite particles through its effect on their electrical double layers in aqueous solutions. In this work, kaolinite was used as a representative clay mineral for studying slime coating during chalcopyrite flotation. The flotation of chalcopyrite in the presence and absence of kaolinite in tap water, seawater, and gypsum-saturated water and the stability of chalcopyrite and kaolinite particles in slurries are presented. Zeta-potential distributions and scanning electron microscopy images were used to characterize and explain the different slime coating degrees and the different flotation performances. Kaolinite particles induced slime coating on chalcopyrite surfaces and reduced chalcopyrite floatability to the greatest extent when the pH value was in the alkaline range. At 0.24wt% of kaolinite, the chalcopyrite floatability was depressed by more than 10% at alkaline pH levels in tap water. Salinity in seawater and gypsum-saturated water compressed the electrical double layers and resulted in extensive slime coating.

Insights into the relation between adhesion force and chalcopyrite-bioleaching by Acidithiobacillus ferrooxidans.

PubMed

Zhu, Jianyu; Wang, Qianfen; Zhou, Shuang; Li, Qian; Gan, Min; Jiang, Hao; Qin, Wenqing; Liu, Xueduan; Hu, Yuehua; Qiu, Guanzhou

2015-02-01

This paper presents a study on the relation between bacterial adhesion force and bioleaching rate of chalcopyrite, which sheds light on the influence of interfacial interaction on bioleaching behavior. In our research, Acidithiobacillus ferrooxidans (A. ferrooxidans) were adapted to grow with FeSO4 · 7H2O, element sulfur or chalcopyrite. Then, surface properties of Acidithiobacillus ferrooxidans and chalcopyrite were analyzed by contact angle, zeta potential and Fourier transform infrared spectroscopy (FTIR). Adhesion force between bacteria and chalcopyrite was measured by atomic force microscopy (AFM). Attachment and bioleaching behaviors were also monitored. The results showed that A. ferrooxidans adapted with chalcopyrite exhibited the strongest adhesion force to chalcopyrite and the highest bioleaching rate. Culture adapted with sulfur bacteria took second place and FeSO4 · 7H2O-adapted bacteria were the lowest. Bioleaching rate and bacterial attachment capacity were positively related to bacterial adhesion force, which is affected by the nature of energy source. According to this work, the attachment of bacteria to chalcopyrite surface is one of the most important aspects that influence the bioleaching process of chalcopyrite. Copyright © 2014 Elsevier B.V. All rights reserved.

Isolation and characterization of Ferroplasma thermophilum sp. nov., a novel extremely acidophilic, moderately thermophilic archaeon and its role in bioleaching of chalcopyrite.

PubMed

Zhou, H; Zhang, R; Hu, P; Zeng, W; Xie, Y; Wu, C; Qiu, G

2008-08-01

To isolate Ferroplasma thermophilum L1(T) from a low pH environment and to understand its role in bioleaching of chalcopyrite. Using serial dilution method, a moderately thermophilic and acidophilic ferrous iron-oxidizing archaeon, named L1(T), was isolated from a chalcopyrite-leaching bioreactor. The morphological, biochemical and physiological characteristics of strain L1(T) and its role in bioleaching of chalcopyrite were studied. Strain L1(T) was a nonmotile coccus that lacked cell wall. Strain L1(T) had a temperature optimum of 45 degrees C and the optimum pH for growth was 1.0. Strain L1(T) was capable of chemomixotrophic growth on ferrous iron and yeast extract. Results of fatty acid analysis, DNA-DNA hybridization, G+C content, and analysis based on 16S rRNA gene sequence indicated that strain L1(T) should be grouped in the genus Ferroplasma, and represented a new species, Ferroplasma thermophilum. Ferroplasma thermophilum in combination with Acidithiobacillus caldus and Leptospirillum ferriphilum could improve the copper dissolution in bioleaching of chalcopyrite. A novel extremely acidophilic, moderately thermophilic archaeon isolated from a bioleaching reactor has been identified as F. thermophilum that played an important role in bioleaching of chalcopyrite at low pH. This study contributes to understand the characteristics of F. thermophilum L1(T) and its role in bioleaching of sulfide ores.

The Archean komatiite-hosted, PGE-bearing Ni-Cu sulfide deposit at Vaara, eastern Finland: evidence for assimilation of external sulfur and post-depositional desulfurization

NASA Astrophysics Data System (ADS)

Konnunaho, J. P.; Hanski, E. J.; Bekker, A.; Halkoaho, T. A. A.; Hiebert, R. S.; Wing, B. A.

2013-12-01

Archean komatiites host important resources of Ni, Cu, Co, and PGE, particularly in Western Australia and Canada. In Finland, several small, low-grade sulfide deposits have been found in komatiites, including the ca. 2.8 Ga Vaara deposit in the Archean Suomussalmi greenstone belt. It occurs in the central part of the serpentinized olivine cumulate zone of a komatiitic extrusive body and is composed of disseminated interstitial sulfides consisting of pyrite, pentlandite, millerite, violarite, and chalcopyrite accompanied by abundant magnetite. Although currently subeconomic, the mineralization is interesting due to the very high chalcophile element contents of the sulfide fraction (38 wt% Ni, 3.4 wt% Cu, 0.7 wt% Co, 22.4 ppm Pd, and 9.5 ppm Pt). The sulfides occur in relatively Cr-poor olivine cumulates suggesting involvement of a chromite-undersaturated magma. The parental magma was an Al-undepleted komatiite with an estimated MgO content of at least 24 wt%. In contrast to the common komatiite types in the eastern Finland greenstone belts, the Vaara rocks are moderately enriched in LREE relative to MREE, suggesting that crustal contamination played an important role in the genesis of the Vaara deposit. Multiple sulfur isotope data reveal considerable mass-independent sulfur isotope fractionation both in country rock sedimentary sulfides (Δ33S ranges from -0.50 to +2.37 ‰) and in the Vaara mineralization (Δ33S ranges from +0.53 to +0.66 ‰), which provides strong evidence for incorporation of crustal sulfur. Extensive replacement of interstitial sulfides by magnetite and the presence of millerite- and violarite-bearing, pyrrhotite-free sulfide assemblages indicate significant post-magmatic, low-temperature hydrothermal oxidation of the primary magmatic pyrrhotite-pentlandite-chalcopyrite assemblages and associated sulfur loss that led to a significant upgrading of the original metal tenors of the Vaara deposit.

The Gibbs free energy of nukundamite (Cu3.38Fe0.62S4): A correction and implications for phase equilibria

USGS Publications Warehouse

Seal, R.R.; Inan, E.E.; Hemingway, B.S.

2001-01-01

The Gibbs free energy of formation of nukundamite (Cu3.38Fe0.62S4) was calculated from published experimental studies of the reaction 3.25 Cu3.38Fe0.62S4 + S2 = 11 CuS + 2 FeS2 in order to correct an erroneous expression in the published record. The correct expression describing the Gibbs free energy of formation (kJ???mol-1) of nukundamite relative to the elements and ideal S2 gas is ??fG?? nukundamite T(K) = -549.75 + 0.23242 T + 3.1284 T0.5, with an uncertainty of 0.6%. An evaluation of the phase equilibria of nukundamite with associated phases in the system Cu-Fe-S as a function of temperature and sulfur fugacity indicates that nukundamite is stable from 224 to 501??C at high sulfidation states. At its greatest extent, at 434??C, the stability field of nukundamite is only 0.4 log f(S2) units wide, which explains its rarity. Equilibria between nukundamite and bornite, which limit the stability of both phases, involve bornite compositions that deviate significantly from stoichiometric Cu5FeS4. Under equilibrium conditions in the system Cu-Fe-S, nukundamite + chalcopyrite is not a stable assemblage at any temperature.

Recent Progress Towards Space Applications Of Thin Film Solar Cells- The German Joint Project 'Flexible CIGSE Thin Film Solar Cells For Space Flight' And OOV

NASA Astrophysics Data System (ADS)

Brunner, Sebastian; Zajac, Kai; Nadler, Michael; Seifart, Klaus; Kaufmann, Christian A.; Caballero, Raquel; Schock, Hans-Werner; Hartmann, Lars; Otte, Karten; Rahm, Andreas; Scheit, Christian; Zachmann, Hendrick; Kessler, Friedrich; Wurz, Roland; Schulke, Peter

2011-10-01

A group of partners from an academic and industrial background are developing a flexible Cu(In,Ga)Se2 (CIGSe) thin film solar cell technology on a polyimide substrate that aims to be a future alternative to current rigid solar cell technologies for space applications. In particular on missions with high radiation volumes, the superior tolerance of chalcopyrite based thin film solar cell (TFSC) technologies with respect to electron and proton radiation, when compared to the established Si- or III-V based technologies, can be advantageous. Of all thin film technologies, those based on CIGSe have the highest potential to reach attractive photovoltaic conversion efficiencies and combine these with low weight in order to realize high power densities on solar cell and generator level. The use of a flexible substrate ensures a high packing density. A working demonstrator is scheduled for flight this year.

Geology, mineralization, and fluid inclusion study of the Kuru-Tegerek Au-Cu-Mo skarn deposit in the Middle Tien Shan, Kyrgyzstan

NASA Astrophysics Data System (ADS)

Soloviev, Serguei G.; Kryazhev, Sergey; Dvurechenskaya, Svetlana

2018-02-01

The Kuru-Tegerek Cu-Au-Mo deposit is situated in a system of Late Carboniferous subduction-related magmatic arcs of the Middle Tien Shan, which together constitute a metallogenic belt of Cu-Au-Mo (±W) porphyry, with local skarns, deposits. The deposit is related to magnetite-series gabbro-diorite to tonalite intrusion. It contains prograde magnesian and calcic skarns with abundant magnetite, associated with gabbro-diorite, and retrograde skarn with Cu mineralization, formed after intrusion of tonalite. Subsequent propylitic alteration introduced abundant chalcopyrite and pyrrhotite, and native Au culminating in zones overprinting magnetite and garnet skarn. Later quartz-muscovite-carbonate veins, formed after intrusion of late mafic quartz monzogabbro dikes, contain chalcopyrite, pyrite, arsenopyrite and other sulfides and sulfosalts, tellurides, and native Au. The earliest retrograde skarn garnet contains gaseous low-salinity (1.7-3.4 wt.% NaCl eq.) fluid inclusions homogenizing at 460-500 °C into vapor, indicating that the early fluid released from crystallizing magma was a low-density vapor. It was followed by more saline (4.0-5.0 wt.% NaCl eq.), high-temperature (400-440 °C) aqueous fluid, as fluid release from the magma progressed. Boiling of this fluid at temperatures of 420 to 370 °C and a pressure of 350-300 bar produced a low-salinity (0.6-1.2 wt.% NaCl eq.), essentially gaseous, and high-salinity (from 39 to 31 wt.% NaCl eq.) brine, with possible metal (including Cu) partitioning into both gaseous and aqueous-saline phases. Boiling was coeval with sulfide deposition in the retrograde skarn. The latest episode of the retrograde skarn stage included direct separation of saline ( 40-42 wt.% NaCl eq.) fluid from crystallizing magma. The separation of saline ( 40 to 14 wt.% NaCl eq.) fluids from a crystallizing magmatic melt continued during the propylitic stage, when fluid cooling from 370 to 320 °C, together with decreasing fO2, caused Cu and especially Au precipitation. A new influx of possibly magma-derived, low-salinity (4.5-6.7 wt.% NaCl eq.) aqueous, and then NaCl-CO2-H2O fluids, corresponds to the phyllic (quartz-muscovite-carbonate-sulfide) stage. These fluids may have a deeper source, associated with the late mafic quartz monzogabbro dikes. Fluid cooling (from 340 to 255 °C) and boiling of the NaCl-CO2-H2O fluid, together with increased fS2, increased the Au endowment.

Photoelectrochemical Hydrogen Production

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

Hu, Jian

The objectives of this project, covering two phases and an additional extension phase, were the development of thin film-based hybrid photovoltaic (PV)/photoelectrochemical (PEC) devices for solar-powered water splitting. The hybrid device, comprising a low-cost photoactive material integrated with amorphous silicon (a-Si:H or a-Si in short)-based solar cells as a driver, should be able to produce hydrogen with a 5% solar-to-hydrogen conversion efficiency (STH) and be durable for at least 500 hours. Three thin film material classes were studied and developed under this program: silicon-based compounds, copper chalcopyrite-based compounds, and metal oxides. With the silicon-based compounds, more specifically the amorphous siliconmore » carbide (a-SiC), we achieved a STH efficiency of 3.7% when the photoelectrode was coupled to an a-Si tandem solar cell, and a STH efficiency of 6.1% when using a crystalline Si PV driver. The hybrid PV/a-SiC device tested under a current bias of -3~4 mA/cm{sup 2}, exhibited a durability of up to ~800 hours in 0.25 M H{sub 2}SO{sub 4} electrolyte. Other than the PV driver, the most critical element affecting the photocurrent (and hence the STH efficiency) of the hybrid PV/a-SiC device was the surface energetics at the a-SiC/electrolyte interface. Without surface modification, the photocurrent of the hybrid PEC device was ~1 mA/cm{sup 2} or lower due to a surface barrier that limits the extraction of photogenerated carriers. We conducted an extensive search for suitable surface modification techniques/materials, of which the deposition of low work function metal nanoparticles was the most successful. Metal nanoparticles of ruthenium (Ru), tungsten (W) or titanium (Ti) led to an anodic shift in the onset potential. We have also been able to develop hybrid devices of various configurations in a monolithic fashion and optimized the current matching via altering the energy bandgap and thickness of each constituent cell. As a result, the short-circuit photocurrent density of the hybrid device (measured in a 2-electrode configuration) increased significantly without assistance of any external bias, i.e. from ≤1 mA/cm{sup 2} to ~5 mA/cm{sup 2}. With the copper chalcopyrite compounds, we have achieved a STH efficiency of 3.7% in a coplanar configuration with 3 a-Si solar cells and one CuGaSe{sub 2} photocathode. This material class exhibited good durability at a photocurrent density level of -4 mA/cm{sup 2} (“5% STH” equivalent) at a fixed potential (-0.45 VRHE). A poor band-edge alignment with the hydrogen evolution reaction (HER) potential was identified as the main limitation for high STH efficiency. Three new pathways have been identified to solve this issue. First, PV driver with bandgap lower than that of amorphous silicon were investigated. Crystalline silicon was identified as possible bottom cell. Mechanical stacks made with one Si solar cell and one CuGaSe{sub 2} photocathode were built. A 400 mV anodic shift was observed with the Si cell, leading to photocurrent density of -5 mA/cm{sup 2} at 0VRHE (compared to 0 mA/cm{sup 2} at the same potential without PV driver). We also investigated the use of p-n junctions to shift CuGaSe{sub 2} flatband potential anodically. Reactively sputtered zinc oxy-sulfide thin films was evaluated as n-type buffer and deposited on CuGaSe{sub 2}. Ruthenium nanoparticles were then added as HER catalyst. A 250 mV anodic shift was observed with the p-n junction, leading to photocurrent density at 0VRHE of -1.5 mA/cm{sup 2}. Combining this device with a Si solar cell in a mechanical stack configuration shifted the onset potential further (+400 mV anodically), leading to photocurrent density of -7 mA/cm{sup 2} at 0VRHE. Finally, we developed wide bandgap copper chalcopyrite thin film materials. We demonstrated that Se can be substituted with S using a simple annealing step. Photocurrent densities in the 5-6 mA/cm{sub 2} range were obtained with red 2.0eV CuInGaS{sub 2} photocathodes. With the metal oxide compounds, we have demonstrated that a WO{sub 3}-based hybrid photoelectrode was feasible. Specifically, we showed that WO{sub 3} paired with an a-Si tandem solar cell can generate short circuit photocurrent density of 2.5 mA/cm{sup 2}, equivalent to STH efficiency of 3.1%. Long-term durability tests demonstrated WO{sub 3} ability to split water over extended periods, for up to 600 hours at current density levels of 2.0-2.5 mA/cm{sup 2}. Efforts have been done to decrease WO{sub 3} bandgap using foreign elements incorporation. We did not manage to reduce the bandgap of WO{sub 3} with this method. However, more promising results have been achieved with bilayered systems, where only the top part of WO{sub 3} films was modified. Also, we have demonstrated that alloying WO{sub 3} with CuO can form 2.2eV bandgap CuWO{sub 4}. Incorporating conductive carbon nanotubes in CuWO{sub 4} reduced its intrinsic bulk resistance. Saturation photocurrent densities in the 0.4-0.5 mA/cm{sub 2} range were achieved. Recently, in collaboration with University of Texas at Arlington, we have identified new quaternary metal oxides with CuWO{sub 4} as primary material host. Our experimental work on ceramics confirmed the theoretical calculations that crowned bismuth as a possible candidate to improve CuWO{sub 4} water splitting efficiency.« less

Molecular solution processing of metal chalcogenide thin film solar cells

NASA Astrophysics Data System (ADS)

Yang, Wenbing

The barrier to utilize solar generated electricity mainly comes from their higher cost relative to fossil fuels. However, innovations with new materials and processing techniques can potentially make cost effective photovoltaics. One such strategy is to develop solution processed photovoltaics which avoid the expensive vacuum processing required by traditional solar cells. The dissertation is mainly focused on two absorber material system for thin film solar cells: chalcopyrite CuIn(S,Se)2 (CISS) and kesterite Cu2ZnSn(S,Se) 4 organized in chronological order. Chalcopyrite CISS is a very promising material. It has been demonstrated to achieve the highest efficiency among thin film solar cells. Scaled-up industry production at present has reached the giga-watt per year level. The process however mainly relies on vacuum systems which account for a significant percentage of the manufacturing cost. In the first section of this dissertation, hydrazine based solution processed CISS has been explored. The focus of the research involves the procedures to fabricate devices from solution. The topics covered in Chapter 2 include: precursor solution synthesis with a focus on understanding the solution chemistry, CISS absorber formation from precursor, properties modification toward favorable device performance, and device structure innovation toward tandem device. For photovoltaics to have a significant impact toward meeting energy demands, the annual production capability needs to be on TW-level. On such a level, raw materials supply of rare elements (indium for CIS or tellurium for CdTe) will be the bottleneck limiting the scalability. Replacing indium with zinc and tin, earth abundant kesterite CZTS exhibits great potential to reach the goal of TW-level with no limitations on raw material availability. Chapter 3 shows pioneering work towards solution processing of CZTS film at low temperature. The solution processed devices show performances which rival vacuum-based techniques and is partially attributed to the ease in controlling composition and CZTS phase through this technique. Based on this platform, comprehensive characterization on CZTS devices is carried out including solar cells and transistors. Especially defects properties are exploited in Chapter 4 targeting to identify the limiting factors for further improvement on CZTS solar cells efficiency. Finally, molecular structures and precursor solution stability have been explored, potentially to provide a universal approach to process multinary compounds.

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

PubMed

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

2016-11-09

We report the preparation of Cu 2 S, In 2 S 3 , CuInS 2 and Cu(In,Ga)S 2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN 1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

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.

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.

Semi-transparent photovoltaic glazing based on electrodeposited CIGS solar cells on patterned molybdenum/glass substrates

NASA Astrophysics Data System (ADS)

Sidali, Tarik; Bou, Adrien; Coutancier, Damien; Chassaing, Elisabeth; Theys, Bertrand; Barakel, Damien; Garuz, Richard; Thoulon, Pierre-Yves; Lincot, Daniel

2018-03-01

In this paper, a new way of preparing semi-transparent solar cells using Cu(In1-xGax)Se2 (CIGS) chalcopyrite semiconductors as absorbers for BIPV applications is presented. The key to the elaboration process consists in the co-electrodeposition of Cu-In-Ga mixed oxides on submillimetric hole-patterned molybdenum substrate, followed by thermal reduction to metallic alloys and selenisation. This method has the advantage of being a selective deposition technique where the thin film growth is carried out only on Mo covered areas. Thus, after annealing, the transparency of the sample is always preserved, allowing light to pass through the device. A complete device (5 × 5 cm2) with 535 μm diameter holes and total glass aperture of around 35% shows an open circuit voltage (VOC) of 400 mV. Locally, the I-V curves reveal a maximum efficiency of 7.7%, VOC of 460 mV, JSC of 24 mA.cm-2 in an area of 0.1 cm2 with 35% aperture. This efficiency on the semi-transparent area is equivalent to a record efficiency of 11.9% by taking into account only the effective area.

High-Resolution AES Mapping and TEM Study of Cu(In,Ga)Se2 Thin Film Growth: Preprint

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

Perkins, C. L.; Yan, Y.; Jones, K.

2001-10-01

Presented at 2001 NCPV Program Review Meeting: TEM and high-resolution AES mapping data on CIGS samples. The chalcopyrite Cu(In,Ga)Se{sub 2} (CIGS) shows promise as an absorber layer in thin polycrystalline solar cells, however, details of the PVD growth of this complicated material remain in a developing stage. Previous workers have postulated the existence of a thin film of liquid Cu{sub x}Se on the growing CIGS film, and that this layer acts as a reservoir of copper as well as a layer in which rapid mass transport is possible. In this paper we present transmission electron microscopy (TEM) and high resolutionmore » Auger electron spectroscopy (AES) mapping data taken on samples that had their growth interrupted at a stage when Cu{sub x}Se was expected to be present. The AES maps show CIGS grains which are highly enriched in copper relative to the rest of the CIGS film, and that these same areas contain almost no indium, results consistent with the presence of CuxSe. Small-area diffraction analysis and energy dispersive spectroscopy (EDS) performed on these same samples independently confirm the presence of Cu{sub x}Se at the surface of growing CIGS films.« less

Epitaxial CuInSe2 thin films grown by molecular beam epitaxy and migration enhanced epitaxy

NASA Astrophysics Data System (ADS)

Abderrafi, K.; Ribeiro-Andrade, R.; Nicoara, N.; Cerqueira, M. F.; Gonzalez Debs, M.; Limborço, H.; Salomé, P. M. P.; Gonzalez, J. C.; Briones, F.; Garcia, J. M.; Sadewasser, S.

2017-10-01

While CuInSe2 chalcopyrite materials are mainly used in their polycrystalline form to prepare thin film solar cells, epitaxial layers have been used for the characterization of defects. Typically, epitaxial layers are grown by metal-organic vapor phase epitaxy or molecular beam epitaxy (MBE). Here we present epitaxial layers grown by migration enhanced epitaxy (MEE) and compare the materials quality to MBE grown layers. CuInSe2 layers were grown on GaAs (0 0 1) substrates by co-evaporation of Cu, In, and Se using substrate temperatures of 450 °C, 530 °C, and 620 °C. The layers were characterized by high resolution X-ray diffraction (HR-XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and atomic force microscopy (AFM). HR-XRD and HR-TEM show a better crystalline quality of the MEE grown layers, and Raman scattering measurements confirm single phase CuInSe2. AFM shows the previously observed faceting of the (0 0 1) surface into {1 1 2} facets with trenches formed along the [1 1 0] direction. The surface of MEE-grown samples appears smoother compared to MBE-grown samples, a similar trend is observed with increasing growth temperature.

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.

Chemical vapor transport of chalcopyrite semiconductors: CuGaS2 and AgGaS2

NASA Astrophysics Data System (ADS)

Lauck, R.; Cardona, M.; Kremer, R. K.; Siegle, G.; Bhosale, J. S.; Ramdas, A. K.; Alawadhi, H.; Miotkowski, I.; Romero, A. H.; Muñoz, A.; Burger, A.

2014-09-01

Crystals of CuGaS2 and AgGaS2 with different isotopic compositions have been grown by chemical vapor transport (CVT) using iodine as the transport agent. Before performing the CVT growth, sulfur and copper were purified by sublimation and etching, respectively. 109Ag and the etched 71Ga isotopes were purified from oxides by vacuum annealing. Transparent yellow orange crystals of CuGaS2 and greenish yellow crystals of AgGaS2 were obtained in the shape of platelets, chunks, rods and needles in sizes of up to 8 mm (CuGaS2) and 30 mm (AgGaS2). These crystals were used to study their electronic, vibrational and thermodynamic properties. Higher excitonic states (n=2,3) were observed at low temperatures with wavelength-modulated reflectivity spectroscopy, thus proving an excellent surface and crystal quality. In addition, the experimentally determined non-monotonic temperature dependence of the excitonic energies can be well fitted by using two Bose-Einstein oscillators and their statistical factors, corresponding to characteristic acoustic and optical phonon frequencies. Isotopic shift of excitonic energies has also been successfully observed in these crystals.

Synthesis of nanoparticle emulsion collector HNP and its application in microfine chalcopyrite flotation

NASA Astrophysics Data System (ADS)

He, G. C.; Ding, J.; Huang, C. H.; Kang, Q.

2018-01-01

Hydrophobic polystyrene nanoparticles bearing thiazole groups named HNP were used as collectors to improve recovery of microfine chalcopyrite in flotation. HNP adsorbs onto microfine particles selectively, which were modified hydrophobically to induce flotation effectively. Particle size and scanning electron microscope analysis for HNP show that HNP is a spherical nano particles with small size, uniform distribution and good dispersion. Infrared spectrum analysis for HNP proved that functional monomer 2-mercapto styrene acrylic thiazole was bonded chemically onto styrene. Flotation test results indicate that HNP is the right collector of chalcopyrite. Especially, the recovery of chalcopyrite is higher than 95% in neutral and acid media. FTIR results reveal that the flotation selectivity of collector HNP is due to strong chemical absorption onto chalcopyrite surface. Zeta potential analysis shows that the zeta potential of chalcopyrite decreased more quickly after interaction with HNP with the increase of pulp pH value, confirming that collector HNP is an anionic collector. Scanning electron microscope conform that HNP has good selective adsorption on chalcopyrite.

Synergistic bioleaching of chalcopyrite and bornite in the presence of Acidithiobacillus ferrooxidans.

PubMed

Zhao, Hongbo; Wang, Jun; Hu, Minghao; Qin, Wenqing; Zhang, Yansheng; Qiu, Guanzhou

2013-12-01

Bioleaching of chalcopyrite and bornite in the presence of Acidithiobacillus ferrooxidans was carried out to investigate the influences between each other during bioleaching. Bioleaching results indicated that bornite accelerated the dissolution of chalcopyrite, and chalcopyrite also accelerated the dissolution of bornite, it could be described as a synergistic effect during bioleaching, this synergistic effect might be attributed to the galvanic effect between chalcopyrite and bornite, and to the relatively low solution potential as the addition of bornite. Significantly amount of elemental sulfur and jarosite formed on the minerals surface might be the main passivation film inhibiting the further dissolution, and the amount of elemental sulfur significantly increased with the addition of bornite. Results of electrochemical measurements indicated that the oxidation and reduction mechanisms of chalcopyrite and bornite were similar, the addition of bornite or chalcopyrite did not change the oxidative and reductive mechanisms, but increased the oxidation rate. Copyright © 2013 Elsevier Ltd. All rights reserved.

Petrogenesis of the Bosworgey granitic cusp in the SW England tin province and its implications for ore mineral genesis

NASA Astrophysics Data System (ADS)

Ball, T. K.; Basham, I. R.

1984-01-01

The Bosworgey granite cusp forms an apical portion of the concealed northern extension of the Tregonning-Godolphin granite ridge. It is characterised by unusually high values of B, P, Mn, Fe, As, Cu, Nb, Ta, Bi, Sn, W, U and S which are present largely as tourmaline, apatite, pyrite, arsenopyrite, chalcopyrite, bismuth, columbite, cassiterite, wolframite and uraninite; and low levels of Zr, Hf, Ti and REE present in zircon, ilmenite and monazite. The granite is classified as Sn and W “specialised” (Tischendorf, 1974) and it belongs to the ilmenite series of Japanese workers. The classification of Chappell and White (1974) (“S” and “I” type granites) is shown to be inapplicable to Cornubian rocks although the Bosworgey samples show characteristics of “S” type granites. The accessory mineral assemblages are typical of high temperature lodes (cassiterite, wolframite, arsenopyrite, chalcopyrite) and the assamblage is concluded to be the cusp analogue of hypothermal lodes produced by extreme differentiation and concentration of volatiles. It is speculated that such granites could provide the parent material for the mesothermal crosscourse mineralisation (pitchblende, bismuth, pyrite, galena, sphalerite).

Hybrid particles and associated methods

DOEpatents

Fox, Robert V; Rodriguez, Rene; Pak, Joshua J; Sun, Chivin

2015-02-10

Hybrid particles that comprise a coating surrounding a chalcopyrite material, the coating comprising a metal, a semiconductive material, or a polymer; a core comprising a chalcopyrite material and a shell comprising a functionalized chalcopyrite material, the shell enveloping the core; or a reaction product of a chalcopyrite material and at least one of a reagent, heat, and radiation. Methods of forming the hybrid particles are also disclosed.

Petrography, geochemistry and geochronology of the host porphyries and associated alteration at the Tuwu Cu deposit, NW China: a case for increased depositional efficiency by reaction with mafic hostrock?

NASA Astrophysics Data System (ADS)

Shen, Ping; Pan, Hongdi; Zhou, Taofa; Wang, Jingbin

2014-08-01

Tuwu is the largest porphyry copper deposit discovered in the Eastern Tianshan Mountains, Xinjiang, China. A newly recognized volcanic complex in the Early Carboniferous Qi'eshan Group at Tuwu consists of basalt, andesite, and diorite porphyry. The plagiogranite porphyry was emplaced into this complex at 332.8±2.5 Ma (U-Pb zircon SIMS determination). Whole-rock element geochemistry shows that the volcanic complex and plagiogranite porphyry formed in the same island arc, although the complex was derived by partial melting of the mantle wedge and the plagiogranite porphyry by partial melting of a subducting slab. The diorite and the plagiogranite porphyries have both been subjected to intense hydrothermal alteration and associated mineralization, but the productive porphyry is the plagiogranite porphyry. Three alteration and mineralization stages, including pre-, syn- and post-ore stages, have been recognized. The pre-ore stage formed a barren propylitic alteration which is widespread in the volcanic complex. The syn-ore stage is divided into three sub-stages: Stage 1 is characterized by potassic alteration with chalcopyrite + bornite + chalcocite; Stage 2 is marked by chlorite-sericite-albite alteration with chalcopyrite ± pyrite ± bornite; Stage 3 is represented by phyllic alteration with chalcopyrite + pyrite ± molybdenite. The post-ore stage produced a barren argillic alteration limited to the diorite porphyry. A specific feature of the Tuwu deposit is that the productive porphyry was emplaced into a very mafic package, and reaction of the resulting fluids with the ferrous iron-rich hostrocks was a likely reason that Tuwu is the largest porphyry in the district.

Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes

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

Muzzillo, Christopher; Klein, Walter E; Li, Zhen

Photoelectrochemical (PEC) water splitting is an elegant method of converting sunlight and water into H2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient, and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV andmore » decreased saturated photocurrent density from 18 to 8 mA/cm2 as measured by chopped-light current-voltage (CLIV) measurements in a 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa3Se5) and 1.86 eV band gaps had exceptional durability and continuously split water for 17 days (~12 mA/cm2 at -1 V vs RHE). This is equivalent to ~17 200 C/cm2, which is a world record for any polycrystalline PEC absorber. These results indicate that CuGa3Se5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.« less

Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes.

PubMed

Muzzillo, Christopher P; Klein, W Ellis; Li, Zhen; DeAngelis, Alexander Daniel; Horsley, Kimberly; Zhu, Kai; Gaillard, Nicolas

2018-06-13

Photoelectrochemical (PEC) water splitting is an elegant method of converting sunlight and water into H 2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient, and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV and decreased saturated photocurrent density from 18 to 8 mA/cm 2 as measured by chopped-light current-voltage (CLIV) measurements in a 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa 3 Se 5 ) and 1.86 eV band gaps had exceptional durability and continuously split water for 17 days (∼12 mA/cm 2 at -1 V vs RHE). This is equivalent to ∼17 200 C/cm 2 , which is a world record for any polycrystalline PEC absorber. These results indicate that CuGa 3 Se 5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.

Simulation of acid mine drainage generation around Küre VMS Deposits, Northern Turkey

NASA Astrophysics Data System (ADS)

Demirel, Cansu; Kurt, Mehmet Ali; Çelik Balci, Nurgül

2015-04-01

This study investigated comparative leaching characteristics of acidophilic bacterial strains under shifting environmental conditions at proposed two stages as formation stage or post acidic mine drainage (AMD) generation. At the first stage, initial reactions associated with AMD generation was simulated in shaking flasks containing massive pyritic chalcopyrite ore by using a pure strain Acidithiobacillus ferrooxidans and a mixed culture of Acidithiobacillus sp. mostly dominated by A. ferrooxidans and A. thiooxidans at 26oC. At the second stage, long term bioleaching experiments were carried out with the same strains at 26oC and 40oC to investigate the leaching characteristics of pyritic chalcopyrite ore under elevated heavy metal and temperature conditions. During the experiments, physicochemical characteristics (e.i. Eh, pH, EC) metal (Fe, Co, Cu, Zn) and sulfate concentration of the experimental solution were monitored during 180 days. Significant acid generation and sulfate release were determined during bioleaching of the ore by mixed acidophilic cultures containing both iron and sulfur oxidizers. In the early stage of the experiments, heavy metal release from the ore was caused by generation of acid due to accelerated bacterial oxidation of the ore. Generally high concentrations of Co and Cu were released into the solution from the experiments conducted by pure cultures of Acidithiobacillus ferrooxidans whereas high Zn and Fe was released into the solution from the mixed culture experiments. In the later stage of AMD generation and post AMD, chemical oxidation is accelerated causing excessive amounts of contamination, even exceeding the amounts resulted from bacterial oxidation by mixed cultures. Acidithibacillus ferrooxidans was found to be more effective in leaching Cu, Fe and Co at higher temperatures in contrary to mixed acidophiles that are more prone to operate at optimal moderate conditions. Moreover, decreasing Fe values are noted in bioleaching experiments with mixed acidophiles at higher temperatures. Further depleted Fe(III) values coinciding with decreasing pH may point to precipitation of secondary phases (i.e. jarosite). This study revealed that the metals (Fe, Cu, Co and Zn) released during short term leaching of the ore (34 days) are generally caused by acid produced by dissolution reactions rather than oxidation. In the long term experiments a more complex biogeochemical reactions (oxidation and dissolution) take place in conjunction. Key words: Bioleaching, AMD, heavy metal release, environment, acidophilic bacteria, Küre copper ore deposits, volcanogenic massive sulfide deposits

Mineralogy and trace element geochemistry of the Co- and Cu-bearing sulfides from the Shilu Fe-Co-Cu ore district in Hainan Province of South China

NASA Astrophysics Data System (ADS)

Wang, Zhilin; Xu, Deru; Zhang, Zhaochong; Zou, Fenghui; Wang, Li; Yu, Liangliang; Hu, Mingyue

2015-12-01

Hosted within the metamorphosed, neritic siliciclastic rocks and sedimentary carbonates of the Proterozoic Shilu Group, the Shilu Fe-Co-Cu ore district in Hainan Province of South China comprises the upper Fe- and the lower Co-Cu ore layers. Combined with the field observation, the mineralogical and geochemical studies of sulfides using electron microprobe and laser ablation ICP-MS analyses recognized three types of Co-Cu ores. Type I is represented by massive ores and mainly comprises the first generation of pyrite (PyI) which occurred either as recrystallized, subhedral to euhedral microcrystal aggregates (PyIa) or as elongated, fine-grained euhedral grains (PyIb) with an orientated alignment parallel to S1 foliation. Type II is banded, disseminated and brecciated ores, and composed of the second generation of pyrite (PyII) which displays internal rhythmic growth zoning, the first generations of chalcopyrite (CcpI) and pyrrhotite (PoI), and associated Co-(Ni)-(As)-sulfide minerals. Type III occurring as veins or veinlets mainly consists of the third generation of pyrite (PyIII) and the second generations of chalcopyrite (CcpII) and pyrrhotite (PoII), of which PyIII appears as subhedral to euhedrall grains or as rims of composite pyrite. The moderate Co and As, and high Ni contents as well as the low Co/Ni ratios (∼2-5) in PyI indicate a sedimentary-metamorphic origin for Type I ores. The higher Co, Ni and As concentrations in PyIb relative to PyIa likely was related to an inhomogeneous deformation-metamorphism. The highest Co (av. 51,195 ppm) in PyII and Ni (av. 3374 ppm) in PoI most likely were linked to the preferred incorporation of Co into pyrite and Ni into pyrrhotite. Combined with the high Ag concentrations in CcpI (av. 266 ppm) and PyII (av. 13.32 ppm), the high Co/Ni ratios in PyII (av. 1241) suggest the derivation of Type II ores from a Co-Cu-Ni-Ag-rich hydrothermal fluid. Further, up to 9 wt.% Co concentrations in PyII show a temperature condition of 310-400 °C. In contrast, the depletion of trace elements in CcpII and PyIII, and the lower Co/Ni ratios (av. 46) in PyIII suggest a Co-poor but Cu-bearing hydrothermal fluid for origin of Type III ores. The complex texture and chemical composition of sulfides combined with previous work confirm a four-stage metallogenesis for the Shilu Co-Cu ores. From early to late, these include: (1) the ca. 1075-880 Ma deposition of the primary Co-Cu ore source beds which most likely were derived from submarine, metalliferous hydrothermal fluids, (2) the syn-structural metamorphism which led to Type I ores due to the South China Caledonian Orogeny, (3) the first stage of hydrothermalism which produced Type II ores and most likely was associated with Indosinian magmatism, and (4) the second stage of hydrothermalism which yielded Type III ores and likely was related to Yanshanian magmatism. The first stage of hydrothermalism was considered to be significant for the Co-Cu enrichment. The Shilu Co-Cu ores thus are better attributed to a BIF origin, but greatly reworked and enriched by late structural deformation and hydrothermal activities.

Copper and Gold Partitioning Between Brine and Vapor as a Function of Reduced Sulfur

NASA Astrophysics Data System (ADS)

Ehlich, J. J.; Frank, M. R.; Bodnar, R. J.

2017-12-01

This study examined Cu and Au partitioning between sulfur-rich vapors (v) and brines (b) at conditions representative of porphyry ore deposits. Experiments were conducted at 700 °C and 100 MPa, with oxygen fugacity, f(O2), buffered by either Ni-NiO or MnO-Mn3O4. Sulfur fugacity, f(S2), was buffered by pyrrhotite + chalcopyrite or bornite + pyrrhotite + chalcopyrite mineral assemblages between log -5.6 and log 0.6. The fugacities of H2S and SO2 were calculated using the known values of fO2 and fS2. In each experiment, a gold capsule was loaded with a sulfide assemblage, a quartz core to trap fluid inclusions, and a 5 wt.% NaCl-equivalent aqueous solution containing NaCl, KCl and HCl with molar NaCl:KCl and NaCl:HCl ratios of 1 and 100, respectively. Coexisting low salinity (v) and high salinity (b) inclusions were trapped in the quartz and their salinities were estimated using microthermometry, and verified against expected salinities from the NaCl-H2O system. Na, K, Fe, Cu, and Au concentrations from 73 b and 39 v fluid inclusions were determined using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Nernst-style partition coefficients between b and v for a given element (Dxb/v) were determined as a function of O2, S2, H2S, and SO2 fugacities. DCub/v ranged from 2.8 to 6.6 and increased with increasing f(O2), decreased with increasing f(S2), and decreased with increasing f(H2S). Gold partition coefficients ranged from 4.6 to 8.5, with DAub/v increasing with increasing f(O2), decreasing with increasing f(S2), and decreasing with increasing f(H2S). The absolute concentrations of Cu and Au increased in both the b and v phases with increasing f(H2S), but the increase was proportionally greater in v than b. Cu and Au partitioned into b relative to v at all conditions, but Dxb/v decreased slightly with decreasing O2 or increasing S2 fugacity. Dxb/v for Cu and Au appear most strongly linked to H2S, consistently decreasing with increasing f(H2S), but our data suggest that Cu and Au prefer chloride-complexes in porphyry systems (Dxb/v always >1). Reduced sulfur species may become increasingly important ligands in the porphyry-epithermal transition, in particularly high f(H2S) systems, or in systems dominated by a low salinity supercritical fluid or vapor.

Selenium, tellurium and precious metal mineralogy in Uchalinsk copper-zinc-pyritic district, the Urals

NASA Astrophysics Data System (ADS)

Vikentev, I.

2016-04-01

During processing the most of Au, Ag, Se, Te, Pb, Bi, Sb, Hg as well as notable part of Cu, Zn and Cd fail for tailings and became heavy metal pollutants. Modes of occurrence of Au, Ag, Te and Se covers two giant VMS deposits: Uchaly (intensively deformed) and Uzelginsk (altered by late hydrothermal processes) as well as middle-sized Molodezn and West Ozern deposits (nondeformed) have been studied. Mineral forms of these elements as well as their presence in disperse mode in common ore minerals (pyrite, chalcopyrite, sphalerite) have been studied using SEM, EPMA, INAA, ICP-MS and LA-ICP-MS.

Leaching of chalcopyrite with sodium hypochlorite

NASA Astrophysics Data System (ADS)

Garlapalli, Ravinder Kumar

Chalcopyrite is the most important copper mineral source and also a refractory mineral for leaching. Several processing routes have been proposed to overcome the environmental problems related to copper extraction from chalcopyrite. In this study, the leaching of chalcopyrite has been investigated with a new reagent sodium hypochlorite (NaOCl). Experiments were carried out in two stages: conversion of chalcopyrite to cupric oxide with NaOCl solution in the first stage, followed by dissolution of the cupric oxide to cupric ion with 1 normal sulfuric acid at room temperature in the second stage. In the first stage leaching, the initial pH varied from 12.5 to 13.7; the temperature, from 35 to 75°C; NaOCl concentration, from 0.2 to 0.85 molar; and the chalcopyrite dosage, from 1 to 10 grams/500 ml. The leaching conversion showed a maximum (68.3%) around pH 13.2 at 0.5 molar of hypochlorite concentration and 65°C in 1 hour. The reagent consumption ratio, defined as the number of moles of hypochlorite consumed to leach one mole of chalcopyrite is found to be much higher than its stoichiometric ratio of 8.5. It reached 57.6 when the solid dosage was 1 gram/500 ml and decreased to 12.9 when the solid dosage was increased to 10 grams/500 ml. It was found that the leaching rate of chalcopyrite in the first stage was controlled by chemical reaction with the activation energy of 50.2 kJ/mol (12.0 kcal/mol). A leaching scheme was identified in which 98% chalcopyrite was leached by adding hypochlorite stock solution stepwise in less than three hours.

Influence of Capping Ligand and Synthesis Method on Structure and Morphology of Aqueous Phase Synthesized CuInSe2 Nanoparticles

NASA Astrophysics Data System (ADS)

Ram Kumar, J.; Ananthakumar, S.; Moorthy Babu, S.

2017-01-01

A facile route to synthesize copper indium diselenide (CuInSe2) nanoparticles in aqueous medium was developed using mercaptoacetic acid (MAA) as capping agent. Two different mole ratios (5 and 10) of MAA were used to synthesize CuInSe2 nanoparticles at room temperature, as well as hydrothermal (high temperature) method. Powder x-ray diffraction analysis reveals that the nanoparticles exhibit chalcopyrite phase and the crystallinity increases with increasing the capping ratio. Raman analysis shows a strong band at 233 cm-1 due to the combination of B2 (E) modes. Broad absorption spectra were observed for the synthesized CuInSe2 nanoparticles. The effective surface capping by MAA on the nanoparticles surface was confirmed through attenuated total reflection-Fourier transform infrared spectral analysis. The thermal stability of the synthesized samples was analyzed through thermogravimetric analysis-differential scanning calorimetry. The change in morphology of the synthesized samples was analyzed through scanning electron microscope and it shows that the samples prepared at room temperature are spherical in shape, whereas hydrothermally synthesized samples were found to have nanorod- and nanoflake-like structures. Transmission electron microscope analysis further indicates larger grains for the hydrothermally prepared samples with 10 mol ratio of MAA. Comparative analyses were made for synthesizing CuInSe2 nanoparticles by two different methods to explore the role of ligand and influence of temperature.

Molecular Characterization of Copper and Cadmium Resistance Determinants in the Biomining Thermoacidophilic Archaeon Sulfolobus metallicus

PubMed Central

Orell, Alvaro; Remonsellez, Francisco; Arancibia, Rafaela; Jerez, Carlos A.

2013-01-01

Sulfolobus metallicus is a thermoacidophilic crenarchaeon used in high-temperature bioleaching processes that is able to grow under stressing conditions such as high concentrations of heavy metals. Nevertheless, the genetic and biochemical mechanisms responsible for heavy metal resistance in S. metallicus remain uncharacterized. Proteomic analysis of S. metallicus cells exposed to 100 mM Cu revealed that 18 out of 30 upregulated proteins are related to the production and conversion of energy, amino acids biosynthesis, and stress responses. Ten of these last proteins were also up-regulated in S. metallicus treated in the presence of 1 mM Cd suggesting that at least in part, a common general response to these two heavy metals. The S. metallicus genome contained two complete cop gene clusters, each encoding a metallochaperone (CopM), a Cu-exporting ATPase (CopA), and a transcriptional regulator (CopT). Transcriptional expression analysis revealed that copM and copA from each cop gene cluster were cotranscribed and their transcript levels increased when S. metallicus was grown either in the presence of Cu or using chalcopyrite (CuFeS2) as oxidizable substrate. This study shows for the first time the presence of a duplicated version of the cop gene cluster in Archaea and characterizes some of the Cu and Cd resistance determinants in a thermophilic archaeon employed for industrial biomining. PMID:23509422

Molecular characterization of copper and cadmium resistance determinants in the biomining thermoacidophilic archaeon Sulfolobus metallicus.

PubMed

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

2013-01-01

Sulfolobus metallicus is a thermoacidophilic crenarchaeon used in high-temperature bioleaching processes that is able to grow under stressing conditions such as high concentrations of heavy metals. Nevertheless, the genetic and biochemical mechanisms responsible for heavy metal resistance in S. metallicus remain uncharacterized. Proteomic analysis of S. metallicus cells exposed to 100 mM Cu revealed that 18 out of 30 upregulated proteins are related to the production and conversion of energy, amino acids biosynthesis, and stress responses. Ten of these last proteins were also up-regulated in S. metallicus treated in the presence of 1 mM Cd suggesting that at least in part, a common general response to these two heavy metals. The S. metallicus genome contained two complete cop gene clusters, each encoding a metallochaperone (CopM), a Cu-exporting ATPase (CopA), and a transcriptional regulator (CopT). Transcriptional expression analysis revealed that copM and copA from each cop gene cluster were cotranscribed and their transcript levels increased when S. metallicus was grown either in the presence of Cu or using chalcopyrite (CuFeS2) as oxidizable substrate. This study shows for the first time the presence of a duplicated version of the cop gene cluster in Archaea and characterizes some of the Cu and Cd resistance determinants in a thermophilic archaeon employed for industrial biomining.

Investigation of post-thermal annealing on material properties of Cu-In-Zn-Se thin films

NASA Astrophysics Data System (ADS)

Güllü, H. H.; Parlak, M.

2017-12-01

The Cu-In-Zn-Se thin film was synthesized by changing the contribution of In in chalcopyrite CuInSe2 with Zn. The XRD spectra of the films showed the characteristic diffraction peaks in a good agreement with the quaternary Cu-In-Zn-Se compound. They were in the polycrystalline nature without any post-thermal process, and the main orientation was found to be in the (112) direction with tetragonal crystalline structure. With increasing annealing temperature, the peak intensities in preferred orientation became more pronounced and grain sizes were in increasing behavior from 6.0 to 25.0 nm. The samples had almost the same atomic composition of Cu0.5In0.5ZnSe2. However, EDS results of the deposited films indicated that there was Se re-evaporation and/or segregation with the annealing in the structure of the film. According to the optical analysis, the transmittance values of the films increased with the annealing temperature. The absorption coefficient of the films was calculated as around 105 cm-1 in the visible region. Moreover, optical band gap values were found to be changing in between 2.12 and 2.28 eV depending on annealing temperature. The temperature-dependent dark- and photo-conductivity measurements were carried out to investigate the electrical characteristics of the films.

Single-source precursors for ternary chalcopyrite materials, and methods of making and using the same

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K. (Inventor); Hepp, Aloysius F. (Inventor); Harris, Jerry D. (Inventor); Jin, Michael Hyun-Chul (Inventor); Castro, Stephanie L. (Inventor)

2006-01-01

A single source precursor for depositing ternary I-III-VI.sub.2 chalcopyrite materials useful as semiconductors. The single source precursor has the I-III-VI.sub.2 stoichiometry built into a single precursor molecular structure which degrades on heating or pyrolysis to yield the desired I-III-VI.sub.2 ternary chalcopyrite. The single source precursors effectively degrade to yield the ternary chalcopyrite at low temperature, e.g. below 500.degree. C., and are useful to deposit thin film ternary chalcopyrite layers via a spray CVD technique. The ternary single source precursors according to the invention can be used to provide nanocrystallite structures useful as quantum dots. A method of making the ternary single source precursors is also provided.

Mineralogical and geochemical characterization of supergene Cu-Pb-Zn-V ores in the Oriental High Atlas, Morocco

NASA Astrophysics Data System (ADS)

Verhaert, Michèle; Bernard, Alain; Dekoninck, Augustin; Lafforgue, Ludovic; Saddiqi, Omar; Yans, Johan

2017-10-01

In the Moroccan High Atlas, two sulfide deposits hosted by Jurassic dolostones underwent significant weathering. In the Cu deposit of Jbel Klakh, several stages of supergene mineralization are distinguished: (1) the replacement of hypogene sulfides in the protolith (chalcopyrite) by secondary sulfides in the cementation zone (bornite, digenite, chalcocite, covellite), (2) the formation of oxidized minerals in the saprolite (malachite, azurite, brochantite) where the environment becomes more oxidizing and neutral, and (3) the precipitation of late carbonates (calcite) and iron (hydr-)oxides in the laterite. The precipitation of carbonates is related to the dissolution of dolomitic host rocks, which buffers the fluid acidity due to the oxidation of sulfides. In the Jbel Haouanit Pb-Zn deposit, the mineral assemblage is dominated by typical calamine minerals, Cu minerals (chalcocite, covellite, malachite), and a Cu-Pb-Zn vanadate (mottramite). Galena is successively weathered in anglesite and cerussite. Sphalerite is weathered in smithsonite, which is rapidly replaced by hydrozincite. Late iron (hydr-)oxides are mainly found at the top of both deposits (laterite). Both deposits are thus characterized by specific mineral zoning, from laterite to protolith, related to variations in the mineralogy and ore grades and probably caused by varying Eh-pH conditions.

Uranium accumulation in modern and ancient Fe-oxide sediments: Examples from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and Yubileynoe massive sulfide deposit (South Urals, Russia)

NASA Astrophysics Data System (ADS)

Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.

2018-05-01

Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.

The effect of Na on Cu-K-In-Se thin film growth

NASA Astrophysics Data System (ADS)

Muzzillo, Christopher P.; Tong, Ho Ming; Anderson, Timothy J.

2018-04-01

Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ∼ 0.85 and K/(K + Cu) ∼ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu1-xKxInSe2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe2 + KInSe2 mixed-phase films. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S)2 absorbers to optimize both initial and long-term photovoltaic power generation.

The effect of Na on Cu-K-In-Se thin film growth

DOE PAGES

Muzzillo, Christopher P.; Tong, Ho Ming; Anderson, Timothy J.

2018-02-27

Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ~ 0.85 and K/(K + Cu) ~ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO 2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu 1-xK xInSe 2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe 2 + KInSe 2 mixed-phase films.more » Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe 2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe 2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe 2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S) 2 absorbers to optimize both initial and long-term photovoltaic power generation.« less

The effect of Na on Cu-K-In-Se thin film growth

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

Muzzillo, Christopher P.; Tong, Ho Ming; Anderson, Timothy J.

Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ~ 0.85 and K/(K + Cu) ~ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO 2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu 1-xK xInSe 2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe 2 + KInSe 2 mixed-phase films.more » Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe 2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe 2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe 2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S) 2 absorbers to optimize both initial and long-term photovoltaic power generation.« less

Fabrication of CuInS2/ZnS quantum dots-based white light-emitting diodes with high color rendering index

NASA Astrophysics Data System (ADS)

Hsiao, Chih-Chun; Su, Yu-Sheng; Chung, Shu-Ru

2017-09-01

Among solid-state lighting technology, phosphor-converted white light-emitting diodes (pc-WLEDs) are excellent candidates to replace incandescent lamps for their merit of high energy conservation, long lifetime, high luminous efficiency as well as polarized emissions. Semiconductor quantum dots (QDs) are emerging color tunable emissive light converters. They have shown significant promise as light emitters, as solar cells, and in biological imaging. It has been demonstrated that the pc-WLED devices integrated with red emissive ZnCdSe QDs show improved color rendering index of device. However, cadmium-based QDs have limited future owing to the well-known toxicity. Recently, non-cadmium luminescence materials, i.e. CuInS2-based QDs, are investigated as desirable low toxic alternatives. Particularly, CuInS2-based QDs exhibit very broad emissions spectra with full width at half maximum (FWHM) of 100-120 nm, large Stokes shifts of 200 300 meV and finely-tunable emissions. In order to adjust emission wavelengths and improved quantum yield (QY), CuInS2/ZnS (CIS/ZnS) core/shell structure was introduced. Therefore, CIS/ZnS QDs have been extensively investigated and be used as color converter in solid-state lighting. Synthesis and application of CuInS2/ZnS core/shell QDs are conducted using a hot injection route. CIS/ZnS core/shell QDs with molar ratio of Cu:In equal to 1:4 are prepared. For WLED fabrication, the CIS/ZnS QD is dispersed in toluene first, and then it is blended with transparent acrylic-based UV resin. Subsequently, the commercial green-emitting Lu3Al5O12: Ce3+ (LuAG) phosphors are mixed with QDs-resin mixture. After that, the QDs-phosphors-resin mixtures are put in the oven at 140 °C for 1 h to evaporate the toluene. Subsequently, the homogeneous QDs-phosphors-resin mixture is dropped on the top of a blue LED chip (InGaN). Then, the device is cured by 400 W UV light to form WLED. The emission wavelength of CIS/ZnS QD exhibits yellow region of 552 nm with QY of 76 %, and with relatively broad bandwidth of 86 nm. The structure of CIS/ZnS belongs to chalcopyrite phase and its average particle size is 3.2 nm. The luminous efficacy, color rendering index (CRI), correlated color temperature (CCT), and CIE chromaticity coordinate of WLED is 47 lm/W, 89, 5661 K, and (0.33, 0.29), respectively.

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.

Fe-U-PGE-Au-Ag-Cu Deposits of the Udokan-Chiney Region (East Siberia, Russia)

NASA Astrophysics Data System (ADS)

Gongalskiy, B.; Krivolutskaya, N.; Murashov, K.; Nistratov, S.; Gryazev, S.

2012-04-01

Introduction. Cupriferous sandstones-shales and magmatic copper-nickel deposits mark out the western and southern boundaries of the Siberian Craton accordingly. Of special interest are the Paleoproterozoic deposits of the Udokan-Chiney mining district (Gongalskiy, Krivolutskaya, 2008). Copper reserves and resources of this region are estimated at more than 50 Mt. Half of them is concentrated at the unique Udokan Deposit and the second half is distributed among sedimentary (Unkur, Pravoingamakitskoye, Sakinskoye, Krasnoye, Burpala) and magmatic deposits of the Chiney (Rudnoye, Verkhnechineyskoye, Kontaktovoye), Luktur and Maylav massifs. Results. It was established that the ores are characterized by similarity in chemical composition (main, major and rare elements that are Ag, Au, PGE) and mineral assemblages with varying proportions. It is important to emphasize that Fe role in mineralization was previously ignored. Meanwhile the Udokan deposit contains 10 Mt of magnetite metacrystals so as chalcocite ores may contain up to 50% magnetite too. It has been recently found that the Chiney titanomagnetite ores comprise commercially significant uranium and rare-earth metal concentrations (Makaryev et al., 2011). Thus the Udokan-Chiney region comprises Cu, Fe, Ti, V, U, REE, Ag, Au, PGE. These deposits differ from similar objects, the Olympic Dam in particular, by a much smaller content of fluid-bearing minerals. Copper mineralization at the Udokan is represented by chalcocite-bornite ores. They occur as ore beds conformable with sedimentary structures or as cross-cutting veins. The central zones of the former are often brecciated. They are rimmed by fine magnetite, bornite, and chalcocite dissemination. Bornite-chalcopyrite and chalcopyrite-pyrite veins are known at the lower levels of the Udokan ore bed. Such ore compositions are predominant in other ore deposits in sedimentary rocks (Pravoingamakitskoye, Unkur) and have a hydrothermal origin. Silver grades are up to 370 g/t in grab samples (Gongalskiy et al., 2008a). The long-lived Udokan-Chiney ore-magmatic has small areal extent of explosive rocks and breccias (n*10 m) with massive sulfide veins (chalcopyrite, pyrrhotite) which are similar to Sudbury offset dikes. While the same vertical zones at the Rudnoye deposit have been confirmed over 0.5 km downward from the lower contact of the Chiney massif. Conclusions. Multielement and similar mineralogical composition ores of different deposits in the Udokan-Chiney area reflect long evolution of ore processes in very movable block of the crust. Observed combination of magmatic, sedimentary and partially hydrothermal deposits is a result of the telescoping of a wide range of metals into a limited area.

Comparative study on the selective chalcopyrite bioleaching of a molybdenite concentrate with mesophilic and thermophilic bacteria.

PubMed

Romano, P; Blázquez, M L; Alguacil, F J; Muñoz, J A; Ballester, A; González, F

2001-03-01

This study evaluates different bioleaching treatments of a molybdenite concentrate using mesophilic and thermophilic bacterial cultures. Further studies on the chemical leaching and the electrochemical behavior of the MoS(2) concentrate were carried out. Bioleaching tests showed a progressive removal of chalcopyrite from the molybdenite concentrate with an increase in temperature. Chemical leaching tests support the idea of an indirect attack of the concentrate. Electrochemical tests indicate that chalcopyrite dissolution is favored when molybdenite is present. Therefore, this type of bioleaching treatment could be applied to purify molybdenite flotation concentrates by selectively dissolving chalcopyrite.

Bio-processing of copper from combined smelter dust and flotation concentrate: a comparative study on the stirred tank and airlift reactors.

PubMed

Vakylabad, Ali Behrad; Schaffie, Mahin; Ranjbar, Mohammad; Manafi, Zahra; Darezereshki, Esmaeel

2012-11-30

To scrutinize the influence of the design and type of the bioreactors on the bioleaching efficiency, the bioleaching were evaluated in a batch airlift and a batch stirred tank bioreactors with mixed mesophilic and mixed moderately thermophilic bacteria. According to the results, maximum copper recoveries were achieved using the cultures in the stirred tank bioreactors. It is worth noting that the main phase of the flotation concentrate was chalcopyrite (as a primary sulphide), but the smelter dust mainly contained secondary copper sulphides such as Cu(2)S, CuS, and Cu(5)FeS(4).Under optimum conditions, copper dissolution from the combined flotation concentrate and smelter dust (as an environmental hazard) reached 94.50% in the STR, and 88.02% in the airlift reactor with moderately thermophilic, after 23 days. Also, copper extractions calculated for the bioleaching using mesophilic bacteria were 48.73% and 37.19% in the STR (stirred tank reactor) and the airlift bioreactor, respectively. In addition, the SEM/EDS, XRD, chemical, and mineralogical analyses and studies confirmed the above results. Copyright © 2012 Elsevier B.V. All rights reserved.

Geology and geochemistry of the Mammoth breccia pipe, Copper Creek mining district, southeastern Arizona: Evidence for a magmatic-hydrothermal origin

USGS Publications Warehouse

Anderson, E.D.; Atkinson, William W.; Marsh, T.; Iriondo, A.

2009-01-01

The Copper Creek mining district, southeastern Arizona, contains more than 500 mineralized breccia pipes, buried porphyry-style, copper-bearing stockworks, and distal lead-silver veins. The breccia pipes are hosted by the Copper Creek Granodiorite and the Glory Hole volcanic rocks. The unexposed Mammoth breccia pipe, solely recognized by drilling, has a vertical extent of 800 m and a maximum width of 180 m. The pipe consists of angular clasts of granodiorite cemented by quartz, chalcopyrite, bornite, anhydrite, and calcite. Biotite 40Ar/ 39Ar dates suggest a minimum age of 61.5??0.7 Ma for the host Copper Creek Granodiorite and 40Ar/39Ar dates on hydrothermal sericite indicate an age of 61.0??0.5 Ma for copper mineralization. Fluid inclusion studies suggest that a supercritical fluid with a salinity of approximately 10 wt.% NaCl equiv. condensed to a dilute aqueous vapor (1-2.8 wt.% NaCl equiv.) and a hypersaline brine (33.4-35.1 wt.% NaCl equiv.). Minimum trapping temperatures are 375??C and trapping depths are estimated at 2 km. Sulfur isotope fractionation of cogenetic anhydrite and chalcopyrite yields a temperature of mineralization of 469??25??C. Calculated oxygen and hydrogen isotope values for fluids in equilibrium with quartz and sericite range from 10.2??? to 13.4??? and -60??? to -39???, respectively, suggesting that the mineralizing fluid was dominantly magmatic. Evidence from the stable isotope and fluid inclusion analyses suggests that the fluids responsible for Cu mineralization within the Mammoth breccia pipe exsolved from a gray porphyry phase found at the base of the breccia pipe. ?? Springer-Verlag 2008.

New geologic, fluid inclusion and stable isotope studies on the controversial Igarapé Bahia Cu-Au deposit, Carajás Province, Brazil

NASA Astrophysics Data System (ADS)

Dreher, Ana M.; Xavier, Roberto P.; Taylor, Bruce E.; Martini, Sérgio L.

2008-02-01

The Igarapé Bahia Cu-Au deposit in the Carajás Province, Brazil, is hosted by steeply dipping metavolcano-sedimentary rocks of the Igarapé Bahia Group. This group consists of a low greenschist grade unit of the Archean (˜2,750 Ma) Itacaiúnas Supergroup, in which other important Cu-Au and iron ore deposits of the Carajás region are also hosted. The orebody at Igarapé Bahia is a fragmental rock unit situated between chloritized basalt, with associated hyaloclastite, banded iron formation (BIF), and chert in the footwall and mainly coarse- to fine-grained turbidites in the hanging wall. The fragmental rock unit is a nearly concordant, 2 km long and 30-250 m thick orebody made up of heterolithic, usually matrix-supported rocks composed mainly of coarse basalt, BIF, and chert clasts derived from the footwall unit. Mineralization is confined to the fine-grained matrix and comprises disseminated to massive chalcopyrite accompanied by magnetite, gold, U- and light rare earth element (LREE)-minerals, and minor other sulfides like bornite, molybdenite, cobaltite, digenite, and pyrite. Gangue minerals include siderite, chlorite, amphibole, tourmaline, quartz, stilpnomelane, epidote, and apatite. A less important mineralization style at Igarapé Bahia is represented by late quartz-chalcopyrite-calcite veins that crosscut all rocks in the deposit area. Fluid inclusions trapped in a quartz cavity in the ore unit indicate that saline aqueous fluids (5 to 45 wt% NaCl + CaCl2 equiv), together with carbonic (CO2 ± CH4) and low-salinity aqueous carbonic (6 wt% NaCl equiv) fluids, were involved in the mineralization process. Carbonates from the fragmental layer have δ13C values from -6.7 to -13.4 per mil that indicate their origin from organic and possibly also from magmatic carbon. The δ34S values for chalcopyrite range from -1.1 to 5.6 per mil with an outlier at -10.8 per mil, implying that most sulfur is magmatic or leached from magmatic rocks, whereas a limited contribution of reduced and oxydized sulfur is also evident. Oxygen isotopic ratios in magnetite, quartz, and siderite yield calculated temperatures of ˜400°C and δ18O-enriched compositions (5 to 16.5 per mil) for the ore-forming fluids that suggest a magmatic input and/or an interaction with 18O-rich, probably sedimentary rocks. The late veins of the Igarapé Bahia deposit area were formed from saline aqueous fluids (2 to 60 wt% NaCl + CaCl2 equiv) with δ18Ofluid compositions around 0 per mil that indicate contribution from meteoric fluids. With respect to geological features, Igarapé Bahia bears similarity with syngenetic, volcanic-hosted massive sulfide (VHMS)-type deposits, as indicated by the volcano-sedimentary geological context, stratabound character, and association with submarine volcanic flows, hyaloclastite, and exhalative beds such as BIF and chert. On the other hand, the highly saline ore fluids and the mineral assemblage, dominated by magnetite and chalcopyrite, with associated gold, U- and LREE-minerals and scarce pyrite, indicate that Igarapé Bahia belongs to the Fe oxide Cu-Au (IOCG) group of deposits. The available geochronologic data used to attest syngenetic or epigenetic origins for the mineralization are either imprecise or may not represent the main mineralization episode but a later, superimposed event. The C, S, and O isotopic results obtained in this study do not clearly discriminate between fluid sources. However, recent B isotope data obtained on tourmaline from the matrix of the fragmental rock ore unit (Xavier, Wiedenbeck, Dreher, Rhede, Monteiro, Araújo, Chemical and boron isotopic composition of tourmaline from Archean and Paleoproterozoic Cu-Au deposits in the Carajás Mineral Province, 1° Simpósio Brasileiro de Metalogenia, Gramado, Brazil, extended abstracts, CD-ROM, 2005) provide strong evidence of the involvement of a marine evaporitic source in the hydrothermal system of Igarapé Bahia. Evaporite-derived fluids may explain the high salinities and the low reduced sulfur mineral paragenesis observed in the deposit. Evaporite-derived fluids also exclude a significant participation of magmatic or mantle-derived fluids, reinforcing the role of nonmagmatic brines in the genesis of Igarapé Bahia. Considering this aspect and the geological features, the possibility that the deposit was generated by a hydrothermal submarine system whose elevated salinity was acquired by leaching of ancient evaporite beds should be evaluated.

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.

Growth and optoelectronic characteristic of n-Si/p-CuIn(S 1-xSe x) 2 thin-film solar cell by solution growth technique

NASA Astrophysics Data System (ADS)

Chavhan, S.; Sharma, R.

2006-07-01

The p-CuIn(S 1-xSe x) 2 (CISS) thin films have been grown on n-Si substrate by solution growth technique. The deposition parameters, such as pH (10.5), deposition time (60 min), deposition temperature (50 °C), and concentration of bath solution (0.1 M) were optimized. Elemental analysis of the p-CuIn(S 1-xSe x) 2 thin film was confirmed by energy-dispersive analysis of X-ray (EDAX). The SEM study of absorber layer shows the uniform morphology of film as well as the continuous smooth deposition onto the n-Si substrates, whose grain size is 130 nm. CuIn(S 1-xSe x) 2 ( x=0.5) reveals (1 1 2) orientation peak and exhibits the chalcopyrite structure with lattice constant a=5.28 Å and c=11.45 Å. The J- V characteristics were measured in dark and light. The device parameters have been calculated for solar cell fabrication, V=411.09 mV, and J=14.55 mA. FF=46.55% and η=4.64% under an illumination of 60 mW/cm 2. The J- V characteristics of the device under dark condition were also studied and the ideality factor was calculated, which is equal to 2.2 for n-Si/p-CuIn(S 0.5Se 0.5) 2 heterojunction thin film.

Catalytic potential of selected metal ions for bioleaching, and potential techno-economic and environmental issues: A critical review.

PubMed

Pathak, Ashish; Morrison, Liam; Healy, Mark Gerard

2017-04-01

Bioleaching is considered to be a low-cost, eco-friendly technique for leaching valuable metals from a variety of matrixes. However, the inherent slow dissolution kinetics and low metal leaching yields have restricted its wider commercial applicability. Recent advancements in bio-hydrometallurgy have suggested that these critical issues can be successfully alleviated through the addition of a catalyst. The catalyzing properties of a variety of metals ions (Ag + , Hg ++ , Bi +++ , Cu ++ , Co ++ etc.) during bioleaching have been successfully demonstrated. In this article, the role and mechanisms of these metal species in catalyzing bioleaching from different minerals (chalcopyrite, complex sulfides, etc.) and waste materials (spent batteries) are reviewed, techno-economic and environmental challenges associated with the use of metals ions as catalysts are identified, and future prospectives are discussed. Based on the analysis, it is suggested that metal ion-catalyzed bioleaching will play a key role in the development of future industrial bio-hydrometallurgical processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of europium substitution for In on structure and photoelectric properties of CuIn{sub 1−x}Eu{sub x}Te{sub 2}

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

Nie, Xiaomeng; Guo, Yongquan

2016-01-15

The structures and optical and electric properties of europium doped CuIn{sub 1−x}Eu{sub x}Te{sub 2} have been studied systematically using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectrum (EDS), ultraviolet and visible spectrophotometer (UV–vis), and standard four-probe method. The studies reveal that the minor europium doping into CuIn{sub 1−x}Eu{sub x}Te{sub 2} could still stabilize the chalcopyrite structure in a solid solution of x=0.1. The lattice parameters are going up with increasing the content of europium in CuIn{sub 1−x}Eu{sub x}Te{sub 2} due to the size effect at In site. The structural refinement confirms that Eu partly substitutes formore » In and occupies the 4b crystal position. SEM morphologies show that the europium doping into CuIn{sub 1−x}Eu{sub x}Te{sub 2} can fine the grains from the largely agglomerated state to the uniformly separated state. The electrical resistivities of single phase CuIn{sub 1−x}Eu{sub x}Te{sub 2} follow a mixture model of hopping conductivity and variable range hopping conductivity. The absorption band-gaps of CuIn{sub 1−x}Eu{sub x}Te{sub 2} at room temperature tend to increase with increasing Eu content. CuIn{sub 1−x}Eu{sub x}Te{sub 2} might be a good candidate for photovoltaic cell. - Graphical abstract: CuIn{sub 0.9}Eu{sub 0.1}Te{sub 2} follows a mixture of hopping conductivity and variable range hopping conductivity mechanism. - Highlights: • Novel europium doped CuIn{sub 1−x}Eu{sub x}Te{sub 2}. • Potential application for devices and solar cells. • A mixture of hopping and variable range hopping conductivity mechanism.« less

Detection of Matrix Elements and Trace Impurities in Cu(In, Ga)Se2 Photovoltaic Absorbers Using Surface Analytical Techniques.

PubMed

Kim, Min Jung; Lee, Jihye; Kim, Seon Hee; Kim, Haidong; Lee, Kang-Bong; Lee, Yeonhee

2015-10-01

Chalcopyrite Cu(In, Ga)Se2 (CIGS) thin films are well known as the next-generation solar cell materials notable for their high absorption coefficient for solar radiation, suitable band gap, and ability for deposition on flexible substrate materials, allowing the production of highly flexible and lightweight solar panels. To improve solar cell performances, a quantitative and depth-resolved elemental analysis of photovoltaic thin films is much needed. In this study, Cu(In, Ga)Se2 thin films were prepared on molybdenum back contacts deposited on soda-lime glass substrates via three-stage evaporation. Surface analyses via AES and SIMS were used to characterize the CIGS thin films and compare their depth profiles. We determined the average concentration of the matrix elements, Cu, In, Ga, and Se, using ICP-AES, XRF, and EPMA. We also obtained depth profiling results using TOF-SIMS, magnetic sector SIMS and AES, and APT, a sub-nanometer resolution characterization technique that enables three-dimensional elemental mapping. The SIMS technique, with its high detection limit and ability to obtain the profiles of elements in parallel, is a powerful tool for monitoring trace elements in CIGS thin films. To identify impurities in a CIGS layer, the distribution of trace elements was also observed according to depth by SIMS and APT.

Mineralogical anomalies and their influences on elemental geochemistry of the main workable coal beds from the Dafang Coalfield, Guizhou, China

USGS Publications Warehouse

Dai, S.; Ren, D.; Li, D.; Chou, C.-L.; Luo, K.

2006-01-01

Mineralogy and geochemistry of the No. 11 Coal bed were investigated by using inductively-coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF), scanning electron microscopy equipped with energy-dispersive X-ray (SEM-EDX), sequential chemical extraction procedure (SCEP), and optical microscopy. The results show that the No. 11 Coal bed has very high contents of veined quartz (Vol. 11.4%) and veined ankerite (Vol. 10.2 %). The veined ankerite was generally coated by goethite and the veined quartz embraced chalcopyrite, sphalerite, and selenio-galena. In addition, a trace amount of kaolinite was filled in the veins. These seven minerals often occur in the same veins. The formation temperatures of the veined ankerite and quartz are 85??C and 180??C respectively, indicating their origins of iron-rich calcic and siliceous low-temperature hydrothermal fluids in different epigenetic periods. Studies have also found that the veined quartz probably formed earlier than the veined ankerite, and at least three distinct ankerite formation stages were observed by the ration of Ca/Sr and Fe/Mn of ankerite. The mineral formation from the early to late stage is in order of sulfide, quartz, kaolinite, ankerite, and goethite. The veined ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn, which are as high as 0.09%, 74.0 ??g/g, 33.6 ??g/g, 185 ??g/g, and 289 ??g/g in this coal seam, respectively. However, the veined quartz is the main carrier of Pd, Pt, and Ir, which are 1.57 ??g/g, 0.15 ??g/g, and 0.007 ??g/g in this coal seam, respectively. In addition, chalcopyrite, sphalerite, and selenio-galena of hydrothermal origin were determined in the veined quartz, and these three sulfide minerals are also important carriers of Cu, Zn and Pb in the No. 11 Coal bed.

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.

Age constraints on the hydrothermal history of the Prominent Hill iron oxide copper-gold deposit, South Australia

NASA Astrophysics Data System (ADS)

Bowden, Bryan; Fraser, Geoff; Davidson, Garry J.; Meffre, Sebastien; Skirrow, Roger; Bull, Stuart; Thompson, Jay

2017-08-01

The Mesoproterozoic Prominent Hill iron-oxide copper-gold deposit lies on the fault-bound southern edge of the Mt Woods Domain, Gawler Craton, South Australia. Chalcocite-bornite-chalcopyrite ores occur in a hematitic breccia complex that has similarities to the Olympic Dam deposit, but were emplaced in a shallow water clastic-carbonate package overlying a thick andesite-dacite pile. The sequence has been overturned against the major, steep, east-west, Hangingwall Fault, beyond which lies the clastic to potentially evaporitic Blue Duck Metasediments. Immediately north of the deposit, these metasediments have been intruded by dacite porphyry and granitoid and metasomatised to form magnetite-calc-silicate skarn ± pyrite-chalcopyrite. The hematitic breccia complex is strongly sericitised and silicified, has a large sericite ± chlorite halo, and was intruded by dykes during and after sericitisation. This paper evaluates the age of sericite formation in the mineralised breccias and provides constraints on the timing of granitoid intrusion and skarn formation in the terrain adjoining the mineralisation. The breccia complex contains fragments of granitoid and porphyry that are found here to be part of the Gawler Range Volcanics/Hiltaba Suite magmatic event at 1600-1570 Ma. This indicates that some breccia formation post-dated granitoid intrusion. Monazite and apatite in Fe-P-REE-albite metasomatised granitoid, paragenetically linked with magnetite skarn formation north of the Hangingwall Fault, grew soon after granitoid intrusion, although the apatite experienced U-Pb-LREE loss during later fluid-mineral interaction; this accounts for its calculated age of 1544 ± 39 Ma. To the south of the fault, within the breccia, 40Ar-39Ar ages yield a minimum age of sericitisation (+Cu+Fe+REE) of dykes and volcanics of ˜1575 Ma, firmly placing Prominent Hill ore formation as part of the Gawler Range Volcanics/Hiltaba Suite magmatic event within the Olympic Cu-Au province of the Gawler Craton.

Chalcopyrite disease in sphalerite: pathology and epidemiology.

USGS Publications Warehouse

Barton, P.B.; Bethke, P.M.

1987-01-01

This descriptive paper identifies three widely occurring textures designated as 'watermelon', 'dusting' and 'bimodal' that characterize the replacement of original Fe-bearing sphalerite by an aggregate of chalcopyrite and low-Fe sphalerite as an integral part of the mineralization process. Replacement probably predominates over alternative modes of origin for small chalcopyrite blebs in sphalerite from most vein and sea-floor massive sulphide deposits that formed in the 200-400oC temperature range and that have not been subsequently subjected to higher T. Sphalerite from the epithermal Ag-Pb-Zn deposit at Creede, Colorado, displays a rich variety of features ("bead chains') that are primary crystal dislocations decorated by exsolved chalcopyrite.-J.A.Z.

The Role of Anionogenic Elements (As, Sb, Mo, Se, S, P, N, Cl, F, C) In The Formation of Technogenic Geochemical Anomalies

NASA Astrophysics Data System (ADS)

Abrosimova, Natalya; Bortnikova, Svetlana

2017-12-01

The study was conducted on the example of sulphide-containing mine tailings with a varying amount of sulphide and arsenide minerals, from three distinct tailings dumps situated in Russia: Karabash Mine Site, South Ural; Komsomolsk tailings impoundment, Kemerovo region; Khovu-Aksy mine site, Tuva Republic. The aim of the study was to compare the mobility of anionogenic elements (As, Sb, Mo, Se, S, P, N, Cl, F, C) and their role in migration, precipitation, and concentration of metals during the water-tailings interaction depending on the physicochemical parameters (pH, Eh) of the medium and the mineral composition of the waste material. Using slightly acidic leaching experiments the quantitative estimation of mobile forms of elements is given. Based on the compositions of the obtained water leaching solutions, aqueous speciation of chemical elements and saturation index of key minerals in the experimental solutions were calculated. The results of calculating forms of chemical elements made it possible to construct series of mobility of metals and metalloids in solutions with different physicochemical parameters. In the alkaline conditions, Sb>As>Cd>Cu>Zn>Fe>Pb, when the medium is acidified, the series changes, As>Cd>Cu>Zn>Pb>Sb>Fe in weakly alkaline conditions, Sb>Mn>As>Zn>Fe however, when the medium is acidified, the series changes to Cd>Mn>Pb>Cu>Zn>Sb>Ni>Fe>As under acidic conditions Cd>Cu>Zn>Pb>Mn>Fe>Se>Mo>Sb>As>Ni. The mineral composition of the tailings was investigated, which will allow to determine the sources of toxic elements and to understand the processes of secondary mineral formation in technogenic objects. Arsenopyrite and pyrite predominate in the heavy fraction of the Komsomolsk tailings impoundment, arsenopyrite grains are often corroded, Sb contained in Sb oxide and Sb sulfide. The pyrite and barite are determined in the solid matter of the Karabash Mine Site and chalcopyrite, sphalerite, tennantite Cu3AsS3, and tetrahedrite (Cu,Fe)12Sb4S13 are determined in the form of inclusions in grains of pyrite.

Investigation of energy gene expressions and community structures of free and attached acidophilic bacteria in chalcopyrite bioleaching.

PubMed

Zhu, Jianyu; Jiao, Weifeng; Li, Qian; Liu, Xueduan; Qin, Wenqing; Qiu, Guanzhou; Hu, Yuehua; Chai, Liyuan

2012-12-01

In order to better understand the bioleaching mechanism, expression of genes involved in energy conservation and community structure of free and attached acidophilic bacteria in chalcopyrite bioleaching were investigated. Using quantitative real-time PCR, we studied the expression of genes involved in energy conservation in free and attached Acidithiobacillus ferrooxidans during bioleaching of chalcopyrite. Sulfur oxidation genes of attached A. ferrooxidans were up-regulated while ferrous iron oxidation genes were down-regulated compared with free A. ferrooxidans in the solution. The up-regulation may be induced by elemental sulfur on the mineral surface. This conclusion was supported by the results of HPLC analysis. Sulfur-oxidizing Acidithiobacillus thiooxidans and ferrous-oxidizing Leptospirillum ferrooxidans were the members of the mixed culture in chalcopyrite bioleaching. Study of the community structure of free and attached bacteria showed that A. thiooxidans dominated the attached bacteria while L. ferrooxidans dominated the free bacteria. With respect to available energy sources during bioleaching of chalcopyrite, sulfur-oxidizers tend to be on the mineral surfaces whereas ferrous iron-oxidizers tend to be suspended in the aqueous phase. Taken together, these results indicate that the main role of attached acidophilic bacteria was to oxidize elemental sulfur and dissolution of chalcopyrite involved chiefly an indirect bioleaching mechanism.

Impact on sediments and water by release of copper from chalcopyrite bearing rock due to acidic mine drainage

NASA Astrophysics Data System (ADS)

Shukla, Anoop Kant; Pradhan, Manoj; Tiwari, Onkar Nath

2018-04-01

Mining activity causes transition of rock-mass from its original position in earth into open environment. The action of environmental elements such air, water, microorganisms leads to oxidation of minerals which constitute the rock. The oxidation of sulphide minerals in presence of moisture releases acidic mine discharge (AMD). The acidic nature of AMD causes leaching of metals from rock minerals. Dissolution of other minerals may occur upon reaction with AMD. Chalcopyrite (CuFeS2) undergoes oxidation in acidic condition releasing copper among other products. This study reveals contamination of copper in sediment samples and seepage water from the tailing dam of a large copper project in located in central India. Elevation was studied using GIS to ascertain to the topographic elevation of tailing dam area. It was located at relatively high altitude causing seepage to flow away from tailing dam. The seepage water from tailing dam was found to be acidic with mean pH value of 4.0 and elevated copper content. Similarly, sediments from seepage water flow displayed elevated copper concentration. The copper concentration in seepage water was found with a mean value of 10.73 mg/l. The sediments from seepage water flow also displayed elevated copper concentration with mean value of 26.92 g/kg. This indicates impact on sediments by release of copper due to acidic mine drainage.

Mineralogy of the epithermal precious and base metal deposit Banská Hodruša at the Rozália Mine (Slovakia)

NASA Astrophysics Data System (ADS)

Kubač, Alexander; Chovan, Martin; Koděra, Peter; Kyle, J. Richard; Žitňan, Peter; Lexa, Jaroslav; Vojtko, Rastislav

2018-03-01

The Au-Ag-Pb-Zn-Cu epithermal deposit Banská Hodruša of intermediate-sulphidation type is located in the Middle Miocene Štiavnica stratovolcano on the inner side of the Carpathian arc in Slovakia. This deposit represents an unusual subhorizontal multi-stage vein system, related to processes of underground cauldron subsidence and exhumation of a subvolcanic granodiorite pluton. Veins are developed on a low-angle normal shear zone, possibly representing a detachment zone in andesitic wall rocks that formed during emplacement and exhumation of the granodiorite pluton. The deposit consists of two parts, separated by a thick sill of quartz-diorite porphyry. The eastern part is currently mined, and the western part has already been depleted. The Banská Hodruša mineralization was formed during four stages: (1) low-grade silicified breccia at subhorizontal structures at the base of the deposit; (2) stockwork of steep veins with rhodonite-rhodochrosite, quartz-sulphide-carbonate and quartz-gold assemblages; (3) thin quartz-gold veins with medium dip in tension cracks inside the shear zone and complementary detachment hosted quartz-base metals-gold veins; (4) Post-ore veins. Gold and electrum (920-730) occur as intergrowths with base metal sulphides or hosted in quartz and carbonates, accompanied by Au-Ag tellurides (hessite, petzite). Rare Te-polybasite and Cu-cervelleite result from re-equilibration of early Te-bearing minerals during cooling. Sulphide minerals include low Fe sphalerite ( 1.25 wt%), galena, chalcopyrite, and pyrite. The wall rock alteration is represented mostly by adularia, illite, chlorite, quartz, calcite and pyrite. Precipitation of gold, Au-Ag tellurides, Mn-bearing minerals and adularia resulted from boiling of fluids due to hydraulic fracturing, as well as opening of dilatational structures within the shear zone.

The Genesis of Precious and Base Metal Mineralization at the Miguel Auza Deposit, Zacatecas, Mexico

NASA Astrophysics Data System (ADS)

Findley, A. A.; Olivo, G. R.; Godin, L.

2009-05-01

The Miguel Auza mine located in Zacatecas State, Mexico, is a vein-type polymetallic epithermal deposit hosted in deformed argillite, siltstone and, greywacke of the Cretaceous Caracol Formation. Silver-rich base metal veins (0.2 m to >1.5 m wide) are spatially associated with the NE-striking, steeply SE- dipping (70-80°) Miguel Auza fault over a strike length of 1.6 km and a depth of 460 m. A 2 km2 monzonitic stock located in the proximity of the mineralized zones, has previously been interpreted as the source of the mineralizing fluids. Four distinct structural stages are correlated with hydrothermal mineral deposition: (I) The Pre-ore stage is characterized by normal faulting, fracturing of host rock, and rotation of bedding planes. This stage consists of quartz, illite, chlorite, +/- pyrite alteration of sedimentary wall rocks. (II) The Pyrite-vein stage is associated with reverse-sense reactivation of early normal faults, dilation of bedding planes/fractures, and deposition of generally barren calcite + pyrite veinlets. (III) The Main-ore stage is related to the development of reverse-fault- hosted massive sulphide veins. During this stage three phases of mineral deposition are recorded: early pyrite and arsenopyrite, intermediate chalcopyrite, pyrite, arsenopyrite, and base metals, and late base metals and Ag-bearing minerals. Associated gangue minerals during the main ore stage are quartz, muscovite, calcite and chlorite. (IV) The Post-ore stage involves late NW-SE striking block faulting, brecciation and calcite veining. Later supergene oxidation of veins led to deposition of Fe-oxides and hydroxides, commonly filling fractures or replacing early-formed sulphide assemblages. The various vein types display classic epithermal textures including open space filling, banding, comb quartz and brecciation. The Ag-bearing minerals comprise pyrargyrite [Ag3(Sb,As)S3], argentotennantite [(Cu,Ag)10(Zn,Fe)2(Sn,As)4S13], polybasite-pearceite [(Ag,Cu)16(Sb,As)2S11], and acanthite [AgS2]; associated sulphides include galena, sphalerite, chalcopyrite, arsenopyrite and pyrite. In the main ore zone, base metal sulphides are commonly intergrown with the Ag-bearing sulfosalts. Analyses of galena show no significant silver values indicating that silver grades are exclusively associated with the Ag-bearing sulfosalts and sulphides. The distribution of the Sb/(Sb + As) ratios in the silver sulfosalts indicate that the ore forming fluid(s) was consistently antimony-rich during the Ag-rich ore deposition with no significant variation laterally, vertically, or along strike of the vein systems. However, Ag/(Ag + Cu) values in argentotennantite decrease along-strike from NE to SW and with depth. Compositions of argentotennantite + pyrargyrite + sphalerite indicate a primary depositional temperature around 325-350° C for the late phase of the Main-ore stage. Compositions of sphalerite also show an increasing trend in FeS (mol %) along strike of the deposit from NE to SW. The geometric relationship between the various structures, vein types, and the regional Miguel Auza fault zone suggest episodic reverse-sense reactivation of normal faults. It is argued that the structural evolution of the area, and, in particular, the Main-ore stage, provided transport pathways for metal-rich fluids and controlled the orientations of ore-bearing veins. Variations in mineral chemistry suggest that the rocks in the NE sector interacted with hotter fluids than in the SW part of the deposit.

Assessment of the geoavailability of trace elements from minerals in mine wastes: analytical techniques and assessment of selected copper minerals

USGS Publications Warehouse

Driscoll, Rhonda; Hageman, Phillip L.; Benzel, William M.; Diehl, Sharon F.; Adams, David T.; Morman, Suzette; Choate, LaDonna M.

2012-01-01

In this study, four randomly selected copper-bearing minerals were examined—azurite, malachite, bornite, and chalcopyrite. The objectives were to examine and enumerate the crystalline and chemical properties of each of the minerals, to determine which, if any, of the Cu-bearing minerals might adversely affect systems biota, and to provide a multi-procedure reference. Laboratory work included use of computational software for quantifying crystalline and amorphous material and optical and electron imaging instruments to model and project crystalline structures. Chemical weathering, human fluid, and enzyme simulation studies were also conducted. The analyses were conducted systematically: X-ray diffraction and microanalytical studies followed by a series of chemical, bio-leaching, and toxicity experiments.

Mineralized breccia clasts: a window into hidden porphyry-type mineralization underlying the epithermal polymetallic deposit of Cerro de Pasco (Peru)

NASA Astrophysics Data System (ADS)

Rottier, Bertrand; Kouzmanov, Kalin; Casanova, Vincent; Bouvier, Anne-Sophie; Baumgartner, Lukas P.; Wälle, Markus; Fontboté, Lluís

2018-01-01

Cerro de Pasco (Peru) is known for its large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) mineralization emplaced at shallow level, a few hundred meters below the paleo-surface, at the border of a large diatreme-dome complex. Porphyry-style veins crosscutting hornfels and magmatic rock clasts are found in the diatreme breccia and in quartz-monzonite porphyry dikes. Such mineralized veins in clasts allow investigation of high-temperature porphyry-style mineralization developed in the deep portions of magmatic-hydrothermal systems. Quartz in porphyry-style veins contains silicate melt inclusions as well as fluid and solid mineral inclusions. Two types of high-temperature (> 600 °C) quartz-molybdenite-(chalcopyrite)-(pyrite) veins are found in the clasts. Early, thin (1-2 mm), and sinuous HT1 veins are crosscut by slightly thicker (up to 2 cm) and more regular HT2 veins. The HT1 vein quartz hosts CO2- and sulfur-rich high-density vapor inclusions. Two subtypes of the HT1 veins have been defined, based on the nature of mineral inclusions hosted in quartz: (i) HT1bt veins with inclusions of K-feldspar, biotite, rutile, and minor titanite and (ii) HT1px veins with inclusions of actinolite, augite, titanite, apatite, and minor rutile. Using an emplacement depth of the veins of between 2 and 3 km (500 to 800 bar), derived from the diatreme breccia architecture and the supposed erosion preceding the diatreme formation, multiple mineral thermobarometers are applied. The data indicate that HT1 veins were formed at temperatures > 700 °C. HT2 veins host assemblages of polyphase brine inclusions, generally coexisting with low-density vapor-rich inclusions, trapped at temperatures around 600 °C. Rhyolitic silicate melt inclusions found in both HT1 and HT2 veins represent melt droplets transported by the ascending hydrothermal fluids. LA-ICP-MS analyses reveal a chemical evolution coherent with the crystallization of an evolved rhyolitic melt. Quartz from both HT1 and HT2 veins also contains secondary, low-temperature ( 300 °C) brine and aqueous fluid inclusions that record the cooling of the system. Both vein types are locally crosscut and/or reopened by a pre-diatreme polymetallic event consisting of pyrite, sphalerite with "chalcopyrite disease," galena, chalcopyrite, tetrahedrite-tennantite, and minor quartz. LA-ICP-MS analyses of mineral and high-temperature fluid inclusions hosted in HT1 and HT2 veins and in situ secondary-ion mass spectrometry oxygen isotope analyses of vein quartz indicate a magmatic signature for the mineralizing fluids with no major meteoric water input and allow reconstruction of the source and chemical evolution of fluids that formed these porphyry-style veins as snapshots of the early and deep mineralizations at Cerro de Pasco. This detailed study of the porphyry-type mineralization hosted in clasts offers a unique opportunity to reconstruct the late magmatic and early hydrothermal evolutions of porphyry mineralization underlying the world-class Cerro de Pasco epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) deposit.

Growth and characterization of epitaxial silver indium diselenide

NASA Astrophysics Data System (ADS)

Pena Martin, Pamela

Photovoltaics (solar cells) are a key player in the renewable energy frontier, and will become increasingly important as their cost per watt continues to drop, especially if fossil fuel costs increase. One particularly promising photovoltaic technology is based on chalcopyrite-structure semiconductors. Within the chalcopyrite compounds the highest efficiency thin film solar cell absorber material to date is Cu(In,Ga)Se2 (CIGS). While current efficiency records are over 21% for single-junction cells, there is still room for improvement. Replacing some of the Cu with Ag has been shown to be beneficial in CIGS devices. However, the Ag- containing chalcopyrites are still relatively unknown in terms of their growth mechanism, energetics, and surface atomic and electronic properties. These are best inferred through study of epitaxial films, yet they have little mention in literature and have not been the subject of a detailed study. This work describes the growth of epitaxial AgInSe2 (AIS) on GaAs substrates, studying the morphology, structure, and surface properties to understand how growth takes place. It also seeks to experimentally determine the surface electronic and atomic structure at the atomic scale to gain insight into the part of the material that forms the heterojunction that collects photon energy in the device. Finally, this work seeks to compare and contrast these findings with what is known about CIGS to determine where similarities and, more importantly, the differences may lie. This study has found that single phase tetragonal AIS can be epitaxially grown on GaAs, as illustrated by x-ray diffraction (XRD), transmission electron microscope (TEM), and surface morphology data. Like CIGS, the close packed polar (112) planes have the lowest energy. The morphology points to a difference in step dynamics, leading to less faceted, straight edged island shapes compared to CIGS. Epitaxial temperature as a function of growth direction shows a different trend in AIS than in CIGS. Interdiffusion of the group III elements across the substrate interface was found to result in an epitaxial intermixed layer between the film and substrate in some cases, which may help mediate the lattice mismatch. At the atomic scale, scanning tunneling microscopy (STM) was used to observe details of the surface morphology, which indicated growth of the (112)A orientation of AIS by a screw dislocation mechanism (other surfaces were not examined by STM but are expected to show similar results). The surface atomic structure was directly imaged for the first time, revealing an arrangement similar to that expected from a bulk terminated surface. The electronic structure shows a gap in surface electronic states with a width comparable to bulk AIS, n-type conduction, and a tail of states near the valence band edge that decay well into the gap. The conduction and valence bands show fluctuations as a function of position on the surface, with greater magnitude in the valence band. The fluctuations in both bands are less than those observed on the surface of CIS by STM. It seems to indicate a reduction in band tails, both in magnitude and spacial extent, in AIS compared to CIS, likely tied to a reduction in point defect concentration at the surface.

The Jebel Ohier deposit—a newly discovered porphyry copper-gold system in the Neoproterozoic Arabian-Nubian Shield, Red Sea Hills, NE Sudan

NASA Astrophysics Data System (ADS)

Bierlein, F. P.; McKeag, S.; Reynolds, N.; Bargmann, C. J.; Bullen, W.; Murphy, F. C.; Al-Athbah, H.; Brauhart, C.; Potma, W.; Meffre, S.; McKnight, S.

2016-08-01

Ongoing exploration in the Red Sea Hills of NE Sudan has led to the identification of a large alteration-mineralization system within a relatively undeformed Neoproterozoic intrusive-extrusive succession centered on Jebel Ohier. The style of mineralization, presence of an extensive stockwork vein network within a zoned potassic-propylitic-argillic-advanced argillic-altered system, a mineralization assemblage comprising magnetite-pyrite-chalcopyrite-bornite (±gold, silver and tellurides), and the recurrence of fertile mafic to intermediate magmatism in a developing convergent plate setting all point to a porphyry copper-gold association, analogous to major porphyry Cu-Au-Mo deposits in Phanerozoic supra-subduction settings such as the SW Pacific. Preliminary U-Pb age dating yielded a maximum constraint of c. 730 Ma for the emplacement of the stockwork system into a significantly older ( c. 800 Ma) volcanic edifice. The mineralization formed prior to regional deformation and accretion of the host terrane to a stable continental margin at by c. 700 Ma, thus ensuring preservation of the deposit. The Jebel Ohier deposit is interpreted as a relatively well-preserved, rare example of a Neoproterozoic porphyry Cu-Au system and the first porphyry Cu-Au deposit to be identified in the Arabian-Nubian Shield.

Preliminary mineralogical data on epithermal ore veins associated with Rosia Poieni porphyry copper deposit, Apuseni Mountains, Romania

NASA Astrophysics Data System (ADS)

Iatan, E. L.; Popescu, Gh. C.

2012-04-01

Rosia Poieni is the largest porphyry copper (±Au±Mo) deposits associated with Neogene magmatic rocks from the South Apuseni Mountains, being located approximately 8 km northeast of the town of Abrud. During a recent examination of some epithermal mineralized veins, crosscutting the porphyry mineralization from the Roşia Poieni deposit, two species of tellurides and one tellurosulfide minerals were identified. The studied samples were collected from the + 1045 m level, SW side of the open pit and are represented by epithermal veins, crosscutting the porphyry copper mineralized body. The thickness of the veins is almost 4 cm. Following reflected-polarized light microscopy to identify the ore-mineral assemblages, the polished sections were studied with a Scanning Electron Microscope (SEM) equipped with a back-scattered electron (BSE) detector to study fine-sized minerals. Quantitative compositional data were determined using a Cameca SX 50 electron microprobe (EMP). Based on optical microscopy, SEM and EMPA three mineral associations have been separated inside the epithermal vein, from the margins to the centre: 1. quartz+tennantite-tetrahedrite+goldfieldite+pyrite+sphalerite; 2. quartz+pyrite+tellurobismutite; 3. chalcopyrite+hessite+vivianite. Goldfieldite occurs in anhedral grains and it is associated with tennantite-tetrahedrite and quartz. The electron microprobe analysis gave a variable content in Te between 13.28-13.39 wt.%, 43.34 wt.% Cu, 0.1 wt. % Fe, 0.2 wt.% Zn, 14.68 wt.% As, 4.35 wt.% Sb and 24.84 wt.% S. The calculated formula for the goldfieldite is Cu11.8Te1.8(Sb,As)4S13.4. The EPM analyses on tetrahedrite-tennantite revealed a low content in Te (0.02-0.03 wt.%) and 42.23 wt.% Cu, 2.67 wt.% Fe, 7.34 wt.% Zn, 0.04 wt.% Sb, 19.28 wt.% As and 28.4 wt.% S. The calculated formula is Cu9.8(Fe,Zn)2.4(Sb,As,Te)3.8S13. The variable ratio of the Te content may reflect a variable content of Te in the hydrothermal fluids from which the tellurian tetrahedrite precipitated. Hessite lies close to the grain boundary between the calchopyrite grains, which is associated with vivianite. Electron microprobe analysis gave 57.73 wt.% Ag and 42.27 wt.% Te with calculated stoichiometric formula Ag1.9Te1.1 . Tellurobismuthite it forms irregular grains and it is associated with quartz and pyrite. Electron microprobe analysis gave 57.20 wt.% Bi and 42.80 wt.% Te with calculated stoichiometric formula Bi2.2Te2.8. Based on the mineral assemblages separated inside the ore vein and on the ratio of the Te content for the different identified tellurium bearing minerals, we can conclude that the Te content of the fluids from which they precipitated, increased from the margins to the centre of the vein. In summary, this study of specimens from Rosia Poieni porphyry copper deposit, has resulted in the recognition of some tellurium-bearing minerals, not reported by previous workers. These minerals are represented by tellurobismutite, hessite and goldfieldite and they are associated with epithermal vein mineralization (pyrite, chalcopyrite, sphalerite, tennantite-tetrahedrite, quartz, vivianite). The presence of tellurium indicates the transition between porphyry-style mineralization to epithermal vein mineralization. Acknowledgements: This work was supported by the strategic grant POSDRU/89/1.5/S58852, Project "Postdoctoral program for training scientific researches" co-financed by the European Social Found within the Sectorial Operational Program Human Resources Development 2007-2013".

Short communication: Adverse effect of surface-active reagents on the bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans.

PubMed

Huerta, G; Escobar, B; Rubio, J; Badilla-Ohlbaum, R

1995-09-01

Oxidation of Fe(II) iron and bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans was adversely affected by isopropylxanthate, a flotation agent, and by LIX 984, a solvent-extraction agent, each at ≤ 1 g/l. The reagents/l were adsorbed on the bacterial surface, decreasing the bacteria's development and preventing biooxidation. Both reagents inhibited the bioleaching of pyrite and LIX 984 also inhibited the bioleaching of chalcopyrite.

Surface and bulk effects of K in Cu 1-xK xIn 1-yGa ySe 2 solar cells

DOE PAGES

Muzzillo, Christopher P.; Anderson, Timothy J.

2017-12-29

Two strategies for enhancing photovoltaic (PV) performance in chalcopyrite solar cells were investigated: Cu 1-xK xIn 1-yGa ySe 2 absorbers with low K content (K/(K+Cu), or x ~ 0.07) distributed throughout the bulk, and CuIn 1-yGa ySe 2 absorbers with KIn 1-yGa ySe 2 grown on their surfaces. Distributing K throughout the bulk absorbers improved power conversion efficiency, open-circuit voltage (VOC) and fill factor (FF) for Ga/(Ga+In) of 0, 0.3 and 0.5. Surface KIn 1-yGa ySe 2 and bulk x ~ 0.07 Cu 1-xK xIn 1-yGa ySe 2 films with Ga/(Ga+In), or y of 0.3 and 0.5 also had improvedmore » efficiency, VOC, and FF, relative to CuIn 1-yGa ySe 2 baselines. On the other hand, y ~ 1 absorbers did not benefit from K introduction. Similar to Cu 1-xK xInSe 2, the formation of Cu 1-xK xGaSe 2 alloys was favored at low temperatures and high Na supply by the substrate, relative to the formation of mixed-phase CuGaSe 2 + KGaSe 2. KIn 1-yGa ySe 2 alloys were grown for the first time, as evidenced by X-ray diffraction and ultraviolet/visible spectroscopy. For all Ga/(Ga+In) compositions, the surface KIn 1-yGa ySe 2 absorbers had superior PV performance in buffered and buffer-free devices. However, the bulk x ~ 0.07 absorbers only outperformed the baselines in buffered devices. The data demonstrate that KIn 1-yGa ySe 2 passivates the surface of CuIn 1-yGa ySe 2 to increase efficiency, VOC, and FF, while bulk Cu 1-xK xIn 1-yGa ySe 2 absorbers with x ~ 0.07 enhance efficiency, VOC, and FF by some other mechanism.« less

Surface and bulk effects of K in Cu 1-xK xIn 1-yGa ySe 2 solar cells

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

Muzzillo, Christopher P.; Anderson, Timothy J.

Two strategies for enhancing photovoltaic (PV) performance in chalcopyrite solar cells were investigated: Cu 1-xK xIn 1-yGa ySe 2 absorbers with low K content (K/(K+Cu), or x ~ 0.07) distributed throughout the bulk, and CuIn 1-yGa ySe 2 absorbers with KIn 1-yGa ySe 2 grown on their surfaces. Distributing K throughout the bulk absorbers improved power conversion efficiency, open-circuit voltage (VOC) and fill factor (FF) for Ga/(Ga+In) of 0, 0.3 and 0.5. Surface KIn 1-yGa ySe 2 and bulk x ~ 0.07 Cu 1-xK xIn 1-yGa ySe 2 films with Ga/(Ga+In), or y of 0.3 and 0.5 also had improvedmore » efficiency, VOC, and FF, relative to CuIn 1-yGa ySe 2 baselines. On the other hand, y ~ 1 absorbers did not benefit from K introduction. Similar to Cu 1-xK xInSe 2, the formation of Cu 1-xK xGaSe 2 alloys was favored at low temperatures and high Na supply by the substrate, relative to the formation of mixed-phase CuGaSe 2 + KGaSe 2. KIn 1-yGa ySe 2 alloys were grown for the first time, as evidenced by X-ray diffraction and ultraviolet/visible spectroscopy. For all Ga/(Ga+In) compositions, the surface KIn 1-yGa ySe 2 absorbers had superior PV performance in buffered and buffer-free devices. However, the bulk x ~ 0.07 absorbers only outperformed the baselines in buffered devices. The data demonstrate that KIn 1-yGa ySe 2 passivates the surface of CuIn 1-yGa ySe 2 to increase efficiency, VOC, and FF, while bulk Cu 1-xK xIn 1-yGa ySe 2 absorbers with x ~ 0.07 enhance efficiency, VOC, and FF by some other mechanism.« less

Computational materials design of attractive Fermion system with large negative effective Ueff in the hole-doped Delafossite of CuAlO2, AgAlO2 and AuAlO2: Charge-excitation induced Ueff < 0

NASA Astrophysics Data System (ADS)

Nakanishi, A.; Fukushima, T.; Uede, H.; Katayama-Yoshida, H.

2015-12-01

On the basis of general design rules for negative effective U(Ueff) systems by controlling purely-electronic and attractive Fermion mechanisms, we perform computational materials design (CMD®) for the negative Ueff system in hole-doped two-dimensional (2D) Delafossite CuAlO2, AgAlO2 and AuAlO2 by ab initio calculations with local density approximation (LDA) and self-interaction corrected-LDA (SIC-LDA). It is found that the large negative Ueff in the hole-doped attractive Fermion systems for CuAlO2 (UeffLDA = - 4.53 eV and UeffSIC-LDA = - 4.20 eV), AgAlO2 (UeffLDA = - 4.88 eV and UeffSIC-LDA = - 4.55 eV) and AuAlO2 (UeffLDA = - 4.14 eV and UeffSIC-LDA = - 3.55 eV). These values are 10 times larger than that in hole-doped three-dimensional (3D) CuFeS2 (Ueff = - 0.44 eV). For future calculations of Tc and phase diagram by quantum Monte Carlo simulations, we propose the negative Ueff Hubbard model with the anti-bonding single π-band model for CuAlO2, AgAlO2 and AuAlO2 using the mapped parameters obtained from ab initio electronic structure calculations. Based on the theory of negative Ueff Hubbard model (Noziéres and Schmitt-Rink, 1985), we discuss |Ueff| dependence of superconducting critical temperature (Tc) in the 2D Delafossite of CuAlO2, AgAlO2 and AuAlO2 and 3D Chalcopyrite of CuFeS2, which shows the interesting chemical trend, i.e., Tc increases exponentially (Tc ∝ exp [ - 1 / | Ueff | ]) in the weak coupling regime | Ueff(- 0.44 eV) | < W(∼ 2 eV) (where W is the band width of the negative Ueff Hubbard model) for the hole-doped CuFeS2, and then Tc goes through a maximum when | Ueff(- 4.88 eV , - 4.14 eV) | ∼ W(2.8 eV , 3.5 eV) for the hole-doped AgAlO2 and AuAlO2, and finally Tc decreases with increasing |Ueff| in the strong coupling regime, where | Ueff(- 4.53 eV) | > W(1.7 eV) , for the hole-doped CuAlO2.

Making Single-Source Precursors of Ternary Semiconductors

NASA Technical Reports Server (NTRS)

Hepp, Aloysius; Banger, Kulbindre K.

2007-01-01

A synthesis route has been developed for the commercial manufacture of single- source precursors of chalcopyrite semiconductor absorber layers of thin-film solar photovoltaic cells. A closely related class of single-source precursors of these semiconductors, and their synthesis routes, were reported in "Improved Single-Source Precursors for Solar-Cell Absorbers" (LEW-17445-1), NASA Tech Briefs, Vol. 31, No. 6 (June 2007), page 56. The present synthesis route is better suited to commercialization because it is simpler and involves the use of commercially available agents, yet offers the flexibility needed for synthesis of a variety of precursors. A single-source precursor of the type of interest here is denoted by the general formula L2M'(mu-ER)2M(ER)2, where L signifies a Lewis base; M signifies Al, In, or Ga; M' signifies Ag or Cu; R signifies an alkyl, aryl, silyl, or perfluorocarbon group; E signifies O, S, Se, or Te; and mu signifies a bridging ligand. This compound can be synthesized in a "one-pot" procedure from ingredients that are readily available from almost any chemical supplier. In a demonstration, the following synthesis was performed: Under anaerobic conditions, InCl3 was reacted with sodium ethanethiolate in methanol in a 1:4 molar ratio to afford the ionic stable intermediate compound Na+[In(SEt)4]- (where Et signifies ethyl group). After approximately 15 minutes, a heterogeneous solution of CuCl and the Lewis base PPh3 (where Ph signifies phenyl) in a 1:2 ratio in a mixture of CH3CN and CH2Cl2 was added directly to the freshly prepared Na+[In(SEt)4]-. After 24 hours, the reaction was essentially complete. The methanolic solution was concentrated, then the product was extracted with CH2Cl2, then the product was washed with dry ether and pentane. The product in its final form was a creamy white solid. Spectroscopic and elemental analysis confirmed that the product was (PPh3)2Cu(mu-SEt)2In(mu-SEt)2, which is known to be a precursor of the ternary semiconductor CuInS2.

Visible scintillation photodetector device incorporating chalcopyrite semiconductor crystals

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

Stowe, Ashley C.; Burger, Arnold

2017-04-04

A photodetector device, including: a scintillator material operable for receiving incident radiation and emitting photons in response; a photodetector material coupled to the scintillator material operable for receiving the photons emitted by the scintillator material and generating a current in response, wherein the photodetector material includes a chalcopyrite semiconductor crystal; and a circuit coupled to the photodetector material operable for characterizing the incident radiation based on the current generated by the photodetector material. Optionally, the scintillator material includes a gamma scintillator material and the incident radiation received includes gamma rays. Optionally, the photodetector material is further operable for receiving thermalmore » neutrons and generating a current in response. The circuit is further operable for characterizing the thermal neutrons based on the current generated by the photodetector material.« less

Novel integration strategy for enhancing chalcopyrite bioleaching by Acidithiobacillus sp. in a 7-L fermenter.

PubMed

Feng, Shoushuai; Yang, Hailin; Zhan, Xiao; Wang, Wu

2014-06-01

An integrated strategy (additional energy substrate-three stage pH control-fed batch) was firstly proposed for efficiently improving chalcopyrite bioleaching by Acidithiobacillus sp. in a 7-L fermenter. The strain adaptive-growing phase was greatly shortened from 8days into 4days with the supplement of additional 2g/L Fe(2+)+2g/L S(0). Jarosite passivation was effectively weakened basing on higher biomass via the three-stage pH-stat control (pH 1.3-1.0-0.7). The mineral substrate inhibition was attenuated by fed-batch fermentation. With the integrated strategy, the biochemical reaction was promoted and achieved a better balance. Meanwhile, the domination course of A. thiooxidans in the microbial community was shortened from 14days to 8days. As the results of integrated strategy, the final copper ion and productivity reached 89.1mg/L and 2.23mg/(Ld), respectively, which was improved by 52.8% compared to the uncontrolled batch bioleaching. The integrated strategy could be further exploited for industrial chalcopyrite bioleaching. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hydrothermal modification of host rock geochemistry within Mo-Cu porphyry deposits in the Galway Granite, western Ireland

NASA Astrophysics Data System (ADS)

Tolometti, Gavin; McCarthy, Will

2016-04-01

Hydrothermal alteration of host rock is a process inherent to the formation of porphyry deposits and the required geochemical modification of these rocks is regularly used to indicate proximity to an economic target. The study involves examining the changes in major, minor and trace elements to understand how the quartz vein structures have influenced the chemistry within the Murvey Granite that forms part of the 380-425Ma Galway Granite Complex in western Ireland. Molybdenite mineralisation within the Galway Granite Complex occurred in close association with protracted magmatism at 423Ma, 410Ma, 407Ma, 397Ma and 383Ma and this continues to be of interest to active exploration. The aim of the project is to characterize hydrothermal alteration associated with Mo-Cu mineralisation and identify geochemical indicators that can guide future exploration work. The Murvey Granite intrudes metagabbros and gneiss that form part of the Connemara Metamorphic complex. The intrusion is composed of albite-rich pink granite, garnetiferous granite and phenocrytic orthoclase granite. Minor doleritic dykes post-date the Murvey Granite, found commonly along its margins. Field mapping shows that the granite is truncated to the east by a regional NW-SE fault and that several small subparallel structures host Mo-Cu bearing quartz veins. Petrographic observations show heavily sericitized feldspars and plagioclase and biotite which have undergone kaolinization and chloritisation. Chalcopyrite minerals are fine grained, heavily fractured found crystallized along the margins of the feldspars and 2mm pyrite crystals. Molybdenite are also seen along the margins of the feldspars, crystallized whilst the Murvey Granite cooled. Field and petrographic observations indicate that mineralisation is structurally controlled by NW-SE faults from the selected mineralization zones and conjugate NE-SW cross cutting the Murvey Granite. Both fault orientations exhibit quartz and disseminated molybdenite mineralization. Extensive hydrothermal alteration is observed within 75 meters of veins that exhibit prominent disseminated mineralisation. To investigate associated geochemical alteration 24 samples were selected along two traverses that cross cut two distinct vein structures. XRF analysis results show that calcium decreases from 1.8 - 0.2 wt% and sulphur increases from 0.2 - 0.9 wt% moving away from the mineralized zones which is to be expected due to their mobile nature. Unexpectedly, minor element data shows no fluctuation in Cu concentrations moving away from either vein structures, despite chalcopyrite found greatest near the vein structures. XRF data analysis is underway to compare the non-mobile and mobile elements to investigate the extent of the decreasing and increasing trends moving proximal to the mineralization zones. The relative decrease in calcium may be caused by the exchange of ion end members between feldspars and this will be tested using a WDS electron micro-probe.

Gold grade of epithermal gold ore at Lamuntet, Brang Rea, West Sumbawa District, West Nusa Tenggara Province, Indonesia

NASA Astrophysics Data System (ADS)

Ernawati, Rika; Idrus, Arifudin; TBMP, Himawan

2017-06-01

Lamuntet is one of gold ore mining area carried out by the Artisanal Small scale Gold Mining (ASGM) located in West Sumbawa, Indonesia. Most of the miners at this area are not the local miners but also those from other regions. Mineralization of this area is strong identified as low sulfidation epithermal system. There are two blocks of this mining location, namely, Ngelampar block with an area of 0.164 km2 and Song block with an area of 0.067 km2. This study was focused on Ngelampar block. The characteristic of epithermal system is the existence of quartz vein with comb, vuggy, and sugary texture. The aim of this research was to analyze the gold grade and other metals, such as Cu, Ag, Pb, As, Zn, and Hg. The research methods included literature study from previous researches, field work, laboratory work, and interpretation. The literature study was performed on previous researches with similar study area. The field work comprised of direct observation and sampling. Fieldwork was done for a week to obtain gold ore/vein. Sixteen samples were analyzed to obtain the grade of ore/metal. The Hg laboratory analysis was then performed on the six samples with the highest gold grade. Laboratory works were conducted at Intertek Jakarta by using Fire Assay (FA) for gold grade and Atomic Absorption Spectrophotometry (AAS) for Cu, Ag, Pb, As, Zn, and Hg. Results of the analysis showed the range of Au was grade (0.1 ppm - 27.8 ppm), Cu was 26 ppm -1740 ppm, Pb was 101 ppm- >4000 ppm, Zn of 73 ppm- >10,000 ppm, Ag of 3 ppm -185 ppm, As was 150 ppm-6530 ppm, and Hg of 0.08 ppm - 1.89 ppm. L1 and L15 had high grade for all values (Au, Ag, Zn, Cu, As, and Hg). Gold mineralization was formed as electrum because of Ag content is higher than 20%. Associated minerals of the samples in the study area were galena, sphalerite, arsenopyrite, and chalcopyrite which showed the characteristic of rich base metal of Pb, Zn, and Cu at LS epithermal.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

PubMed

Chawla, Parul; Singh, Son; Sharma, Shailesh Narain

2014-01-01

In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern-Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor-acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

Mass change calculations of hydrothermal alterations within the volcanogenic metasediments hosted Cu-Pb (-Zn) mineralization at Halilar area, NW Turkey

NASA Astrophysics Data System (ADS)

Kiran Yildirim, Demet; Abdelnasser, Amr; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Halilar Cu-Pb (-Zn) mineralization that is formed in the volcanogenic metasediments of Bagcagiz Formation at Balikesir province, NW Turkey, represents locally vein-type deposit as well as restricted to fault gouge zone directed NE-SW along with the lower boundary of Bagcagiz Formation and Duztarla granitic intrusion in the study area. Furthermore, This granite is traversed by numerous mineralized sheeted vein systems, which locally transgress into the surrounding metasediments. Therefore, this mineralization closely associated with intense hydrothermal alteration within brecciation, and quartz stockwork veining. The ore mineral assemblage includes chalcopyrite, galena, and some sphalerite with covellite and goethite formed during three phases of mineralization (pre-ore, main ore, and supergene) within an abundant gangue of quartz and calcite. The geologic and field relationships, petrographic and mineralogical studies reveal two alteration zones occurred with the Cu-Pb (-Zn) mineralization along the contact between the Bagcagiz Formation and Duztarla granite; pervasive phyllic alteration (quartz, sericite, and pyrite), and selective propylitic alteration (albite, calcite, epidote, sericite and/or chlorite). This work, by using the mass balance calculations, reports the mass/volume changes (gain and loss) of the chemical components of the hydrothermal alteration zones associated with Halilar Cu-Pb (-Zn) mineralization at Balikesir area (Turkey). It revealed that the phyllic alteration has enrichments of Si, Fe, K, Ba, and LOI with depletion of Mg, Ca, and Na reflect sericitization of alkali feldspar and destruction of ferromagnesian minerals. This zone has high Cu and Pb with Zn contents represents the main mineralized zone. On the other hand, the propylitic zone is characterized by addition of Ca, Na, K, Ti, P, and Ba with LOI and Cu (lower content) referring to the replacement of plagioclase and ferromagnesian minerals by albite, calcite, epidote, and sericite with chlorite. Keywords: Mass balance calculations; hydrothermal alterations; Cu-Pb (-Zn) mineralization; Halilar area; NW Turkey

PHOTONICS AND NANOTECHNOLOGY Laser synthesis and modification of composite nanoparticles in liquids

NASA Astrophysics Data System (ADS)

Tarasenko, N. V.; Butsen, A. V.

2010-12-01

The works devoted to the formation and modification of nanoparticles using laser ablation of solid targets in liquids are reviewed. Several approaches to implement laser ablation in liquids, aimed at synthesising nanoparticles of complex composition, are considered: direct laser ablation of a target of corresponding composition, laser ablation of a combined target composed of two different metals, laser irradiation of a mixture of two or more colloidal solutions, and laser ablation in reactive liquids. The properties of two-component bimetallic systems (Ag — Cu, Ag — Au), semiconductor nanocrystals (ZnO, CdSe), chalcopyrite nanoparticles, and doped oxide nanoparticles (ZnO:Ag, Gd2O2:Tb3+) formed as a result of single- and double-pulse laser ablation in different liquids (water, ethanol, acetone, solutions of polysaccharides) are discussed.

Multi-omics reveal the lifestyle of the acidophilic, mineral-oxidizing model species Leptospirillum ferriphilumT.

PubMed

Christel, Stephan; Herold, Malte; Bellenberg, Sören; El Hajjami, Mohamed; Buetti-Dinh, Antoine; Pivkin, Igor V; Sand, Wolfgang; Wilmes, Paul; Poetsch, Ansgar; Dopson, Mark

2017-11-17

Leptospirillum ferriphilum plays a major role in acidic, metal rich environments where it represents one of the most prevalent iron oxidizers. These milieus include acid rock and mine drainage as well as biomining operations. Despite its perceived importance, no complete genome sequence of this model species' type strain is available, limiting the possibilities to investigate the strategies and adaptations Leptospirillum ferriphilum T applies to survive and compete in its niche. This study presents a complete, circular genome of Leptospirillum ferriphilum T DSM 14647 obtained by PacBio SMRT long read sequencing for use as a high quality reference. Analysis of the functionally annotated genome, mRNA transcripts, and protein concentrations revealed a previously undiscovered nitrogenase cluster for atmospheric nitrogen fixation and elucidated metabolic systems taking part in energy conservation, carbon fixation, pH homeostasis, heavy metal tolerance, oxidative stress response, chemotaxis and motility, quorum sensing, and biofilm formation. Additionally, mRNA transcript counts and protein concentrations were compared between cells grown in continuous culture using ferrous iron as substrate and bioleaching cultures containing chalcopyrite (CuFeS 2 ). Leptospirillum ferriphilum T adaptations to growth on chalcopyrite included a possibly enhanced production of reducing power, reduced carbon dioxide fixation, as well as elevated RNA transcripts and proteins involved in heavy metal resistance, with special emphasis on copper efflux systems. Finally, expression and translation of genes responsible for chemotaxis and motility were enhanced. IMPORTANCE Leptospirillum ferriphilum is one of the most important iron-oxidizers in the context of acidic and metal rich environments during moderately thermophilic biomining. A high-quality circular genome of Leptospirillum ferriphilum T coupled with functional omics data provides new insights into its metabolic properties, such as the novel identification of genes for atmospheric nitrogen fixation, and represents an essential step for further accurate proteomic and transcriptomic investigation of this acidophile model species in the future. Additionally, light is shed on Leptospirillum ferriphilum T adaptation strategies to growth on the copper mineral chalcopyrite. This data can be applied to deepen our understanding and optimization of bioleaching and biooxidation, techniques that present sustainable and environmentally friendly alternatives to many traditional methods for metal extraction. Copyright © 2017 Christel et al.

Publications - SR 58 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

; Arsenopyrite; Barite; Base Metals; Big Delta; Bismuth; Chalcopyrite; Chicken Pluton; Cliff Mine; Coal ; Delta Junction; Diamond Drilling; Diamonds; Donlin Creek; Drift Mine; Drilling; Duke Island; Economic

Selective separation of pyrite and chalcopyrite by biomodulation.

PubMed

Chandraprabha, M N; Natarajan, K A; Modak, Jayant M

2004-09-01

Selective separation of pyrite from other associated ferrous sulphides at acidic and neutral pH has been a challenging problem. This paper discusses the utility of Acidithiobacillus ferrooxidans for the selective flotation of chalcopyrite from pyrite. Consequent to interaction with bacterial cells, pyrite remained depressed even in the presence of potassium isopropyl xanthate collector while chalcopyrite exhibited significant flotability. However, when the minerals were conditioned together, the selectivity achieved was poor due to the activation of pyrite surface by the copper ions in solution. The selectivity was improved when the sequence of conditioning with bacterial cells and collector was reversed, since the bacterial cells were able to depress collector interacted pyrite effectively, while having negligible effect on chalcopyrite. The observed behaviour is analysed and discussed in detail. The separation obtained was significant both at acidic and alkaline pH. This selectivity achieved was retained when the minerals were interacted with both bacterial cells and collector simultaneously.

Chanabayaite, Cu2(N3C2H2)Cl(NH3,Cl,H2O,□)4, a new mineral containing triazolate anion

NASA Astrophysics Data System (ADS)

Chukanov, N. V.; Zubkova, N. V.; Möhn, G.; Pekov, I. V.; Pushcharovsky, D. Yu.; Zadov, A. E.

2015-12-01

A new mineral, chanabayaite, has been discovered at a guano deposit located at Mt. Pabellón de Pica near the village of Chanabaya, Iquique Province, Tarapacá region, Chile. It is associated with salammoniac, halite, joanneumite, nitratine and earlier chalcopyrite. Chanabayaite occurs as blue translucent imperfect prismatic crystals, up to 0.05 × 0.1 × 0.5 mm in size, and their radial aggregates. Chanabayaite is brittle, with a Mohs' hardness of 2. The cleavage is perfect on (001) and imperfect on (100) and (010). D meas = 1.48(2) g/cm3, D calc = 1.464 g/cm3. The mineral is optically biaxial (-), α = 1.561(2), β = 1.615(3), γ = 1.620(2), 2 V meas = 25(10)°, 2 V calc = 33°. Pleochroism is strong, Z ≈ Y (deep blue) ≫ X (pale blue with gray tint). IR spectrum is given. The chemical composition (electron microprobe data for Cu, Fe and Cl; gas chromatography data for H, N, C and O) is as follows (wt %): 32.23 Cu, 1.14 Fe, 16.13 Cl, 3.1 H, 29.9 N, 12.2 C, 3.4 O, total is 98.1. The empirical formula is ( Z = 4): Cu1.92Fe0.08Cl1.72N8.09C3.85H11.66O0.81. The structural model was based on the single-crystal X-ray diffraction data ( R = 0.1627). Chanabayaite is orthorhombic, space group Imma, a = 19.484(3), b = 7.2136(10), c = 11.999(4) Å, V = 1686.5(7) Å3, Z = 2. In chanabayaite, chains of the corner-sharing Cu(l)-centered octahedra and single Cu(2)-centered octahedra are linked via 1,2,4-triazolate anions C2N3H2 -. NH3 and Cl- are additional ligands coordinating Cu2+. Chanabayaite is a transformational mineral species formed by leaching of Na and one third of Cl and partial dehydration of the protophase Na2Cu2Cl3(N3C2H2)2(NH3)2 • 4H2O. The strongest reflections in the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are detected: 10.19 (100) (101), 6.189 (40) (011), 5.729 (23) (301), 5.216 (75) (211, 202), 4.964 (20) (400), 2.830 (20) (602, 413, 503), 2.611 (24) (123, 422, 404).

Fabrication of CuInS2-sensitized solar cells via an improved SILAR process and its interface electron recombination.

PubMed

Xu, Xueqing; Wan, Qingcui; Luan, Chunyan; Mei, Fengjiao; Zhao, Qian; An, Ping; Liang, Zhurong; Xu, Gang; Zapien, Juan Antonio

2013-11-13

Tetragonal CuInS2 (CIS) has been successfully deposited onto mesoporous TiO2 films by in-sequence growth of InxS and CuyS via a successive ionic layer absorption and reaction (SILAR) process and postdeposition annealing in sulfur ambiance. X-ray diffraction and Raman measurements showed that the obtained tetragonal CIS consisted of a chalcopyrite phase and Cu-Au ordering, which related with the antisite defect states. For a fixed Cu-S deposition cycle, an interface layer of β-In2S3 formed at the TiO2/CIS interface with suitable excess deposition of In-S. In the meantime, the content of the Cu-Au ordering phase decreased to a reasonable level. These facts resulted in the retardance of electron recombination in the cells, which is proposed to be dominated by electron transfer from the conduction band of TiO2 to the unoccupied defect states in CIS via exponentially distributed surface states. As a result, a relatively high efficiency of ~0.92% (V(oc) = 0.35 V, J(sc) = 8.49 mA cm(-2), and FF = 0.31) has been obtained. Last, but not least, with an overloading of the sensitizers, a decrease in the interface area between the sensitized TiO2 and electrolytes resulted in deceleration of hole extraction from CIS to the electrolytes, leading to a decrease in the fill factor of the solar cells. It is indicated that the unoccupied states in CIS with energy levels below EF0 of the TiO2 films play an important role in the interface electron recombination at low potentials and has a great influence on the fill factor of the solar cells.

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.

Role of target-substrate distance on the growth of CuInSe{sub 2} thin films by pulsed laser ablation technique

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

Rawat, Kusum; Dhruvashi; Department of Electronic Science, University of Delhi South Campus, Delhi 110021

2016-05-06

CuInSe{sub 2} thin films have been deposited on corning glass substrates by pulsed laser ablation technique. The chamber pressure and substrate temperature was maintained at 1 × 10{sup −6} torr and 550°C respectively during deposition of the films. The influence of target to substrate (T-S) distance on the structural and optical properties of thin films have been investigated by grazing incidence x-ray diffraction, Raman spectroscopy, scanning electron microscope and UV-Vis-NIR spectroscopy. The study reveals that thin films crystallized in a chalcopyrite structure with highly preferential orientation along (112) plane. Optimum T-S distance has been attained for the growth of thinmore » films with large grain size. An intense Raman peak at 174 cm{sup −1} corresponding to dominant A{sub 1} vibration mode is gradually shifted to smaller wavenumber with the increase in T-S distance. The optical bandgap energy of the films was evaluated and found to vary with the T-S distance. The bandgap tailing was observed to obey the Urbach rule and the Urbach energy was also calculated for the films. Scanning electron micrographs depicts uniform densely packed grains and EDAX studies revealed the elemental composition of CuInSe{sub 2} thin films.« less

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.

Insights to the effects of free cells on community structure of attached cells and chalcopyrite bioleaching during different stages.

PubMed

Feng, Shoushuai; Yang, Hailin; Wang, Wu

2016-01-01

The effects of free cells on community structure of attached cells and chalcopyrite bioleaching by Acidithiobacillus sp. during different stages were investigated. The attached cells of Acidithiobacillus thiooxidans owned the community advantage from 14thd to the end of bioprocess in the normal system. The community structure of attached cells was greatly influenced in the free cells-deficient systems. Compared to A. thiooxidans, the attached cells community of Acidithiobacillus ferrooxidans had a higher dependence on its free cells. Meanwhile, the analysis of key biochemical parameters revealed that the effects of free cells on chalcopyrite bioleaching in different stages were diverse, ranging from 32.8% to 64.3%. The bioleaching contribution of free cells of A. ferrooxidans in the stationary stage (8-14thd) was higher than those of A. thiooxidans, while the situation was gradually reversed in the jarosite passivation inhibited stage (26-40thd). These results may be useful in guiding chalcopyrite bioleaching. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Co-Cu-Au deposits in metasedimentary rocks-A preliminary report

USGS Publications Warehouse

Slack, J.F.; Causey, J.D.; Eppinger, R.G.; Gray, J.E.; Johnson, C.A.; Lund, K.I.; Schulz, K.J.

2010-01-01

A compilation of data on global Co-Cu-Au deposits in metasedimentary rocks refines previous descriptive models for their occurrence and provides important information for mineral resource assessments and exploration programs. This compilation forms the basis for a new classification of such deposits, which is speculative at this early stage of research. As defined herein, the Co-Cu-Au deposits contain 0.1 percent or more by weight of Co in ore or mineralized rock, comprising disseminated to semi-massive Co-bearing sulfide minerals with associated Fe- and Cu-bearing sulfides, and local gold, concentrated predominantly within rift-related, siliciclastic metasedimentary rocks of Proterozoic age. Some deposits have appreciable Ag ? Bi ? W ? Ni ? Y ? rare earth elements ? U. Deposit geometry includes stratabound and stratiform layers, lenses, and veins, and (or) discordant veins and breccias. The geometry of most deposits is controlled by stratigraphic layering, folds, axial-plane cleavage, shear zones, breccias, or faults. Ore minerals are mainly cobaltite, skutterudite, glaucodot, and chalcopyrite, with minor gold, arsenopyrite, pyrite, pyrrhotite, bismuthinite, and bismuth; some deposits have appreciable tetrahedrite, uraninite, monazite, allanite, xenotime, apatite, scheelite, or molybdenite. Magnetite can be abundant in breccias, veins, or stratabound lenses within ore or surrounding country rocks. Common gangue minerals include quartz, biotite, muscovite, K-feldspar, albite, chlorite, and scapolite; many deposits contain minor to major amounts of tourmaline. Altered wall rocks generally have abundant biotite or albite. Mesoproterozoic metasedimentary successions constitute the predominant geologic setting. Felsic and (or) mafic plutons are spatially associated with many deposits and at some localities may be contemporaneous with, and involved in, ore formation. Geoenvironmental data for the Blackbird mining district in central Idaho indicate that weathering of abundant Fe, S, As, Co, and Cu in sulfide minerals of the deposits produces acidic waters, especially in pyrite-rich deposits; mine runoff has high concentrations of Fe, Cu, and Mn that exceed U.S. drinking water or aquatic life standards.

A Numerical Evaluation on the Viability of Heap Thermophilic Bioleaching of Chalcopyrite

NASA Astrophysics Data System (ADS)

Vilcaez, J.; Suto, K.; Inoue, C.

2007-03-01

The present numerical evaluation explores into the interactions among the many variables governing the mass and heat transport processes that take place in a heap thermophilic bioleaching system. The necessity of using mesophiles together with thermophiles is proved by tracing the activity of both microorganisms individually at each point throughout the heap. The role of key variables such as the fraction of FeS2 per CuFeS2 leached was quantified and its importance highlighted. In this evaluation, the heat transfer process plays the main role because of the heat accumulation required to maintain the heap temperature within the range of 60 °C to 80 °C where thermophilic microorganisms are capable of completing the unfinished dissolution of copper started by mesophilic microorganisms at 30 °C. The evaluation was done taking into consideration: biological activity as function of the temperature in the heap, heat loss due to conduction and advection from the top and bottom of the heap, and mass transfer between the gas and liquid phases as a function of temperature. The exothermic nature of the leaching reactions of CuFeS2 and FeS2 makes the system auto-thermal.

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.

U-Pb, Re-Os and Ar-Ar dating of the Linghou polymetallic deposit, Southeastern China: Implications for metallogenesis of the Qingzhou-Hangzhou metallogenic belt

NASA Astrophysics Data System (ADS)

Tang, Yanwen; Xie, Yuling; Liu, Liang; Lan, Tingguan; Yang, Jianling; Sebastien, Meffre; Yin, Rongchao; Liang, Songsong; Zhou, Limin

2017-04-01

The Qingzhou-Hangzhou metallogenic belt (QHMB) in Southeastern China has gained increasingly attention in recent years. However, due to the lack of reliable ages on intrusions and associated deposits in this belt, the tectonic setting and metallogenesis of the QHMB have not been well understood. The Linghou polymetallic deposit in northwestern Zhejiang Province is one of the typical deposits of the QHMB. According to the field relationships, this deposit consists of the early Cu-Au-Ag and the late Pb-Zn-Cu mineralization stages. Molybdenite samples with a mineral assemblage of molybdenite-chalcopyrite-pyrite ± quartz are collected from the copper mining tunnel near the Cu-Au-Ag ore bodies. Six molybdenite samples give the Re-Os model ages varying from 160.3 to 164.1 Ma and yield a mean age of 162.2 ± 1.4 Ma for the Cu-Au-Ag mineralization. Hydrothermal muscovite gives a well-defined Ar-Ar isochron age of 160.2 ± 1.1 Ma for the Pb-Zn-Cu mineralization. Three phases of granodioritic porphyry have been distinguished in this deposit, and LA-ICP-MS zircon U-Pb dating shows that they have formed at 158.8 ± 2.4 Ma, 158.3 ± 1.9 Ma and 160.6 ± 2.1 Ma, comparable to the obtained ages of the Cu-Au-Ag and Pb-Zn-Cu mineralization. Therefore, these intrusive rocks have a close temporal and spatial relationship with the Cu-Au-Ag and Pb-Zn-Cu ore bodies. The presences of skarn minerals (e.g., garnet) and vein-type ores, together with the previous fluid inclusion and H-O-C-S-Pb isotopic data, clearly indicate that the Cu-Au-Ag and Pb-Zn-Cu mineralization are genetically related to these granodiorite porphyries. This conclusion excludes the possibility that this deposit is of ;SEDEX; type and formed in a sag basin of continental rifts setting as previously proposed. Instead, it is proposed that the Linghou polymetallic and other similar deposits in the QHMB, such as the 150-160 Ma Yongping porphyry-skarn Cu-Mo, Dongxiang porphyry? Cu, Shuikoushan/Kangjiawang skarn Pb-Zn, Fozichong skarn Pb-Zn and Dabaoshan porphyry-skarn deposits are of magmatic-hydrothermal origin and likely formed in a subduction-related setting. This work provides new insight that these intrusion-related deposits (e.g., porphyry and skarn types) of middle to late Jurassic age can be the most important targets for exploration in the QHMB.

Solution-based colloidal synthesis of hybrid P3HT: Ternary CuInSe2 nanocomposites using a novel combination of capping agents for low-cost photovoltaics

NASA Astrophysics Data System (ADS)

Sharma, Shailesh Narain; Chawla, Parul; Akanksha; Srivastava, A. K.

2016-06-01

In this work, ternary CuInSe2 (CISe) chalcopyrite nanocrystallites efficiently passivated by a novel combination of capping agents viz: aniline and 1-octadecene during chemical route synthesis were dispersed in conducting polymer matrix poly(3-hexylthiophene) (P3HT). By varying the composition and concentration of the ligands, the properties of the resulting CISe nanocrystallites and its corresponding polymer nanocomposites thus could be tailored. The structural, morphological and optical studies accomplished by various complimentary techniques viz. Transmission Electron Microscopy (TEM), Contact angle, Photoluminescence (PL) and Raman have enabled us to compare the different hybrid organic (polymer)-inorganic nanocomposites. On the basis of aniline-octadecene equilibrium phase diagram, the polydispersity of the CISe nanocrystals could be tuned by using controlled variations in the reaction conditions of nucleation and growth such as composition of the solvent and temperature. To the best of author's knowledge, the beneficial effects of both the capping agents; aniline and octadecene contributing well in tandem in the development of large-sized (100-125 nm) high quality, sterically- and photo-oxidative stable polycrystalline CISe and its corresponding polymer (P3HT):CISe composites with enhanced charge transfer efficiency has been reported for the first time. The low-cost synthesis and ease of preparation renders this method of great potential for its possible application in low-cost hybrid organic-inorganic photovoltaics. The figure shows the Temperature vs Mole fraction graph of two different phases (aniline and 1-octadecene) in equilibrium.

Heterocoagulation of chalcopyrite and pyrite minerals in flotation separation.

PubMed

Mitchell, Timothy K; Nguyen, Anh V; Evans, Geoffrey M

2005-06-30

Heterocoagulation between various fine mineral particles contained within a mineral suspension with different structural and surface chemistry can interfere with the ability of the flotation processes to selectively separate the minerals involved. This paper examines the interactions between chalcopyrite (a copper mineral) and pyrite (an iron mineral often bearing gold) as they approach each other in suspensions with added chemicals, and relates the results to the experimental data for the flotation recovery and selectivity. The heterocoagulation was experimentally studied using the electrophoretic light scattering (ELS) technique and was modelled by incorporating colloidal forces, including the van der Waals, electrostatic double layer and hydrophobic forces. The ELS results indicated that pyrite has a positive zeta potential (zeta) up to its isoelectric point (IEP) at approximately pH 2.2, while chalcopyrite has a positive zeta up to its IEP at approximately pH 5.5. This produces heterocoagulation of chalcopyrite with pyrite between pH 2.2 and pH 5.5. The heterocoagulation was confirmed by the ELS spectra measured with a ZetaPlus instrument from Brookhaven and by small-scale flotation experiments.

Synthesis, structural and electronic properties of monodispersed self-organized single crystalline nanobricks of isocubanite CuFe{sub 2}S{sub 3}

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

Lyubutin, Igor S., E-mail: lyubutinig@mail.ru; Lin, Chun-Rong, E-mail: crlin@mail.nptu.edu.tw; Starchikov, Sergey S.

2015-01-15

The nanoparticles with a pure cubic phase of isocubanite CuFe{sub 2}S{sub 3} are successfully synthesized for the first time. The particles are self-organized into the single crystalline nanocomposites with a shape of “bricks” which are well ordered in a certain anisotropic orientation. All bricks have nearly the same shape and dimensions and may be considered as monodispersed nanobricks. Magnetic measurements show paramagnetic behavior of the compound down to 4.2 K with the antiferromagnetic correlation between iron ions. An average magnetic moment is about 2.8–3.0 μ{sub B} per formula unit CuFe{sub 2}S{sub 3}. Mössbauer spectroscopy data reveal that the ferric ionsmore » in isocubanite are in the high-spin state (spin S=5/2) whereas the ferrous ions are in the intermediate-spin state (S=1). The Fe{sup 3+} and Fe{sup 2+} ions are distributed randomly over tetrahedral sites and the electron exchange between these ions is absent. This can explain nonmagnetic behavior of isocubanite. In the suggested method, the combined nanocomposites containing the magnetic chalcopyrite CuFeS{sub 2} and the nonmagnetic isocubanite CuFe{sub 2}S{sub 3} can be synthesized in a certain sequence. Such composites could be useful for the applied nanotechnology. - Graphical abstract: Self-organized single crystalline “nanobricks” of isocubanite CuFe{sub 2}S{sub 3} synthesized by a thermal pyrolysis method. - Highlights: • Self-organized single crystalline “nanobricks” of CuFe{sub 2}S{sub 3} were synthesized. • All bricks are nearly monodispersed and well-ordered in a certain anisotropic orientation. • XRD, HRTEM, magnetic measurements and Mössbauer spectroscopy were used for characterization. • Nanobricks are paramagnetic down to 4.2 K with effective magnetic moment about 3.0 μ{sub B} per f.u. • Mössbauer spectroscopy data indicate different spin states of Fe{sup 2+} and Fe{sup 3+} ions.« less

Porphyry Cu indicator minerals in till as an exploration tool: Example from the giant pebble porphyry Cu-Au-Mo deposit, Alaska, USA

USGS Publications Warehouse

Kelley, Karen D.; Eppinger, Robert G.; Lang, J.; Smith, Steven M.; Fey, David L.

2011-01-01

Porphyry Cu indicator minerals are mineral species in clastic sediments that indicate the presence of mineralization and hydrothermal alteration associated with porphyry Cu and associated skarn deposits. Porphyry Cu indicator minerals recovered from shallow till samples near the giant Pebble Cu-Au-Mo porphyry deposit in SW Alaska, USA, include apatite, andradite garnet, Mn-epidote, visible gold, jarosite, pyrite, and cinnabar. Sulphide minerals other than pyrite are absent from till, most likely due to the oxidation of the till. The distribution of till samples with abundant apatite and cinnabar suggest sources other than the Pebble deposit. With three exceptions, all till samples up-ice of the Pebble deposit contain 40grains/10kg) are in close proximity to smaller porphyry and skarn occurrences in the region. The distribution of Mn-epidote closely mimics the distribution of garnet in the till samples and further supports the interpretation that these minerals most likely reflect skarns associated with the porphyry deposits. All but two till samples, including those up-ice from the deposit, contain some gold grains. However, tills immediately west and down-ice of Pebble contain more abundant gold grains, and the overall number of grains decreases in the down-ice direction. Furthermore, all samples in the immediate vicinity of Pebble contain more than 65% pristine and modified grains compared to mostly re-shaped grains in distal samples. The pristine gold in till reflects short transport distances and/or liberation of gold during in-situ weathering of transported chalcopyrite grains. Jarosite is also abundant (1-2 500 grains/10kg) in samples adjacent to and up to 7 km down-ice from the deposit. Most jarosite grains are rounded and preliminary Ar/Ar dates suggest the jarosite formed prior to glaciation and it implies that a supergene cap existed over Pebble West. Assuming this interpretation is accurate, it suggests a shallow level of erosion of the Pebble deposit by glacial processes. Overall the results of this study indicate that porphyry Cu indicator minerals in till samples may be useful in the exploration for porphyry deposits in SW Alaska.

SHRIMP U-Pb ages of xenotime and monazite from the Spar Lake red bed-associated Cu-Ag deposit, western Montana: Implications for ore genesis

USGS Publications Warehouse

Aleinikoff, John N.; Hayes, Timothy S.; Evans, Karl V.; Mazdab, Frank K.; Pillers, Renee M.; Fanning, C. Mark

2012-01-01

Xenotime occurs as epitaxial overgrowths on detrital zircons in the Mesoproterozoic Revett Formation (Belt Supergroup) at the Spar Lake red bed-associated Cu-Ag deposit, western Montana. The deposit formed during diagenesis of Revett strata, where oxidizing metal-bearing hydrothermal fluids encountered a reducing zone. Samples for geochronology were collected from several mineral zones. Xenotime overgrowths (1–30 μm wide) were found in polished thin sections from five ore and near-ore zones (chalcocite-chlorite, bornite-calcite, galena-calcite, chalcopyrite-ankerite, and pyrite-calcite), but not in more distant zones across the region. Thirty-two in situ SHRIMP U-Pb analyses on xenotime overgrowths yield a weighted average of 207Pb/206Pb ages of 1409 ± 8 Ma, interpreted as the time of mineralization. This age is about 40 to 60 m.y. after deposition of the Revett Formation. Six other xenotime overgrowths formed during a younger event at 1304 ± 19 Ma. Several isolated grains of xenotime have 207Pb/206Pb ages in the range of 1.67 to 1.51 Ga, and thus are considered detrital in origin. Trace element data can distinguish Spar Lake xenotimes of different origins. Based on in situ SHRIMP analysis, detrital xenotime has heavy rare earth elements-enriched patterns similar to those of igneous xenotime, whereas xenotime overgrowths of inferred hydrothermal origin have hump-shaped (i.e., middle rare earth elements-enriched) patterns. The two ages of hydrothermal xenotime can be distinguished by slightly different rare earth elements patterns. In addition, 1409 Ma xenotime overgrowths have higher Eu and Gd contents than the 1304 Ma overgrowths. Most xenotime overgrowths from the Spar Lake deposit have elevated As concentrations, further suggesting a genetic relationship between the xenotime formation and Cu-Ag mineralization.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

The genesis of Mo-Cu deposits and mafic igneous rocks in the Senj area, Alborz magmatic belt, Iran

NASA Astrophysics Data System (ADS)

Nabatian, Ghasem; Li, Xian-Hua; Wan, Bo; Honarmand, Maryam

2017-11-01

The geochemical and isotopic investigations were provided on the Upper Eocene Senj mafic intrusion and Mo-Cu mineralization to better understand the tectono-magmatic evolution and metallogeny of the central part of the Alborz magmatic belt. The Senj mafic intrusion is composed of gabbro to monzodiorite and monzonite in lithology, and intruded as a sill into volcano-sedimentary rocks of the Eocene Karaj Formation. The Karaj Formation consists of volcano-sedimentary rocks, such as altered crystalline to shaly tuffs. The Senj intrusion (39.7 ± 0.4 Ma) shows LILE and LREE enrichment and negative anomaly of Nb, Ta and Ti, the geochemical signatures similar to those from subduction-related mafic magmas. The Hf-O zircon analyses yield ɛHf(t) values of + 4.1 to + 11.1 and δ18O values of + 4.8 to + 6.2‰. The zircon isotopic signatures together with shoshonitic affinity in the Senj mafic samples suggest partial melting of an enriched lithospheric mantle that had already been metasomatized by slab-derived melts and fluids. The Mo-Cu mineralization mainly occurs as veins and veinlets in the volcano-sedimentary rocks of the Karaj Formation and is dominated by molybdenite with minor amounts of chalcopyrite, bornite, pyrite and tetrahedrite-tennantite. The associated gangue minerals are tremolite, actinolite, quartz, calcite, chlorite and epidote. The Senj Mo-Cu deposit formed in volcano-sedimentary rocks following the emplacement of the Late Eocene Senj sill. The source of molybdenite in the Senj deposit is dominantly from crustal materials as it is revealed by Re contents in the molybdenite minerals (0.5 to 0.7 ppm). In fact, the molybdenite occurrence may be a remobilization process related to the emplacement of the Senj mafic magma.

Review of the inorganic geochemistry of peats and peatland waters

NASA Astrophysics Data System (ADS)

Shotyk, William

1988-06-01

The major floristic and geochemical differences between bogs, fens, and swamps are summarized, and the most common peat types described. This is followed by a critical, historical review of the literature. The methods used to measure the pH of peatland (mire) waters are examined, and the pH range of various peatland types is reported. In addition, horizontal and vertical pH variations are illustrated, and factors affecting the pH of these waters reviewed. The cause of the low pH of surface waters of Sphagnum bogs (approximately pH 4) is critically investigated, and the relative importance of dissolved CO 2 and other inorganic acids, and organic acids to the low pH is assessed. Cation exchange on the surfaces of Sphagnum mosses is found to be a relatively unimportant acidification mechanism, but important to the chemical ecology of the plants. The redox chemistry of mire waters is described in terms of the geochemistry of such redox indicators as O 2, CO 2, CH 4, CO, H 2, H 2S, SO 42-, native Cu, and siderite (FeCO 3). Published studies of Eh in peatlands are cited, and the problems of Eh measurement and interpretation are explored. The chemical composition of mire waters (major and trace metals, and nonmetallic species) is examined, and factors affecting their composition reported. The abundance and distribution of mineral matter in peats is described, and the occurrence and formation of minerals of Fe (pyrite and other sulphides, siderite, vivianite), Cu (chalcopyrite, native Cu, covellite) and Zn (smithsonite and wurtzite) investigated. The abundance and distribution of major elements (Si, Al, Na, K, Mg, Ca) and trace metals (Ni, V, Cr, Fe, Mn, Cu, U, Zn, Pb) is described, and factors affecting their solubility examined.

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

Copper-arsenic decoupling in an active geothermal system: A link between pyrite and fluid composition

NASA Astrophysics Data System (ADS)

Tardani, Daniele; Reich, Martin; Deditius, Artur P.; Chryssoulis, Stephen; Sánchez-Alfaro, Pablo; Wrage, Jackie; Roberts, Malcolm P.

2017-05-01

Over the past few decades several studies have reported that pyrite hosts appreciable amounts of trace elements which commonly occur forming complex zoning patterns within a single mineral grain. These chemical zonations in pyrite have been recognized in a variety of hydrothermal ore deposit types (e.g., porphyry Cu-Mo-Au, epithermal Au deposits, iron oxide-copper-gold, Carlin-type and Archean lode Au deposits, among others), showing, in some cases, marked oscillatory alternation of metals and metalloids in pyrite growth zones (e.g., of Cu-rich, As-(Au, Ag)-depleted zones and As-(Au, Ag)-rich, Cu-depleted zones). This decoupled geochemical behavior of Cu and As has been interpreted as a result of chemical changes in ore-forming fluids, although direct evidence connecting fluctuations in hydrothermal fluid composition with metal partitioning into pyrite growth zones is still lacking. In this study, we report a comprehensive trace element database of pyrite from the Tolhuaca Geothermal System (TGS) in southern Chile, a young and active hydrothermal system where fewer pyrite growth rims and mineralization events are present and the reservoir fluid (i.e. ore-forming fluid) is accessible. We combined the high-spatial resolution and X-ray mapping capabilities of electron microprobe analysis (EMPA) with low detection limits and depth-profiling capacity of secondary-ion mass spectrometry (SIMS) in a suite of pyrite samples retrieved from a ∼1 km drill hole that crosses the argillic (20-450 m) and propylitic (650-1000 m) alteration zones of the geothermal system. We show that the concentrations of precious metals (e.g., Au, Ag), metalloids (e.g., As, Sb, Se, Te), and base and heavy metals (e.g., Cu, Co, Ni, Pb) in pyrite at the TGS are significant. Among the elements analyzed, As and Cu are the most abundant with concentrations that vary from sub-ppm levels to a few wt.% (i.e., up to ∼5 wt.% As, ∼1.5 wt.% Cu). Detailed wavelength-dispersive spectrometry (WDS) X-ray maps and SIMS depth vs. isotope concentration profiles reveal that pyrites from the TGS are characterized by chemical zoning where the studied elements occur in different mineralogical forms. Arsenic and Co occur as structurally bound elements in pyrite, Cu and Au in pyrite can occur as both solid solution and submicron-sized particles of chalcopyrite and native Au (or Au tellurides), respectively. Pyrites from the deeper propylitic zone do not show significant zonation and high Cu-(Co)-As concentrations correlate with each other. In contrast, well-developed zonations were detected in pyrite from the shallow argillic alteration zone, where Cu(Co)-rich, As-depleted cores alternate with Cu(Co)-depleted, As-rich rims. These microanalytical data were contrasted with chemical data of fluid inclusions in quartz and calcite veins (high Cu/As ratios) and borehole fluid (low Cu/As ratios) reported at the TGS, showing a clear correspondence between Cu and As concentrations in pyrite-forming fluids and chemical zonation in pyrite. These observations provide direct evidence supporting the selective partitioning of metals into pyrite as a result of changes in ore-forming fluid composition, most likely due to separation of a single-phase fluid into a low-density vapor and a denser brine, capable of fractionating Cu and As.

Multi-omics Reveals the Lifestyle of the Acidophilic, Mineral-Oxidizing Model Species Leptospirillum ferriphilumT

PubMed Central

2017-01-01

ABSTRACT Leptospirillum ferriphilum plays a major role in acidic, metal-rich environments, where it represents one of the most prevalent iron oxidizers. These milieus include acid rock and mine drainage as well as biomining operations. Despite its perceived importance, no complete genome sequence of the type strain of this model species is available, limiting the possibilities to investigate the strategies and adaptations that Leptospirillum ferriphilum DSM 14647T (here referred to as Leptospirillum ferriphilumT) applies to survive and compete in its niche. This study presents a complete, circular genome of Leptospirillum ferriphilumT obtained by PacBio single-molecule real-time (SMRT) long-read sequencing for use as a high-quality reference. Analysis of the functionally annotated genome, mRNA transcripts, and protein concentrations revealed a previously undiscovered nitrogenase cluster for atmospheric nitrogen fixation and elucidated metabolic systems taking part in energy conservation, carbon fixation, pH homeostasis, heavy metal tolerance, the oxidative stress response, chemotaxis and motility, quorum sensing, and biofilm formation. Additionally, mRNA transcript counts and protein concentrations were compared between cells grown in continuous culture using ferrous iron as the substrate and those grown in bioleaching cultures containing chalcopyrite (CuFeS2). Adaptations of Leptospirillum ferriphilumT to growth on chalcopyrite included the possibly enhanced production of reducing power, reduced carbon dioxide fixation, as well as elevated levels of RNA transcripts and proteins involved in heavy metal resistance, with special emphasis on copper efflux systems. Finally, the expression and translation of genes responsible for chemotaxis and motility were enhanced. IMPORTANCE Leptospirillum ferriphilum is one of the most important iron oxidizers in the context of acidic and metal-rich environments during moderately thermophilic biomining. A high-quality circular genome of Leptospirillum ferriphilumT coupled with functional omics data provides new insights into its metabolic properties, such as the novel identification of genes for atmospheric nitrogen fixation, and represents an essential step for further accurate proteomic and transcriptomic investigation of this acidophile model species in the future. Additionally, light is shed on adaptation strategies of Leptospirillum ferriphilumT for growth on the copper mineral chalcopyrite. These data can be applied to deepen our understanding and optimization of bioleaching and biooxidation, techniques that present sustainable and environmentally friendly alternatives to many traditional methods for metal extraction. PMID:29150517

Fluid Inclusion characteristics of syn-late orogenic Co-Ni-Cu-Au deposits in the Siegerland District of the Rhenish Massif, Germany

NASA Astrophysics Data System (ADS)

Wohlgemuth, Christoph; Hellmann, André; Meyer, Franz Michael

2013-04-01

The Siegerland District is located in the fold-and-thrust-belt of the Rhenish Massif and hosts various syn- late orogenic vein-hosted hydrothermal mineralization types. Peak-metamorphism and deformation occurred at 312-316 ± 10 Ma (Ahrendt et al., 1978) at pT-conditions of 280 - 320 °C and 0.7 - 1.4 kbar (Hein, 1993). The district is known for synorogenic siderite-quartz mineralization formed during peak-metamorphic conditions. At least 4 syn-late orogenic mineralization types are distinguished: Co-Ni-Cu-Au, Pb-Zn-Cu, Sb-Au and hematite-digenite-bornite mineralization (Hellmann et al., 2012b). Co-Ni-Cu-Au mineralization of the Siegerland District belongs to the recently defined class of metasediment hosted synorogenic Co-Cu-Au deposits (i.e. Slack et al, 2010). Ore minerals are Fe-Co-Ni sulpharsenides, bearing invisible gold, chalcopyrite, and minor As-bearing pyrite. The gangue is quartz. The alteration mineralogy comprises chlorite, illite-muscovite and quartz. The epigenetic quartz veins are closely related to the formation of reverse faults (Hellmann et al., 2011a). Microthermometric studies of fluid inclusions concerning the relationship between mineralization and microstructures have not been done so far for this deposit-class and this will be addressed here. Fluid inclusions are investigated in hydrothermally formed vein-quartz, selected from Co-Ni-Cu-Au mineralization bearing veins showing only minor overprints by later mineralization types. Two quartz generations are distinguished: subhedral quartz-I showing growth zonation and fine grained, recrystallized- and newly formed quartz-II grains forming irregular masses and fracture fillings in quartz-I. Co-Ni-Fe sulpharsenides and chalcopyrite are closely intergrown with quartz-II, implying their contemperaneous formation. However, fluid inclusions in quartz-II are often small, therefore fluid inclusions in quartz-I have been mostly investigated. In total, 180 inclusions from 4 different deposits have been studied. The fluid inclusions are located on healed intragranular trails in quartz-I grains and subordinate in quartz-II. The inclusions are 5-20 μm in size and are aqueous biphase (L+V) showing a constant L/V ratio of 4. Homogenization is always to the liquid with Th (L) = 170-250°C (202°C mean). The salinity is moderate, with a range in Tm between -8 to -3°C, corresponding to 5 - 10 mass-% NaCl eq. (8.2 mass-% mean). There is no difference between fluid inclusions investigated in quartz-I and quartz-II. Despite the common occurrence of siderite in synorogenic siderite-quartz-veins, carbonate is absent in the alteration assemblage, implying a low CO2-activity in the fluids. Isochore calculations, combined with the paleo-geothermal gradient deduced for peak metamorphic conditions (Oncken, 1991) shows that the trapping temperature of the fluid is likely in the range between 220-300°C. The study shows that Co-Ni-Cu-Au mineralization has formed at the district scale from a relative homogeneous, aqueous fluid of moderate salinity, which may have been derived from the devolatilization of the sedimentary pile in deeper crustal regions. Ahrendt, H., Hunziker, J.C. and Weber, K. (1978). Z.dt.geol.Ges.129, 229-247. Hein, U.F. (1993). Min. Mag. 57, 451-476. Hellmann, A., Wagner, T., Meyer, F.M. (2012b). Tagungsband Geologica Belgica 2012. Hellmann, A., Meyer F.M., Cormann, A., Peters, M. (2011a). Referate-Band MinPet 2011, 40. Oncken, O (1991). Annales de la Société géologique de Belgique 2, 139-159. Slack, J.F., et al. (2010). USGS Open File Report 2010-2012, 13 pp.

Effect of pH values on the extracellular polysaccharide secreted by Acidithiobacillus ferrooxidans during chalcopyrite bioleaching

NASA Astrophysics Data System (ADS)

Yu, Run-lan; Liu, Jing; Tan, Jian-xi; Zeng, Wei-min; Shi, Li-juan; Gu, Guo-hua; Qin, Wen-qing; Qiu, Guan-zhou

2014-04-01

The pH value plays an important role in the bioleaching of sulphide minerals. The effect of pH values on the extracellular polysaccharide secreted by Acidithiobacillus ferrooxidans was investigated in different phases of bacterial growth during chalcopyrite bioleaching. It is found that extracellular polysaccharide secretion from the cells attached to chalcopyrite is more efficiently than that of the free cells in the bioleaching solution. Three factors, pH values, the concentration of soluble metal ions, and the bacterial growth and metabolism, affect extracellular polysaccharide secretion in the free cells, and are related to the bacterial growth phase. Extracellular polysaccharide secretion from the attached cells is mainly dependent on the pH value of the bacterial culture.

Alteration geochemistry of the volcanic-hosted Dedeninyurdu, Yergen and Fındıklıyar Cu-Fe mineralization, Northern part of Gökçedoǧan Village, Çorum-Kargi Region, Turkey: Implications for the rare earth elements geochemical characteristics

NASA Astrophysics Data System (ADS)

Ozturk, Sercan; Gumus, Lokman; Abdelnasser, Amr; Yalçin, Cihan; Kumral, Mustafa; Hanilçi, Nurullah

2016-04-01

This study deals with the rare earth element (REE) geochemical behavior the alteration zonesassociated with the volcanic-hosted Cu-Femineralization at the northern part of Gökçedoǧan village, Çorum-Kargi region (N Turkey) which are Dedeninyurdu, Yergen and Fındıklıyar mineralization. The study areacomprises Bekirli Formation, Saraycık Formation, Beşpınar Formation, and Ilgaz Formation. Saraycık Formation consists ofUpper Cretaceous KargıOphiolites, pelagic limestone, siltstone, chert and spilitic volcanic rocks. Fe-Cu mineralization occurred in the spiliticvolcanic rocks of Saraycık Formation representing the host rockand is related with the silicification and sericitizationalteration zones. Dedeninyurdu and Yergen mineralization zone directed nearly N75-80oEis following structural a line but Fındıklıyar mineralization zone has nearly NW direction. The ore mineralogy in these zonesinclude pyrite, chalcopyrite, covellite, hematite with malachite, goethite and a limonite as a result of oxidation. The geochemical characteristics of REE of the least altered spiliticbasalt show flat light and heavy REE with slight positive Eu- and Sr-anomalies according to their chondrite-, N-type MORB, and primitive mantle-normalized REE patterns. While the REE geochemical features of the altered rocks collected from the different alteration zones show that there are negative Eu and Sr anomalies as a result of leaching during the alteration processes.There are positive and negative correlations between K2O index with LREE and HREE, respectively. This is due to the additions of K and La during the alteration processes referring to the pervasive sericitization alteration is the responsible for the Cu-Fe mineralization at the study area. Keywords: Cu-Fe mineralization, Spilitic volcanic rocks, alteration, Rare earth elements (REE) geochemistry.

A Moderately Thermophilic Mixed Microbial Culture for Bioleaching of Chalcopyrite Concentrate at High Pulp Density

PubMed Central

Wang, Yuguang; Zeng, Weimin; Qiu, Guanzhou; Chen, Xinhua

2014-01-01

Three kinds of samples (acid mine drainage, coal mine wastewater, and thermal spring) derived from different sites were collected in China. Thereafter, these samples were combined and then inoculated into a basal salts solution in which different substrates (ferrous sulfate, elemental sulfur, and chalcopyrite) served as energy sources. After that, the mixed cultures growing on different substrates were pooled equally, resulting in a final mixed culture. After being adapted to gradually increasing pulp densities of chalcopyrite concentrate by serial subculturing for more than 2 years, the final culture was able to efficiently leach the chalcopyrite at a pulp density of 20% (wt/vol). At that pulp density, the culture extracted 60.4% of copper from the chalcopyrite in 25 days. The bacterial and archaeal diversities during adaptation were analyzed by denaturing gradient gel electrophoresis and constructing clone libraries of the 16S rRNA gene. The results show that the culture consisted mainly of four species, including Leptospirillum ferriphilum, Acidithiobacillus caldus, Sulfobacillus acidophilus, and Ferroplasma thermophilum, before adapting to a pulp density of 4%. However, L. ferriphilum could not be detected when the pulp density was greater than 4%. Real-time quantitative PCR was employed to monitor the microbial dynamics during bioleaching at a pulp density of 20%. The results show that A. caldus was the predominant species in the initial stage, while S. acidophilus rather than A. caldus became the predominant species in the middle stage. F. thermophilum accounted for the greatest proportion in the final stage. PMID:24242252

Classification of time-of-flight secondary ion mass spectrometry spectra from complex Cu-Fe sulphides by principal component analysis and artificial neural networks.

PubMed

Kalegowda, Yogesh; Harmer, Sarah L

2013-01-08

Artificial neural network (ANN) and a hybrid principal component analysis-artificial neural network (PCA-ANN) classifiers have been successfully implemented for classification of static time-of-flight secondary ion mass spectrometry (ToF-SIMS) mass spectra collected from complex Cu-Fe sulphides (chalcopyrite, bornite, chalcocite and pyrite) at different flotation conditions. ANNs are very good pattern classifiers because of: their ability to learn and generalise patterns that are not linearly separable; their fault and noise tolerance capability; and high parallelism. In the first approach, fragments from the whole ToF-SIMS spectrum were used as input to the ANN, the model yielded high overall correct classification rates of 100% for feed samples, 88% for conditioned feed samples and 91% for Eh modified samples. In the second approach, the hybrid pattern classifier PCA-ANN was integrated. PCA is a very effective multivariate data analysis tool applied to enhance species features and reduce data dimensionality. Principal component (PC) scores which accounted for 95% of the raw spectral data variance, were used as input to the ANN, the model yielded high overall correct classification rates of 88% for conditioned feed samples and 95% for Eh modified samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Investigation of defect properties in Cu(In,Ga)Se 2 solar cells by deep-level transient spectroscopy

NASA Astrophysics Data System (ADS)

Kerr, L. L.; Li, Sheng S.; Johnston, S. W.; Anderson, T. J.; Crisalle, O. D.; Kim, W. K.; Abushama, J.; Noufi, R. N.

2004-09-01

The performance of the chalcopyrite material Cu(In,Ga)Se 2 (CIGS) used as an absorber layer in thin-film photovoltaic devices is significantly affected by the presence of native defects. The deep-level transient spectroscopy (DLTS) technique is used in this work to characterize the defect properties, yielding relevant information about the defect types, their capture cross-sections, and energy levels and densities in the CIGS cells. Three solar cells developed using different absorber growth technologies were analyzed using DLTS, capacitance-voltage ( C- V), and capacitance-temperature ( C- T) techniques. It was found that CIS cells grown at the University of Florida exhibits a middle-gap defect level that may relate to the cell's low fill factor and open-circuit voltage values observed. A high efficiency ( ηc>18%) CIGS cell produced by the National Renewable Energy Laboratory (NREL) was found to contain three minority-carrier (electron) traps and a 13% CIGS cell produced by the Energy Photovoltaics Inc. (EPV) exhibited one majority (hole) trap. The approach followed using the DLTS technique serves as a paradigm for revealing the presence of significant defect levels in absorber materials, and may be used to support the identification of remedial processing operations.

Geological structure and ore mineralization of the South Sopchinsky and Gabbro-10 massifs and the Moroshkovoe Lake target, Monchegorsk area, Kola Peninsula, Russia

NASA Astrophysics Data System (ADS)

Pripachkin, Pavel V.; Rundkvist, Tatyana V.; Miroshnikova, Yana A.; Chernyavsky, Alexey V.; Borisenko, Elena S.

2016-12-01

The South Sopchinsky massif (SSM), Gabbro-10 (G-10) massif, and Moroshkovoe Lake (ML) target Monchegorsk area, Kola Peninsula, are located at the junction of the Monchepluton and Monchetundra layered intrusions. The intrusions were studied in detail as they are targets for platinum-group element (PGE) mineralization. The rocks in these targets comprise medium- to coarse-grained mesocratic to leucocratic gabbronorites, medium-grained mesocratic to melanocratic norites and pyroxenites, and various veins mainly comprising norite, plagioclase-amphibole-magnetite rocks, and quartz-magnetite rocks. The veins contain Ni-Cu-PGE mineralization associated with magnetite and chromite. In all targets, the contacts between gabbronorite and norite-pyroxenite are undulating, and the presence of magmatic (intrusive) breccias suggests that these rocks formed through mingling of two distinct magmatic pulses. In places, the gabbronorites clearly crosscut the modal layering of the norites and pyroxenites. Trace element data indicate that the gabbronorites have similar compositions to rocks of the upper part of the Monchetundra intrusion, whereas the norites and pyroxenites resemble rocks from the lower to intermediate stratigraphic levels of the Monchepluton, such as in the Nude-Poaz and Sopcha massifs. Sulfide mineralization in the studied targets principally consists of secondary bornite, millerite, and chalcopyrite. In contrast, the primary sulfide assemblage within the layered sequence of the adjacent Monchepluton is characterized by pentlandite, chalcopyrite, and pyrrhotite. Therefore, the mineralization in the studied targets is interpreted to be of a contact style. We argue that the studied area represents the contact zone between gabbronorites of the Monchetundra intrusion and norites and pyroxenites of the Monchepluton. In addition, the rocks were overprinted by postmagmatic veining and remobilization of contact style sulfide and PGE mineralization.

Mineralogy of the Chaparra IOCG deposit, southern Peru

NASA Astrophysics Data System (ADS)

Yáñez, Juan; Alfonso, Pura

2014-05-01

The Chaparra IOCG, located in southern Peru, near Chala, is mined and exploited by small-scale miners for gold, however, it has not been studied until now. Here we present a preliminary geological and mineralogic study of this deposit. Powder X ray diffraction, electron microscopy and electron microprobe were used to characterize the mineralization. This deposit is hosted in magmatic rocks from the Coastal Batholith. Host rocks belong to the Linga Super-unit, of Upper Cretaceous age and are mainly constituted by monzonites, monzogabbros and diorites. Major alterations are the propylitic (chlorite - albite - quartz), advanced argillic (jarosite - natrojarosite) and sericitic (muscovite-sericite-quartz). Gypsum and other alteration minerals such as potassium feldspar and phlogopite, vermiculite and natrolite are widespread. Mineralization occurs mainly in quartz veins up to 1 m thick, emplaced filling fractures. Ore mineralogy is mainly composed of hematite, goethite, and sulphides (mainly pyrite, chalcopyrite and covellite). Gold and REE-rich minerals also occur. Native gold can reach up to 1 mm in size, but usually is few μm in size. Its composition is 82-92 wt% Au, up to 12 wt% of Ag and Fe can reach up to 4 wt%. The paragenetic sequence in the Chaparra deposit was divided into three stages: (I) primary mineralization, (II) Fracture filling, and (III) supergene alteration. The sequence begins with the crystallization of magnetite, quartz, pyrrhotite and pyrite. Subsequently, native gold, native Bismuth and uraninite crystallices together with the former minerals, in which are enclosed. Later, monacite is formed, being enclosed in quartz. Pyrite also presents small grains of chalcopyrite inside. Galena, sphalerite and arsenopyrite also are formed, whether included in pyrite or outside. Scarce grains of sakuraiite also occur in this stage. Structural formula of sakuraiie from this deposit is Cu 01.78-1.90 Zn 0.07-12Fe 1.16-124In 0.22-0.26Sn 0.79-082S4). Indium content of this mineral is between 5.43 and 6.41 wt%. At the end of this stage hematite and Cu-rich minerals, mainly tetrahedrite and covellite are formed. In addition, other sulphosalts, as tennantite and annivite are generated. Rrutile, zircon, apatite and subsequently ferrocordierite are also formed. In the stage (II) fractures are produced and filled by tetrahedrite, garavellite and native bismuth. Finally, in the stage (III) supergene alteration generates goethite, jarosite, gypsum, scorodite and yodargirite.

Pressure-induced structural transition in chalcopyrite ZnSiP2

NASA Astrophysics Data System (ADS)

Bhadram, Venkata S.; Krishna, Lakshmi; Toberer, Eric S.; Hrubiak, Rostislav; Greenberg, Eran; Prakapenka, Vitali B.; Strobel, Timothy A.

2017-05-01

The pressure-dependent phase behavior of semiconducting chalcopyrite ZnSiP2 was studied up to 30 GPa using in situ X-ray diffraction and Raman spectroscopy in a diamond-anvil cell. A structural phase transition to the rock salt type structure was observed between 27 and 30 GPa, which is accompanied by soft phonon mode behavior and simultaneous loss of Raman signal and optical transmission through the sample. The high-pressure rock salt type phase possesses cationic disorder as evident from broad features in the X-ray diffraction patterns. The behavior of the low-frequency Raman modes during compression establishes a two-stage, order-disorder phase transition mechanism. The phase transition is partially reversible, and the parent chalcopyrite structure coexists with an amorphous phase upon slow decompression to ambient conditions.

FTIR studies of xanthate adsorption on chalcopyrite, pentlandite and pyrite surfaces

NASA Astrophysics Data System (ADS)

Zhang, Yahui; Cao, Zhao; Cao, Yongdan; Sun, Chuanyao

2013-09-01

The Fourier transform infrared (FTIR) spectra of sodium butyl xanthate, dibutyl dixanthogen, metal xanthate compounds and surfaces of chalcopyrite, pentlandite and pyrite treated with sodium butyl xanthate solution were systematically studied. The products of xanthate adsorpted on the three different minerals were characterized by comparing their FTIR spectra to those of dixanthogen and metal xanthate. Both metal xanthate and dixanthogen are formed on the surfaces of these minerals. However, the relative proportions of metal xanthate to dixanthogen on the minerals are different. In the cases of chalcopyrite and pentlandite, the quantity of metal xanthate is larger than that of dixanthogen. For pyrite, on the contrary, the quantity of dixanthogen is much greater than that of ferric xanthate. Therefore, the formation of dixanthogen is more essential for the flotation of pyrite.

Silver-bearing minerals in the Xinhua hydrothermal vein-type Pb-Zn deposit, South China

NASA Astrophysics Data System (ADS)

Wang, Minfang; Zhang, Xubo; Guo, Xiaonan; Pi, Daohui; Yang, Meijun

2018-02-01

Electron probe microanalysis (EPMA) results are reported for newly identified silver-bearing minerals from the Xinhua deposit, Yunkaidashan area, South China. The Xinhua deposit is a hydrothermal vein-type Pb-Zn deposit and is hosted in the Pubei Complex, which consists of a cordierite-biotite granite with a U-Pb zircon age of 244.3 ± 1.8-251.9 ± 2.2 Ma. The mineralization process is subdivided into four mineralization stages, characterized by the following mineral associations: mineralization stage I with quartz, pyrite, and sphalerite; mineralization stage II with siderite, galena, and tetrahedrite; mineralization stage III with quartz and galena; and mineralization stage IV with quartz, calcite, and baryte. Tetrahedrite series minerals, such as freibergite, argentotetrahedrite, and tennantite are the main Ag-bearing minerals in the Xinhua deposit. The greatest concentration of silver occurs in phases from mineralization stage II. Microscopic observations reveal close relationship between galena and tetrahedrite series minerals that mostly occur as irregular inclusions within galena. The negative correlation between Cu and Ag in the lattices of tetrahedrite series minerals suggests that Cu sites are occupied by Ag atoms. Zn substitution for Fe in argentotetrahedrite and Cd substitution for Pb in tetrahedrite are also observed. Micro-thermometric data reveal that both homogenization temperatures and calculated salinities of hydrothermal fluids decrease progressively from the early to the later mineralization stages. The metal ions, such as Ag+, Cu+, Pb2+, and Zn2+, are transported as chlorine complex ions in the early mineralization stage and as bisulfide complex ions in the late mineralization stage, caused by changes in oxygen fugacity, temperature, and pH of the hydrothermal fluids. Because of the varying solubility of different metal ions, Pb2+, Zn2+, and Cu2+ ions are initially precipitated as galena, sphalerite, and chalcopyrite, respectively. With decreasing temperature of the fluids, Pb2+ ions are incorporated along with Cu+, Sb3+, and As3+ ions into sulfosalt minerals, and Ag+ ions are coprecipitated with Cu+, Sb3+, and As3+ ions forming tetrahedrite series minerals or replacing earlier sulfides and sulfosalts.

Characterisation of the antiferromagnetic transition of Cu2FeSnS4, the synthetic analogue of stannite

NASA Astrophysics Data System (ADS)

Caneschi, A.; Cipriani, C.; di Benedetto, F.; Sessoli, R.

2003-04-01

Magnetisation measurements between 260 and 1.9K were performed on the synthetic analogue of stannite, Cu_2FeSnS_4, tetragonal Ioverline{4}2m. Fe(II) ions, in the high spin S=2 configuration for tetrahedral coordination, are responsible for the high temperature paramagnetism. In agreement with Bernardini et al. (2000), an antiferromagnetic transition was observed, lowering temperature below 8K. Refined measurements evidenced a T_N=6.1K for the Néel temperature. In spite of a small difference, observed in the behaviour between the zero-field cooled and the field cooled curves, which suggests the possible presence of a spin-glass phase, the AC measurements did not provide evidence of dependence of the magnetic susceptibility on frequency, as expected in spin-glass systems. On the basis of the experimental data, in agreement with the existent literature (Fries et al., 1997), a collinear antiferromagnetic structure should be preferred. The Fe ions, in fact, are distributed in two sublattices obtained by magnetic differentiation of the symmetry equivalent (0,0,0) and (frac{1}{2}frac{1}{2}frac{1}{2}) Fe positions (wyckoff: 2a). The low value for the Nèel temperature, as compared e.g. to the room-temperature antiferromagnet chalcopyrite (CuFeS_2), very close in composition and structure to stannite, is to be related to the increased distance between the Fe ions (˜6.6Å). This weak interaction is not detected in natural samples, where diamagnetic Zn(II) replace paramagnetic Fe(II), thus increasing the mean Fe-Fe distance. Fries, T., Shapira, Y., Palacio, F., Moròn, M.C., McIntyre, G.J., Kershaw, R., Wold, A. and McNiff, E.J. Jr. (1997): Mangetic ordering of the antiferromagnet Cu_2MnSnS_4 from magnetisation and neutron-scattering measurements. Phys. Rev. B, 6(9), 5424-5431 Bernardini, G.P., Borrini, D., Caneschi, A. Di Benedetto, F., Gatteschi, D., Ristori, S. and Romanelli, M. (2000): EPR and SQUID magnetometry study of Cu_2FeSnS_4 (stannite) and Cu_2ZnSnS_4 (kesterite). Phys. Chem. Minerals, 7, 453-461

Lithology, petrography and Cu occurrence of the Neoproterozoic glacial Mwale Formation at the Shanika syncline (Tenke Fungurume, Congo Copperbelt; Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Mambwe, Pascal; Milan, Luke; Batumike, Jacques; Lavoie, Sébastien; Jébrak, Michel; Kipata, Louis; Chabu, Mumba; Mulongo, Sonya; Lubala, Toto; Delvaux, Damien; Muchez, Philippe

2017-05-01

The Mwale Formation that constitutes the base of the Nguba Group in the Neoproterozoic Katanga Supergroup has recently attracted renewed interest for copper mineral exploration. We present new field observations combined with detailed logging and petrography of MWAS0001 drill hole at Shanika syncline in the Tenke Fungurume Mining District. Our study has enabled us to subdivide the Mwale Formation into 7 distinct sequences. This succession is host to glaciogenic, glaciomarine, glaciofluvial and glaciolacustrine deposits. Glaciomarine beds are typically a deposit by debris flow in deep water marine environment, induced by basin wide tectonics and glaciation influence. Glaciofluvial beds were deposited in shallow water, fluvial deltaic environment. The glaciolacustrine environment is indicated by dropstones occurring in the laminated mudstone and rhythmites with dispersed clasts observed in the siltstone and conglomerate. These beds are interlayered within the glaciogenic beds, and are characterised by variable clast composition (felsic, mafic and metamorphic). The clasts are very poorly sorted, angular, rounded to moderately rounded, faceted or striated, and supported in a sandy argillaceous or mud matrix. Two main episodes of sulphide mineralisation are distinguished in the Mwale Formation. The diagenetic episode consists of disseminated euhedral and framboidal pyrites. The hydrothermal episode is associated with Mg-metasomatism and characterised by low grade copper mineralisation that occurs (i) in veins filled with carbonate-chlorite and carbonate-quartz-chlorite-Cu sulphides, such as chalcocite, chalcopyrite and bornite, and (ii) as disseminated sulphides within the host rock. This second episode is late to post-orogenic and can be correlated with late brittle tectonics within the Lufilian arc. The other alteration types include silicification and potassic alteration; however, these alterations are not associated with mineralisation.

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.

Evolution of Sulfobacillus thermosulfidooxidans secreting alginate during bioleaching of chalcopyrite concentrate.

PubMed

Yu, R-L; Liu, A; Liu, Y; Yu, Z; Peng, T; Wu, X; Shen, L; Liu, Y; Li, J; Liu, X; Qiu, G; Chen, M; Zeng, W

2017-06-01

To explore the distribution disciplinarian of alginate on the chalcopyrite concentrate surface during bioleaching. The evolution of Sulfobacillus thermosulfidooxidans secreting alginate during bioleaching of chalcopyrite concentrate was investigated through gas chromatography coupled with mass spectrometry (GC-MS) and confocal laser scanning microscope (CLSM), and the critical synthetic genes (algA, algC, algD) of alginate were analysed by real-time polymerase chain reaction (RT-PCR). The GC-MS analysis results indicated that there was a little amount of alginate formed on the mineral surface at the early stage, while increasing largely to the maximum value at the intermediate stage, and then kept a stable value at the end stage. The CLSM analysis of chalcopyrite slice showed the same variation trend of alginate content on the mineral surface. Furthermore, the RT-PCR results showed that during the early stage of bioleaching, the expressions of the algA, algC and the algD genes were all overexpressed. However, at the final stage, the algD gene expression decreased in a large scale, and the algA and algC decreased slightly. This expression pattern was attributed to the fact that algA and algC genes were involved in several biosynthesis reactions, but the algD gene only participated in the alginate biosynthesis and this was considered as the key gene to control alginate synthesis. The content of alginate on the mineral surface increased largely at the beginning of bioleaching, and remained stable at the end of bioleaching due to the restriction of algD gene expression. Our findings provide valuable information to explore the relationship between alginate formation and bioleaching of chalcopyrite. © 2017 The Society for Applied Microbiology.

Pressure-induced structural transition in chalcopyrite ZnSiP 2

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

Bhadram, Venkata S.; Krishna, Lakshmi; Toberer, Eric S.

The pressure-dependent phase behavior of semiconducting chalcopyrite ZnSiP 2 was studied up to 30 GPa using in situ X-ray diffraction and Raman spectroscopy in a diamond-anvil cell. A structural phase transition to the rock salt type structure was observed between 27 and 30 GPa, which is accompanied by soft phonon mode behavior and simultaneous loss of Raman signal and optical transmission through the sample. The high-pressure rock salt type phase possesses cationic disorder as evident from broad features in the X-ray diffraction patterns. The behavior of the low-frequency Raman modes during compression establishes a two-stage, order-disorder phase transition mechanism. Themore » phase transition is partially reversible, and the parent chalcopyrite structure coexists with an amorphous phase upon slow decompression to ambient conditions.« less

Methods for forming particles

DOEpatents

Fox, Robert V.; Zhang, Fengyan; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin

2016-06-21

Single source precursors or pre-copolymers of single source precursors are subjected to microwave radiation to form particles of a I-III-VI.sub.2 material. Such particles may be formed in a wurtzite phase and may be converted to a chalcopyrite phase by, for example, exposure to heat. The particles in the wurtzite phase may have a substantially hexagonal shape that enables stacking into ordered layers. The particles in the wurtzite phase may be mixed with particles in the chalcopyrite phase (i.e., chalcopyrite nanoparticles) that may fill voids within the ordered layers of the particles in the wurtzite phase thus produce films with good coverage. In some embodiments, the methods are used to form layers of semiconductor materials comprising a I-III-VI.sub.2 material. Devices such as, for example, thin-film solar cells may be fabricated using such methods.

Leaching of Chalcopyrite with Thiobacillus ferrooxidans: Effect of Surfactants and Shaking

PubMed Central

Duncan, D. W.; Trussell, P. C.; Walden, C. C.

1964-01-01

The rate of leaching of chalcopyrite by Thiobacillus ferrooxidans has been greatly accelerated by using shaken flasks in place of stationary bottles or percolators. A further increase in rate and extent of leaching was obtained by the use of Tween 20, 40, 60, and 80, Triton X-100, Quaker TT 5386, and Hyamine 2389. Tween 20 was the most effective surfactant. No individual component of the Tween molecule was responsible for the improved leaching. The Tween-to-chalcopyrite ratio is more important than the Tween-to-medium ratio. The effect of the surfactants is probably due to increased contact between the mineral surface and the organism, and shaking provides the necessary oxygen. Rates and yields obtained by use of surfactants and shaking as aids to microbiological leaching approach those obtained with acidified erric sulfate leaching. PMID:14131359

First find of platinum group metals in the ore of Kirganik copper-porphyry deposit (Kamchatka)

NASA Astrophysics Data System (ADS)

Sidorov, E. G.; Ignatyev, E. K.; Chubarov, V. M.

2017-08-01

The Kirganik copper-porphyry deposit is situated in the central part of the Sredinnyi Mountain Range of Kamchatka and is confined to fields of development of potassic orthoclase metasomatite and hypabyssal intrusions of shonkinite. Platinum group metals (PGMs), such as merenskyite, kotulskite, keithconnite, and temagamite, were discovered in the chalcopyrite-bornite and chalcopyrite-bornite-chalcosine ore of the deposit for the first time.

Rocks Whose Compositions are Determined by Flow Differentiation of Olivine- and Sulfide Droplet-Laden Magma: the Jinchuan Story

NASA Astrophysics Data System (ADS)

Li, C.; Ripley, E. M.; de Waal, S. A.; Xu, Z.

2002-12-01

The Jinchuan intrusion in western China is an elongated, deeply-dipping dyke-like body of dominantly olivine-rich ultramafic rocks of high magnesium basaltic magma. It hosts the second largest Ni-Cu sulfide deposit in the world. More than 500 million tones of sulfide ore grading 1.2 percent Ni and 0.7 percent Cu occur mostly as next-textured and disseminated sulfide (pyrrhotite, pentlendite and chalcopyrite) with cumulus olivine in about half of the rocks of the intrusion. Based on different petrological zonations, the Jinchuan intrusion is further divided into three segments: eastern, central and western segments. The central segment is characterized by concentric enrichments of cumulus olivine and sulfide, whereas the eastern and western segments are characterized by the increase of both cumulus olivine and sulfide toward the footwall. The forsterite contents of fresh olivine from different segments are similar and vary between 82 and 86 mole percent. The small range of olivine compositional variation corresponds to less than 6 percent of fractional crystallization. Mass balance calculations based on sulfide solubility in basaltic magma indicate that the volume of the parental magma of the sulfide is many times larger than that which is currently represented in the intrusion. Large amounts of cumulus olivine (more than 40 weight percent) in the marginal samples and high concentrations of sulfide in the intrusion are consistent with an interpretation that the Jinchuan intrusion was formed by olivine- and sulfide droplet-laden magma ascending through a subvertical conduit to a higher level. Differentiation processes of the olivine- and sulfide droplet-laden magma varied in different parts of the conduit. Sub-vertical flow differentiation controlled the central segment of the conduit, resulting in further enrichment of olivine crystals and sulfide droplets in the conduit center. In contrast, sub-lateral flow and gravitational differentiation dominated in the eastern and western segments, resulting in further enrichments of olivine crystals and sulfide droplets toward the footwall contact.

Geology and reconnaissance stable isotope study of the Oyu Tolgoi porphyry Cu-Au system, South Gobi, Mongolia

USGS Publications Warehouse

Khashgerel, B.-E.; Rye, R.O.; Hedenquist, J.W.; Kavalieris, I.

2006-01-01

The Oyu Tolgoi porphyry Cu-Au system in the South Gobi desert, Mongolia, comprises five deposits that extend over 6 km in a north-northeast-oriented zone. They occur in a middle to late Paleozoic are terrane and are related to Late Devonian quartz monzodiorite intrusions. The Hugo Dummett deposits are the northernmost and deepest, with up to 1,000 m of premineral sedimentary and volcanic cover rock remaining. They are the largest deposits discovered to date and characterized by high-grade copper (>2.5% Cu) and gold (0.5-2 g/t) mineralization associated with intense quartz veining and several phases of quartz monzodiorite intruded into basaltic volcanic host rocks. Sulfide minerals in these deposits are zoned outward from a bornite-dominated core to chalcopyrite, upward to pyrite ?? enargite and covellite at shallower depth. The latter high-sulfidation-state sulfides are hosted by advanced argillic alteration mineral associations. This alteration is restricted mainly to dacitic ash-flow tuff that overlies the basaltic volcanic rock and includes ubiquitous quartz and pyrophyllite, kaolinite, plus late dickite veins, as well as K alunite, Al phosphate-sulfate minerals, zunyite, diaspore, topaz, corundum, and andalusite. A reconnaissance oxygen-hydrogen and sulfur isotope study was undertaken to investigate the origin of several characteristic alteration minerals in the Oyu Tolgoi system, with particular emphasis on the Hugo Dummett deposits. Based on the isotopic composition of O, H, and S (??18O(SO4) = 8.8-20.1???, ??D = -73 to -43???, ??34S = 9.8-17.9???), the alunite formed from condensation of magmatic vapor that ascended to the upper parts of the porphyry hydrothermal system, without involvement of significant amounts of meteoric water. The isotopic data indicate that pyrophyllite (??18O = 6.5-10.9???, ??D = -90 to -106???) formed from a magmatic fluid with a component of meteoric water. Muscovite associated with quartz monzodiorite intrusions occurs in the core of the Hugo Dummett deposits, and isotopic data (??18O = 3.0-9.0???, ??D = -101 to -116%o) show it formed from a magmatic fluid with water similar in composition to that which formed the pyrophyllite. Mg chlorite (??18O = 5.5???, ??D = -126???) is a widespread mineral retrograde after hydrothermal biotite and may have formed from fluids similar to those related to the muscovite during cooling of the porphyry system. By contrast, paragenetically later and postmineralization alteration fluid, which produced dickite (??18O = -4.1 to +3.3???, ??D = -130 to -140???), shows clear evidence for mixing with substantial amounts of meteoric water. Relatively low ??D values (-140???) for this meteoric water component may indicate that its source was at high elevations. The geologic structure, nature of alteration, styles of mineralization, and stable isotope data indicate that the Oyu Tolgoi deposits constitute a typical porphyry system formed in an island-arc setting. The outward zonation of sulfide minerals for the Hugo Dummett deposits, from a bornite-dominated core to chalcopyrite and pyrite-enargite, can be interpreted to be related to a cooling magmatic hydrothermal system which transgressed outward over enclosing advanced argillic alteration. This resulted in some unusual alteration and sulfide parageneses, such as topaz, or pyrite, enargite, and tennantite, entrained by high-grade bornite. ?? 2006 by Economic Geology.

Alteration geochemistry of the volcanic-hosted Dedeninyurdu, Yergen and Fındıklıyar Fe-Cu mineralization at Gökçedoǧan, Çorum-Kargi region, Turkey

NASA Astrophysics Data System (ADS)

Gumus, Lokman; Öztürk, Sercan; Yalçın, Cihan; Abdelnasser, Amr; Hanilçi, Nurullah; Kumral, Mustafa

2016-04-01

This study is to determine the mass/volume gain and loss of the major and trace elements during the alteration processes on Dedeninyurdu, Yergen and Fındıklıyar Fe-Cu mineralizations of the area. Fe-Cu mineralization occurred in the spilitic volcanic a rock of Saraycık Formation is associated with the different types of alteration zones which are pyritization, silicification and sericitization. The study area comprises Bekirli Formation, Saraycık Formation, Beşpınar Formation, and Ilgaz Formation. Saraycık formation consists of spilitic volcanic rocks with pelagic limestone, siltstone and chert. The ore mineralogical data show that the pyrite, chalcopyrite, covellite, hematite, malachite and goethite formed during three phases of mineralization. As well as the geologic and petrographic studies reveal three alteration zones with definite mineral assemblages; phyllic alteration (quartz + sericite + pyrite) that represents the main alteration and mineralized zone; propylitic alteration; and carbonatized sericitic alteration zone. The boundaries between these zones are gradual. Mass balance calculations suggested that the phyllic alteration zone represented by gain in Si, Fe, K, S, and LOI and loss in Mg, Ca, and Na refers to silicification, sericitization and pyritization as well as replacement of Fe-Mg silicate and plagioclase. While, in the propylitic alteration zone, enrichment of Si, Fe, Mg, LOI and S occurred with depletions of Ca, Na, and K reflecting chloritization alteration type. On the other hand, carbonatized sericitic alteration zone shows local gain in Si, CaO and K reflects the occurrence of calc-silicate alteration. All alteration zones contain a large proportion of sulfide minerals (gain in S) with increase in loss on ignition (LOI). Keywords: Alteration geochemistry; Mass balance calculation, Fe-Cu mineralization; phyllic alteration, propylitic alteration.

Enhancement of gold recovery using bioleaching from gold concentrate

NASA Astrophysics Data System (ADS)

Choi, S. H.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

2012-04-01

The gold in refractory ores is encapsulated as fine particles (sometimes at a molecular level) in the crystal structure of the sulfide (typically pyrite with or without arsenopyrite) matrix. This makes it impossible to extract a significant amount of refractory gold by cyanidation since the cyanide solution cannot penetrate the pyrite/arsenopyrite crystals and dissolve gold particles, even after fine grinding. To effectively extract gold from these ores, an oxidative pretreatment is necessary to break down the sulfide matrix. The most popular methods of pretreatment include nitric acid oxidation, roasting, pressure oxidation and biological oxidation by microorganisms. This study investigated the bioleaching efficiency of Au concentrate under batch experimental conditions (adaptation cycles and chemical composition adaptation) using the indigenous acidophilic bacteria collected from gold mine leachate in Sunsin gold mine, Korea. We conducted the batch experiments at two different chemical composition (CuSO4 and ZnSO4), two different adaptation cycles 1'st (3 weeks) and 2'nd (6 weeks). The results showed that the pH in the bacteria inoculating sample decreased than initial condition and Eh increased. In the chemical composition adaptation case, the leached accumulation content of Fe and Pb was exhibited in CuSO4 adaptation bacteria sample more than in ZnSO4 adaptation bacteria samples, possibly due to pre-adaptation effect on chalcopyrite (CuFeS2) in gold concentrate. And after 21 days on the CuSO4 adaptation cycles case, content of Fe and Pb was appeared at 1'st adaptation bacteria sample(Fe - 1.82 and Pb - 25.81 times per control sample) lower than at 2'nd adaptation bacteria sample(Fe - 2.87 and Pb - 62.05 times per control sample). This study indicates that adaptation chemical composition and adaptation cycles can play an important role in bioleaching of gold concentrate in eco-/economic metallurgy process.

Correlation Between Microstructure and Optical Properties of Cu (In0.7, Ga0.3) Se2 Grown by Electrodeposition Technique

NASA Astrophysics Data System (ADS)

Chihi, Adel; Bessais, Brahim

2017-01-01

Polycrystalline thin films Cu (In0.7, Ga0.3) Se2 (CIGSe) were grown on copper foils at various cathodic potentials by using an electrodeposition technique. Scanning electron microscopy showed that the average diameter of CIGSe grains increase from 0.1 μm to 1 μm when the cathodic potential decreases. The structure and surface morphology were investigated by x-ray diffraction and atomic force microscopy (AFM) techniques. This structure study shows that the thin films were well crystallized in a chalcopyrite structure without unwanted secondary phases with a preferred orientation along (112) plane. Energy-dispersive x-ray analyses confirms the existence of CIGSe single phase on a copper substrate. AFM analysis indicated that the root mean square roughness decreases from 64.28 to 27.42 when the potential deposition increases from -0.95 V to -0.77 V. Using Raman scattering spectroscopy, the A1 optical phonon mode was observed in 173 cm-1 and two other weak peaks were detected at 214 cm-1 and 225 cm-1 associated with the B2 and E modes of the CIGSe phase. Through spectroscopy ellipsometry analysis, a three-layer optical model was exploited to derive the optical properties and layer thickness of the CIGSe film by least-squares fitting the measured variation in polarization light versus the obtained microstructure.

Effects of pyrite and sphalerite on population compositions, dynamics and copper extraction efficiency in chalcopyrite bioleaching process.

PubMed

Xiao, Yunhua; Liu, Xueduan; Dong, Weiling; Liang, Yili; Niu, Jiaojiao; Gu, Yabing; Ma, Liyuan; Hao, Xiaodong; Zhang, Xian; Xu, Zhen; Yin, Huaqun

2017-07-01

This study used an artificial microbial community with four known moderately thermophilic acidophiles (three bacteria including Acidithiobacillus caldus S1, Sulfobacillus thermosulfidooxidans ST and Leptospirillum ferriphilum YSK, and one archaea, Ferroplasma thermophilum L1) to explore the variation of microbial community structure, composition, dynamics and function (e.g., copper extraction efficiency) in chalcopyrite bioleaching (C) systems with additions of pyrite (CP) or sphalerite (CS). The community compositions and dynamics in the solution and on the ore surface were investigated by real-time quantitative PCR (qPCR). The results showed that the addition of pyrite or sphalerite changed the microbial community composition and dynamics dramatically during the chalcopyrite bioleaching process. For example, A. caldus (above 60%) was the dominant species at the initial stage in three groups, and at the middle stage, still dominated C group (above 70%), but it was replaced by L. ferriphilum (above 60%) in CP and CS groups; at the final stage, L. ferriphilum dominated C group, while F. thermophilum dominated CP group on the ore surface. Furthermore, the additions of pyrite or sphalerite both made the increase of redox potential (ORP) and the concentrations of Fe 3+ and H + , which would affect the microbial community compositions and copper extraction efficiency. Additionally, pyrite could enhance copper extraction efficiency (e.g., improving around 13.2% on day 6) during chalcopyrite bioleaching; on the contrary, sphalerite restrained it.

Interface engineering of Cu(In,Ga)Se2 and atomic layer deposited Zn(O,S) heterojunctions

NASA Astrophysics Data System (ADS)

Schmidt, Sebastian S.; Merdes, Saoussen; Steigert, Alexander; Klenk, Reiner; Kaufmann, Christian A.; Simsek Sanli, Ekin; van Aken, Peter A.; Oertel, Mike; Schneikart, Anja; Dimmler, Bernhard; Schlatmann, Rutger

2017-08-01

Atomic layer deposition of Zn(O,S) is an attractive dry and Cd-free process for the preparation of buffer layers for chalcopyrite solar modules. As we previously reported, excellent cell and module efficiencies were achieved using absorbers from industrial pilot production. These absorbers were grown using a selenization/sulfurization process. In this contribution we report on the interface engineering required to adapt the process to sulfur-free multi source evaporated absorbers. Different approaches to a local sulfur enrichment at the heterojunction have been studied by using surface analysis (XPS) and scanning transmission electron microscopy. We correlate the microstructure and element distribution at the interface with device properties obtained by electronic characterization. The optimized completely dry process yields cell efficiencies >16% and 30 × 30 cm2 minimodule efficiencies of up to 13.9% on industrial substrates. Any degradation observed in the dry heat stress test is fully reversible after light soaking.

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

NASA Astrophysics Data System (ADS)

Park, Jung-Woo; Campbell, Ian H.; Ickert, Ryan B.; Allen, Charlotte M.

2013-02-01

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO2 range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7-7.8 ppb Pd, 0.025-0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu-Au deposits.

Determining Prehistoric Mining Practices in Southeastern Europe Using Copper Isotopes

NASA Astrophysics Data System (ADS)

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

2017-04-01

Copper was first smelted from malachite at 5000 BCE in Serbia. There the Eneolithic (Copper Age) began with the production of small jewelry pieces and progressed to the casting of massive copper tools near its end, approximately 2000 years later. However, copper metallurgy in southeastern Europe ceased or significantly decreased in the later third millennium, several centuries before the Bronze Age began. Whether this metallurgical hiatus was the result a cultural shift or depletion of natural resources remains an ongoing subject of debate. It has been speculated that the marked reduction in metal production at the Eneolithic-Bronze Age transition was due to the exhaustion of surficial weathered oxide ores and the technical inability to smelt the underlying sulfide minerals. The behavior of copper isotopes in near-surface environments allows us to differentiate highly weathered oxide ores that occur at Earth's surface from non-weathered sulfide ores that occur at greater depth. The oxidation of copper generates fluids and associated minerals that are enriched in the 65Cu isotope. Thus, oxidative weathering of sulfide ores leads to the development of three stratified isotopic reservoirs for copper: 1) oxides above the water table that are enriched in 65Cu; 2) residual weathered sulfides minerals at the water table that are depleted in 65Cu; and 3) non-fractionated, non-weathered sulfide ore below the water table. And so, the transformative shift to sulfide-based metallurgy will be delineated by a significant decrease in δ65Cu in copper artifacts corresponding to the first use of 65Cu-depleted residual ore. The degree of variability of primary ore composition from numerable ore deposits would likely result in the overlap of copper isotope composition between populations of artifacts. Therefore, shifts in the mean copper isotope values and associated standard deviations would best reflect changes in ores use. A baseline value of -0.2‰ ±0.5 (1) was determined from an average of 164 published measurements from chalcopyrite and bornite from 8 epithermal and massive sulfide deposits. Twenty-two (88%) of Eneolithic artifacts (n=25) have values greater than this, whereas eight (73%) of the Early Bronze age artifacts (n=11) yield compositions less than -0.2‰. The mean of Middle Bronze Age, Late Bronze Age and Early Iron Age (n=86) cluster near -0.2‰. This pattern is consistent with a progression to the mining of ore assemblages from increasing depths through prehistory. The shift from 65Cu-enriched to 65Cu-depleted copper in artifacts across the Eneolithic-Bronze Age boundary at 2500 BCE indicates that accessible near-surface oxide ore reserves were depleted after approximately two millennia of mining, and that the beginning of the Bronze Age in the Balkans corresponded to the acquisition of pyrotechnology which allowed for the extraction of metals from sulfide minerals and the resumption of copper mining activity in the region.

Genesis of the Bangbule Pb-Zn-Cu polymetallic deposit in Tibet, western China: Evidence from zircon U-Pb geochronology and S-Pb isotopes

NASA Astrophysics Data System (ADS)

Kan, Tian; Zheng, Youye; Gao, Shunbao

2016-04-01

The Banbule Pb-Zn-Cu skarn deposit is located in the Longger-Gongbujiangda volcanic magma arc in the Gangdese-Nyainqentanglha Plate. It is the only lead-zinc polymetallic deposit discovered in the westernmost Nyainqentanglha metallogenic belt. The measured and indicated resources include 0.9 Mt of Pb+Zn (4.77% Pb and 4.74% Zn, respectively), 6499 t of Cu, and 178 t of Ag (18.75g/t Ag). The orebodies mainly occur as lenses, veins and irregular shapes in the contact zone between the quartz-porphyry and limestone of the Upper Permian Xiala Formation, or in the boundaries between limestone and sandstone. Pb-Zn-Cu mineralization in the Banbule deposit is closely associated with skarns. The ore minerals are dominated by galena, sphalerite, chalcopyrite, bornite, and magnetite, with subordinate pyrite, malachite, and azurite. The gangue minerals are mainly garnet, actinolite, diopside, quartz, and calcite. The ore-related quartz-porphyry displays LA-ICP-MS zircon U-Pb age of 77.31±0.74 Ma. The δ34S values of sulfides define a narrow range of -0.8 to 4.7‰ indicating a magmatic source for the ore-forming materials. Lead isotopic systematics yield 206Pb/204Pb of 18.698 to 18.752, 207Pb/204Pb of 15.696 to 15.760, and 208Pb/204Pb of 39.097 to 39.320. The data points are constrained around the growth curves of upper crust and orogenic belt according to the tectonic discrimination diagrams. The calculated Δβ - Δγ values plot within the magmatic field according to the discrimination diagram of Zhu et al. (1995). The S-Pb isotopic data suggest that Bangbule is a typical skarn deposit, and the Pb-Zn-Cu mineralization is genetically related to the quartz-porphyry in the mining district. The discovery of the Bangbule deposit indicates that there is metallogenic potential in the westernmost Nyainqentanglha belt, which is of great importance for the exploration work in this area.

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.

The role of impurity ions in the formation of phase composition of Norilsk ore types

NASA Astrophysics Data System (ADS)

Mashukov, Anatoly; Mashukova, Alla

2013-04-01

Using the methods of X-ray and Mössbauer spectroscopy, scanning electron microscopy, there were studied the samples of Norilsk ore types in order to identify compounds containing Cu and Ni. Depending on elemental composition there were singled out two sample series. Maximum concentration in percentage of selected elements for this series is presented below. 1: Ni (0), Cu (0,42), S (11,2), O (20,2), H (0.02), Fe(46,8), Ca (5,85), Mg (1,75), K (0,47), Na (0). 2: Ni (4,93), Cu (0), S (14,9), O (27,1), H (0,11), Fe (28,1), Ca (14,9), Mg (0), K (0), Na (1,61). The research conducted by using the method of scanning electron microscopy and the X-ray microanalysis showed that iron and sulfur are spread uniformly over the scanned area. Sulfur is absent in the inclusions containing Fe and Ni. There are areas, sizes 8 - 120 microns, strongly enriched by Fe. The inclusions of rectangular and rhomboid shapes sizes 8 - 15 microns contain Ni as the content of Fe increases. There were identified the inclusions having a high content of Cu, with a maximum concentration of Ni. The presence of native elements testifies to the reducing mode of ore formation processes. The phases, containing Cu ? Ni, have a complex composition: pentlandite (FeNiS2), chalcopyrite (CuFeS2), bornite (CuFeS4), nickelhexahydrite (NiSO4 [6H2O]), wroewolfeite (Cu4 (OH) 6 (SO4) • 2H2O), pyrrhotine (Fe7S8), pyrite (FeS2). The position of the absorption lines in the magnetically ordered areas indicates the presence of stoichiometric FeS and CuFeS2. Some of the samples of this group have broadened lines, indicating the existence of various positions of the Fe ions in the sublattices. The ingrowths of CuFeS2 are characterized by the degree of the structure defectiveness, by various impurities, which is reflected in the studied parameters. As regards the other sample series, containing FeS and CuFeS2 in pyrrhotine matrix of Fe 1-xSx, the spectra are the superposition of the unsolved doublet, which shows the presence of paramagnetic areas. The magnetic phase has the spectrum composed of two six-linear spectrums. The peaks on the spectrum borders show the oxide presence. The isomer shifts of the samples range from 0 to 1.394 mm/s, quadrupole splitting ranges from 0 to 2.688 mm/s. This indicates that the local electronic structure depends on the genesis of compounds. Thus, most of the bulk of Cu, Ni is not dissipated in the crystal lattices of the ore, but it is part of the ore sulphides. The presence of the characteristic structures of the solid solutions decomposition shows a wide temperature range of sulphide crystallization.

Community dynamics of attached and free cells and the effects of attached cells on chalcopyrite bioleaching by Acidithiobacillus sp.

PubMed

Yang, Hailin; Feng, Shoushuai; Xin, Yu; Wang, Wu

2014-02-01

The community dynamics of attached and free cells of Acidithiobacillus sp. were investigated and compared during chalcopyrite bioleaching process. In the mixed strains system, Acidithiobacillus ferrooxidans was the dominant species at the early stage while Acidithiobacillus thiooxidans owned competitive advantage from the middle stage to the end of bioprocess. Meanwhile, compared to A. ferrooxidans, more significant effects of attached cells on free biomass with A. thiooxidans were shown in either the pure or mixed strains systems. Moreover, the effects of attached cells on key chemical parameters were also studied in different adsorption-deficient systems. Consistently, the greatest reduction of key chemical ion was shown with A. thiooxidans and the loss of bioleaching efficiency was high to 50.5%. These results all demonstrated the bioleaching function of attached cells was more efficient than the free cells, especially with A. thiooxidans. These notable results would help us to further understand the chalcopyrite bioleaching. Copyright © 2013 Elsevier Ltd. All rights reserved.

Metallogeny of the Mont-de-l'Aigle IOCG deposit, Gaspé Peninsula, Québec, Canada

NASA Astrophysics Data System (ADS)

Simard, M.; Beaudoin, G.; Bernard, J.; Hupé, A.

2006-09-01

The Mont-de-l’Aigle deposit is located in the northern part of Dome Lemieux, in the Connecticut Valley-Gaspé Synclinorium, Gaspé Peninsula, Québec. The Dome Lemieux is a subcircular antiform of Siluro-Devonian sedimentary rocks that is cut by numerous mafic and felsic sills and dikes of Silurian to Late Devonian age. Plutonism occurred in a continental within-plate extensional setting typical of orogenic collapse. The Cu-Fe (± Au) mineralization of Mont-de-l’Aigle occurs in veins, stockworks, and breccias. Mineralization is located near or within N-S and NW-SE faults cutting sedimentary rocks. IOCG mineralization postdates intrusions, skarns, hornfels, and epithermal mineralization typical of the southern part of the Dome Lemieux. The paragenetic sequence comprises: (1) pervasive sodic, potassic, chlorite, and silica alteration, (2) hematite, quartz, pyrite, magnetite, and chalcopyrite veins, stockworks and breccias and, (3) dolomite ± hematite veins and veinlets cutting the earlier mineralization. Intrusions display proximal sodic and potassic alteration, whereas sedimentary rocks have proximal decalcification, silicification, and potassic alteration. Both intrusive and sedimentary rocks are affected by a pervasive distal chlorite (± silica) alteration. The sulfur isotope composition of pyrite and chalcopyrite (δ34S=-1.5 to 4.8‰) suggests that sulfur was derived mainly from igneous rocks. Fluid δ18O (-0.4 to 2.65‰) indicates meteoric or seawater that reacted with the country rocks. Mixing of hot magmatic fluids with a cooler fluid, perhaps meteoric or seawater is suggested for mineral deposition and alteration of the Mont-de-l’Aigle deposit. The mineralogy, alteration, and sulfur isotope composition of the Mont-de-l’Aigle deposit compare well with IOCG deposits worldwide, making the Mont-de-l’Aigle deposit a rare example of Paleozoic IOCG mineralization, formed at shallow depth, within a low metamorphic grade sedimentary rock sequence.

LASER APPLICATIONS AND OTHER ASPECTS OF QUANTUM ELECTRONICS Nonlinearity, optoelectronic properties, and their correlations for some mixed ternary defect chalcopyrites

NASA Astrophysics Data System (ADS)

Dutta Roy, S.

2010-12-01

The refractive index, optical nonlinearity, lowest energy band gap, and other related parameters of some mixed defect ternary chalcopyrites are calculated using Levine's bond charge model and its modification developed by Samanta et al. for multinary and mixed compounds. The dependence of the band gap energy on the average quantum number, molecular weight, and anion displacement parameter is shown for the first time, which will be very useful for designing various optoelectronic and nonlinear laser devices.

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.

Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

USGS Publications Warehouse

Seal, R.R.; Hammarstrom, J.M.; Johnson, A.N.; Piatak, N.M.; Wandless, G.A.

2008-01-01

The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

Flotation performances and surface properties of chalcopyrite with xanthate collector added before and after grinding

NASA Astrophysics Data System (ADS)

Peng, Huiqing; Wu, Di; Abdelmonem, Mohamed

In this study, effects of the collector added before grinding and after grinding on the subsequent flotation and mineral surface properties were investigated. The pH was controlled at 10 during the grinding and flotation processes opened to the atmosphere. With enough amounts of sodium butyl xanthate addition, adding the collector before grinding recovered more chalcopyrite than adding it after grinding in single mineral flotation. The Eh of each ground pulp before and after conditioning were measured and it was found that adding collector before grinding obtained higher and relatively suitable pulp potential for chalcopyrite flotation. Particle size analyses of the flotation products indicate that the different flotation recoveries occurred due to the different flotation losses in fine particles (<20 μm). XPS analyses focused on the fine particles of flotation feedings and found that more carbon and oxygen, and less iron were remained on mineral surfaces when the collector was added before grinding, due to the higher collector adsorption capacity, larger free oxygen adsorbance and less iron oxide/hydroxide species.

Selective excitation of window and buffer layers in chalcopyrite devices and modules

DOE PAGES

Glynn, Stephen; Repins, Ingrid L.; Burst, James M.; ...

2018-02-02

Window and buffer layers in chalcopyrite devices are well known to affect junctions, conduction, and photo-absorption properties of the device. Some of these layers, particularly 'buffers,' which are deposited directly on top of the absorber, exhibit metastable effects upon exposure to light. Thus, to understand device performance and/or metastability, it is sometimes desirable to selectively excite different layers in the device stack. Absorption characteristics of various window and buffer layers used in chalcopyrite devices are measured. These characteristics are compared with emission spectra of common and available light sources that might be used to optically excite such layers. Effects ofmore » the window and buffer absorption on device quantum efficiency and metastability are discussed. For the case of bath-deposited Zn(O,S) buffers, we conclude that this layer is not optically excited in research devices or modules. Furthermore, this provides a complimentary mechanism to the chemical differences that may cause long time constants (compared to devices with CdS buffers) associated with reaching a stable 'light-soaked' state.« less

Co-culture microorganisms with different initial proportions reveal the mechanism of chalcopyrite bioleaching coupling with microbial community succession.

PubMed

Ma, Liyuan; Wang, Xingjie; Feng, Xue; Liang, Yili; Xiao, Yunhua; Hao, Xiaodong; Yin, Huaqun; Liu, Hongwei; Liu, Xueduan

2017-01-01

The effect of co-culture microorganisms with different initial proportions on chalcopyrite bioleaching was investigated. Communities were rebuilt by six typical strains isolated from the same habitat. The results indicated, by community with more sulfur oxidizers at both 30 and 40°C, the final copper extraction rate was 19.8% and 6.5% higher, respectively, than that with more ferrous oxidizers. The variations of pH, redox potential, ferrous and copper ions in leachate also provided evidences that community with more sulfur oxidizers was more efficient. Community succession of free and attached cells revealed that initial proportions played decisive roles on community dynamics at 30°C, while communities shared similar structures, not relevant to initial proportions at 40°C. X-ray diffraction analysis confirmed different microbial functions on mineral surface. A mechanism model for chalcopyrite bioleaching was established coupling with community succession. This will provide theoretical basis for reconstructing an efficient community in industrial application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Selective excitation of window and buffer layers in chalcopyrite devices and modules

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

Glynn, Stephen; Repins, Ingrid L.; Burst, James M.

Window and buffer layers in chalcopyrite devices are well known to affect junctions, conduction, and photo-absorption properties of the device. Some of these layers, particularly 'buffers,' which are deposited directly on top of the absorber, exhibit metastable effects upon exposure to light. Thus, to understand device performance and/or metastability, it is sometimes desirable to selectively excite different layers in the device stack. Absorption characteristics of various window and buffer layers used in chalcopyrite devices are measured. These characteristics are compared with emission spectra of common and available light sources that might be used to optically excite such layers. Effects ofmore » the window and buffer absorption on device quantum efficiency and metastability are discussed. For the case of bath-deposited Zn(O,S) buffers, we conclude that this layer is not optically excited in research devices or modules. Furthermore, this provides a complimentary mechanism to the chemical differences that may cause long time constants (compared to devices with CdS buffers) associated with reaching a stable 'light-soaked' state.« less

Insight into the mechanism revealing the peroxidase mimetic catalytic activity of quaternary CuZnFeS nanocrystals: colorimetric biosensing of hydrogen peroxide and glucose

NASA Astrophysics Data System (ADS)

Dalui, Amit; Pradhan, Bapi; Thupakula, Umamahesh; Khan, Ali Hossain; Kumar, Gundam Sandeep; Ghosh, Tanmay; Satpati, Biswarup; Acharya, Somobrata

2015-05-01

Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications.Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications. Electronic supplementary information (ESI) available: Fig. S1-S13. See DOI: 10.1039/c5nr01728a

Organometallic chemical vapor deposition and characterization of ZnGe(1-x)Si(x)P2-Ge alloys on GaP substrates

NASA Technical Reports Server (NTRS)

Xing, G. C.; Bachmann, K. J.; Posthill, J. B.; Timmons, M. L.

1991-01-01

In this paper, we report the epitaxial growth of ZnGe(1-x)Si(x)P2-Ge alloys on GaP substrates by open tube OMCVD. The chemical composition of the alloys characterized by energy dispersive X-ray spectroscopy shows that alloys with x up to 0.13 can be deposited on (001) GaP. Epitaxial growth with mirror smooth surface morphology has been achieved for x less than or equals to 0.05. Selected area electron diffraction pattern of the alloy shows that the epitaxial layer crystallizes in the chalcopyrite structure with relatively weak superlattice reflections indicating certain degree of randomness in the cation sublattice. Hall measurements show that the alloys are p-type, like the unalloyed films; the carrier concentration, however, dropped about 10 times from 2 x 10 exp 18 to 2 x 10 exp 17/cu cm. Absorption measurements indicate that the band tailing in the absorption spectra of the alloy has been shifted about 0.04 eV towards shorter wavelength as compared to the unalloyed material.

Geology of the Göçükdibi Cu-Pb-Zn Mineralization, Gökçedoǧan, Çorum (Turkey): Preliminary Findings on Its Formation

NASA Astrophysics Data System (ADS)

Yalçin, Cihan; Hanilçi, Nurullah; Kumral, Mustafa; Abdelnasser, Amr

2016-04-01

Göçükdibi Cu-Pb-Zn mineralization is located 3 km north west of Gökçedoǧan village where is 30 km east of the Kargı, Çorum. The geology of the mineralization area is represented by Mesozoic and Upper Pliocene lithostratigraphic units in different origin. These units with respect to their structural locations have identified as autochthonous and allachtonous. The autochthonous units which are the basement of the region are represented by Bekirli Metamorphites (Triassic-Liassic) and Beşpınar formation (Upper Cretaceous-Lower Eocene) which overlies the Bekirli Metamorphites as angular discordance. The allachtonous units are represented by Saraycık formation belongs to Kargı Ophioltic Melange, and located on the autochthonous units as tectonically. These allocthonous units are the product of the Neotethyan Ocean. The autochthonous and allachtonous units are overlaid by Upper Pliocene Ilgaz Formation and Plio-Quaternary stream sediments. The Cu-Pb-Zn mineralization is located in northwest of the Gökçedoǧan village within the Bekirli Metamorphites. The ore zone has N80E direction, 5 m wide and 120 m in length. The mineralizations which follow NE-SW trending structural line occurred as alternation with quartz-chlorite schists of the Bekirli Metamorphites. The mineralization is generally concordant to the foliation of schist's and also occurred as disseminated in the wall rocks. The ore paragenesis comprises with pyrite, chalcopyrite, sphalerite and galenit as the main sulphide minerals, and the malachite, azurite and limonite as the production of the oxidation. Preliminary data such as relationship between the ore and host rock, inner-structure of the ore and indicate that the Gökçedoǧan Cu-Pb-Zn mineralization was likely to have originated syngenetic. In addition, the geochemical behaviour of rare earth elements (REE) of the altered and mineralized samples collected from the alteration zone show that light REE enrichment with fair depletion of heavy REE during the alteration processes with positive Eu anomalies. As well as there is a positive correlation between K2O index and LREE that reveal the addition of K and La and the sericitization is the main alteration associated with the studied deposit. Key Words: Cu-Pb-Zn mineralization, Syngenetic, Bekirli Metamorphites, Gökçedoǧan.

Structural control on fluid flow at the Dominga IOCG deposit in Northern Chile: insights from microtextural analysis

NASA Astrophysics Data System (ADS)

Heuser, G.; Arancibia, G.; Veloso, E. A.; Reich, M.; Morales, H.

2017-12-01

The Fe-Cu paragenetic assemblages at the Cretaceous Dominga IOCG deposit in northern Chile (2082 Mt at 23% Fe, 0.07% Cu) show a spatial and genetic affinity with major structural systems in the district: the Early Structural System (ESS), El Tofo Structural System (ETSS) and Intermediate Structural System (ISS), developed under different tectonic regimes, from transtension (ESS) to transpression (ETSS, ISS). The ESS is a NE-ENE-trending right-lateral strike slip duplex related to the formation of biotite-magnetite mineralization in Fe-rich bands parallel to bedding (stage I), and magnetite-apatite-actinolite-quartz hydrothermal breccia (stage II). The ETSS is a NNE left-lateral fault breccia related to K-feldspar veins and anhydrite-chalcopyrite hydrothermal breccia (stage III). The ISS is a NW-WNW left lateral strike slip duplex composed of calcite veins (stage IV). However, an understanding of fault-driven fluid flow mechanisms and their impact on the studied Fe-Cu deposit is still lacking. We analyzed representative textures from veins and hydrothermal breccias of stages II, III and IV. Microstructural analysis was made in thin/polished sections normal and parallel to the vein wall using optical and scanning electron microscopy techniques. Stage II shows euhedral magnetite with ilmenite lamellae exsolution textures and intergrowths between magnetite and anhedral mosaic quartz. Hydrothermal breccias contain euhedral quartz with double-terminated crystal shapes and concentric growth zoning surrounded by plumose quartz. Stage III exhibits zoned K-feldspar veins, banded plumose quartz veins, and mosaic subhedral anhydrite. Stage IV is characterized by banded veins of plumose and rhombic calcite, and dilational jogs with rhombic calcite. The observed microtextures suggest slow cooling of high temperature Fe-Cu-rich fluid, suspension in aqueous fluid during crystal growth, and boiling. Despite the different tectonic regimes, the paleo-fluids at the Dominga IOCG deposit were emplaced under similar conditions during the main activity of each structural system, i.e., 1) development of veins related to fluid overpressure and 2) episodic boiling triggered by abrupt pressure drop. Acknowledgements: CONICYT Ph.D. Scholarship, Millennium Nucleus for Metal Tracing Along Subduction NC 130065.

Tectono-metallogenetic evolution of the Fe-Cu deposit of Dominga, northern Chile

NASA Astrophysics Data System (ADS)

Veloso, E.; Cembrano, J.; Arancibia, G.; Heuser, G.; Neira, S.; Siña, A.; Garrido, I.; Vermeesch, P.; Selby, D.

2017-04-01

The Dominga district in northern Chile (2082 Mt at 23.3 % Fe, 0.07 % Cu) shows a spatial and genetic affinity among distinctive structural elements and Fe-Cu-rich paragenetic mineral assemblages. Deep seated, NE-to-E striking structural elements form a right-lateral duplex-like structural system (early structural system, ESS) that cuts a regionally extensive alteration (stage I) zone. The EES system served as a locus and as path for the emplacement of biotite-magnetite alteration/mineralization (stage IIa) as veins and Fe-bearing layers following altered volcano sedimentary strata. NW-striking actinolite-magnetite hydrothermal breccias, coeval with and part of the ESS, include apatite (stage IIb) crystallized at 127 ± 15 Ma (U-Pb, 2σ). The ESS was also the locus of subsequent alteration/mineralization represented by K-feldspar, epidote, and albite (stage IIIa) and Fe-Cu-rich (vermiculite-anhydrite-chalcopyrite, stage IIIb) mineral associations. Shallowly developed, NNE-striking, left-lateral structural elements defining the El Tofo Structural System (ETSS)—probably part of the Atacama Fault System—clearly crosscut the ESS. Minerals associated with alteration/mineralization stage IIIb also occur as veins and as part of hydrothermal breccias of the ETSS, marking the transition from the ESS to ETSS. Molybdenite associated with alteration/mineralization stage IIIb yielded a Re-Os age of 127.1 ± 0.7 Ma (2σ). Both the ESS and ETSS were cut by left-lateral, NW- to E-striking shallowly developed structural elements (Intermediate Structural System, ISS) on which a hematite-calcite assemblage (stage IV) occurs mostly as infill material of veins and fault veins. The ISS is cut by N-striking, left-lateral, and shallowly developed structural elements (Late Structural System, LSS) showing no evidence of alteration/mineralization. Estimated strain and stress fields indicate an overall NW-trending shortening/compression and NE-trending stretching/tension strike-slip regime probably due to oblique subduction during the Mesozoic. However, the orientations of the stress and strain fields calculated for each structural system suggest a back-and-forth rotation pattern during transition from one structural system to the other—as they change between transtension and transpression—and between alteration/mineralization stages.

Mineralogical variation of skarn ore from the Tellerhäuser deposit, Pöhla, Germany

NASA Astrophysics Data System (ADS)

Simons, Bethany; Andersen, Jens Christian; Rollinson, Gavyn; Armstrong, Robin; Dolgopolova, Alla; Seltmann, Reimar; Stanley, Chris; Roscher, Marco

2017-04-01

The polymetallic Zn-Fe-Sn-Cu-In skarns at Pöhla Tellerhäuser in the western Erzgebirge represent some of the largest unexploited occurrences of Sn and In in Europe. The skarns developed in schists and gneisses at the margin of the Schwarzenberg Gneiss cupola and the Eibenstock granites. The flat-lying skarn layers display extreme mineralogical variability with alternating units of pyroxene, sphalerite, magnetite, amphibole and calc-silicate skarns with hanging wall schist and feeder stockwork. The polymetallic skarn ores represent a complex challenge for mineral processing, with fine-grained, locked target minerals and partitioning of target metals into silicates (e.g. Sn in malayaite). Optical microscopy, QEMSCAN® and electron-probe microanalysis have been used to determine the mineralogical variability of the skarn types with the aim to determine the deportment of the target metals to guide mineral processing test work. The composition of the skarns is extremely variable reflecting the complex mineralogy and indicating substantial variability associated with replacement reactions through the protolith(s). Cassiterite (SnO2) is the dominant Sn-bearing mineral in all the skarn types. However, the skarns also carry malayaite (CaSnO[SiO4], up to 0.03 vol%), which locally dominates over cassiterite. Cassiterite is intergrown with Fe-amphibole, grossular garnet, fluorite and magnetite. The cassiterite is unaltered, but some grains have rare iron oxide rims and inclusions. Malayaite shows a similar association to cassiterite and is intergrown as clusters of grains with silicate gangue, particularly Fe amphibole and grossular garnet and remains unaltered with no inclusions. Zinc is exclusively hosted in sphalerite and varies from 0.02 wt.% in the hanging wall schist to 36.5 wt.% in the sphalerite skarn. The high Zn values are accompanied by high values of Cd (locally in excess of 1000 ppm) and In (up to 180 ppm). Sphalerite grains are locally up to 4 mm, subhedral with chalcopyrite disease and pyrite epitaxial growth along contacts between sphalerite and magnetite. Inclusions in sphalerite include bornite, enargite, chalcocite and arsenopyrite. Magnetite comprises up to 94 vol% (mean 32 vol%) of the magnetite skarn and displays extensive haematite alteration. Intergrown with magnetite are subordinate cassiterite and sphalerite with chalcopyrite disease and high In concentrations. The mineralogical complexity is the most significant challenge for processing of the Tellerhäuser ore. Some Sn is locked within silicates leading to an expected loss in processing. The diverse gangue mineralogy is likely to interfere with traditional gravity and magnetic separation techniques. Biohydrometallurgy may offer a particularly attractive method of recovery for Zn, Cu and In. This contribution is sponsored by the EU Horizon 2020 project "FAME" (grant 641650)

Formation of the Vysoká-Zlatno Cu-Au skarn-porphyry deposit, Slovakia

NASA Astrophysics Data System (ADS)

Koděra, Peter; Lexa, Jaroslav; Fallick, Anthony E.

2010-12-01

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu-Au skarn-porphyry mineralisation, related to granodiorite/quartz-diorite porphyry dyke clusters and stocks. Vysoká-Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg-Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na-Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31-70 wt.% NaCl eq. and temperatures of liquid-vapour homogenization (Th) of 186-575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1-31 wt.% NaCl eq. and Th of 320-360°C. Quartz-chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0-3 wt.% NaCl eq. and Th of 323-364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ18Ofluid 2.5-12.3‰) with a minor meteoric component. Corresponding low δDfluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile-brittle transition. The magma chamber at ˜5-6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid-vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.

Direct observation of heavy metal-mineral association from the Clark Fork River Superfund Complex: Implications for metal transport and bioavailability

USGS Publications Warehouse

Hochella, M.F.; Moore, J.N.; Putnis, C.V.; Putnis, A.; Kasama, T.; Eberl, D.D.

2005-01-01

Two sets of samples from riverbeds and adjacent floodplains, separated by 80 river kilometers, were collected from the Clark Fork River Superfund Complex, Montana, (the largest Superfund site in the United States), and studied primarily with transmission electron microscopy (TEM) with several supporting techniques to determine heavy metal-mineral association. Seven of the eight samples studied were strongly influenced by material that once resided in mining and smelting dumps and impoundments; this material was transported downstream sometime during the last century and a half from the Butte/Anaconda areas. The eighth sample was from a deeper floodplain level and dates to premining days. The TEM observations afford a direct look, down to the nanometer level, at secondary mineral formation as a result of the breakdown of sulfides and silicates in the acid environment of this massive mine-drainage system. In the shallow, oxic floodplain sediments, heavy metals of concern in this system (As, Cu, Pb, and Zn) are taken up by the formation of sulfates (particularly Pb in jarosite), as well as hydrous metal oxides (As, Cu, Pb, and Zn in and on ferrihydrite, and a possibly new vernadite-like mineral). The oxides are long-lived in these systems, as they were also found in the anoxic riverbeds. Metals are also taken up by the formation of sulfides in sulfate-reducing environments as observed in the formation of nanoclusters of chalcopyrite and sphalerite. In all samples, clays make up between 5 and 20% of the sediment and carry significant amounts of Cu and Zn. The hydrous oxides, secondary sulfides, and clays provide several routes for metal transport downstream over long distances. Besides the potential bioavailability of heavy metals exchanged on and off the hydrous metal oxides and clays, nanometer-sized sulfides may also be highly reactive in the presence of biologic systems. Copyright ?? 2005 Elsevier Ltd.

The Stypsi-Megala Therma porphyry-epithermal mineralization, Lesvos Island, Greece: new mineralogical and geochemical data

NASA Astrophysics Data System (ADS)

Periferakis, Argyrios; Voudouris, Panagiotis; Melfos, Vasilios; Mavrogonatos, Constantinos; Alfieris, Dimitrios

2017-04-01

Lesvos Island is located at the NE part of the Aegean Sea and mostly comprises post-collisional Miocene volcanic rocks of shoshonitic to calc-alkaline geochemical affinities. In the northern part of the Island, the Stypsi Cu-Mo±Au porphyry prospect, part of the Stypsi caldera, is hosted within hydrothermally altered intrusives and volcanics [1]. Porphyry-style mineralization is developed in a microgranite porphyry that has intruded basaltic trachyandesitic lavas. Propylitic alteration occurs distal to the mineralization, whereas sodic-calcic alteration related to quartz-actinolite veinlets, and a phyllic overprint associated with a dense stockwork of banded black quartz±carbonate veinlets, characterizes the core of the system. Alunite-kaolinite advanced argillic alteration occurs at higher topographic levels and represents a barren lithocap to the porphyry mineralization. Intermediate-sulfidation (IS) milky quartz-carbonate veins overprint the porphyry mineralization along a NNE-trending fault that extends further northwards to Megala Therma, where it hosts IS base metal-rich Ag-Au mineralization [2]. New mineralogical data from the Megala Therma deposit suggest Ag-famatinite, Te-polybasite and Ag-tetrahedrite as the main carriers of Ag in the mineralization. Porphyry-style ores at Stypsi consist of magnetite postdated by pyrite and then by chalcopyrite, molybdenite, sphalerite, galena and bismuthinite within the black quartz stockworks or disseminated in the wallrock [1]. The dark coloration of quartz in the veinlets is due to abundant vapor-rich fluid inclusions. Quartz is granular and fine-grained and locally elongated perpendicular to the vein walls. Botryoidal textures are continuous through quartz grains, suggesting quartz recrystallization from a silica gel, a feature already described by [3] from banded quartz veinlets in porphyry Au deposits at Maricunga, Chile. Bulk ore analyses from porphyry-style mineralization at Stypsi displayed similar geochemical anomalies to those previously reported by [1] but also provide additional information in a series of elements: Cu (up to 843 ppm), Mo (up to 76 ppm), Au (up to 120 ppb), Pb (up to 339ppm), Zn (up to 815ppm), Se (up to 10ppm), Te (up to 4 ppm), Bi (up to 4 ppm) and Sn (up to 23 ppm). The Lesvos Island may be interpreted as the westward extension of the Eocene-Miocene Biga peninsula Cu-Au porphyry belt, with potential for future discoveries of Cu-Mo±Au deposits in the Aegean area. [1] Voudouris P, Alfieris D (2005) New porphyry-Cu±Mo occurrences in northeastern Aegean/Greece: Ore mineralogy and transition to epithermal environment. In: Mao J, Bierlein FP (eds) Mineral deposit research: Meeting the global challenge. Springer Verlag, 473-476; [2] Kontis E, Kelepertsis AE, Skounakis S (1994) Geochemistry and alteration facies associated with epithermal precious metal mineralization in an active geothermal system, northern Lesvos, Greece. Min Deposita, 29:430-433; [3] Muntean JL, Einaudi MT (2000) Porphyry Gold Deposits of the Refugio District, Maricunga Belt, Northern Chile. Econ. Geology, 95, 1445-1472.

Occurrence of the Visible Gold and Sn-Bearing Mineral in Seafloor Hydrothermal Sulfides at Central Indian Ridge, 12.4°S

NASA Astrophysics Data System (ADS)

Choi, S. K.; Pak, S. J.; Kim, J.; Park, J. W.; Son, S. K.

2017-12-01

Sn-rich chimney fragments (up to 1,720 ppm) were recovered with ultramafic rocks from ocean core complex (OCC-4-1) of Central Indian Ridge, 12.4°S. The chimney fragments are featured by barite-free and Zn-rich (up to 50.1 wt.%) ores. The chimney fragments are mainly composed of sphalerite, isocubanite, pyrrhotite, chalcopyrite and marcasite with galena and electrum as minor minerals. The precipitation sequences of the minerals are categorized into three stages by mineral assemblage; early stage with low-temperature minerals, late stage with high-temperature minerals and seawater weathering stage with covellite, Fe-oxyhydroxides and amorphous silica. Early stage is characterized by sphalerite, intermittently showing colloform-texture, closely co-existed with anhedral marcasite and minor galena, whereas late stage is dominated by aggregates of isocubanite with chalcopyrite exsolution lamellae, pyrrhotite partially replaced by long prismatic marcasite and FeS enriched sphalerite (up to 42.69 FeS mole%). Electrums, main phase of gold mineralization, are mostly visible grains (< 3 um in diameter), occuring in sphalerite and isocubanite as inclusions and/or free gold in amorphous silica through the whole mineralization stages. On the basis of semi-quantified analysis, electrum grains are likely to have Au-rich composition. High Sn concentrations are typically observed in altered rim along the grain boundaries between sphalerite and isocubanite, going up to 5.5 wt.% in sphalerite. LA-ICP-MS mapping exhibits that Sn is preferentially incorporated into sphalerite relative to isocubanite, especially showing the highest values in boundaries between both minerals, but significantly lower in marcasite. Stoichiometry of Sn-enriched sphalerite rim seems to have a uniform ratio of atomic proportion of Cu to Sn as almost 2:1, implying that stannite micro-inclusions may result in Sn-enrichment. The LA-ICP-MS spectra also shows abrupt increase in Sn signal intensity, indicating Sn-bearing inclusions are distributed within sphalerite. Therefore, Sn-bearing mineral in sphalerite and isocubanite is likely to be fine particle of stannite in late stage and subsequently one of the possible ways to precipitate these particles could be reworking process of previously deposited Sn-bearing sulfides.

Influence of Organic Solvents on Chalcopyrite Oxidation Ability of Thiobacillus ferrooxidans

PubMed Central

Torma, Arpad E.; Itzkovitch, Irwin J.

1976-01-01

It has been shown that organic solvents used primarily for the extraction of metals from aqueous leach liquors decrease both the surface tension of the aqueous phase and the chalcopyrite oxidation ability of Thiobacillus ferrooxidans. For the reagents and modifiers investigated, the order of inhibition was found to be LIX 70 < LIX 73 < LIX 71 < LIX 64N < LIX 65N < TBP ∼ isodecanol ∼ nonylphenol < LIX 63 <<< D2EHPA ∼ Kelex 100 < Kelex 120 <<< Alamine 336 ∼ Alamine 308 ∼ Alamine 310 < Alamine 304 < Adogen 381 ∼ Aliquat 336 < Adogen 364. To avoid limitation in bacterial activity, organic matter should be removed from the recycling liquor prior to leaching. PMID:16345164

Revealing the optoelectronic and thermoelectric properties of the Zintl quaternary arsenides ACdGeAs{sub 2} (A = K, Rb)

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

Azam, Sikander; Khan, Saleem Ayaz; Goumri-Said, Souraya, E-mail: Souraya.Goumri-Said@chemistry.gatech.edu

Highlights: • Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) are chalcopyrite and semiconductors. • Their direct band gap is suitable for PV, optolectronic and thermoelectric applications. • Combination of DFT and Boltzmann transport theory is employed. • The present arsenides are found to be covalent materials. - Abstract: Chalcopyrite semiconductors have attracted much attention due to their potential implications in photovoltaic and thermoelectric applications. First principle calculations were performed to investigate the electronic, optical and thermoelectric properties of the Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) using the full potential linear augmented plane wave method andmore » the Engle–Vosko GGA (EV–GGA) approximation. The present compounds are found semiconductors with direct band gap and covalent bonding character. The optical transitions are investigated via the dielectric function (real and imaginary parts) along with other related optical constants including refractive index, reflectivity and energy-loss spectrum. Combining results from DFT and Boltzmann transport theory, we reported the thermoelectric properties such as the Seebeck’s coefficient, electrical and thermal conductivity, figure of merit and power factor as function of temperatures. The present chalcopyrite Zintl quaternary arsenides deserve to be explored for their potential applications as thermoelectric materials and for photovoltaic devices.« less

Selective Adhesion of Thiobacillus ferrooxidans to Pyrite

PubMed Central

Ohmura, Naoya; Kitamura, Keiko; Saiki, Hiroshi

1993-01-01

Bacterial adhesion to mineral surfaces plays an important role not only in bacterial survival in natural ecosystems, but also in mining industry applications. Selective adhesion was investigated with Thiobacillus ferrooxidans by using four minerals, pyrite, quartz, chalcopyrite, and galena. Escherichia coli was used as a control bacterium. Contact angles were used as indicators of hydrophobicity, which was an important factor in the interaction between minerals and bacteria. The contact angle of E. coli in a 0.5% sodium chloride solution was 31°, and the contact angle of T. ferrooxidans in a pH 2.0 sulfuric acid solution was 23°. E. coli tended to adhere to more hydrophobic minerals by hydrophobic interaction, while T. ferrooxidans selectively adhered to iron-containing minerals, such as pyrite and chalcopyrite. Ferrous ion inhibited the selective adhesion of T. ferrooxidans to pyrite competitively, while ferric ion scarcely inhibited such adhesion. When selective adhesion was quenched by ferrous ion completely, adhesion of T. ferrooxidans was controlled by hydrophilic interactions. Adhesion of E. coli to pyrite exhibited a liner relationship on langmuir isotherm plots, but adhesion of T. ferrooxidans did not. T. ferrooxidans recognized the reduced iron in minerals and selectively adhered to pyrite and chalcopyrite by a strong interaction other than the physical interaction. PMID:16349106

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.

The complicated substrates enhance the microbial diversity and zinc leaching efficiency in sphalerite bioleaching system.

PubMed

Xiao, Yunhua; Xu, YongDong; Dong, Weiling; Liang, Yili; Fan, Fenliang; Zhang, Xiaoxia; Zhang, Xian; Niu, Jiaojiao; Ma, Liyuan; She, Siyuan; He, Zhili; Liu, Xueduan; Yin, Huaqun

2015-12-01

This study used an artificial enrichment microbial consortium to examine the effects of different substrate conditions on microbial diversity, composition, and function (e.g., zinc leaching efficiency) through adding pyrite (SP group), chalcopyrite (SC group), or both (SPC group) in sphalerite bioleaching systems. 16S rRNA gene sequencing analysis showed that microbial community structures and compositions dramatically changed with additions of pyrite or chalcopyrite during the sphalerite bioleaching process. Shannon diversity index showed a significantly increase in the SP (1.460), SC (1.476), and SPC (1.341) groups compared with control (sphalerite group, 0.624) on day 30, meanwhile, zinc leaching efficiencies were enhanced by about 13.4, 2.9, and 13.2%, respectively. Also, additions of pyrite or chalcopyrite could increase electric potential (ORP) and the concentrations of Fe3+ and H+, which were the main factors shaping microbial community structures by Mantel test analysis. Linear regression analysis showed that ORP, Fe3+ concentration, and pH were significantly correlated to zinc leaching efficiency and microbial diversity. In addition, we found that leaching efficiency showed a positive and significant relationship with microbial diversity. In conclusion, our results showed that the complicated substrates could significantly enhance microbial diversity and activity of function.

Full potential calculations on the electron bandstructures of Sphalerite, Pyrite and Chalcopyrite

NASA Astrophysics Data System (ADS)

Edelbro, R.; Sandström, Å.; Paul, J.

2003-02-01

The bulk electronic structures of Sphalerite, Pyrite and Chalcopyrite have been calculated within an ab initio, full potential, density functional approach. The exchange term was approximated with the Dirac exchange functional, the Vosko-Wilk-Nusair parameterization of the Cepler-Alder free electron gas was used for correlation and linear combinations of Gaussian type orbitals were used as basis functions. The Sphalerite (zinc blende) band gap was calculated to be direct with a width of 2.23 eV. The Sphalerite valence band was 5.2 eV wide and composed of a mixture of sulfur and zinc orbitals. The band below the valence band located around -6.2 eV was mainly composed of Zn 3d orbitals. The S 3s orbitals gave rise to a band located around -12.3 eV. Pyrite was calculated to be a semiconductor with an indirect band gap of 0.51 eV, and a direct gap of 0.55 eV. The valence band was 1.25 eV wide and mainly composed of non-bonding Fe 3d orbitals. The band below the valence band was 4.9 eV wide and composed of a mixture of sulfur and iron orbitals. Due to the short inter-atomic distance between the sulfur dumbbells, the S 3s orbitals in Pyrite were split into a bonding and an anti-bonding range. Chalcopyrite was predicted to be a conductor, with no band-crossings at the Fermi level. The bands at -13.2 eV originate from the sulfur 3s orbitals and were quite similar to the sulfur 3s bands in Sphalerite, though somewhat shifted to lower energy. The top of the valence band consisted of a mixture of orbitals from all the atoms. The lower part of the same band showed metal character. Computational modeling as a tool for illuminating the flotation and leaching processes of Pyrite and Chalcopyrite, in connection with surface science experiments, is discussed.

Selenization of CIS and CIGS layers deposited by chemical spray pyrolysis

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

Babu, B. J.; Egaas, B.; Velumani, S.

Cu(In1-xGax)Se2 (CIGS) thin films with x=0 (CIS) and x=0.3 (CIGS) were prepared on Mo-coated glass substrate by using chemical spray pyrolysis at a substrate temperature of 350 degrees C, followed by selenization treatment at 550 degrees C in selenium environment under N2 gas flow. X-ray diffraction patterns of as-deposited CIGS layers on Mo showed polycrystalline chalcopyrite phase with an intense (112) plane. Splitting of (204)/(220) and (116)/(312) planes for the film with x=0.3 reveals deviation of tetragonal nature. Field emission scanning electron microscopy cross-sectional images of selenized films showed clear re-crystallization of grains. During the selenization process of the CIGSmore » absorber, a thin interface layer of MoSe2 is formed. Line mapping of Mo/CIGS layer showed more gallium segregation at the interface of back contact resulting in band gap grading. Chemical composition and mapping of the as-deposited and selenized samples were determined by energy dispersive analysis of X-rays. This work leads to fabrication of low cost and large scale Mo/CIGS/CdS/ZnO/ZnO:Al device structure.« less

Multiphase formation of the Obří důl polymetallic skarn deposit, West Sudetes, Bohemian Massif: geochemistry and Re-Os dating of sulfide mineralization

NASA Astrophysics Data System (ADS)

Veselovský, František; Ackerman, Lukáš; Pašava, Jan; Žák, Karel; Haluzová, Eva; Creaser, Robert A.; Dobeš, Petr; Erban, Vojtěch; Tásler, Radko

2017-10-01

The Obří důl Fe-Cu-As polymetallic sulfide skarn deposit is developed in a metamorphic series in the West Sudetes, Bohemian Massif. It consists of lenses of marble, calc-silicate rocks, and skarns. We studied the Gustav orebody, which is located few hundred meters away from the contact with a large, late-orogenic Variscan Krkonoše-Jizera Plutonic Complex (KJPC) emplaced into shallow crust. Mineralogical and fluid inclusion study evidence indicates that the main sulfide stage, dominated by pyrrhotite, arsenopyrite, and chalcopyrite originated from aqueous hydrothermal fluids with salinity up to 8 wt% NaCl eq. with minimum homogenization temperatures ranging from 324 to 358 °C. These fluids mainly replaced carbonate-rich lithologies. Carbon, oxygen, and strontium isotope data in Ca-rich rocks imply total overprinting by channelized metasomatic fluid flow, which is most probably related to the intrusion of the KJPC, whereas δ34S values of sulfides argue for a magmatic source of sulfur. The Re-Os age of arsenopyrite overlaps published age data for the KJPC and suggests synchronous formation of the main sulfide mineralization and pluton emplacement.

Multiphase formation of the Obří důl polymetallic skarn deposit, West Sudetes, Bohemian Massif: geochemistry and Re-Os dating of sulfide mineralization

NASA Astrophysics Data System (ADS)

Veselovský, František; Ackerman, Lukáš; Pašava, Jan; Žák, Karel; Haluzová, Eva; Creaser, Robert A.; Dobeš, Petr; Erban, Vojtěch; Tásler, Radko

2018-06-01

The Obří důl Fe-Cu-As polymetallic sulfide skarn deposit is developed in a metamorphic series in the West Sudetes, Bohemian Massif. It consists of lenses of marble, calc-silicate rocks, and skarns. We studied the Gustav orebody, which is located few hundred meters away from the contact with a large, late-orogenic Variscan Krkonoše-Jizera Plutonic Complex (KJPC) emplaced into shallow crust. Mineralogical and fluid inclusion study evidence indicates that the main sulfide stage, dominated by pyrrhotite, arsenopyrite, and chalcopyrite originated from aqueous hydrothermal fluids with salinity up to 8 wt% NaCl eq. with minimum homogenization temperatures ranging from 324 to 358 °C. These fluids mainly replaced carbonate-rich lithologies. Carbon, oxygen, and strontium isotope data in Ca-rich rocks imply total overprinting by channelized metasomatic fluid flow, which is most probably related to the intrusion of the KJPC, whereas δ34S values of sulfides argue for a magmatic source of sulfur. The Re-Os age of arsenopyrite overlaps published age data for the KJPC and suggests synchronous formation of the main sulfide mineralization and pluton emplacement.

Late Carboniferous porphyry copper mineralization at La Voluntad, Neuquén, Argentina: Constraints from Re-Os molybdenite dating

NASA Astrophysics Data System (ADS)

Garrido, Mirta; Barra, Fernando; Domínguez, Eduardo; Ruiz, Joaquin; Valencia, Victor A.

2008-07-01

The La Voluntad porphyry Cu-Mo deposit in Neuquén, Argentina, is one of several poorly known porphyry-type deposits of Paleozoic to Early Jurassic age in the central and southern Andes. Mineralization at La Voluntad is related to a tonalite porphyry from the Chachil Plutonic Complex that intruded metasedimentary units of the Piedra Santa Complex. Five new Re-Os molybdenite ages from four samples representing three different vein types (i.e., quartz-molybdenite, quartz-sericite-molybdenite and quartz-sericite-molybdenite ± chalcopyrite-pyrite) are identical within error and were formed between ~312 to ~316 Ma. Rhenium and Os concentrations range between 34 to 183 ppm and 112 to 599 ppb, respectively. The new Re-Os ages indicate that the main mineralization event at La Voluntad, associated to sericitic alteration, was emplaced during a time span of 1.7 ± 3.2 Ma and that the deposit is Carboniferous in age, not Permian as previously thought. La Voluntad is the oldest porphyry copper deposit so far recognized in the Andes and indicates the presence of an active magmatic arc, with associated porphyry style mineralization, at the proto-Pacific margin of Gondwana during the Early Pennsylvanian.

Geology, geochronology, and geochemistry of the Yinachang Fe-Cu-Au-REE deposit of the Kangdian region of SW China: Evidence for a Paleo-Mesoproterozoic tectono-magmatic event and associated IOCG systems in the western Yangtze Block

NASA Astrophysics Data System (ADS)

Hou, Lin; Ding, Jun; Deng, Jun; Peng, Hui-juan

2015-05-01

Numerous Fe-Cu-Au-rare earth element (REE) deposits have been identified within the Paleoproterozoic Dongchuan Group of the Kangdian region of SW China. This region hosts the Yinachang deposit, which contains more than 16.8 Mt Fe, 682.6 kt Cu, and significant amounts of Au and the REEs. Both the Haizi dolerite and a magmatic breccia in the central part of the Kangdian region are thought to be related to the Dongchuan dolerite in the northern part of this region; all three of these units provide evidence of the tectono-magmatic history of the Kunyang Rift and are closely spatially and temporally related to Fe-Cu-Au-REE mineralization in this region. Here, we present a new zircon U-Pb age for the Haizi dolerite (1764.7 ± 5.7 Ma), which is consistent with the known age of the Dongchuan dolerite (1765 ± 57 Ma), allowing the determination of the precise timing of Paleo-Mesoproterozoic intraplate mafic magmatism in this region (1.72-1.77 Ga). The breccia in this region formed during magmatism at around 1.73-1.74 Ga, as documented by zircon U-Pb dating of matrix material within the Yinachang magmatic breccia (1739 ± 13 Ma). The geochemistry of Haizi and Dongchuan dolerite samples provides evidence of intraplate extension in the Kangdian region, the majority of which was concentrated along the Kunyang Rift. The Kangdian region underwent variable degrees of extension, as evidenced by the fact that break-up in the central part of this region occurred earlier than in the north. This also led to the emplacement of deeper-sourced alkaline magmas (usually OIB-type magmas) in the central part of this region. The iron-oxide copper gold (IOCG) mineralization in the Kangdian region is associated with the upwelling of mantle material. A chalcopyrite Re-Os age of 1648 ± 14 Ma from the Yinachang Fe-Cu-Au-REE deposit obtained during this study is some 50-100 Myr younger than the timing of emplacement of the deeply sourced Haizi and Dongchuan dolerites. The Yinachang deposit is a typical IOCG-type deposit, and the presence of this and other deposits in the Kangdian region indicates that this region hosts an intraplate extension-related IOCG system within the western edge of the Yangtze Block, China.

Cu(In,Ga)Se2 thin films annealed using a continuous wave Nd:YAG laser (λ0 = 532 nm): Effects of laser-annealing time

NASA Astrophysics Data System (ADS)

Yoo, Myoung Han; Ko, Pil Ju; Kim, Nam-Hoon; Lee, Hyun-Yong

2017-12-01

Preparation of Cu(In,Ga)Se2 (CIGS) thin films has continued to face problems related to the selenization of sputtered Cu-In-Ga precursors when using H2Se vapor in that the materials are highly toxic and the facilities extremely costly. Another obstacle facing the production of CIGS thin films has been the required annealing temperature, as it relates to the decomposition temperature of a typical flexible polymer substrate. A novel laser-annealing process for CIGS thin films, which does not involve the selenization process and which can be performed at a lower temperature, has been proposed. Following sputtering with a Cu0.9In0.7Ga0.3Se2 target, the laser-annealing of the CIGS thin film was performed using a continuous 532-nm Nd:YAG laser with an annealing time of 200 - 1000 s at a laser optical power of 2.75 W. CIGS chalcopyrite (112), (220/204), and (312/116) phases, with some weak diffraction peaks corresponding to the Cu-Se- or the In-Se-related phases, were successfully obtained for all the CIGS thin films that had been laser-annealed at 2.75 W. The lattice parameters, the d-spacing, the tetragonal distortion parameter, and the strain led to the crystallinity being worse and grain size being smaller at 600 s while better crystallinity was obtained at 200 and 800 s, which was closely related to the deviations from molecularity and stoichiometry, which were greatest at 600 s while the values exhibited near-stoichiometric compositions at 200 and 800 s. The band gaps of the laser-annealed CIGS thin films were within a range of 1.765 - 1.977 eV and depended on the internal stress. The mean absorbance of the laser-annealed CIGS thin films was within a range of 1.598 - 1.900, suggesting that approximately 97.47 - 98.74% of the incident photons in the visible spectral region were absorbed by this 400-nm film. The conductivity types exhibited the same deviations (Δ m > 0 and Δ s < 0) in all the laser-annealed CIGS thin films. After laser-annealing, the resistivity fell abruptly to a range of 3.551 × 10 -2 - 1.022 × 10 -1 Ω·cm. The carrier concentration was on the order of 1019 - 1021 cm -3, and the carrier mobility was 5.7 × 10 -2 - 5.7 × 100 cm2/V·s.

Noble Gas Isotope Evidence for Mantle Volatiles in the Cu-Mo Porphyry and Main Stage Polymetallic Veins at Butte, Montana

NASA Astrophysics Data System (ADS)

Hofstra, A. H.; Rusk, B. G.; Manning, A. H.; Hunt, A. G.; Landis, G. P.

2017-12-01

Recent studies suggest that volatiles released from mafic intrusions may be important sources of heat, sulfur, and metals in porphyry Cu-Mo-Au and epithermal Au-Ag deposits associated with intermediate to silicic stocks. The huge Cu-Mo porphyry and Main Stage polymetallic vein deposits at Butte are well suited to test this hypothesis because there is no geologic or isotopic evidence of basaltic intrusions in the mine or drill holes. The Butte porphyry-vein system is associated with quartz monzonite stocks and dikes within the southwest part of the Late Cretaceous Boulder batholith. The Boulder batholith was emplaced into Mesoproterozoic to Mesozoic sedimentary rocks and Late Cretaceous volcanic rocks. The Boulder batholith and Butte intrusions have Sri and eNd values indicative of crustal contamination. Eu and Ce anomalies in zircon from Butte intrusions provide evidence of oxidation due to magma degassing. To ascertain the source of volatiles in this system, 11 samples from the Cu-Mo porphyry and 16 from Main Stage veins were selected. The isotopic composition of Ar, Ne, and He extracted from fluid inclusions in quartz, magnetite, pyrite, chalcopyrite, sphalerite, galena, enargite, and covellite were determined. Helium isotopes exceed blank levels in all samples and Ne and Ar in some samples. On a 38Ar/36Ar vs. 40Ar/36Ar diagram, data plot near air. On a 20Ne/22Ne vs. 21Ne/22Ne diagram, data extend from air along the trajectories of OIB and MORB. On a 36Ar/4He vs. 3He/4He RA diagram, data extend from crust toward the air-mantle mixing line. The maximum 3He/4He RA values in the Cu-Mo porphyry (2.86) and Main Stage veins (3.46) are from pyrite and these values correspond to 36 and 43 % mantle helium. The Ne and He results show that fluid inclusions contain volatiles discharged from mantle magmas and that these volatiles were diluted by groundwater containing He derived from country rocks. Despite the lack of mafic intrusions in the Butte magmatic center, noble gas isotopes show that volatiles derived from concealed mafic intrusions were present in the hydrothermal system. Discharge of hot volatiles from mafic magma chambers at depth may be required to prevent the overlying magma column from quenching and, thus, allow for the repeated buildup and release of sulfur- and metal-bearing fluids from apical intrusions.

Layered hydrothermal barite-sulfide mound field, East Diamante Caldera, Mariana volcanic arc

USGS Publications Warehouse

Hein, James R.; de Ronde, Cornel E. J.; Koski, Randolph A.; Ditchburn, Robert G.; Mizell, Kira; Tamura, Yoshihiko; Stern, Robert J.; Conrad, Tracey; Ishizuka, Osamu; Leybourne, Matthew I.

2014-01-01

East Diamante is a submarine volcano in the southern Mariana arc that is host to a complex caldera ~5 × 10 km (elongated ENE-WSW) that is breached along its northern and southwestern sectors. A large field of barite-sulfide mounds was discovered in June 2009 and revisited in July 2010 with the R/V Natsushima, using the ROV Hyper-Dolphin. The mound field occurs on the northeast flank of a cluster of resurgent dacite domes in the central caldera, near an active black smoker vent field. A 40Ar/39Ar age of 20,000 ± 4000 years was obtained from a dacite sample. The mound field is aligned along a series of fractures and extends for more than 180 m east-west and >120 m north-south. Individual mounds are typically 1 to 3 m tall and 0.5 to 2 m wide, with lengths from about 3 to 8 m. The mounds are dominated by barite + sphalerite layers with the margins of each layer composed of barite with disseminated sulfides. Rare, inactive spires and chimneys sit atop some mounds and also occur as clusters away from the mounds. Iron and Mn oxides are currently forming small (<1-m diam, ~0.5-m tall) knolls on the top surface of some of the barite-sulfide mounds and may also drape their flanks. Both diffusely and focused fluids emanate from the small oxide knolls. Radiometric ages of the layered barite-sulfide mounds and chimneys vary from ~3,920 to 3,350 years. One layer, from an outcrop of 10- to 100-cm-thick Cu-rich layers, is notably younger with an age of 2,180 years. The Fe-Mn oxides were <5 years old at the time of collection in 2009.Most mound, chimney, and layered outcrop samples are dominated by barite, silica, and sphalerite; other sulfides, in decreasing order of abundance, are galena, chalcopyrite, and rare pyrite. Anglesite, cerussite, and unidentified Pb oxychloride and Pb phosphate minerals occur as late-stage interstitial phases. The samples contain high Zn (up to 23 wt %), Pb (to 16 wt %), Ag (to 487 ppm), and Au (to 19 ppm) contents. Some layered outcrop samples are dominated by chalcopyrite resulting in ≤4.78 wt % Cu in a bulk sample (28 wt % for a single lens), with a mean of 0.28 wt % for other samples. Other significant metal enrichments are Sb (to 1,320 ppm), Cd (to 1,150 ppm), and Hg (to 55 ppm).The East Diamante mound field has a unique set of characteristics compared to other hydrothermal sites in the Mariana arc and elsewhere. The geochemical differences may predominantly reflect the distribution of fractures and faults and consequently the rock/water ratio, temperature of the fluid in the upper parts of the circulation system, and extensive and prolonged mixing with seawater. The location of mineralization is controlled by fractures. Following resurgent doming within the caldera, mineralization resulted from focused flow along small segments of linear fractures rather than from a point source, typical of hydrothermal chimney fields. Based on the mineral assemblage, the maximum fluid temperatures were ~260°C, near the boiling point for the water depths of the mound field (367–406 m). Lateral fluid flow within the mounds precipitated interstitial sphalerite, silica, and Pb minerals within a network of barite with disseminated sulfides; silica was the final phase to precipitate. The current low-temperature precipitation of Fe and Mn oxides and silica may represent rejuvenation of the system.

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide-Cu (-Ag-Au) deposits, south-central Perú

NASA Astrophysics Data System (ADS)

Chen, Huayong; Kyser, T. Kurtis; Clark, Alan H.

2011-10-01

The Marcona-Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide-copper-gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3-4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite-biotite-calcic amphibole assemblages are inferred to have crystallized from a 700-800°C Fe oxide melt with a δ18O value from +5.2‰ to +7.7‰. Stage M-IV magnetite-phlogopite-calcic amphibole-sulphide assemblages were subsequently precipitated from 430-600°C aqueous fluids with dominantly magmatic isotopic compositions (δ34S = +0.8‰ to +5.9‰; δ18O = +9.6‰ to +12.2‰; δD = -73‰ to -43‰; and δ13C = -3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide-calcite-amphibole assemblages (stage M-V) were deposited from fluids with similar δ34S (+1.8‰ to +5.0‰), δ18O (+10.1‰ to +12.5‰) and δ13C (-3.4‰), but higher δD values (average -8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite-pyrite assemblages precipitated from a magmatic fluid (δ34S = +0.8‰ to +3.9‰; δ18O = +9.5‰ to +11.5‰) at 540-600°C, whereas ensuing chalcopyrite-bornite-digenite-chalcocite-hematite-calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ34S ≥ +29‰, δ18O = 0.1‰ and δ13C = -8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (-K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite-pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.

Geochemical, microtextural and petrological studies of the Samba prospect in the Zambian Copperbelt basement: a metamorphosed Palaeoproterozoic porphyry Cu deposit.

NASA Astrophysics Data System (ADS)

Master, Sharad; Mirrander Ndhlovu, N.

2015-04-01

Ever since Wakefield (1978, IMM Trans., B87, 43-52) described a porphyry-type meta-morphosed Cu prospect, the ca 50 Mt, 0.5% Cu Samba deposit (12.717°S, 27.833°E), hosted by porphyry-associated quartz-sericite-biotite schists in northern Zambia, there has been controversy about its origin and significance. This is because it is situated in the basement to the world's largest stratabound sediment-hosted copper province, the Central African Copperbelt, which is hosted by rocks of the Neoproterozoic Katanga Supergroup. Mineralization in the pre-Katangan basement has long played a prominent role in ore genetic models, with some authors suggesting that basement Cu mineralization may have been recycled into the Katangan basin through erosion and redeposition, while others have suggested that the circulation of fluids through Cu-rich basement may have leached out the metals which are found concentrated in the Katangan orebodies. On the basis of ca 490-460 Ma Ar-Ar ages, Hitzman et al. (2012, Sillitoe Vol., SEG Spec. Publ., 16, 487-514) suggested that Samba represents late-stage impregnation of copper mineralization into the basement, and that it was one of the youngest copper deposits known in the Central African Copperbelt. If the Samba deposit really is that young, then it would have post-dated regional deformation and metamorphism (560-510 Ma), and it ought to be undeformed and unmetamorphosed. The Samba mineralization consists of chalcopyrite and bornite, occurring as disseminations, stringers and veinlets, found in a zone >1 km along strike, in steeply-dipping lenses up to 10m thick and >150m deep. Our new major and trace element XRF geochemical data (14 samples) show that the host rocks are mainly calc-alkaline metadacites. Cu is correlated with Ag (Cu/Ag ~10,000:1) with no Au or Mo. Our study focused on the microtextures and petrology of the Samba ores. We confirm that there is alteration of similar style to that accompanying classical porphyry Cu mineralization, including potassic (biotite+sericite+ quartz), propylitic (clinozoisite+chlorite+saussuritized plagioclase), phyllic (sericite+quartz+ pyrite+hydromuscovite/illite) and argillic (kaolinite+chlorite+dolomite) alteration. The clays were identified with XRD. All the rocks show penetrative deformational textures and fabrics. Our textural studies show that phyllic zone pyrite crystals have quartz-rich pressure shadows, and they predate all phases of deformation. Similarly, in the potassic zone, fracture-controlled biotite stringers in particular orientations are deformed, and partly replaced by chlorite, again showing their pre-deformational, pre-metamorphic origin. Copper sulfide-bearing quartz veinlets are deformed. Many of the alteration assemblages containing biotite or sericite have been deformed into crenulated schists, showing that they were formed early in the deformation history. Coupled with the dating of a Samba metavolcanic rock at 1964±12 Ma (Rainaud et al., 2005, JAES, 42, 1-31), we regard the Samba deposit as a metamorphosed Palaeoproterozoic porphyry-type Cu deposit, which has undergone deformation, and retrograde metamorphism of its alteration assemblages, during the Neoproterozoic Lufilian Orogeny, followed by post-tectonic cooling, which occurred throughout the Copperbelt at about 480±20 Ma. Samba, together with the Mkushi deposits, is part of a long-lived (>100 Ma) Palaeoproterozoic porphyry-Cu province in the Zambian Copperbelt basement, and ore genetic theories for the Copperbelt mineralization must now seriously take this into account.

Microthermometry of enargite-hosted fluid inclusions from the Lepanto, Philippines, high-sulfidation Cu sbnd Au deposit

NASA Astrophysics Data System (ADS)

Mancano, D. P.; Campbell, A. R.

1995-10-01

The spatial relation between porphyry and high-sulfidation epithermal deposits is particularly well revealed in the Mankayan mineral district of northern Luzon, Philippines, where the Lepanto high-sulfidation Cu sbnd Au deposit lies over and adjacent to the Far Southeast (FSE) porphyry Cu sbnd Au deposit. Consequently, a study was undertaken to characterize the fluids responsible for epithermal mineralization in this environment. The ore stage at Lepanto consists of enargite-luzonite (Cu 3AsS 4), pyrite, tennantite-tetrahedrite, and chalcopyrite. Infrared petrography of the enargite reveals variable transparency, with growth banding and twinning visible in euhedral specimens. Two phase (liquid > vapor) fluid inclusions occur as primary and secondary types ranging from <1 to 80 micrometers in length, with tabular, cylindrical, or oval shapes. Homogenization temperatures ( Th) of fluid inclusions in enargite were measured from within the lateral (3.0 km) and vertical (0.5 km) extent of the enargite mineralization. These values show a cooling trend toward the northwest, away from the area over the porphyry deposit, with average Th ranging from 285°C (proximal) to 166°C (distal). Ice melting temperatures ( Tm) were measured using a cycling technique, as ice was usually not visible in frozen inclusions. Apparent salinities range from 4.5 to 0.2 eq. wt% NaCl, with samples from the margins of the deposit showing a general decrease in apparent salinity with lower Th. Secondary fluid inclusions in quartz phenocrysts tend to have a higher average Th and lower apparent salinities compared to enargite-hosted inclusion fluids from the same locations. Several samples of pyrite are also transparent to IR radiation, and show internal features such as growth banding, and in one instance a two phase (liquid > vapor) fluid inclusion. This inclusion yielded a salinity of 1.2 eq. wt% NaCl. There is a large discrepancy in Th and apparent salinities between the enargite mineralization and the subjacent porphyry deposit despite contemporaneous formation, suggesting that the hot, (>500°C) hypersaline, magmatic brines associated with porphyry mineralization did not directly ascend to the elevation of the enargite deposit. However, absorbtion of magmatic vapors into overlying meteoric water may have created the mineralizing fluid of the Lepanto deposit. As this liquid moved to the northwest along the Lepanto fault, it was cooled and diluted by mixing with groundwater, resulting in enargite deposition.

Trace and minor elements in sphalerite from metamorphosed sulphide deposits

NASA Astrophysics Data System (ADS)

Lockington, Julian A.; Cook, Nigel J.; Ciobanu, Cristiana L.

2014-12-01

Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.

Low-cost fabrication of ternary CuInSe{sub 2} nanocrystals by colloidal route using a novel combination of volatile and non-volatile capping agents

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

Chawla, Parul; Narain Sharma, Shailesh, E-mail: shailesh@nplindia.org; Singh, Son

2014-11-15

Wet-route synthesis of CuInSe{sub 2} (CISe) nanocrystals has been envisaged with the utilization of the unique combination of coordinating ligand and non coordinating solvent. Our work demonstrates the formation of a single-phase, nearly stoichiometric and monodispersive, stable and well-passivated colloidal ternary CISe nanocrystals (band gap (E{sub g})∼1.16 eV) using a novel combination of ligands; viz. volatile arylamine aniline and non-volatile solvent 1-octadecene. The synthesis and growth conditions have been manoeuvred using the colligative properties of the mixture and thus higher growth temperature (∼250 °C) could be attained that promoted larger grain growth. The beneficial influence of the capping agents (anilinemore » and 1-octadecene) on the properties of chalcopyrite nanocrystals has enabled us to pictorally model the structural, morphological and optoelectronic aspects of CISe nanoparticles. - Graphical abstract: Without resorting to any post-selenization process and using the colligative properties of the mixture comprising of volatile aniline and non-volatile 1-octadecene to manoeuvre the growth conditions to promote Ostwald ripening, a single phase, monodispersive and nearly stoichiometric ternary CISe nanocrystals are formed by wet-synthesis route. - Highlights: • Wet-route synthesis of CISe nanocrystals reported without post-selenization process. • Single-phase, stable and well-passivated colloidal ternary CISe nanocrystals formed. • Novel combination of capping agents: volatile aniline and non-volatile 1-octadecene. • Higher growth temperature attained using the colligative properties of the mixture. • Metallic salts presence explains exp. and theoretical boiling point difference.« less

Tunable optical properties of ZnCdTe2-xSex(x =0.625) chalcopyrite for photovoltaics; a mBJLDA approach

NASA Astrophysics Data System (ADS)

Kashyap, Manish K.; Paudyal, D.; Harmon, B. N.

In the present study, we have performed ab-initio simulations of sp-element defect in ZnCdTe2-xSex (x =0.625) chalcopyrite to check the tuning of band gap as compared to the pristine case. The exchange and correlation (XC) effects are taken into account by an orbital independent modified Becke-Johnson (mBJ) potential as coupled with Local Density Approximation (LDA) for these calculations. The calculated energy band structures show a direct band gap at the point in the brillouin zone for the pristine as well as the defected case and the band gap decreases with inclusion of sp-disorder. The imaginary dielectric function predicts the optical band gap of pristine ZnCdTe2 very close to the experimental value and the results are in reasonable agreement without applying any scissor operator. With inclusion of sp-element defect, the optical spectra is tuned to optimal region, suitable for photovoltaics. It is apparent that mBJ functional is well suited for calculating electronic structure of pristine as well as defected ZnCdTe2chalcopyrite. MKK acknowledges financial support from UGC, India in the form of RAMAN Post-doctoral fellowship. This work at Ames Laboratory was supported by the DOE, Office of Basic Energy Sciences, Materials Sciences Division under contract No. DE-AC02-07CH11358.

First insights on the molybdenum-copper Bled M'Dena complex (Eglab massif, Algeria)

NASA Astrophysics Data System (ADS)

Lagraa, Karima; Salvi, Stefano; Béziat, Didier; Debat, Pierre; Kolli, Omar

2017-03-01

Molybdenum-Copper showings in the Eglab massif (eastern part of the Reguibat rise of Algeria), are found in quartz-monzodiorite and granodiorite of the Bled M'Dena complex, a Paleoproterozoic circular structure of ∼5 km in diameter, comprising volcanic and intrusive suites. The latter consist of quartz-diorite, quartz-monzodiorite and granodiorite with a metaluminous normative composition. They display an "adakitic character" with moderate light rare-earth element (LREE) enrichment, minor Eu anomalies, high Sr/Y ratio and low Yb concentration, suggestive of a hydrous, arc magma of volcanic-arc affinity. The mineralization occurs mostly in quartz + molybdenite + chalcopyrite stockwork veins marked by widespread propylitic alteration along the selvages. Molybdenite and chalcopyrite are commonly associated with calcite, which precipitated at relatively late stages of the hydrothermal alteration. Fluid inclusions related to the mineralization stage, range from aqueous to aqueous-carbonic to solid bearing. The latter inclusions have the highest homogenization temperature (up to ∼400 °C), are salt saturated, and commonly contain molybdenite and/or chalcopyrite crystals. The petrology and geochemistry of the host rocks, the style of the hydrothermal alteration, the ore mineral associations, and the characteristics of the fluid inclusions, are all coherent in indicating that the Bled M'Dena represents a Paleoproterozoic porphyry style Mo mineralization, which is far unreported in the African continent.

Expression of Critical Sulfur- and Iron-Oxidation Genes and the Community Dynamics During Bioleaching of Chalcopyrite Concentrate by Moderate Thermophiles.

PubMed

Zhou, Dan; Peng, Tangjian; Zhou, Hongbo; Liu, Xueduan; Gu, Guohua; Chen, Miao; Qiu, Guanzhou; Zeng, Weimin

2015-07-01

Sulfate adenylyltransferase gene and 4Fe-4S ferredoxin gene are the key genes related to sulfur and iron oxidations during bioleaching system, respectively. In order to better understand the bioleaching and microorganism synergistic mechanism in chalcopyrite bioleaching by mixed culture of moderate thermophiles, expressions of the two energy metabolism genes and community dynamics of free and attached microorganisms were investigated. Specific primers were designed for real-time quantitative PCR to study the expression of these genes. Real-time PCR results showed that sulfate adenylyltransferase gene was more highly expressed in Sulfobacillus thermosulfidooxidans than that in Acidithiobacillus caldus, and expression of 4Fe-4S ferredoxin gene was higher in Ferroplasma thermophilum than that in S. thermosulfidooxidans and Leptospirillum ferriphilum. The results indicated that in the bioleaching system of chalcopyrite concentrate, sulfur and iron oxidations were mainly performed by S. thermosulfidooxidans and F. thermophilum, respectively. The community dynamics results revealed that S. thermosulfidooxidans took up the largest proportion during the whole period, followed by F. thermophilum, A. caldus, and L. ferriphilum. The CCA analysis showed that 4Fe-4S ferredoxin gene expression was mainly affected (positively correlated) by high pH and elevated concentration of ferrous ion, while no factor was observed to prominently influence the expression of sulfate adenylyltransferase gene.

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.

Gold-bearing skarns

USGS Publications Warehouse

Theodore, Ted G.; Orris, Greta J.; Hammerstrom, Jane M.; Bliss, James D.

1991-01-01

In recent years, a significant proportion of the mining industry's interest has been centered on discovery of gold deposits; this includes discovery of additional deposits where gold occurs in skarn, such as at Fortitude, Nevada, and at Red Dome, Australia. Under the classification of Au-bearing skarns, we have modeled these and similar gold-rich deposits that have a gold grade of at least 1 g/t and exhibit distinctive skarn mineralogy. Two subtypes, Au-skarns and byproduct Au-skarns, can be recognized on the basis of gold, silver, and base-metal grades, although many other geological factors apparently are still undistinguishable largely because of a lack of detailed studies of the Au-skarns. Median grades and tonnage for 40 Au-skarn deposits are 8.6 g/t Au, 5.0 g/t Ag, and 213,000 t. Median grades and tonnage for 50 byproduct and Au-skarn deposits are 3.7 g/t Au, 37 g/t Ag, and 330,000 t. Gold-bearing skarns are generally calcic exoskarns associated with intense retrograde hydrosilicate alteration. These skarns may contain economic amounts of numerous other commodities (Cu, Fe, Pb, Zn, As, Bi, W, Sb, Co, Cd, and S) as well as gold and silver. Most Au-bearing skarns are found in Paleozoic and Cenozoic orogenic-belt and island-arc settings and are associated with felsic to intermediate intrusive rocks of Paleozoic to Tertiary age. Native gold, electru, pyrite, pyrrhotite, chalcopyrite, arsenopyrite, sphalerite, galena, bismuth minerals, and magnetite or hematite are the most common opaque minerals. Gangue minerals typically include garnet (andradite-grossular), pyroxene (diopside-hedenbergite), wollastonite, chlorite, epidote, quartz, actinolite-tremolite, and (or) calcite.

Single Source Precursors for Thin Film Solar Cells

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Hollingsworth, Jennifer A.; Harris, Jerry D.; Cowen, Jonathan; Buhro, William E.; Hepp, Aloysius F.

2002-01-01

The development of thin film solar cells on flexible, lightweight, space-qualified substrates provides an attractive cost solution to fabricating solar arrays with high specific power, (W/kg). The use of a polycrystalline chalcopyrite absorber layer for thin film solar cells is considered as the next generation photovoltaic devices. At NASA GRC we have focused on the development of new single source precursors (SSP) and their utility to deposit the chalcopyrite semi-conducting layer (CIS) onto flexible substrates for solar cell fabrication. The syntheses and thermal modulation of SSPs via molecular engineering is described. Thin-film fabrication studies demonstrate the SSPs can be used in a spray CVD (chemical vapor deposition) process, for depositing CIS at reduced temperatures, which display good electrical properties, suitable for PV (photovoltaic) devices.

Geology of the Huron River pitchblende occurrence, Baraga County, Michigan

USGS Publications Warehouse

Vickers, R.C.

1955-01-01

Pitchblende and secondary uranium minerals occur as very small, discontinuous stringers and pods in calcite and quartz cementing the breccia within a low-angle shear zone that dips about 10 degrees to the southwest. The shear zone has a thickness of 10 to 30 feet and cuts black, locally carbonaceous slates of the upper Huronian Precambrian Michigamme slate. Mineral deposition during two hypogene stages and one supergene stage was identified in polished sections. The first phase consisted of the introduction of quartz and minor hematite into the sheared slate. After fracturing of the quartz the second stage was initiated by deposition of calcite, pyrite, rutile, pitchblende, bornite, sphalerite, chalcopyrite, galena, and greenockite. The supergene stage consisted of the development of metatyuyamunite, chalcopyrite, chalcocite, covellite, cuprite, volborthite, malachite, and goethite.

Remanence carrying minerals in meteorites: a journey through an exotic jungle

NASA Astrophysics Data System (ADS)

Rochette, P.; Gattacceca, J.; Uehara, M.

2011-12-01

Well-known remanence carrying minerals in meteorites are magnetite and pyrrhotite, familiar on Earth, and Fe-Ni metal alloys. In Fe-Ni metal the difficulty in interpreting paleomagnetic data is due to the presence of multiple metastable phases which follow complex transformation paths during thermal treatment. A minor phase, tetrataenite (ordered Fe0.5Ni0.5), usually carries most of the remanence [1]. It is intimately mixed with high susceptibility phases (kamacite and taenite), implying strong interaction effects. FeNi phosphide and carbide (schreibersite and cohenite), often associated with metal, are usually overlooked although they may be responsible for the remanence of enstatite chondrites and some lunar basalts, with Tc around 200°C. They are also likely responsible for the claim of "magnetic carbon" found in Canyon Diablo meteorite [2]. Sulfides, a wide variety of which occurs in meteorites, provide even more thrill. Concerning pyrrhotite, there is still imperfect understanding of the observation that not monoclinic but hexagonal pyrrhotite is the ferromagnetic phase present in some martian meteorites and Rumuruti chondrites. The most common sulfide in meteorites, troilite (FeS), is an antiferromagnet (TN= 320°C), showing a susceptibility anomaly at 140°C. Recently a transition toward weak ferromagnetism has been proposed below 60-70 K [3]. However it has been shown subsequently that this weak ferromagnetism is due to impurities of chromite [4] an ubiquitous phase in meteorites that becomes ferromagnetic below a Tc of 40 to 150 K (a wide range linked to the various possible substitutions). Other sulfides found in meteorites show low temperature transitions. Alabandite ( (Fe,Mn)S) and Daubreelite (FeCr2S4) have been reviewed in [3]. Chalcopyrite (FeCuS2), an antiferromagnet at room temperature, shows magnetic ordering of Cu+ ions at 50 K with appearance of weak ferromagnetism [5]. Magnetic properties of cubanite (Fe2CuS3), a RT ferrimagnet found in CI chondrites and Martian meteorites will also be presented [6]. Most cited minerals exhibit high pressure phase transitions in the 3-5 GPa range and thus are remagnetized by moderate impact.

Fluid evolution of Au-Cu zones in Um Balad area, North Eastern Desert of Egypt: Implications from mineral chemistry and fluid inclusions

NASA Astrophysics Data System (ADS)

Abd El Monsef, Mohamed; Salem, Ibrahim; Slobodník, Marek; Ragab, Ahmed

2018-07-01

Scanning electron microscope (SEM), Electron microprobe (EMPA) and fluid inclusion studies of the ore body, as well as geochemical analyses of country rocks were performed to determine the nature and characteristics of the mineralizing fluid responsible for Au-Cu deposits in Um Balad area, Northern Eastern Desert of Egypt. The Um Balad Au-Cu deposits are confined to well developed-quartz veins and veinlets cutting through the hosting country rocks. Petrographic and geochemical investigations of the hosting rocks distinguished between two main rock units; 1) metagabbro-diorite rocks with tholeiitic nature derived in island arc/continental margin tectonic regime, and 2) granodiorite rocks formed from calc-alkaline magma in continental margin regime. Wallrock alterations are represented by propylitic and argillic types. The mineralized quartz veins are striking in NE-SW direction and dipping between (35°-45°) in SE direction, other mineralized mafic dykes enriched with auriferous quartz veinlets are trending NE-SW and dipping 70°/SE. The main ore minerals are represented by gold, chalcopyrite, pyrite, sphalerite, malachite, covellite and goethite. While, geffroyite, cuprite, chrysocolla, pseudomalachite, britholite, wolframite, scheelite, hematite and rutile are detected as minor constituents. Fluid inclusions microthermometry and isochore calculations combined with chlorite geothermometry revealed that the Um Balad deposits were formed at temperature ranging from 305 °C to 325 °C and pressure between (100-500 bar). The mineralization had been developed in the shallow levels, beneath the water table at depth of 350-1760 m, rather than common mesothermal vein-type deposits in Egypt. Magmatic water have been suggested as the main source for the mineralized fluid. The transportation of the gold metal seems to be happen as bisulfide complexes in moderately acidic environment. The deposition was resulted from combination of changes in physico-chemical parameters, temperature and pressure plus the instability of the reduced sulfur complexes. A contamination with metamorphic and/or meteoric water was also proposed that has strong influence during the depositional process.

Positive temperature variation of the bandgap energy in the single-crystalline chalcopyrite semiconductor AgInS{sub 2}

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

Ozaki, Shunji, E-mail: ozaki@el.gunma-u.ac.jp; Horikoshi, Yoshimichi

2014-02-07

Optical absorption spectra have been measured on the single-crystalline chalcopyrite semiconductor AgInS{sub 2} using polarized light at T = 10–300 K. The bandgap energy E{sub g} of AgInS{sub 2} shows unusual temperature dependence at low temperatures. The resultant temperature coefficient ∂E{sub g}/∂T is found to be positive at T < 130 K and negative above 130 K. This result has been successfully explained by considering the effects of thermal expansion and electron–phonon interaction. The free-exciton emission of photoluminescence spectra also indicates positive temperature dependence of the peak energies at low temperatures. The exciton binding energy of AgInS{sub 2} is determined to be 26.4 meV.

Prediction of electronic and optical properties of ZnAl2Te4 defect chalcopyrite semiconductor: an ab-initio study

NASA Astrophysics Data System (ADS)

Mayengbam, Rishikanta; Tripathy, S. K.; Pandey, B. P.

2018-03-01

In this paper, we have investigated the structural, electronic and optical properties of ZnAl2Te4 defect chalcopyrite semiconductor using generalized gradient approximation (GGA) within density functional theory (DFT). We have calculated the optimized lattice constants (a and c) and compared with the available experimental values. The optimized lattice constants have been used to calculate the energy band gap and found to be 1.57 eV. The partial density of states and total density of states have been discussed in detail. The frequency dependent dielectric constant and refractive index have been calculated and plotted in the energy range 0-13 eV. All the above parameters have been compared with the available experimental and theoretical values and found good agreement between them.

Redbed-type gold mineralisation, Kupferschiefer, south-west Poland

NASA Astrophysics Data System (ADS)

Piestrzyński, Adam; Pieczonka, Jadwiga; Głuszek, Adam

2002-06-01

A new type of gold mineralisation containing minor amounts of platinum and palladium has been found proximal to the secondary redox interface located below the Cu-Ag Kupferschiefer orebody of the Polkowice-Sieroszowice mine in the south-western part of the Lubin-Sieroszowice district, Poland. This deposit can be classified as redbed-type gold. Our study shows that gold, platinum and palladium occur in secondary red-coloured sections of the basal Zechstein sedimentary rocks and in the uppermost Weissliegendes sandstone. Noble metal mineralisation occurs within an average interval of 0.22 m, which lies directly below the copper ores. The average grade of the horizon is 2.25 ppm Au, 0.138 ppm Pt and 0.082 ppm Pd with a metal content of several tens of tonnes of gold. A transition zone has been recognised between the gold-bearing horizon and the copper deposit. This transition zone is characterised by the presence of low grades of copper (<0.2 wt%) and elevated gold contents (>0.5 ppm). Native gold accompanied by electrum, mercury-bearing gold, haematite, covellite, chalcocite, bornite and chalcopyrite has been identified in the gold-bearing horizon. In some sections, Pd-arsenides, tetra-auricupride, Co-arsenides, clausthalite, tennantite, digenite, yarrowite, spionkopite and galena have also been noted.

Production of Ultrafine, High-purity Ceramic Powders Using the US Bureau of Mines Developed Turbomill

NASA Technical Reports Server (NTRS)

Hoyer, Jesse L.

1993-01-01

Turbomilling, an innovative grinding technology developed by the U.S. Bureau of Mines in the early 1960's for delaminating filler-grade kaolinitic clays, has been expanded into the areas of particle size reduction, material mixing, and process reaction kinetics. The turbomill, originally called an attrition grinder, has been used for particle size reduction of many minerals, including natural and synthetic mica, pyrophyllite, talc, and marble. In recent years, an all-polymer version of the turbomill has been used to produce ultrafine, high-purity, advanced ceramic powders such as SiC, Si3N4, TiB2, and ZrO2. In addition to particle size reduction, the turbomill has been used to produce intimate mixtures of high surface area powders and whiskers. Raw materials, TiN, AlN, and Al2O3, used to produce a titanium nitride/aluminum oxynitride (TiN/AlON) composite, were mixed in the turbomill, resulting in strength increases over samples prepared by dry ball milling. Using the turbomill as a leach vessel, it was found that 90.4 pct of the copper was extracted from the chalcopyrite during a 4-hour leach test in ferric sulfate versus conventional processing which involves either roasting of the ore for Cu recovery or leaching of the ore for several days.

The enhancing of Au-Ag-Te content in tellurium-bearing ore mineral by bio-oxidation-leaching

NASA Astrophysics Data System (ADS)

Kim, PyeongMan; Kim, HyunSoo; Myung, EunJi; Kim, YoonJung; Lee, YongBum; Park*, CheonYoung

2015-04-01

The purpose of this study is to enhance the content of valuable metals such as Au-Ag-Te in tellurium-bearing minerals by bio-oxidation-leaching. It was confirmed that pyrite, chalcopyrite, sphalerite and galena were produced together with tellurium-bearing minerals including hessite, sylvanite and tellurobismuthite from ore minerals and concentrates through microscopic observation and SEM/EDS analysis. In a bio-oxidation-leaching experiment, with regard to Au, Ag, Te, Cu and Fe, the changes in the amount of leaching and the content of leaching residues were compared and analyzed with each other depending on the adaptation of an indigenous microbe identified as Acidithiobacillus ferrooxidans. As a result of the experiment, the Au-Ag-Te content in tellurium-bearing ore mineral was enhanced in the order of physical oxidation leaching, physical/non-adaptive bio-oxidation-leaching and physical/adaptive biological leaching. It suggests that the bio-oxidation-leaching using microbes adapted in tellurium-bearing ore mineral can be used as a pre-treatment and a main process in a recovery process of valuable metals. "This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"

Hydrothermal alteration, ore fluid characteristics, and gold depositional processes along a trondhjemite-komatiite contact at Tarmoola, Western Australia

USGS Publications Warehouse

Duuring, P.; Hagemann, S.G.; Cassidy, K.F.; Johnson, C.A.

2004-01-01

Tarmoola is a structurally controlled Archean orogenic gold deposit hosted in greenschist facies metamorphosed komatiite and trondhjemite in the Leonora district of the Eastern Goldfields province, Yilgarn craton. High-grade (>1 g/t Au) orebodies are located in komatiite wall rock adjacent to the eastern and northeastern margins of the asymmetrical, north-south-striking, Tarmoola trondhjemite intrusion. Gold-bearing veins post-date trondhjemite emplacement (ca. 2700 Ma), quartz diorite dikes (ca. 2667 Ma), and regional greenschist facies metamorphism. Textures and crosscutting relationships in gold-bearing veins indicate two stages of hydrothermal fluid infiltration associated with a single gold-related hydrothermal event: a volumetrically dominant, but gold-poor, stage I fluid and a gold-rich stage II fluid. Gold-bearing veins contain stage I milky quartz and pyrite that are overprinted by stage II quartz-ankerite-muscovite-chalcopyrite-sphalerite-galena-gold-tellurides ?? albite ?? chlorite ?? fuchsite ?? epidote ?? scheelite. Stage I hydrothermal alteration assemblages are different in trondhjemite and komatiite due to contrasting reactions between a common ore fluid and disparate wall-rock chemistry. Stage II fluid-wall rock interaction was minor compared to stage I and is indicated by the overprinting of stage I mineral assemblages by stage II microveins. Wall-rock alteration proximal to veins in trondhjemite is characterized by replacement of igneous plagioclase, amphibole, biotite, and metamorphic chlorite by hydrothermal quartz, muscovite, ankerite, calcite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold, whereas in proximal alteration in komatiite, metamorphic chlorite and talc are replaced by ankerite, quartz, muscovite, albite, chlorite, fuchsite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold. The stage II fluid was enriched in H2O, CO2, Si, Ca, K, Na, S, Au, Ag, Cu, Pb, W, Bi, As, Mo, Zn, and Te. Based on fluid inclusion studies and stage II mineral equilibria, gold deposited from a homogeneous, neutral to slightly alkaline (pH 5.1-5.5), reduced, low-salinity (<5.5 wt % NaCl equiv) fluid that had a bulk composition of 78 mole percent H2O and 21 mole percent CO2, and trace amounts of CH4, C2H6, H2, Ar, H2S, and He. Gold deposition occurred at 300?? ?? 50??C and 0.5 to 3.0 kbars. Assuming lithostatic fluid pressures, gold precipitated at a 2- to 10-km depth. Stage II gray quartz ??18Ofluid values range from 5.9 to 7.5 per mil, whereas ??Dfluid values calculated from the dehydration of muscovite grains and measured directly from bulk fluid inclusion analyses of stage II gray quartz have ranges of -9 to -35 and -27 to -28 per mil, respectively. Hydrothermal ore fluids were transported from greater crustal depths to the site of gold deposition during the district-scale D3 event by shallowly W dipping, reverse brittle-ductile shear zones in supracrustal rock and along the steeply east dipping trondhjemite contact. Associated subhorizontal east-west shortening caused the reactivation of the eastern trondhjemite margin and subparallel foliation, which facilitated the transport of hydrothermal fluids and the generation of gold-bearing veins and hydrothermal alteration zones in komatiite. East-west-striking fractures in trondhjemite aided the lateral migration of ore fluids away from trondhjemite margins and the formation of east-west-striking gold-bearing veins and broad alteration zones. Gold was most likely transported in the stage II fluid as bisulfide complexes. The sulfidation of trondhjemite and komatiite wall rock by the stage II fluid caused the destabilization of An bisulfide complexes and gold deposition. Potassium, Ca, and CO2 metasomatism of komatiite wall rock may have enhanced gold deposition via the acidification of the stage II fluid. The physicochemical characteristics of the Tarmoola ore fluid and relative timing of gold mineralization are consistent with the Yilgarn-wide,

Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

NASA Astrophysics Data System (ADS)

Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

2006-12-01

Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but displays a more pronounced jump of 1.3‰ at the zinc sulfide boundary and no obvious increase of the δ65Cu in the Si rich zone. Similarly with Zn, there is a 0.35‰ increase of the δ^{64}Zn, but no outer wall increase. Fe, on the other hand, has variation of the same order as transect A, and shows a 0.6‰ increase of the δ56Fe in both the zns-anh and Si rich zones. These profiles are likely the result of a combination of diffusion and advection processes, fluid mineral equilibria, and mineral-mineral equilibria. High δ values of the outer zones likely reflect oxidation reactions with seawater. Processes responsible for isotopic variations within interior zones of the structure are ambiguous. Kinetic effects and biological activity may play a role, as Zn, which is not redox sensitive and only minimally coordination sensitive, has profiles that are qualitatively similar to Cu and Fe, but less analytically pronounced. Our findings are within the range of other published results, and further illustrate such measurable metal isotope variation exists not only on the vent field scale among chimneys, but systematically within chimney walls.

Identification of sulfur sources and isotopic equilibria in submarine hot-springs using multiple sulfur isotopes

NASA Astrophysics Data System (ADS)

McDermott, Jill M.; Ono, Shuhei; Tivey, Margaret K.; Seewald, Jeffrey S.; Shanks, Wayne C.; Solow, Andrew R.

2015-07-01

Multiple sulfur isotopes were measured in metal sulfide deposits, elemental sulfur, and aqueous hydrogen sulfide to constrain sulfur sources and the isotopic systematics of precipitation in seafloor hydrothermal vents. Areas studied include the Eastern Manus Basin and Lau Basin back-arc spreading centers and the unsedimented basalt-hosted Southern East Pacific Rise (SEPR) and sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Chalcopyrite and dissolved hydrogen sulfide (H2S) δ34S values range from -5.5‰ to +5.6‰ in Manus Basin samples, +2.4‰ to +6.1‰ in Lau Basin samples, and +3.7‰ to +5.7‰ in SEPR samples. Values of δ34S for cubic cubanite and H2S range from -1.4‰ to +4.7‰ in Guaymas Basin samples. Multiple sulfur isotope systematics in fluid-mineral pairs from the SEPR and Lau Basin show that crustal host rock and thermochemical reduction of seawater-derived dissolved sulfate (SO4) are the primary sources of sulfur in mid-ocean ridge and some back-arc systems. At PACMANUS and SuSu Knolls hydrothermal systems in the Eastern Manus Basin, a significant contribution of sulfur is derived from disproportionation of magmatic sulfur dioxide (SO2), while the remaining sulfur is derived from crustal host rocks and SO4 reduction. At the sedimented Guaymas Basin hydrothermal system, sulfur sources include crustal host rock, reduced seawater SO4, and biogenic sulfide. Vent fluid flow through fresher, less-mature sediment supplies an increased quantity of reactant organic compounds that may reduce 34S-enriched SO4, while fluid interaction with more highly-altered sediments results in H2S characterized by a small, but isotopically-significant input of 34S-depleted biogenic sulfides. Near-zero Δ33S values in all samples implicate the abiotic processes of SO4 reduction and leaching of host rock as the major contributors to sulfur content at a high temperature unsedimented mid-ocean ridge and at a back-arc system. Δ33S values indicate that SO2 disproportionation is an additional process that contributes sulfur to a different back-arc system and to acid spring-type hydrothermal fluid circulation. At the sedimented Guaymus Basin, near-zero Δ33S values are also observed, despite negative δ34S values that indicate inputs of biogenic pyrite for some samples. In contrast with previous studies reporting isotope disequilibrium between H2S and chalcopyrite, the δ34S values of chalcopyrite sampled from the inner 1-2 mm of a chimney wall are within ±1‰ of δ34S values for H2S in the paired vent fluid, suggesting equilibrium fluid-mineral sulfur isotope exchange at 300-400 °C. Isotopic equilibrium between hydrothermal fluid H2S and precipitating chalcopyrite implies that sulfur isotopes in the chalcopyrite lining across a chimney wall may accurately record past hydrothermal activity.

Chemical Vapor Deposition for Ultra-lightweight Thin-film Solar Arrays for Space

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Raffaelle, Ryne P.; Banger, Kulbinder K.; Jin, Michael H.; Lau, Janice E.; Harris, Jerry D.; Cowen, Jonathan E.; Duraj, Stan A.

2002-01-01

The development of thin-film solar cells on flexible, lightweight, space-qualified substrates provides an attractive cost solution to fabricating solar arrays with high specific power, (W/kg). The use of a polycrystalline chalcopyrite absorber layer for thin film solar cells is considered as the next generation photovoltaic devices. A key technical issues outlined in the 2001 U.S. Photovoltaic Roadmap, is the need to develop low cost, high throughput manufacturing for high-efficiency thin film solar cells. At NASA GRC we have focused on the development of new single-source-precursors (SSPs) and their utility to deposit the chalcopyrite semi-conducting layer (CIS) onto flexible substrates for solar cell fabrication. The syntheses and thermal modulation of SSPs via molecular engineering is described. Thin-film fabrication studies demonstrate the SSPs can be used in a spray CVD process, for depositing CIS at reduced temperatures, which display good electrical properties, suitable for PV devices.

(012)-cut chalcopyrite ZnGeP2 as a high-bandwidth terahertz electro-optic detection crystal

NASA Astrophysics Data System (ADS)

Carnio, B. N.; Greig, S. R.; Firby, C. J.; Zawilski, K. T.; Schunemann, P. G.; Elezzabi, A. Y.

2017-02-01

The detection properties of a chalcopyrite zinc germanium diphosphide (ZnGeP2, ZGP) electro-optic (EO) crystal, having thickness of 1080 μm and cut along the <012> plane, is studied in the terahertz (THz) frequency range. Outstanding phase matching is achieved between the optical probe pulse and the THz frequency components, leading to a large EO detection bandwidth. ZGP has the ability to measure frequencies that are 1.3 and 1.2 times greater than that of ZnTe for crystal thicknesses of 1080 and 500 μm, respectively. Furthermore, the ZGP crystal is able to detect frequency components that are >=4.6 times larger than both ZnSe and GaP (for crystal thicknesses of 1080 μm) and >=2.2 times larger than ZnSe and GaP (for crystal thicknesses of 500 μm).

Bacterial consortium for copper extraction from sulphide ore consisting mainly of chalcopyrite

PubMed Central

Romo, E.; Weinacker, D.F.; Zepeda, A.B.; Figueroa, C.A.; Chavez-Crooker, P.; Farias, J.G.

2013-01-01

The mining industry is looking forward for bacterial consortia for economic extraction of copper from low-grade ores. The main objective was to determine an optimal bacterial consortium from several bacterial strains to obtain copper from the leach of chalcopyrite. The major native bacterial species involved in the bioleaching of sulphide ore (Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, Leptospirillum ferrooxidans and Leptospirillum ferriphilum) were isolated and the assays were performed with individual bacteria and in combination with At. thiooxidans. In conclusion, it was found that the consortium integrated by At. ferrooxidans and At. thiooxidans removed 70% of copper in 35 days from the selected ore, showing significant differences with the other consortia, which removed only 35% of copper in 35 days. To validate the assays was done an escalation in columns, where the bacterial consortium achieved a higher percentage of copper extraction regarding to control. PMID:24294251

Formation of albitite-hosted uranium within IOCG systems: the Southern Breccia, Great Bear magmatic zone, Northwest Territories, Canada

NASA Astrophysics Data System (ADS)

Montreuil, Jean-François; Corriveau, Louise; Potter, Eric G.

2015-03-01

Uranium and polymetallic U mineralization hosted within brecciated albitites occurs one kilometer south of the magnetite-rich Au-Co-Bi-Cu NICO deposit in the southern Great Bear magmatic zone (GBMZ), Canada. Concentrations up to 1 wt% U are distributed throughout a 3 by 0.5 km albitization corridor defined as the Southern Breccia zone. Two distinct U mineralization events are observed. Primary uraninite precipitated with or without pyrite-chalcopyrite ± molybdenite within magnetite-ilmenite-biotite-K-feldspar-altered breccias during high-temperature potassic-iron alteration. Subsequently, pitchblende precipitated in earthy hematite-specular hematite-chlorite veins associated with a low-temperature iron-magnesium alteration. The uraninite-bearing mineralization postdates sodic (albite) and more localized high-temperature potassic-iron (biotite-magnetite ± K-feldspar) alteration yet predates potassic (K-feldspar), boron (tourmaline) and potassic-iron-magnesium (hematite ± K-feldspar ± chlorite) alteration. The Southern Breccia zone shares attributes of the Valhalla (Australia) and Lagoa Real (Brazil) albitite-hosted U deposits but contains greater iron oxide contents and lower contents of riebeckite and carbonates. Potassium, Ni, and Th are also enriched whereas Zr and Sr are depleted with respect to the aforementioned albitite-hosted U deposits. Field relationships, geochemical signatures and available U-Pb dates on pre-, syn- and post-mineralization intrusions place the development of the Southern Breccia and the NICO deposit as part of a single iron oxide alkali-altered (IOAA) system. In addition, this case example illustrates that albitite-hosted U deposits can form in albitization zones that predate base and precious metal ore zones in a single IOAA system and become traps for U and multiple metals once the tectonic regime favors fluid mixing and oxidation-reduction reactions.

Hydrothermal processes in the Edmond deposits, slow- to intermediate-spreading Central Indian Ridge

NASA Astrophysics Data System (ADS)

Cao, Hong; Sun, Zhilei; Zhai, Shikui; Cao, Zhimin; Jiang, Xuejun; Huang, Wei; Wang, Libo; Zhang, Xilin; He, Yongjun

2018-04-01

The Edmond hydrothermal field, located on the Central Indian Ridge (CIR), has a distinct mineralization history owing to its unique magmatic, tectonic, and alteration processes. Here, we report the detailed mineralogical and geochemical characteristics of hydrothermal metal sulfides recovered from this area. Based on the mineralogical investigations, the Edmond hydrothermal deposits comprise of high-temperature Fe-rich massive sulfides, medium-temperature Zn-rich sulfide chimney and low-temperature Ca-rich sulfate mineral assemblages. According to these compositions, three distinctive mineralization stages have been identified: (1) low-temperature consisting largely of anhydrite and pyrite/marcasite; (2) medium-high temperature distinguished by the mineral assemblage of pyrite, sphalerite and chalcopyrite; and (3) low-temperature stage characterized by the mineral assemblage of colloidal pyrite/marcasite, barite, quartz, anglesite. Several lines of evidence suggest that the sulfides were influenced by pervasive low-temperature diffuse flows in this area. The hydrothermal deposits are relatively enriched in Fe (5.99-18.93 wt%), Zn (2.10-10.00 wt%) and Ca (0.02-19.15 wt%), but display low Cu (0.28-0.81 wt%). The mineralogical varieties and low metal content of sulfides in the Edmond hydrothermal field both indicate that extensive water circulation is prevalent below the Edmond hydrothermal field. With regard to trace elements, the contents of Pb, Ba, Sr, As, Au, Ag, and Cd are significantly higher than those in other sediment-starved mid-ocean ridges, which is indicative of contribution from felsic rock sources. Furthermore, the multiphase hydrothermal activity and the pervasive water circulation underneath are speculated to play important roles in element remobilization and enrichment. Our findings deepen our understanding about the complex mineralization process in slow- to intermediate-spreading ridges globally.

Controlling the physical parameters of crystalline CIGS nanowires for use in superstrate configuration using vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Lee, Dongjin; Jeon, H. C.; Kang, T. W.; Kumar, Sunil

2018-03-01

Indium tin oxide (ITO) is a suitable candidate for smart windows and bifacial semi-transparent solar cell applications. In this study, highly crystalline CuInGaSe2 (CIGS) nanowires were successfully grown by horizontal-type vapor phase epitaxy on an ITO substrate. Length, diameter, and density of the nanowires were studied by varying the growth temperature (500, 520, and 560 °C), time (3.5, 6.5, and 9.5 h), and type of catalyst (In, Au, and Ga). Length, diameter, and density of the nanowires were found to be highly dependent on the growth conditions. At an optimized growth period and temperature of 3.5 h and 520 °C, respectively, the length and diameter of the nanowires were found to increase when grown in a catalyst-free environment. However, the density of the nanowires was found to be higher while using a catalyst during growth. Even in a catalyst-free environment, an Indium cluster formed at the bottom of the nanowires. The source of these nanowires is believed to be Indium from the ITO substrate which was observed in the EDS measurement. TEM-based EDS and line EDS indicated that the nanowires are made up of CIGS material with a very low Gallium content. XRD measurements also show the appearance of wurtzite CIS nanowires grown on ITO in addition to the chalcopyrite phase. PL spectroscopy was done to see the near-band-edge emission for finding band-to-band optical transition in this material. Optical response of the CIGS nanowire network was also studied to see the photovoltaic effect. This work creates opportunities for making real solar cell devices in superstrate configuration.

Exploration of gold occurrences in alteration zones at Dungash district, Southeastern Desert of Egypt using ASTER data and geochemical analyses

NASA Astrophysics Data System (ADS)

Salem, S. M.; El Sharkawi, M.; El-Alfy, Z.; Soliman, N. M.; Ahmed, S. E.

2016-05-01

The present study aims at exploration of new gold occurrences in the alteration zones at Dungash district. Processed ASTER images band ratios 7/6 × 4/6 and (7 + 9/8), field geology and mineralogical and geochemical data help characterize three types of alterations in three areas 1 to 3 that may be targeted for Au exploration. Area1 confined to the metavolcanics located in the SE of Dungash gold mine and revealed silicified and sericitized type alterations, composed of quartz, epidote, chlorite, biotite and opaque minerals mainly pyrite and chalcopyrite. Area2 occurs in the gabbro-diorite rocks at Abu Meraiwa area NE of Dungash gold mine, which are rich in kaolinite, illite, sericite, pyrite, arsenopyrite and chalcopyrite that record kaolinitized alteration. Area3 is hosted in carbonaceous listwaenized serpentinite thus indicating the role of listwaenitization type alteration in ore genesis. It is composed of calcite, chromite, pyrite, arsenopyrite, chalcopyrite and Ni-bearing sulphides. Au contents in area 1 range between 0.12 and 14.91 ppm, and between 6.1 and 16.3 ppm in area 2, while gold values in area 3 vary from <0.01 to 0.03 ppm. Dungash district is comprised of Pan-African assemblages of ophiolitic ultramafics thrusted over the island arc metavolcanics of dacitic- andesite composition. Gabbro-diorite rocks are intruded in the ultramafics and the acidic metavolcanics as well as diorite-quartz diorite suite intruded in the intermediate metavolcanics. Several acidic dykes, granitic dykes and quartz veins cut through the different rocks types.

Genetic Pd, Pt, Au, Ag, and Rh mineralogy in Noril'sk sulfide ores

NASA Astrophysics Data System (ADS)

Spiridonov, E. M.; Kulagov, E. A.; Serova, A. A.; Kulikova, I. M.; Korotaeva, N. N.; Sereda, E. V.; Tushentsova, I. N.; Belyakov, S. N.; Zhukov, N. N.

2015-09-01

The undeformed ore-bearing intrusions of the Noril'sk ore field (NOF) cut through volcanic rocks of the Late Permian-Early Triassic trap association folded in brachysynclines. Due to the nonuniform load on the roof of intrusive bodies, most sulfide melts were squeezed, up to the tops of ore-bearing intrusions; readily fusible Ni-Fe-Cu sulfide melts were almost completely squeezed. In our opinion, not only one but two stages of mineralization developed at the Noril'sk deposits: (i) syntrap magmatic and (ii) epigenetic post-trap metamorphic-hydrothermal. All platinum-group minerals (PGM) and minerals of gold are metasomatic in the Noril'sk ores. They replaced sulfide solid solutions and exsolution structures. All types of PGM and Au minerals occur in the ores, varying in composition from pyrrhotite to chalcopyrite, talnakhite, mooihoekite, and rich in galena; they are localized in the inner and outer contact zones and differ only in the quantitative proportions of ore minerals. The aureoles of PGM and Au-Ag minerals are wider than the contours of sulfide bodies and coincide with halos of fluid impact on orebodies and adjacent host rocks. The pneumatolytic PGM and Au-Ag minerals are correlated in abundance with the dimensions of sulfide bodies. Their amounts are maximal in veins of late fusible ore composed of eutectic PbS ss and iss intergrowths, as well as at their contacts. The Pd and Pt contents in eutectic sulfide ores of NOF are the world's highest. In the process of noble-metal mineral formation, the fluids supply Pd, Pt, Au, As, Sb, Sn, Bi, and a part of Te, whereas Fe, Ni, Cu, Pb, Ag, Rh, a part of Te and Pd are leached from the replaced sulfide minerals. The pneumatolytic PGM of the early stage comprises Pd and Pt intermetallic compounds enriched in Au along with Pd-Pt-Fe-Ni-Cu-Sn-Pb(As) and (Pd,Pt,Au)(Sn,Sb,Bi,Te,As) solid solutions. Pneumatolytic PGM and Au minerals of the middle stage are products of solid-phase transformation and recrystallization of early PGM in combination with the newly formed mineral species Sb-paolovite-insizwaite-geversite-maslovite, niggliite, tetraferroplatinum, rustenburgite-atokite-zvyagintsevite, moncheite, majakite, plumbopalladinite, polarite in association with altaite. The late minerals of the middle stage include stannopalladinite, tatianaite-taimyrite, Ag-Pd-Pt tetraauricupride, and cuproauride. PGM and Au-Ag minerals of the late stage are represented by sobolevskite-sudburyite-kotulskite, maslovite-michenerite, low-Sb paolovite, hessite, cabriite, Au-Ag minerals with fineness of 870-003, froodite, Sb-free insizwaite, Bi-free geversite, and Sb-free niggliite. Electrum and küstelite in PGM aggregates are not zoned. Crystals of Au-Ag minerals that grow over PGM minerals are smoothly zoned. Their zoning may be direct (crystal margins are enriched in Ag), inverse, oscillatory, and complex. Despite favorable annealing conditions, exsolution structures are not identified in Au-Ag minerals from the Noril'sk ores. Sperrylite—the latest of pneumatolytic PGM—occurs as metacrysts up to 14 cm in size. Sperrylite, which replaces high-Sb minerals, contains up to 11 wt % Sb. Pneumatolytic noble-metal minerals originated under the effect of the fluids released during crystallization of sulfide melts in an extremely reductive setting and at extremely low fS2; temperature drops from ~450 to ~350°C. Metamorphic-hydrothermal Ag mineralization (native silver, Hg-silver, sulfides and selenides, chalcopyrite-lenaite solid solutions, argentopentlandite), Pd mineralization (vysotskite, palladoarsenide, vincentite, Sb-free Ag-paolovite, malyshevite, native palladium), and Pt mineralization (kharaelakhite, cooperite, native platinum) develop in those parts of orebodies that are affected by low-grade metamorphism.

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

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.

A deep hydrothermal fault zone in the lower oceanic crust, Samail ophiolite Oman

NASA Astrophysics Data System (ADS)

Zihlmann, B.; Mueller, S.; Koepke, J.; Teagle, D. A. H.

2017-12-01

Hydrothermal circulation is a key process for the exchange of chemical elements between the oceans and the solid Earth and for the extraction of heat from newly accreted crust at mid-ocean ridges. However, due to a dearth of samples from intact oceanic crust, or continuous samples from ophiolites, there remain major short comings in our understanding of hydrothermal circulation in the oceanic crust, especially in the deeper parts. In particular, it is unknown whether fluid recharge and discharge occurs pervasively or if it is mainly channeled within discrete zones such as faults. Here, we present a description of a hydrothermal fault zone that crops out in Wadi Gideah in the layered gabbro section of the Samail ophiolite of Oman. Field observations reveal a one meter thick chlorite-epidote normal fault with disseminated pyrite and chalcopyrite and heavily altered gabbro clasts at its core. In both, the hanging and the footwall the gabbro is altered and abundantly veined with amphibole, epidote, prehnite and zeolite. Whole rock mass balance calculations show enrichments in Fe, Mn, Sc, V, Co, Cu, Rb, Zr, Nb, Th and U and depletions of Si, Ca, Na, Cr, Zn, Sr, Ba and Pb concentrations in the fault rock compared to fresh layered gabbros. Gabbro clasts within the fault zone as well as altered rock from the hanging wall show enrichments in Na, Sc, V, Co, Rb, Zr, Nb and depletion of Cr, Ni, Cu, Zn, Sr and Pb. Strontium isotope whole rock data of the fault rock yield 87Sr/86Sr ratios of 0.7046, which is considerably more radiogenic than fresh layered gabbro from this locality (87Sr/86Sr = 0.7030 - 0.7034), and similar to black smoker hydrothermal signatures based on epidote, measured elsewhere in the ophiolite. Altered gabbro clasts within the fault zone show similar values with 87Sr/86Sr ratios of 0.7045 - 0.7050, whereas hanging wall and foot wall display values only slightly more radiogenic than fresh layered gabbro.The secondary mineral assemblages and strontium isotope compositions of the fault rock, clasts and hanging wall indicate interaction with a seawater-derived hydrothermal fluid during oceanic spreading at an ancient mid-ocean ridge. The considerable elemental mass changes in the fault rocks and surrounds compared to the primary layered gabbros suggests extensive hydrothermal fluid flow and exchange deep within the ocean crust.

Influences of the Tonga Subduction Zone on seafloor massive sulfide deposits along the Eastern Lau Spreading Center and Valu Fa Ridge

NASA Astrophysics Data System (ADS)

Evans, Guy N.; Tivey, Margaret K.; Seewald, Jeffrey S.; Wheat, C. Geoff

2017-10-01

This study investigates the morphology, mineralogy, and geochemistry of seafloor massive sulfide (SMS) deposits from six back-arc hydrothermal vent fields along the Eastern Lau Spreading Center (ELSC) and Valu Fa Ridge (VFR) in the context of endmember vent fluid chemistry and proximity to the Tonga Subduction Zone. To complement deposit geochemistry, vent fluid analyses of Cu, Zn, Ba, Pb and H2,(aq) were completed to supplement existing data and enable thermodynamic calculations of mineral saturation states at in situ conditions. Results document southward increases in the abundance of mantle-incompatible elements in hydrothermal fluids (Ba and Pb) and SMS deposits (Ba, Pb, As, and Sb), which is also expressed in the abundance of barite (BaSO4) and galena (PbS) in SMS deposits. These increases correspond to a decrease in distance between the ELSC/VFR and the Tonga Subduction Zone that correlates with a change in crustal lithology from back-arc basin basalt in the north to mixed andesite, rhyolite, and dacite in the south. Barite influences deposit morphology, contributing to the formation of horizontal flanges and squat terraces. Results are also consistent with a regional-scale lowering of hydrothermal reaction zone temperatures from north to south (except at the southernmost Mariner vent field) that leads to lower-temperature, higher-pH vent fluids relative to mid-ocean ridges of similar spreading rates (Mottl et al., 2011). These fluids are Cu- and Zn-poor and the deposits formed from these fluids are Cu-poor but Zn-rich. In contrast, at the Mariner vent field, higher-temperature and lower pH vent fluids are hypothesized to result from higher reaction zone temperatures and the localized addition of acidic magmatic volatiles (Mottl et al., 2011). The Mariner fluids are Cu- and Zn-rich and vent from SMS deposits that are rich in Cu but poor in Zn with moderate amounts of Pb. Thermodynamic calculations indicate that the contrasting metal contents of vent fluids and SMS deposits can be accounted for by vent fluid pH. Wurtzite/sphalerite ((Zn, Fe)S) and galena (PbS) are saturated at higher temperatures in higher-pH, Zn-, Cu-, and Pb-poor ELSC/VFR vent fluids, but are undersaturated at similar temperatures in low-pH, Zn-, Cu-, and Pb-rich vent fluids from the Mariner vent field. Indicators of pH in the ELSC and VFR SMS deposits include the presence of co-precipitated wurtzite and chalcopyrite along conduit linings in deposits formed from higher pH fluids, and different correlations between concentrations of Zn and Ag in bulk geochemical analyses. Significant positive bulk geochemical Zn:Ag correlations occur for deposits at vent fields where hydrothermal fluids have a minimum pH (at 25 °C) < 3.3, while correlations of Zn:Ag are weak or negative for deposits at vent fields where the minimum vent fluid pH (at 25 °C) > 3.6. Data show that the compositions of the mineral linings of open conduit chimneys (minerals present, mol% FeS in (Zn,Fe)S) that precipitate directly from hydrothermal fluids closely reflect the temperature and sulfur fugacity of sampled hydrothermal fluids. These mineral lining compositions thus can be used as indicators of hydrothermal fluid temperature and composition (pH, metal content, sulfur fugacity).

Matrix Effects Originating from Coexisting Minerals and Accurate Determination of Stable Silver Isotopes in Silver Deposits.

PubMed

Guo, Qi; Wei, Hai-Zhen; Jiang, Shao-Yong; Hohl, Simon; Lin, Yi-Bo; Wang, Yi-Jing; Li, Yin-Chuan

2017-12-19

Except for extensive studies in core formation and volatile-element depletion processes using radiogenic Ag isotopes (i.e., the Pd-Ag chronometer), recent research has revealed that the mass fractionation of silver isotopes is in principle controlled by physicochemical processes (e.g., evaporation, diffusion, chemical exchange, etc.) during magmatic emplacement and hydrothermal alteration. As these geologic processes only produce very minor variations of δ 109 Ag from -0.5 to +1.1‰, more accurate and precise measurements are required. In this work, a robust linear relationship between instrumental mass discrimination of Ag and Pd isotopes was obtained at the Ag/Pd molar ratio of 1:20. In Au-Ag ore deposits, silver minerals have complex paragenetic relationships with other minerals (e.g., chalcopyrite, sphalerite, galena, pyrite, etc.). It is difficult to remove such abundant impurities completely because the other metals are tens to thousands of times richer than silver. Both quantitative evaluation of matrix effects and modification of chemical chromatography were carried out to deal with the problems. Isobaric inferences (e.g., 65 Cu 40 Ar + to 105 Pd, 208 Pb 2+ to 104 Pd, and 67 Zn 40 Ar + to 107 Ag + ) and space charge effects dramatically shift the measured δ 109 Ag values. The selection of alternative Pd isotope pairs is effective in eliminating spectral matrix effects so as to ensure accurate analysis under the largest possible ranges for metal impurities, which are Cu/Ag ≤ 50:1, Fe/Ag ≤ 600:1, Pb/Ag ≤ 10:1, and Zn/Ag ≤ 1:1, respectively. With the modified procedure, we reported silver isotope compositions (δ 109 Ag) in geological standard materials and typical Au-Ag ore deposit samples varying from -0.029 to +0.689 ‰ with external reproducibility of ±0.009-0.084 ‰. A systemic survey of δ 109 Ag (or ε 109 Ag) variations in rocks, ore deposits, and environmental materials in nature is discussed.

Identifying Au-based Te alloys for optical data storage

NASA Astrophysics Data System (ADS)

Wamwangi, D.; Detemple, R.; Woeltgens, H.-W.; Wuttig, M.; Zhang, X.

2004-06-01

Au18Sb23Te59 and Au19In26Te55 have been investigated to determine their suitability as phase change recording alloys. Recrystallization experiments identify Au18Sb23Te59 as a suitable phase change material with a recrystallization time of 110 ns and high optical contrast. Coupled to the high optical contrast is a considerable density increase of 4% upon crystallization which allows phase change recording for the Au18Sb23Te59 alloy. On the other hand no recrystallization has been observed optically for Au19In26Te55 due to its low optical contrast of less than 1%. This is related to a lower density contrast of 2%. The crystallization for the Au18Sb23Te59 and Au19In26Te55 alloys observed from temperature-dependent sheet resistance measurements have yielded transition temperatures of 113 and 175 °C, and activation barriers of 1.61±0.01 eV and 2.42±0.02 eV, respectively. We report a cubic structure (a=2.99±0.002 Å) for the Au18Sb23Te59 alloy and a chalcopyrite structure (a=6.50±0.018 Å and 12.27±0.025 Å) for the Au19In26Te55 material. These results confirm that suitable phase change alloys possess cubic structures rather than the chalcopyrite structure typical for sp3 bonded semiconductors.

Publications - SR 60 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

Mapping Advisory Board STATEMAP Publications Geophysics Program Information Geophysical Survey ; Aeromagnetic Survey; Airborne Geophysical Survey; Alaska Highway Corridor; Alaska Peninsula; Alaska, State of ; Bismuth; Chalcopyrite; Chandalar Mining District; Cleary Summit; Coal; Conductivity Survey; Construction

The role of carbon dioxide in the transport and fractionation of metals by geological fluids

NASA Astrophysics Data System (ADS)

Kokh, Maria A.; Akinfiev, Nikolay N.; Pokrovski, Gleb S.; Salvi, Stefano; Guillaume, Damien

2017-01-01

Although carbon dioxide is one of the major components of crustal fluids responsible for ore deposit formation, its effect on transport and precipitation of metals remains unknown, due to a lack of direct experimental data and physical-chemical models for CO2-rich fluids. To fill this gap, we combined laboratory experiments and thermodynamic modeling to systematically quantify the role played by CO2 for the solubility of economically important metals such as Fe, Cu, Zn, Au, Mo, Pt, Sn under hydrothermal conditions. Solubility measurements of common ore minerals of these metals (FeS2, CuFeS2, ZnS, Au, MoS2, PtS, SnO2) were performed, using a flexible-cell reactor equipped with a rapid sampling device, in a single-phase fluid (CO2-H2O-KCl) at 350-450 °C and 600-750 bar, buffered with iron sulfide and oxide and alkali-aluminosilicate mineral assemblages. In addition, another type of experiments was conducted to measure gold solubility in more sulfur-rich supercritical CO2-H2O-S-NaOH fluids at 450 °C and 700 bar using a batch reactor that allows fluid quenching. Our results show that the solubilities of Si, Au, Mo, Pt and Cu either decrease (within <1 log unit) or remain constant upon CO2 increase, whereas those of Fe, Zn and Sn increase significantly (>1 log unit) with CO2 contents in the fluid increasing from 0 to 50 wt%. These data were interpreted using a simple model that does not require any new adjustable parameters, and is based on the dielectric constant of the H2O-CO2 solvent and on the Born solvation parameter for the dominant metal-bearing species in an aqueous fluid. Our predictions using this model suggest that in a supercritical CO2-H2O-S-salt fluid typical of metamorphic Au deposits, in equilibrium with pyrite and chalcopyrite, the Cu/Fe ratio decreases by up to 2 orders of magnitude with an increase of CO2 content from 0 to 70 wt%. This effect is due to the decrease of the fluid dielectric constant in the presence of CO2, which favors the stability of neutral species (FeCl20) compared to charged ones (CuCl2-). Our results explain the Fe enrichment and Cu depletion in metamorphic gold deposits formed by CO2-rich fluids. The transport of gold is unfavorable in the presence of CO2 only in S-rich (>0.5 wt% S) fluids in which Au forms the negatively charged Au(HS)2- and Au(HS)S3- complexes. By contrast, it is only weakly affected in S-poor (<0.1 wt% S) acidic-to-neutral fluids in which the uncharged Au(HS)0 complex predominates. Thus, even at very high CO2 contents (>50 wt% CO2), the capacity of such fluids to transport gold (up to 100s ppb Au) remains comparable to that of aqueous fluids. These findings are in agreement with analyses of natural fluid inclusions in metamorphic deposits. In more saline oxidizing and S-rich fluids such as those in magmatic porphyry Cu-Au deposits, the Fe, Cu, and Au solubilities in the presence of CO2 decrease by ∼1 order of magnitude with CO2 increasing to 20-30 wt%, following the decrease in the stability of their dominant charged species (FeCl42-, CuCl2-, Au(HS)2- and Au(HS)S3-), but stay almost constant at higher CO2 contents (30-70 wt%) as controlled by the neutral species (FeCl20, Cu(HS)0 and Au(HS)0). Such solubility trends suggest a new potential trigger of ore precipitation in porphyry systems by CO2 pulses from the magmatic chamber, which may operate along with commonly admitted depositional mechanisms such as cooling, vapor-brine immiscibility, and water-rock interaction. The direct effect of CO2 on the mobility of Pt and Mo, metals that likely form hydrogen sulfide and oxy-hydroxide complexes, respectively, is expected to be weak in most settings. Among the studied elements, Sn is the only one whose solubility may be favored at high CO2 content (>20 wt%) due to carbonate complexing. This study demonstrates, for the first time, that, contrary to common belief, the presence of CO2 in a supercritical fluid may lead to enhanced mobility or, on contrary, to massive precipitation of some metals, depending on salinity and sulfur content, and, more generally, to significant fractionations between different metals.

Gene identification and substrate regulation provide insights into sulfur accumulation during bioleaching with the psychrotolerant acidophile Acidithiobacillus ferrivorans.

PubMed

Liljeqvist, Maria; Rzhepishevska, Olena I; Dopson, Mark

2013-02-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments.

Gene Identification and Substrate Regulation Provide Insights into Sulfur Accumulation during Bioleaching with the Psychrotolerant Acidophile Acidithiobacillus ferrivorans

PubMed Central

Liljeqvist, Maria; Rzhepishevska, Olena I.

2013-01-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments. PMID:23183980

Barite-polymetallic mineralization of Zmeinogorsk ore district and some genetic aspects of its formation

NASA Astrophysics Data System (ADS)

Bestemianova, K. V.; Grinev, O. M.

2017-12-01

Zmeinogorsky ore district is located in the northwest part of Ore Altai megatrough, which has long-lasting history of its development and complicated geological structure. Within the ore district, which is the northwest part of the devonian Zmeinogorsk-Bystrushinsky trough, ore mineralization is associated with the system of northwest border faults and cross branch faults. There were four main stages and five phases of minerogenesis. The first stage is the stage of oregenesis beginning and quartz-chlorite-sericite wall-rock alteration rocks formation. Ore deposition and intense tectonics took place during the second stage. The third stage is the most longstanding and productive ore formation stage. There are five distinct minerogenesis phases within this stage. The fourth stage expressed in erosion development and supergene alteration of already formed ore bodies with oxidation zone formation. Main ore minerals are pyrite, chalcopyrite, sphalerite and galena. Minor minerals are tetrahedrite, bornite, tennantite and chalcocite. Precious metals minerals are acanthite, gold, electrum, gold and silver amalgams. Barren minerals are barite, quartz, calcite, gypsum. According to obtained data average isotopic composition of third stage sulphides is: pyrite -0,2‰, chalcopyrite 0‰, galena +0,5‰, sphalerite -1,2‰ for the first complex; chalcopyrite -1,9‰, galena -3,4‰, sphalerite -2,3‰, tetrahedrite -3,7‰ for the second complex; tennantite -12,8‰, bornite -8,9‰ for the third complex. Sulfur isotopic compoisiton variations indicate source inhomogeneity. Thus, there was dominant source change from mantle one in the beginning to crustal one in the end. Main oregenesis stages took place in the range of temperatures between 170 and 210°С and in the mineral-forming solutions salinity range between 3 and 10 wt % NaCl equiv.

Concealed basalt-matrix diatremes with Cu-Au-Ag-(Mo)-mineralized xenoliths, Santa Cruz Porphyry Cu-(Mo) System, Pinal County, Arizona

USGS Publications Warehouse

Vikre, Peter; Graybeal, Frederick T.; Koutz, Fleetwood R.

2014-01-01

The Santa Cruz porphyry Cu-(Mo) system near Casa Grande, Arizona, includes the Sacaton mine deposits and at least five other concealed, mineralized fault blocks with an estimated minimum resource of 1.5 Gt @ 0.6% Cu. The Late Cretaceous-Paleocene system has been dismembered and rotated by Tertiary extension, partially eroded, and covered by Tertiary-Quaternary basin-fill deposits. The mine and mineralized fault blocks, which form an 11 km (~7 miles) by 1.6 km (~1 mile) NE-SW–trending alignment, represent either pieces of one large deposit, several deposits, or pieces of several deposits. The southwestern part of the known system is penetrated by three or more diatremes that consist of heterolithic breccia pipes with basalt and clastic matrices, and subannular tuff ring and maar-fill sedimentary deposits associated with vents. The tephra and maar-fill deposits, which are covered by ~485 to 910 m (~1,600–3,000 ft) of basin fill, lie on a mid-Tertiary erosion surface of Middle Proterozoic granite and Late Cretaceous porphyry, which compose most xenoliths in pipes and are the host rocks of the system. Some igneous xenoliths in the pipes contain bornite-chalcopyrite-covellite assemblages with hypogene grades >1 wt % Cu, 0.01 ounces per ton (oz/t) Au, 0.5 oz/t Ag, and small amounts of Mo (<0.01 wt %). These xenoliths were derived from mineralized rocks that have not been encountered in drill holes, and attest to additional, possibly higher-grade deposits within or subjacent to the known system.The geometry, stratigraphy, and temporal relationships of pipes and tephras, interpreted from drill hole spacing and intercepts, multigenerational breccias and matrices, reequilibrated and partially decomposed sulfide-oxide mineral assemblages, melted xenoliths, and breccia matrix compositions show that the diatremes formed in repeated stages. Initial pulses of basalt magma fractured granite, porphyry, and other crustal rocks during intrusion, transported multi-sized fragments of these rocks upward, and partially melted small fragments. Rapid decompression of magma induced catastrophic devolatilization that ruptured overlying rocks to the surface, and generated fragment-volatile suspensions that abraded conduits into near-vertical cylindrical structures. Fragments entrained in suspensions were milled and sorted, and ejected as basal surge, pyroclastic deposits, and airfall tephra that built tuff rings around vents and filled vent depressions. Comminuted m- to mm-sized fragments of wall rocks in magma and suspensions that remained in conduits solidified as heterolithic breccias. Subsequent pulses of basalt magma ascended through the same conduits, brecciated older heterolithic breccias, devolatilized, and quenched, leaving two or more generations of nested and mingled heterolithic breccias and internal zones of fluidized fragments. Tephra and maar-fill deposits from later eruptions are composed of more hydrous and oxidized minerals than earlier tephras, reflecting a higher proportion of water in transport fluid which, based on fluid inclusion populations in mineralized xenoliths, was saline water and CO2. The large vertical extent (~600 m; ~2,000 ft) of basalt matrix in pipes, near-paleosurface matrix vesiculation, and plastically deformed basalt lapilli indicates that diatreme eruptions were predominantly phreatic.Diatreme xenoliths represent crustal stratigraphy and, as in the Santa Cruz system, provide evidence of concealed mineral resources that can guide exploration drilling through cover. Vectors to the source of bornite-dominant xenoliths containing >1% Cu and significant Au and Ag could be determined by refinement of breccia pipe geometries, by reassembly of mineralized fault blocks using modal, chemical, and temporal characteristics of hydrothermal mineral assemblages and fluid inclusions, and by paleodrainage analysis.

New potassium-argon data on the age of mineralization and metamorphism in the Willow Creek mining district, southern Talkeetna Mountains, Alaska: A section in The United States Geological Survey in Alaska: Accomplishments during 1977

USGS Publications Warehouse

Silberman, Miles L.; Csejtey, Bela; Smith, James G.; Lanphere, Marvin A.; Wilson, Frederic H.

1978-01-01

The now largely abandoned Willow Creek mining district, southern Talkeetna Mountains, Alaska, produced nearly $18,000,000 in gold and minor silver between 1909 and the early 1950's. Mineralized quartz veins, which contain gold and silver along with minor quantities of base metals (in pyrite, galena, chalcopyrite, sphalerite, molybdenite, and arsenopyrite), cut Late Cretaceous and early Tertiary tonalite and quartzmica schist of probable Jurassic age (Ray, 1954; Silberman and others, 1976; Bela Csejtey, Jr., unpub. data, 1978).

Orickite and coyoteite, two new sulfide minerals from Coyote Peak, Humboldt County, California.

USGS Publications Warehouse

Erd, Richard C.; Czamanske, G.K.

1983-01-01

Minute quantities of orickite and coyoteite occur with rare alkali iron sulphides in a mafic alkalic diatreme near Orick, Humboldt County. Orickite, NaxKyCu0.95Fe1.06zH2O (x,y < 0.03, z < 0.5), is hexagonal, a 3.695, c 6.16 A, D 4.212 g/cm3, Z = 4. The strongest XRD reflections are 3.08(100), 3.20(90), 2.84(60), 1.73(55), 1.583(30) A. The mineral is brass yellow, opaque, weakly pleochroic, but strongly anisotropic (greyish brown to greyish blue) in reflected light. Orickite is compositionally near to Fe-rich chalcopyrite, but it may be related to synthetic chalcogenides with a distorted wurtzite-(2H) structure. Coyoteite, NaFe3S5.2H2O, is triclinic, P1 or P1, a 7.409(8), b 9.881(6), c 6.441(3) A, alpha 100o25(3)', beta 104o37(5)', gamma 81o29(5)', D 2.879 g/cm3, Z = 2; strongest XRD reflections are 5.12(100), 7.13(90), 3.028(80), 3.080(70), 9.6(60), 5.60(60) A. Coyoteite is black, opaque, weakly pleochroic (pale brownish grey) and strongly anisotropic (grey to dull golden orange) in reflected light. It is unstable under normal atmospheric conditions. -J.A.Z.

Abandoned mine slags analysis by EPMA WDS X-ray mapping

NASA Astrophysics Data System (ADS)

Guimarães, F.; Rosado, L.; Morais, C.; Candeias, A. E.; Pinto, A. P.; Mirão, J.

2010-02-01

Mining activity on the Iberian Pyritic Belt (Portugal and Spain) started before Phoenician times, became particularly intense during the Roman occupation of the Iberian Peninsula (for gold), and after the industrial revolution (for gold, copper, zinc, lead and sulphur). The commonest ore of this region is a massive polymetalic sulphide accumulation, where pyrite (FeS2) is the main mineral, with variable concentrations of chalcopyrite (CuFeS2), sphalerite (ZnS), galena (PbS), arsenopyrite (FeAsS2), other sulphides and sulfosalts which include minor elements like Mn, Co, Ni, Se, Cd, Sb, Te, Hg and Bi. Some of the main and minor elements of these ores are hazardous and the drainage basins of pollutant source areas often induce health concerns in the resident population. Electron probe microanalysis study followed previous optical and XRD analysis of the slags. The study focused on the identification of phases how sulphide and metallic phases are distributed within the material and infer about leachable elements during weathering. Electron probe X-ray maps show evidences of different behaviour between the elements: Ca and Zn are completely leached; iron is retained in oxyhydroxides, lead and arsenic precipitate as sulphates. Electron probe microanalysis studies are essential to understand complex materials as earth materials. Nevertheless, care is required to a correct interpretation of data and most quantitative compositional data are not trustworthy.

Leaching: use of a thermophilic and chemoautotrophic microbe.

PubMed

Brierley, C L; Murr, L E

1973-02-02

A chemoautotrophic, thermophilic, and acidophilic microorganism capable of oxidizing reduced sulfur and iron compounds and leaching concentrates of molybdenite and chalcopyrite at 60 degrees C has been characterized by transmission and scanning electron microscopy. This constitutes the first direct observations of microorganisms on ore fines.

Chemical and physical insight on the local properties of the phosphides XSiP2 (X = Be, Mg, Cd, Zn and Hg) under pressure: from first principles calculations

NASA Astrophysics Data System (ADS)

Ouahrani, Tarik

2013-09-01

Local properties of the XSiP2 (X = Be, Mg, Cd, Zn and Hg) compounds are revisited through the partition of static thermodynamic properties under pressure. We pay attention to the metallization that occurs when the investigated compounds undergo a phase transition from chalcopyrite to the NaCl structure. Electron localization function analysis shows that the local valence basin attractors values decrease as a function of pressure. As the pressure increases, the tetragonal distortion ( c/ a) diminishes while the degree of ionicity enhances. In addition, by means of atom in molecule approach, atomic-like local compressibility and pressures are analyzed. We found that the basins volumes of the investigated compounds in the NaCl phase have lower compressibilities than those in the chalcopyrite phase. According to the predicted core-valence basins, the phosphorus cation is found to be the more affected by the hydrostatic pressure.

First-principles study of structural, electronic, linear and nonlinear optical properties of Ga{2}PSb ternary chalcopyrite

NASA Astrophysics Data System (ADS)

Ouahrani, T.; Reshak, A. H.; de La Roza, A. Otero; Mebrouki, M.; Luaña, V.; Khenata, R.; Amrani, B.

2009-12-01

We report results from first-principles density functional calculations using the full-potential linear augmented plane wave (FP-LAPW) method. The generalized gradient approximation (GGA) and the Engel-Vosko-generalized gradient approximation (EV-GGA) were used for the exchange-correlation energy of the structural, electronic, linear and nonlinear optical properties of the chalcopyrite Ga2PSb compound. The valence band maximum (VBM) is located at the Γv point, and the conduction band minimum (CBM) is located at the Γc point, resulting in a direct band gap of about 0.365 eV for GGA and 0.83 eV for EV-GGA. In comparison with the experimental one (1.2 eV) we found that EV-GGA calculation gives energy gap in reasonable agreement with the experiment. The spin orbit coupling has marginal influence on the optical properties. The ground state quantities such as lattice parameters (a, c and u), bulk modules B and its pressure derivative B^primeare evaluated.

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

Analysis of the structural, electronic and optic properties of Ni doped MgSiP{sub 2} semiconductor chalcopyrite compound

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

Kocak, Belgin, E-mail: koakbelgin@gmail.com; Ciftci, Yasemin Oztekin, E-mail: yasemin@gazi.edu.tr

2016-03-25

The structural, electronic band structure and optic properties of the Ni doped MgSiP{sub 2} chalcopyrite compound have been performed by using first-principles method in the density functional theory (DFT) as implemented in Vienna Ab-initio Simulation Package (VASP). The generalized gradient approximation (GGA) in the scheme of Perdew, Burke and Ernzerhof (PBE) is used for the exchange and correlation functional. The present lattice constant (a) follows generally the Vegard’s law. The electronic band structure, total and partial density of states (DOS and PDOS) are calculated. We present data for the frequency dependence of imaginary and real parts of dielectric functions ofmore » Ni doped MgSiP{sub 2}. For further investigation of the optical properties the reflectivity, refractive index, extinction coefficient and electron energy loss function are also predicted. Our obtained results indicate that the lattice constants, electronic band structure and optical properties of this compound are dependent on the substitution concentration of Ni.« less

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.

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

USGS Publications Warehouse

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

2018-01-01

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

Mineralogy, paragenesis, and mineral zoning of the Bulldog Mountain vein system, Creede District, Colorado

USGS Publications Warehouse

Plumlee, Geoffrey S.; Heald Whitehouse-Veaux, Pamela

1994-01-01

The Bulldog Mountain vein system, Creede district, Colorado, is one of four major epithermal vein systems from which the bulk of the district's historical Ag-Pb-Zn-Cu production has come. Ores deposited along the vein system were discovered in 1965 and were mined from 1969 to 1985.Six temporally gradational mineralization stages have been identified along the Bulldog Mountain vein system, each with a characteristic suite of minerals deposited or leached and a characteristic distribution within the vein system; some of these stages are also strongly zoned within the vein system. Stage A was dominated by deposition of rhodochrosite along the lower levels of the Bulldog Mountain ore zone. Stage B in the northern parts of the ore zone is characterized by abundant fine-grained sphalerite and galena, with lesser tetrahedrite and minor chlorite and hematite. With increasing elevation to the south, stage B ores become progressively more barite and silver rich, with alternating barite and fine-grained sphalerite + galena generations; native silver + or - acanthite assemblages are also locally abundant within southern stage B barite sulfide ores, whereas chalcopyrite and other Cu and Ag sulfides and sulfosalts are present erratically in minor amounts. Stage C in the upper and northern portions of the ore zone is characterized by abundant quartz and fluorite, minor adularia, hematite, Mn siderite, sphalerite, and galena, and major leaching of earlier barite; to the south, some barite and sulfides may have been deposited. Stage D sphalerite and galena were deposited in the upper and northern portions of the ore zone; a barite- and silver-rich facies of this stage may also be present in the southern portions of the vein system. Late in stage D, mineralogically complex assemblages containing chalcopyrite, tetrahedrite, polybasite, bornite, pyrargyrite, and a variety of other sulfides and sulfosalts were deposited in modest amounts throughout the vein system. This complex assemblage marked the transition to stage E. During stage E, the final sulfide stage, abundant botryoidal pyrite and marcasite with lesser stibnite, sphalerite, and sulfosalts were deposited primarily along the top of the Bulldog Mountain ore zone. Stage F, the final mineralization stage along the vein system, is marked by wire silver and concurrent leaching of earlier sulfides and sulfosalts; this stage may reflect the transition to a supergene environment.The sequence of mineralization stages identified in this study along the Bulldog Mountain system can be correlated with corresponding stages identified by other researchers along the OH and P veins, and the southern Amethyst vein system. Mineral zoning patterns identified along the Bulldog Mountain vein system also parallel larger scale zoning patterns across the central and southern Creede district.The complex variations in mineral assemblages documented in time and space along the Bulldog Mountain vein system were produced by the combined effects of many processes. Large-scale changes in vein mineralogy over time produced discrete mineralization stages. Short-term mineralogical fluctuations produced complex interbanding of mineralogically distinct generations. Fluid chemistry evolution within the vein system produced large-scale lateral zoning patterns within certain stages. Hypogene leaching substantially modified the distributions of some minerals. Finally, structural activity, mineral deposition, and mineral leaching modified fluid flow pathways repeatedly during mineralization, and so added to the complex mineral distribution patterns within the vein system.

Stable aqueous based Cu nanoparticle ink for printing well-defined highly conductive features on a plastic substrate.

PubMed

Jeong, Sunho; Song, Hae Chun; Lee, Won Woo; Lee, Sun Sook; Choi, Youngmin; Son, Wonil; Kim, Eui Duk; Paik, Choon Hoon; Oh, Seok Heon; Ryu, Beyong-Hwan

2011-03-15

With the aim of inkjet printing highly conductive and well-defined Cu features on plastic substrates, aqueous based Cu ink is prepared for the first time using water-soluble Cu nanoparticles with a very thin surface oxide layer. Owing to the specific properties, high surface tension and low boiling point, of water, the aqueous based Cu ink endows a variety of advantages over conventional Cu inks based on organic solvents in printing narrow conductive patterns without irregular morphologies. It is demonstrated how the design of aqueous based ink affects the basic properties of printed conductive features such as surface morphology, microstructure, conductivity, and line width. The long-term stability of aqueous based Cu ink against oxidation is analyzed through an X-ray photoelectron spectroscopy (XPS) based investigation on the evolution of the surface oxide layer in the aqueous based ink.

Design and exploration of semiconductors from first principles: A review of recent advances

NASA Astrophysics Data System (ADS)

Oba, Fumiyasu; Kumagai, Yu

2018-06-01

Recent first-principles approaches to semiconductors are reviewed, with an emphasis on theoretical insight into emerging materials and in silico exploration of as-yet-unreported materials. As relevant theory and methodologies have developed, along with computer performance, it is now feasible to predict a variety of material properties ab initio at the practical level of accuracy required for detailed understanding and elaborate design of semiconductors; these material properties include (i) fundamental bulk properties such as band gaps, effective masses, dielectric constants, and optical absorption coefficients; (ii) the properties of point defects, including native defects, residual impurities, and dopants, such as donor, acceptor, and deep-trap levels, and formation energies, which determine the carrier type and density; and (iii) absolute and relative band positions, including ionization potentials and electron affinities at semiconductor surfaces, band offsets at heterointerfaces between dissimilar semiconductors, and Schottky barrier heights at metal–semiconductor interfaces, which are often discussed systematically using band alignment or lineup diagrams. These predictions from first principles have made it possible to elucidate the characteristics of semiconductors used in industry, including group III–V compounds such as GaN, GaP, and GaAs and their alloys with related Al and In compounds; amorphous oxides, represented by In–Ga–Zn–O transparent conductive oxides (TCOs), represented by In2O3, SnO2, and ZnO; and photovoltaic absorber and buffer layer materials such as CdTe and CdS among group II–VI compounds and chalcopyrite CuInSe2, CuGaSe2, and CuIn1‑ x Ga x Se2 (CIGS) alloys, in addition to the prototypical elemental semiconductors Si and Ge. Semiconductors attracting renewed or emerging interest have also been investigated, for instance, divalent tin compounds, including SnO and SnS; wurtzite-derived ternary compounds such as ZnSnN2 and CuGaO2; perovskite oxides such as SrTiO3 and BaSnO3; and organic–inorganic hybrid perovskites, represented by CH3NH3PbI3. Moreover, the deployment of first-principles calculations allows us to predict the crystal structure, stability, and properties of as-yet-unreported materials. Promising materials have been explored via high-throughput screening within either publicly available computational databases or unexplored composition and structure space. Reported examples include the identification of nitride semiconductors, TCOs, solar cell photoabsorber materials, and photocatalysts, some of which have been experimentally verified. Machine learning in combination with first-principles calculations has emerged recently as a technique to accelerate and enhance in silico screening. A blend of computation and experimentation with data science toward the development of materials is often referred to as materials informatics and is currently attracting growing interest.

Ferrotochilinite, 6FeS · 5Fe(OH)2, a new mineral from the Oktyabr'sky deposit, Noril'sk district, Siberia, Russia

NASA Astrophysics Data System (ADS)

Pekov, I. V.; Sereda, E. V.; Polekhovsky, Yu. S.; Britvin, S. N.; Chukanov, N. V.; Yapaskurt, V. O.; Bryzgalov, I. A.

2013-12-01

A new mineral, ferrotochilinite, ideally 6FeS · 5Fe(OH)2, was found at the Oktyabr'sky Mine, Oktyabr'skoe Cu-Ni deposit, Noril'sk, Krasnoyarsk krai, Siberia, Russia. It is associated with ferrovalleriite, magnetite and Fe-rich, chlorite-like phyllosilicate in the cavities of pentlandite-mooihoekite-cubanite ore with subordinate magnetite and chalcopyrite. Ferrotochilinite occurs as flattened on [001], prismatic to elongated lamellar crystals up to 0.1 × 0.5 × 3.2 mm, typically split and curved. Aggregates (up to 6.5 mm in size) are fanlike, rosette-like, or chaotic. Ferrotochilinite is dark bronze. The streak is black. The luster is moderately metallic. The Mohs' hardness is ca. 1; VHN is 13 kg/mm2. Cleavage is {001} perfect, micalike. Individuals are flexible, inelastic. D(calc) = 3.467 g/cm3. In reflected light, ferrotochilinite is gray, with the hue changing from pale beige to bluish; bireflectance is distinct. Anisotropy is distinct, with gray bluish to yellowish beige rotation colors. No internal reflections. Reflectance values [ R min- R max, % (λ, nm)] are: 11.6-11.4 (470), 11.2-12.4 (546), 11.1-13.6 (589), 11.0-15.5 (650). The IR spectrum shows the presence of (OH) groups bonded with Fe cations and the absence of H2O molecules. Chemical composition (wt %; electron probe; H content is calculated) is as follows: 0.02 Mg, 61.92 Fe, 0.03 Ni, 0.09 Cu, 19.45 S, 16.3 O, 1.03 H calc; the total is 98.84. The empirical formula calculated on the basis of 6 S atoms is: Mg0.01Fe10.96Ni0.005Cu0.015S6(OH)10.07 = (Fe5.98Cu0.0015Ni0.005)Σ6S6(OH)9.80(Fe{4.89/2+}Mg0.01)Σ4.90(OH)9.80Fe{0.09/3+}(OH)0.27. Ferrotochilinite is monoclinic, space group is C2/ m, Cm or C2, the unit-cell dimensions are: a = 5.463(5), b = 15.865(17), c = 10.825(12) Å, β = 93.7(1)°, V = 936(3) Å3, Z = 2. The strongest reflections in the X-ray powder diffraction pattern ( d, Å- I[ hkl]) are: 10.83-13[001], 5.392-100[002], 3.281-7[023], 2.777-7[150], 2.696-12[004, ], 2.524-12[, ], 2.152-8[134, 153], 1.837-11[135, ]. Ferrotochilinite is a structural analog of tochilinite, with Fe2+ instead of Mg in the hydroxide part. The type specimen is deposited in Fersman Mineralogical Museum of Russian Academy of Sciences, Moscow.

Mesozoic Magmatism and Base-Metal Mineralization in the Fortymile Mining District, Eastern Alaska - Initial Results of Petrographic, Geochemical, and Isotopic Studies in the Mount Veta Area

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Slack, John F.; Aleinikoff, John N.; Mortensen, James K.

2009-01-01

We present here the initial results of a petrographic, geochemical, and isotopic study of Mesozoic intrusive rocks and spatially associated Zn-Pb-Ag-Cu-Au prospects in the Fortymile mining district in the southern Eagle quadrangle, Alaska. Analyzed samples include mineralized and unmineralized drill core from 2006 and 2007 exploration by Full Metal Minerals, USA, Inc., at the Little Whiteman (LWM) and Fish prospects, and other mineralized and plutonic samples collected within the mining district is part of the USGS study. Three new ion microprobe U-Pb zircon ages are: 210 +- 3 Ma for quartz diorite from LWM, 187 +- 3 Ma for quartz monzonite from Fish, and 70.5 +- 1.1 Ma for altered rhyolite porphyry from Fish. We also present 11 published and unpublished Mesozoic thermal ionization mass spectrometric U-Pb zircon and titanite ages and whole-rock geochemical data for the Mesozoic plutonic rocks. Late Triassic and Early Jurassic plutons generally have intermediate compositions and are slightly foliated, consistent with synkinematic intrusion. Several Early Jurassic plutons contain magmatic epidote, indicating emplacement of the host plutons at mesozonal crustal depths of greater than 15 km. Trace-element geochemical data indicate an arc origin for the granitoids, with an increase in the crustal component with time. Preliminary study of drill core from the LWM Zn-Pb-Cu-Ag prospect supports a carbonate-replacement model of mineralization. LWM massive sulfides consist of sphalerite, galena, and minor pyrite and chalcopyrite, in a gangue of calcite and lesser quartz; silver resides in Sb-As-Ag sulfosalts and pyrargyrite, and probably in submicroscopic inclusions within galena. Whole-rock analyses of LWM drill cores also show elevated In, an important metal in high-technology products. Hypogene mineralized rocks at Fish, below the secondary Zn-rich zone, are associated with a carbonate host and also may be of replacement origin, or alternatively, may be a magnetite-bearing Zn skarn. Cu-Zn-Pb-Ag-Au showings at the Oscar pros-pect occur in marble-hosted magnetite and pyrrhotite skarn that is spatially related to the stocks, dikes, and sills of the Early Jurassic syenite of Mount Veta. Mineralized rocks at the Eva Creek Ag-Zn-Pb-Cu prospect are within 1.5 km of the Mount Veta pluton, which is epidotized and locally altered along its contact with metamorphosed country rock east of the prospect. We report five new sulfide Pb-isotopic analyses from the LWM, Oscar, and Eva Creek prospects and compare these sulfide Pb-isotopic ratios with those for sulfides from nearby deposits and prospects in the Yukon-Tanana Upland and with feldspar Pb-isotopic ratios for Mesozoic plutons in the region. Disparities between the Pb-isotopic ratios for sulfides and igneous feldspars are consistent with a carbonate-replacement model for both the LWM and Eva Creek prospects. The presence in the Fortymile district of base-metal sulfides within both calc-silicate-rich skarns and the calc-silicate-free carbonate replacement deposits may reflect multistage mineralization by magmatic-hydrothermal systems during the emplacement of two or more magmatically unrelated igneous intrusions. Alternatively, all of the mineralized occurrences could be products of one regionally zoned system that formed during the intrusion of a single pluton. In addition to the likely origin of some of the base-metal occurrences by intrusion-related hydrothermal fluids, proximity of the LWM prospect to the northeast-striking, high-angle Kechumstuk Fault suggests that fluid flow along the fault also played an important role during carbonate-replacement mineralization.

Micronized copper wood preservatives: an efficiency and potential health risk assessment for copper-based nanoparticles.

PubMed

Civardi, Chiara; Schwarze, Francis W M R; Wick, Peter

2015-05-01

Copper (Cu) is an essential biocide for wood protection, but fails to protect wood against Cu-tolerant wood-destroying fungi. Recently Cu particles (size range: 1 nm-25 μm) were introduced to the wood preservation market. The new generation of preservatives with Cu-based nanoparticles (Cu-based NPs) is reputedly more efficient against wood-destroying fungi than conventional formulations. Therefore, it has the potential to become one of the largest end uses for wood products worldwide. However, during decomposition of treated wood Cu-based NPs and/or their derivate may accumulate in the mycelium of Cu-tolerant fungi and end up in their spores that are dispersed into the environment. Inhaled Cu-loaded spores can cause harm and could become a potential risk for human health. We collected evidence and discuss the implications of the release of Cu-based NPs by wood-destroying fungi and highlight the exposure pathways and subsequent magnitude of health impact. Copyright © 2015 Elsevier Ltd. All rights reserved.

Protectiveness of water quality criteria for copper in western United States waters relative to predicted olfactory responses in juvenile Pacific salmon.

PubMed

DeForest, David K; Gensemer, Robert W; Van Genderen, Eric J; Gorsuch, Joseph W

2011-07-01

Copper (Cu) can impair olfaction in juvenile Pacific salmon (as well as other fishes), thus potentially inhibiting the ability of juveniles to avoid predators or to find food. Because Cu is commonly elevated in stormwater runoff in urban environments, storm events may result in elevated Cu concentrations in salmon-bearing streams. Accordingly, there is concern that existing Cu criteria, which were not derived using data for olfactory-related endpoints, may not be adequately protective of juvenile salmon. However, a modification of the US Environmental Protection Agency (USEPA) biotic ligand model (BLM) for deriving site-specific Cu criteria was recently proposed, which accounted for the sensitivity of olfactory endpoints. The modification was based on olfactory inhibition in juvenile coho salmon (Oncorhynchus kisutch) exposed to Cu in various combinations of pH, hardness, alkalinity, and dissolved organic carbon (DOC) concentrations. We used that olfactory-based BLM to derive 20% inhibition concentrations (IC20) values for Cu for 133 stream locations in the western United States. The olfactory BLM-based IC20 values were compared to the existing hardness-based Cu criteria and the USEPA's BLM-based Cu criteria for these representative natural waters of the western United States. Of the 133 sampling locations, mean hardness-dependent acute and chronic Cu criteria were below the mean olfactory-based BLM IC20 value in 122 (92%) and 129 (97%) of the waters, respectively (i.e., <20% olfactory impairment would have been predicted at the mean hardness-based Cu criteria concentrations). Waters characterized by a combination of high hardness and very low DOC were most likely to have hardness-based Cu criteria that were higher than the olfactory-based BLM IC20 values, because DOC strongly influences Cu bioavailability in the BLM. In all waters, the USEPA's current BLM-based criteria were below the mean olfactory-based BLM IC20 values, indicating that the USEPA's BLM-based criteria are protective of olfactory impairment in juvenile salmon. Copyright © 2011 SETAC.

Optical and electrical properties of Cu-based all oxide semi-transparent photodetector

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

Kim, Hong-Sik; Patel, Malkeshkumar; Yadav, Pankaj

2016-09-05

Zero-bias operating Cu oxide-based photodetector was achieved by using large-scale available sputtering method. Cu oxide (Cu{sub 2}O or CuO) was used as p-type transparent layer to form a heterojunction by contacting n-type ZnO layer. All metal-oxide materials were employed to realize transparent device at room temperature and showed a high transparency (>75% at 600 nm) with excellent photoresponses. The structural, morphological, optical, and electrical properties of Cu oxides of CuO and Cu{sub 2}O are evaluated in depth by UV-visible spectrometer, X-ray diffraction, scanning electron microscopy, atomic force microscopy, Kelvin probe force microscopy, and Hall measurements. We may suggest a route ofmore » high-functional Cu oxide-based photoelectric devices for the applications in flexible and transparent electronics.« less

Data from geologic investigations in the Yemen Arab Republic during 1976

USGS Publications Warehouse

Grolier, Maurice J.; Domenico, J.A.; Donato, Mary; Tibbitts, G.C.; Overstreet, W.C.; Ibrahim, Mohammad Mukred

1977-01-01

The results of semiquantitative spectrographic analyses for 31 elements in 126 specimens of rocks from the Yemen Arab Republic, collected mainly during February 1976 from the Precambrian area in the southeastern part of the country, provide background data for use in geochemical evaluation of areas potentially favorable for mineral deposits. Gold and thorium were undetected; the lower limits of determination are 10 parts per million (ppm) and 20 ppm, respectively. For the other elements, the abundances follow geochemical norms for crustal distribution: (1) Fe, Nb, and Zr in Holocene weathering products; (2) Ca and Sr in Pliocene limestone; (3) Mo in Pliocene(?) or Miocene(?) dikes; (4) Be, La, and Sn in Miocene(?) alkalic granite; (5) As, Be, and La in Tertiary and/or Cretaceous felsic tuff; (6) V in Tertiary and/or Cretaceous carbonaceous sedimentary rocks interbedded with volcanic rocks; (7) Be, La, Sn, and Zr in Tertiary and/or Cretaceous undivided volcanics; (8) Sn and W in Precambrian felsite and pegmatite; (9) Co, Cr, Ni, and Ti in Precambrian mafic rocks; (10) Mg and Sr in Precambrian marble and calcsilicate rocks; (11) Y in Precambrilan schist; (12) B and Sc dispersed in rocks of many ages; and (13) Ag, Ba, Bi, Cd, Cu, Mn, Pb, Sb, Sn, and Zn in a hydrothermal replacement deposit in Precambrian sediment. None of the rocks contained as much as 205 ppm equivalent uranium. The highest values for Ag, Cu, Pb, Zn, and Cd were obtained on a sample of hydrothermally altered siltstone not personally collected by the writers. It was said to have come from the Ma'rib area in the eastern part of the Yemen Arab Republic. The source must be studied, because this single sample is high-grade base-metal ore. Among the samples collected by the writers, the economically most significant are altered tuffs, ignimbrites, and felsites exposed between Jibal Hufash and Manakhah on the road from Hudaydah to San'a'. They are strongly anomalous for As and weakly anomalous, variously, for Hg, Mo, and Pb, which elements may constitute an epigenetic dispersion pattern from hidden sulfide deposits. Inasmuch as chalcopyrite and native copper have been reported in the vicinity of Jabal Haraz in the Manakhah area, the rocks of the Yemen Volcanics in this region should be explored for base-metal sulfide deposits. The first results of paleontologic examinations of fossils collected during 1975 and 1976 are presented, as are a list of Landsat images covering the Yemen Arab Republic, and a selected bibliography of reports on geology and the allied sciences relating to the Yemen Arab Republic.

Investigation on microwave heating for direct leaching of chalcopyrite ores and concentrates

NASA Astrophysics Data System (ADS)

Onol, Kubra; Saridede, Muhlis Nezihi

2013-03-01

The use of microwave energy in materials processing is a relatively new development presenting numerous advantages because of the rapid heating feature. Microwave technology has great potential to improve the extraction efficiency of metals in terms of both a reduction in required leaching time and an increase in the recovery of valuable metals. This method is especially pertinent in view of the increased demand for environment-friendly processes. In the present study, the influence of microwave heating on the direct leaching of chalcopyrite ores and concentrates were investigated. The results of microwave leaching experiments were compared with those obtained under conventional conditions. During these processes, parameters such as leaching media, temperature, and time have been worked to determine the optimum conditions for proper copper dissolution. Experimental results show that microwave leaching is more efficient than conventional leaching. The optimum leaching conditions for microwave leaching are the solid-to-liquid ratio of 1:100 g/mL, the temperature of 140°C, the solution of 0.5 M H2SO4 + 0.05 M Fe2(SO4)3, and the time of 1 h.

Dissolution characteristics of sericite in chalcopyrite bioleaching and its effect on copper extraction

NASA Astrophysics Data System (ADS)

Dong, Ying-bo; Li, Hao; Lin, Hai; Zhang, Yuan

2017-04-01

The effects of sericite particle size, rotation speed, and leaching temperature on sericite dissolution and copper extraction in a chalcopyrite bioleaching system were examined. Finer particles, appropriate temperature and rotation speed for Acidithiobacillus ferrooxidans resulted in a higher Al3+ dissolution concentration. The Al3+ dissolution concentration reached its highest concentration of 38.66 mg/L after 48-d leaching when the sericite particle size, temperature, and rotation speed were -43 μm, 30°C, and 160 r/min, respectively. Meanwhile, the sericite particle size, rotation speed, and temperature can affect copper extraction. The copper extraction rate is higher when the sericite particle size is finer. An appropriately high temperature is favorable for copper leaching. The dissolution of sericite fitted the shrinking core model, 1-(2/3) α-(1- α)2/3 = k 1 t, which indicates that internal diffusion is the decision step controlling the overall reaction rate in the leaching process. Scanning electron microscopy analysis showed small precipitates covered on the surface of sericite after leaching, which increased the diffusion resistance of the leaching solution and dissolved ions.

The community dynamics of major bioleaching microorganisms during chalcopyrite leaching under the effect of organics.

PubMed

Li, Qihou; Tian, Ye; Fu, Xian; Yin, Huaqun; Zhou, Zhijun; Liang, Yiting; Qiu, Guanzhou; Liu, Jie; Liu, Hongwei; Liang, Yili; Shen, Li; Cong, Jing; Liu, Xueduan

2011-08-01

To determine the effect of organics (yeast extract) on microbial community during chalcopyrite bioleaching at different temperature, real-time polymerase chain reaction (PCR) was employed to analyze community dynamics of major bacteria applied in bioleaching. The results showed that yeast extract exerted great impact on microbial community, and therefore influencing bioleaching rate. To be specific, yeast extract was adverse to this bioleaching process at 30°C due to decreased proportion of important chemolithotrophs such as Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. However, yeast extract could promote bioleaching rate at 40°C on account of the increased number and enhanced work of Ferroplasma thermophilum, a kind of facultative bacteria. Similarly, bioleaching rate was enhanced under the effect of yeast extract at 50°C owing to the work of Acidianus brierleyi. At 60°C, bioleaching rate was close to 100% and temperature was the dominant factor determining bioleaching rate. Interestingly, the existence of yeast extract greatly enhanced the relative competitiveness of Ferroplasma thermophilum in this complex bioleaching microbial community.

The Case of Carpathian (Transylvanian) Gold and its Use for Archaeological Items

NASA Astrophysics Data System (ADS)

Stan, D.; Constantinescu, B.; Vasilescu, A.; Radtke, M.; Reinholz, U.; Pop, D.; Ionescu, C.

2009-04-01

Romania was one of Europe's main gold-producing areas since the antiquity, especially through the ore deposits in the "Golden Quadrilateral" of the Western Carpathians. The Babeş-Bolyai University in Cluj-Napoca hosts a gold collection consisting of about 500 samples, most of them from Roşia Montană. The geochemical investigation of Romanian gold by using SR-XRF and micro-PIXE is currently in progress; some preliminary results point to interesting features. The goal of the study is to verify if Transylvanian gold was used to manufacture Romanian archaeological objects. This is realized by using information related to trace elements: Sb, Te, Pb - recognized fingerprints for Carpathian Mountains mines and Sn characteristic for the panned river-bed (alluvional) gold. To solve these issues, samples (grains, nuggets, fine gold "sand") from various Transylvanian mines and rivers and some very small (few milligrams) fragments of archaeological objects are measured. Another outcome of this SR-XRF experiment is to obtain the elemental characterization (Au, Ag and Cu) of representative gold mines, subject of interest for the assignement of any other archaeological artifacts to one of the Central European gold sources. During the experiment, point spectra for 22 natural gold samples and 18 "micronic" samples from archaeological objects were acquired at 34 keV excitation SR energy, using a spatially resolved SR-XRF set-up mounted for analyses at the hard X-ray beam line - BAMline at BESSY, Berlin. A summary for the characterization of Transylvanian native gold is the following: high (8 - 30%) Ag amounts and low (0.2 - 1%) Cu amounts; placer deposits contain as fingerprint Sn (150-300 ppm) - most probably from river bed cassiterite; primary deposits present as fingerprints Te (200-2000 ppm), Sb (150-300 ppm) - however, the samples are very inhomogeneous. The micro-PIXE experiment was performed at the AN 2000 Van de Graaff accelerator of Laboratori Nazionali di Legnaro. Elemental maps of gold samples were obtained, complemented by nuclear microprobe point analyses in selected areas of the mapped gold crystals. At Roşia Montană, the mapping evidenced a peculiar microfabric consisting of mm-sized laths of a Zn-S rich phase (with minor Cu and Fe). Au content shows a wide compositional range: 36-57%. A clear chemical inhomogeneity of the Au/Ag ratio, as well as of the local concentration of other elements (Cu, As, Sb, Te, Pb, Fe) was noticed at submilimeter scale. The presence of associated mineral phases (such as Cu, Ag, chalcopyrite, galena, sphalerite, arsenopyrite, pyrite/marcasite and non-metallic minerals) at microscopic scale could be thus illustrated. As concerning the archaeological samples, for "koson" dacian coins, the type "with monogram" is made from refined (more than 97%) gold with no Sb, Te or Sn traces (remelted gold) and the type "without monogram" is clearly made from alluvial gold, partially combined with primary Transylvanian gold (Sn and Sb traces detected). The greek "pseudolysimachus" type staters (contemporary with "kosons") are made from refined remelted gold (no Sn, Sb, Te presence).

Geochemistry of pyrite and chalcopyrite from an active black smoker in 49.6°E Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Yuan, Bo; Yang, Yaomin; Yu, Hongjun; Zhao, Yuexia; Ding, Qingfeng; Yang, Jichao; Tang, Xin

2017-06-01

Active hydrothermal chimneys, as the product of submarine hydrothermal activity, can be used to determine the fluid evolution and formation process of potential volcanic-hosted massive sulfide deposits. A hard-won specimen from an active hydrothermal chimney was collected in the 49.6°E ultraslow-spreading Southwest Indian Ridge (SWIR) field through a television-guided grab. A geochemical study of prominent sulfide (e.g., pyrite and chalcopyrite) included in this sample was performed using laser ablation inductively coupled plasma mass spectroscopy. The early sulfides produced at low temperature are of disseminated fine-grained anhedral morphology, whereas the late ones with massive, coarse euhedral features precipitated in a high-temperature setting. The systematic variations in the contents of minor and trace elements are apparently related to the crystallization sequence, as well as to texture. Micro-disseminated anhedral sulfides rich in Pb, As, Ni, Ba, Mn, Mo, U, and V were formed during the initial chimney wall growth, whereas those rich in Sn, Se, and Co with massive, coarse euhedral morphology were formed within the late metallogenic stage. The hydrothermal fluid composition has experienced a great change during the chimney growth. Such a conclusion is consistent with that indicated by using principal component analysis, which is a powerful statistical analysis method widely used to project multidimensional datasets (e.g., element contents in different mineral phases) into a few directions. This distribution pattern points to crystallographic controls on minor and trace element uptake during chimney growth, occurring with concomitant variations in the fluid composition evolutionary history. In this pyrite-chalcopyrite-bearing active hydrothermal chimney at the SWIR, the metal concentration and precipitation of sulfides largely occurred at the seafloor as a result of mixing between the upwelling hot hydrothermal fluid and cold seawater. Over the course of mixing, significant variations in metal solubility were caused by changes in temperature, pH, and redox conditions in the parental fluid phase.

The Niassa Gold Belt, northern Mozambique - A segment of a continental-scale Pan-African gold-bearing structure?

NASA Astrophysics Data System (ADS)

Bjerkgard, T.; Stein, H. J.; Bingen, B.; Henderson, I. H. C.; Sandstad, J. S.; Moniz, A.

2009-01-01

The Niassa Gold Belt, in northernmost Mozambique, is hosted in the Txitonga Group, a Neoproterozoic rift sequence overlying Paleoproterozoic crust of the Congo-Tanzania Craton and deformed during the Pan-African Orogeny. The Txitonga Group is made up of greenschist-facies greywacke and schist and is characterized by bimodal, mainly mafic, magmatism. A zircon U-Pb age for a felsic volcanite dates deposition of the sequence at 714 ± 17 Ma. Gold is mined artisanally from alluvial deposits and primary chalcopyrite-pyrite-bearing quartz veins containing up to 19 ppm Au have been analyzed. In the Cagurué and M'Papa gold fields, dominantly N-S trending quartz veins, hosted in metagabbro and schist, are regarded as tension gashes related to regional strike-slip NE-SW-trending Pan-African shear zones. These gold deposits have been classified as mesozonal and metamorphic in origin. Re-Os isotopic data on sulfides suggest two periods of gold deposition for the Cagurué Gold Field. A coarse-crystalline pyrite-chalcopyrite assemblage yields an imprecise Pan-African age of 483 ± 72 Ma, dating deposition of the quartz veins. Remobilization of early-formed sulfides, particularly chalcopyrite, took place at 112 ± 14 Ma, during Lower Cretaceous Gondwana dispersal. The ˜483 Ma assemblage yields a chondritic initial 187Os/ 188Os ratio of 0.123 ± 0.058. This implies a juvenile source for the ore fluids, possibly involving the hosting Neoproterozoic metagabbro. The Niassa Gold Belt is situated at the eastern end of a SW-NE trending continental-scale lineament defined by the Mwembeshi Shear Zone and the southern end of a NW-SE trending lineament defined by the Rukwa Shear Zone. We offer a review of gold deposits in Zambia and Tanzania associated with these polyphase lineaments and speculate on their interrelation.

Characterization of porosity in sulfide ore minerals: A USANS/SANS study

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

Xia, F.; Zhao, J.; Etschmann, B. E.

Porosity plays a key role in the formation and alteration of sulfide ore minerals, yet our knowledge of the nature and formation of the residual pores is very limited. Herein, we report the application of ultra-small-angle neutron scattering and small-angle neutron scattering (USANS/SANS) to assess the porosity in five natural sulfide minerals (violarite, marcasite, pyrite, chalcopyrite, and bornite) possibly formed by hydrothermal mineral replacement reactions and two synthetic sulfide minerals (violarite and marcasite) prepared experimentally by mimicking natural hydrothermal conditions. USANS/SANS data showed very different pore size distributions for these minerals. Natural violarite and marcasite tend to possess less poresmore » in the small size range (<100 nm) compared with their synthetic counterparts. This phenomenon is consistent with a higher degree of pore healing or diagenetic compaction experienced by the natural violarite and marcasite. Surprisingly, nanometer-sized (<20 nm) pores were revealed for a natural pyrite cube from La Rioga, Spain, and the sample has a pore volume fraction of ~7.7%. Both chalcopyrite and bornite from the massive sulfide assemblage of the Olympic Dam deposit in Roxby Downs, South Australia, were found to be porous with a similar pore volume fraction (~15%), but chalcopyrite tends to have a higher proportion of nanometer-size pores centered at ~4 nm while bornite tends to have a broader pore size distribution. The specific surface area is generally low for these minerals ranging from 0.94 to 6.28 m2/g, and the surfaces are generally rough as surface fractal behavior was observed for all these minerals. This investigation has demonstrated that USANS/SANS is a very useful tool for analyzing porosity in ore minerals. We believe that with this quantified porosity information a deeper understanding of the complex fluid flow behavior within the porous minerals can be expected.« less

Distribution and solubility limits of trace elements in hydrothermal black smoker sulfides: An in-situ LA-ICP-MS study

NASA Astrophysics Data System (ADS)

Wohlgemuth-Ueberwasser, Cora C.; Viljoen, Fanus; Petersen, Sven; Vorster, Clarisa

2015-06-01

The key for understanding the trace metal inventory of currently explored VHMS deposits lies in the understanding of trace element distribution during the formation of these deposits on the seafloor. Recrystallization processes already occurring at the seafloor might liberate trace elements to later hydrothermal alteration and removement. To investigate the distribution and redistribution of trace elements we analyzed sulfide minerals from 27 black smoker samples derived from three different seafloor hydrothermal fields: the ultramafic-hosted Logatchev hydrothermal field on the Mid-Atlantic Ridge, the basaltic-hosted Turtle Pits field on the mid-atlantic ridge, and the felsic-hosted PACMANUS field in the Manus basin (Papua New Guinea). The sulfide samples were analyzed by mineral liberation analyser for the modal abundances of sulfide minerals, by electron microprobe for major elements and by laser ablation-inductively coupled plasma-mass spectrometry for As, Sb, Se, Te, and Au. The samples consist predominantly of chalcopyrite, sphalerite, pyrite, galena and minor isocubanite as well as inclusions of tetrahedrite-tennantite. Laser ablation spectra were used to evaluate the solubility limits of trace elements in different sulfide minerals at different textures. The solubility of As, Sb, and Au in pyrite decreases with increasing degree of recrystallization. When solubility limits are reached these elements occur as inclusions in the different sulfide phases or they are expelled from the mineral phase. Most ancient VHMS deposits represent felsic or bimodal felsic compositions. Samples from the felsic-hosted PACMANUS hydrothermal field at the Pual ridge (Papua New Guinea) show high concentrations of Pb, As, Sb, Bi, Hg, and Te, which is likely the result of an additional trace element contribution derived from magmatic volatiles. Co-precipitating pyrite and chalcopyrite are characterized by equal contents of Te, while chalcopyrite that replaced pyrite (presumably during black smoker growth) is enriched in Te relative to pyrite. These higher Te concentrations may be related to higher fluid temperature.

Geology of the Wood and East Calhoun mines, Central City District, Gilpin County, Colorado

USGS Publications Warehouse

Drake, Avery Ala

1955-01-01

The Wood-East Calhoun mine area is underlain by complexly folded Precambrian gneiss and pegmatite. The major fold in the area is an anticline that trends about N. 60° E. The Precambrian rocks are intruded by bostonite porphyry dikes of Tertiary age. All the rocks are cut by east- to northeast - trending faults that have been filled by precious metal-sulfide veins which have been worked chiefly for gold. The Wood vein occurs in an east-trending fault; the Calhoun vein occurs in a northeast-trending fault. Much of the uranium production of the Central City district has come from the Wood vein on Quartz Hill. The veins consist chiefly of quartz; pyrite is the chief metallic mineral and chalcopyrite is next in abundance. Sphalerite, galena, tetrahedrite-tennantite, and pitchblende are locally present. Deposition began with alteration-stage quartz and pyrite followed in order by pitchblend, light-yellow pyrite, massive quartz, yellow pyrite, shalerite, comb quartz, chalcopyrite, tetrahedrite-tennantite, galena, chalcopyrite, pyrite, and gray to light-brown fine-grained quartz. The veins of the Central City district are zoned, with quartz-pyrite veins near the center and galena-sphalerite veins on the periphery. The known pitchblende bodies are in the transition between these, but paragenetically, the pitchblende is earlier than all other metallic minerals. A trace element study of the ore indicates an association of zirconium and molybdenum with uranium, of bismuth, antimony, and arsenic with copper, and of cadmium with zinc. The pitchblende and other ore minerals are concentrated in ore shoots. The shoots are in open spaces controlled by the competency of the wall rocks, the presence of a prevailing direction of weakness in the rocks, and changes in strike and dip of the vein. The pitchblende is thought to be a local constituent of the quartz-pyrite ores and to owe its origin to residual solutions from the quartz bostonite magma.

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.

The Effect of Mo Particles Addition in Ag-Cu-Ti Filler Alloy on Ti(C,N)-Based Cermet/45 Steel-Brazed Joints

NASA Astrophysics Data System (ADS)

He, Hu; Du, Xueming; Huang, Xiaokai; Xu, Weijian; Yao, Zhenhua

2018-05-01

Reliable brazing of Ti(C,N)-based cermet and 45 steel was successfully achieved by using the Mo-particle-reinforced Ag-Cu-Ti composite filler. The effects of Mo content on the interfacial microstructure and mechanical properties of Ti(C,N)-based cermet/45 steel joints were analyzed. The results showed that the joint microstructure was primarily composed of Ni3Ti+Cu3Ti2, Ag(s,s)+Cu(s.s), CuTi+Mo, Ti-based solid solution, and FeTi+Fe2Ti. With the increase in Mo content in filler, the thickness of the Ni3Ti+Cu3Ti2 layer adjacent to the Ti(C,N)-based cermet decreases, while more blocky Ti-Cu intermetallic were observed in the brazing seam. The shear strength of the joint could be significantly improved by adding suitable amounts of Mo into the Ag-Cu-Ti filler, and the peak value of 263 MPa was achieved when the alloys were brazed with Ag-Cu-Ti+8wt.%Mo composite filler at 920 °C for 20 min.

Copper-Substituted Lead Perovskite Materials Constructed with Different Halides for Working (CH3NH3)2CuX4-Based Perovskite Solar Cells from Experimental and Theoretical View.

PubMed

Elseman, Ahmed Mourtada; Shalan, Ahmed Esmail; Sajid, Sajid; Rashad, Mohamed Mohamed; Hassan, Ali Mostafa; Li, Meicheng

2018-04-11

Toxicity and chemical instability issues of halide perovskites based on organic-inorganic lead-containing materials still remain as the main drawbacks for perovskite solar cells (PSCs). Herein, we discuss the preparation of copper (Cu)-based hybrid materials, where we replace lead (Pb) with nontoxic Cu metal for lead-free PSCs, and investigate their potential toward solar cell applications based on experimental and theoretical studies. The formation of (CH 3 NH 3 ) 2 CuX 4 [(CH 3 NH 3 ) 2 CuCl 4 , (CH 3 NH 3 ) 2 CuCl 2 I 2 , and (CH 3 NH 3 ) 2 CuCl 2 Br 2 ] was discussed in details. Furthermore, it was found that chlorine (Cl - ) in the structure is critical for the stabilization of the formed compounds. Cu-based perovskite-like materials showed attractive absorbance features extended to the near-infrared range, with appropriate band gaps. Green photoluminescence of these materials was obtained because of Cu + ions. The power conversion efficiency was measured experimentally and estimated theoretically for different architectures of solar cell devices.

Ultrasensitive and highly selective detection of Cu2 + ions based on a new carbazole-Schiff

NASA Astrophysics Data System (ADS)

Yin, Jun; Bing, Qijing; Wang, Lin; Wang, Guang

2018-01-01

A new chemosensor for Cu2 + based on Schiff base with high sensitivity and selectivity was designed and synthesized. The fluorescence intensity of the chemosensor in CH3CN solution was enhanced 160-fold after the addition of 10 equiv. Cu2 + over other metal ions. In addition, it also facilitates colorimetric detection for Cu2 + in CH3CN solution. The chemosensor displayed low detection limit and fast response time to Cu2 +.

Influence of Oxygen on Cu Distribution Behavior Between Molten Iron and FeS-Based Flux

NASA Astrophysics Data System (ADS)

Kang, Youngjo; Shin, Kil-Sun; Morita, Kazuki

2018-06-01

Cu distribution behavior between molten iron and a sulfide flux was investigated under different oxygen contents in the sulfide flux to clarify the effect of oxygen content in FeS-based flux on Cu removal. The activity coefficient of CuS0.5 could be experimentally estimated according to the oxygen content. Based on the present result, the possibility of Cu removal by sulfide flux containing a certain amount of oxide was discussed.

Fluorescent probe based subcellular distribution of Cu(II) ions in living electrotrophs isolated from Cu(II)-reduced biocathodes of microbial fuel cells.

PubMed

Tao, Ye; Xue, Hua; Huang, Liping; Zhou, Peng; Yang, Wei; Quan, Xie; Yuan, Jinxiu

2017-02-01

Based on the four indigenous electrotrophs (Stenotrophomonas maltophilia JY1, Citrobacter sp. JY3, Pseudomonas aeruginosa JY5 and Stenotrophomonas sp. JY6) isolated from well adapted Cu(II)-reduced biocathodes of microbial fuel cells (MFCs), a rhodamine based Cu(II) fluorescent probe was used to imaginably and quantitatively track subcellular Cu(II) ions in these electrotrophs. Cathodic electrons led to more Cu(II) ions (14.3-30.1%) in the intracellular sites at operation time of 2-3h with Cu(II) removal rates of 2.90-3.64mg/Lh whereas the absence of cathodic electrons prolonged the appearance of more Cu(II) ions (16.6-22.5%) to 5h with Cu(II) removal rates of 1.96-2.28mg/Lh. This study illustrates that cathodic electrons directed more Cu(II) ions for quicker entrance into the electrotrophic cytoplasm, and gives an alternative approach for developing imaging and functionally tracking Cu(II) ions in the electrotrophs of MFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mineralogy, fluid inclusion petrography, and stable isotope geochemistry of Pb-Zn-Ag veins at the Shizhuyuan deposit, Hunan Province, southeastern China

NASA Astrophysics Data System (ADS)

Wu, Shenghua; Mao, Jingwen; Yuan, Shunda; Dai, Pan; Wang, Xudong

2018-01-01

The Shizhuyuan polymetallic deposit is located in the central part of the Nanling region, southeastern China, and consists of proximal W-Sn-Mo-Bi skarns and greisens and distal Pb-Zn-Ag veins. The sulfides and sulfosalts in the distal veins formed in three distinct stages: (1) an early stage of pyrite and arsenopyrite, (2) a middle stage of sphalerite and chalcopyrite, and (3) a late stage of galena, Ag-, Sn-, and Bi-bearing sulfides and sulfosalts, and pyrrhotite. Combined sulfide and sulfosalt geothermometry and fluid inclusion analyses indicate that the early stage of mineralization occurred at a temperature of 400 °C and involved boiling under hydrostatic pressure ( 200 bar), with the temperature of the system dropping during the late stage to 200 °C. Laser Raman analysis indicates that the fluid inclusions within the studied minerals are dominated by H2O, although some contain carbonate solids and CH4 gas. Vein-hosted sulfides have δ34S values of 3.8-6.3‰ that are interpreted as indicative of a magmatic source of sulfur. The mineralization process can be summarized as follows: an aqueous fluid exsolved on final crystallization of the Qianlishan pluton, ascended along fracture zones, cooled to <400 °C, and boiled under hydrostatic conditions, and with decreasing temperature and sulfur fugacity, sulfide and sulfosalt minerals precipitated successively from the Ag-Cu-Zn-Fe-Pb-Sb-As-S-bearing fluid system.

Mineralogy and geochemistry of El Dorado epithermal gold deposit, El Sauce district, central-northern Chile

NASA Astrophysics Data System (ADS)

Carrillo-Rosúa, J.; Morales-Ruano, S.; Morata, D.; Boyce, A. J.; Belmar, M.; Fallick, A. E.; Fenoll Hach-Alí, P.

2008-03-01

The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47'S Lat., 70°43'W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06-0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21-0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ18O and δD for the hydrothermal fluids were between 3 and 10‰ and between -95 and -75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit.

In-situ Pb isotope analysis of Fe-Ni-Cu sulphides by laser ablation multi-collector ICPMS: New insights into ore formation in the Sudbury impact melt sheet

NASA Astrophysics Data System (ADS)

Darling, J. R.; Storey, C. D.; Hawkesworth, C. J.; Lightfoot, P. C.

2012-12-01

Laser-ablation (LA) multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is ideally suited to in situ determination of isotope ratios in sulphide minerals. Using samples of magmatic sulphide ore from the Sudbury impact structure, we test LA-MC-ICPMS analytical protocols that aim to meet a range of analytical challenges in the analysis of Pb isotopes. These include: potential matrix sensitive isotopic fractionation; interferences on Pb isotopes; low melting points of many sulphide minerals; the availability of standards. Magmatic sulphides of wide ranging mineralogy (pyrrhotite, pentlandite, chalcopyrite, pyrite and sphalerite) were analysed for Pb isotopic composition, using the silicate glass NIST SRM 610 as an external standard to correct for instrumental mass-fractionation. Despite matrix sensitive melting and re-deposition around ablation pits, several lines of evidence indicate that all analyses are accurate, within typical analytical uncertainties of 0.003-2% (2σ), and that the defined approach is insensitive to compositional diversity in sample matrix: (a) laser ablation and dissolution based measurements of sulphide powders are in agreement; (b) analyses from each sample define isochron ages within uncertainty of the known crystallization age (1850 Ma); (c) the results of sulphide measurements by laser ablation are consistent with age-corrected feldspar analyses from the same samples. The results have important implications for ore formation in Sudbury. The Pb isotope data regressions are consistent with age corrected feldspar analyses from each respective sample, which together with time integrated Th/U ratios that match whole rock values (3.1, 4.0 and 6.1 for the Worthington, Copper Cliff and Parkin Offset Dykes, respectively) indicate chemical equilibrium between the silicate and sulphide systems during ore formation. The sulphides within each respective sample have indistinguishable model initial Pb isotope ratios (207Pb/204Pbm), irrespective of mineralogy or texture, indicating a common origin for ores within each of three different Offset Dykes. Furthermore, variations between Offset Dykes (e.g., 207Pb/204Pbm = 15.514 ± 0.012, 15.399 ± 0.009 and 15.275 ± 0.003) show that the ores have differing crustal sources on previously unrecognized scales. Mass balance considerations, particularly for MgO, Ni and Cu, indicate that the spatial distribution of mafic target rocks played a significant role in controlling the mineralization potential in different parts of the melt sheet.

New insights into the petrogenesis of the Jameson Range layered intrusion and associated Fe-Ti-P-V-PGE-Au mineralisation, West Musgrave Province, Western Australia

NASA Astrophysics Data System (ADS)

Karykowski, Bartosz T.; Polito, Paul A.; Maier, Wolfgang D.; Gutzmer, Jens; Krause, Joachim

2017-02-01

The Mesoproterozoic Jameson Range intrusion forms part of the Giles Complex, Musgrave Province, Western Australia. It is predominantly mafic in composition comprising olivine-bearing gabbroic lithologies with variable amounts of magnetite and ilmenite. Lithologies containing more than 50 vol% magnetite and ilmenite are classified as magnetitites. The Jameson Range hosts several of these magnetitites forming laterally extensive layers, which can be traced for at least 19 km as continuous magnetic anomalies. Similar occurrences of magnetitites are known from the upper parts of other layered intrusions, such as the Bushveld Complex. In addition, the intrusion hosts several P-rich zones, one of which is at least 59 m in thickness containing 1.0 wt% P2O5. The P-rich zones are not directly associated with the magnetitites, but they mostly occur slightly above them. The mineral chemistry of the Jameson Range cumulates is relatively evolved with olivine compositions ranging from Fo44 to Fo60 and plagioclase compositions varying between An56 and An59. The Mg# (100 × Mg / (Mg + Fe)) of ortho- and clinopyroxene ranges from 60 to 61 and from 70 to 75, respectively. Magnetite compositions are characterised by low TiO2 concentrations varying from 0.39 to 3.04 wt% representing near end-member magnetite with up to 1.2 wt% Cr and 1.3 wt% V, respectively. The basal magnetite layer reaches up to 68.8 wt% Fe2O3(t) and 24.2 wt% TiO2, and it is also markedly enriched in Cu (up to 0.3 wt% Cu), V (up to 1.05 wt% V2O5) and platinum-group elements (PGE) (up to 2 ppm Pt + Pd). Sulphide minerals comprising bornite, chalcopyrite and minor pentlandite occur finely disseminated in the magnetitite and account for the elevated base metal and PGE concentrations. Modelling indicates that the PGE mineralisation was formed at very high R factors of up to 100,000, which is typical for PGE reefs in layered intrusions. Whole rock geochemical and mineralogical data of the magnetite layers and their host rocks further allow for a refinement of current formation models of layered igneous sequences. Several lines of evidence suggest that the magnetite layers formed in response to primarily density-controlled mineral sorting within crystal slurries, although the grain size also affects the sorting process.

Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites.

PubMed

Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei; Mitzi, David B; Yan, Yanfa

2017-09-25

Recently, Cu I - and Ag I -based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only Ag I -based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu I -based analogues. Here we show that, owing to the much higher energy level for the Cu 3d 10 orbitals than for the Ag 4d 10 orbitals, Cu I atoms energetically favor 4-fold coordination, forming [CuX 4 ] tetrahedra (X=halogen), but not 6-fold coordination as required for [CuX 6 ] octahedra. In contrast, Ag I atoms can have both 6- and 4-fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu I halide double perovskites may instead lead to non-perovskites containing [CuX 4 ] tetrahedra, as confirmed by our material synthesis efforts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Sn Grain Orientation on the Cu6Sn5 Formation in a Sn-Based Solder Under Current Stressing

NASA Astrophysics Data System (ADS)

Lin, Chih-Fan; Lee, Shang-Hua; Chen, Chih-Ming

2012-08-01

A SnAgCu-based solder stripe between two Cu electrodes is current stressed with a density of 5 × 104 A/cm2 at 393 K (120 °C). After current stressing for 24 hours, electromigration induces the Cu dissolution from the cathode-side Cu electrode, leading to the Cu6Sn5 formation in the solder stripe. Very interestingly, the Cu6Sn5 phase is selectively formed within a specific Sn grain. Electron backscattering diffraction analysis indicates the crystallographic orientations of Sn grains play an important role in the selective Cu6Sn5 formation.

A novel electrochemical sensor based on Cu3P@NH2-MIL-125(Ti) nanocomposite for efficient electrocatalytic oxidation and sensitive detection of hydrazine

NASA Astrophysics Data System (ADS)

Wang, Minghua; Yang, Longyu; Hu, Bin; Liu, Yongkang; Song, Yingpan; He, Linghao; Zhang, Zhihong; Fang, Shaoming

2018-07-01

A novel electrocatalyst based on amine-functionalized Ti-based metal-organic framework (NH2-MIL-125(Ti)) embedded with Cu3P nanocrystals (denoted by Cu3P@NH2-MIL-125(Ti)) was synthesized and used for electrocatalytic oxidation and detection of hydrazine in aqueous solution. A series of Cu3P@NH2-MIL-125(Ti) nanocomposites were obtained by adding Cu3P nanoparticles into the preparation system of NH2-MIL-125(Ti), with the Cu3P nanocrystals derived from the phospatization of Cu(OH)2 at high temperature. Based on the detailed characterizations and analysis of the chemical and physical performances of the series of Cu3P@NH2-MIL-125(Ti) nanocomposites at dosages of Cu3P nanocrystals at 5, 20, 50, and 100 mg, the good synergic effect between the Cu3P (50 mg) and the NH2-MIL-125(Ti) endows the as-prepared Cu3P50@NH2-MIL-125(Ti) nanocomposite with the excellent electrocatalytic activity toward the electrocatalytic oxidation of hydrazine. The Cu3P50@NH2-MIL-125(Ti)-based electrochemical sensor exhibited a detection limit of 79 nM (S/N = 3) within a wider linear range from 5 μM to 7.5 mM. Moreover, the developed sensor exhibited high selectivity toward the detection of hydrazine with the addition of certain common interferents and good applicability in real samples. All of these results imply that the Cu3P50@NH2-MIL-125(Ti) nanocomposite could be promising for detecting hydrazine and offer potential applications in the field of electroanalytical chemistry.

Pre-1991 sulfur transfer between mafic injections and dacite magma in the Mt. Pinatubo reservoir

USGS Publications Warehouse

Di, Muro A.; Pallister, J.; Villemant, B.; Newhall, C.; Semet, M.; Martinez, M.; Mariet, C.

2008-01-01

Before the 1991-1992 activity, a large andesite lava dome belonging to the penultimate Pinatubo eruptive period (Buag ??? 500??BP) formed the volcano summit. Buag porphyritic andesite contains abundant amphibole-bearing microgranular enclaves of basaltic-andesite composition. Buag enclaves have lower K2O and incompatible trace element (LREE, U, Th) contents than mafic pulses injected in the Pinatubo reservoir during the 1991-1992 eruptive cycle. This study shows that Buag andesite formed by mingling of a hot, water-poor and reduced mafic magma with cold, hydrous and oxidized dacite. Depending on their size, enclaves experienced variable re-equilibration during mixing/mingling. Re-equilibration resulted in hydration, oxidation and transfer of mobile elements (LILE, Cu) from the dacite to the mafic melts and prompted massive amphibole crystallization. In Buag enclaves, S-bearing phases (sulfides, apatite) and melt inclusions in amphibole and plagioclase record the evolution of sulfur partition among melt, crystal and fluid phases during magma cooling and oxidation. At high temperature, sulfur is partitioned between andesitic melt and sulfides (Ni-pyrrhotite). Magma cooling, oxidation and hydration resulted in exsolution of a S-Cl-H2O vapor phase at the S-solubility minimum near the sulfide-sulfate redox boundary. Primary magmatic sulfide (pyrrhotite) and xenocrystic sulfide grains (pyrite), recycled together with olivines and pyroxenes from old mafic intrusives, were replaced by Cu-rich phases (chalcopyrite, cubanite) and, partially, by Ba-Sr sulfate. Sulfides degassed and transformed into residual spongy magnetite in response to fS2 drop during final magma ascent and decompression. Our research suggests that a complete evaluation of the sulfur budget at Pinatubo must take into account the en route S assimilation from the country rocks. Moreover, this study shows that the efficiency of sulfur transfer between mafic recharges and injected magmas is controlled by the extent and rate of mingling, hydrous flushing and melt oxidation. Vigorous mixing/mingling and transformation of the magmatic recharge into a spray of small enclaves is required in order to efficiently strip their primary S-content that otherwise remains locked in the sulfides. Hydrous flushing increases the magma oxidation state of the recharges and modifies their primary volatile concentrations that cannot be recovered by the study of late-formed mineral phases and melt inclusions. Conversely, S stored in both late-formed Cu-rich sulfides and interstitial rhyolitic melt represents the pre-eruptive sulfur budget immediately available for release from mafic enclaves during their decompression. ?? 2008 Elsevier B.V.

San Rafael, Peru: geology and structure of the worlds richest tin lode

NASA Astrophysics Data System (ADS)

Mlynarczyk, Michael S. J.; Sherlock, Ross L.; Williams-Jones, Anthony E.

2003-08-01

The San Rafael mine exploits an unusually high grade, lode-type Sn-Cu deposit in the Eastern Cordillera of the Peruvian Central Andes. The lode is centered on a shallow-level, Late Oligocene granitoid stock, which was emplaced into early Paleozoic metasedimentary rocks. It has a known vertical extent exceeding 1,200 m and displays marked vertical primary metal zoning, with copper overlying tin. The tin mineralization occurs mainly as cassiterite-quartz-chlorite veins and as cassiterite in breccias. The bulk of it is hosted by a K-feldspar megacrystic, biotite- and cordierite-bearing leucomonzogranite, which is the most distinctive phase of the pluton. Copper mineralization occurs predominantly in the veins that straddle the metasedimentary rock-intrusion contact or are hosted entirely by slates. Both tin and copper mineralization are associated with strong chloritic alteration, which is superimposed on an earlier episode of sericitization and tourmaline-quartz veining. Based on the distribution of alteration and ore mineralogy, cassiterite deposition and subsequent chalcopyrite precipitation are believed to have been the result of a single, prolonged hydrothermal event. The source of the metals is inferred to be a highly evolved, peraluminous magma, related to the leucomonzogranitic phase of the San Rafael pluton. Preliminary fluid inclusion microthermometry suggests that ore deposition took place during the mixing of moderate and low salinity fluids, which were introduced in a series of pulses. Several large fault-jogs, created by sinistral-normal, strike-slip movement, are interpreted to have focused synkinematic magmatic fluids and permitted their effective mixing with meteoric waters. It is proposed that this mixing led to rapid oxidation of Sn (II) chloride species and caused supersaturation of the fluids in cassiterite, resulting in the development of localized, high-grade ore shoots. A favorable structural regime that promoted large-scale mixing of two fluids originating under very different physico-chemical conditions appears to have been the key factor responsible for the unusual richness of the deposit.

Direct-writing of copper-based micropatterns on polymer substrates using femtosecond laser reduction of copper (II) oxide nanoparticles

NASA Astrophysics Data System (ADS)

Mizoshiri, Mizue; Ito, Yasuaki; Sakurai, Junpei; Hata, Seiichi

2017-04-01

Copper (Cu)-based micropatterns were fabricated on polymer substrates using femtosecond laser reduction of copper (II) oxide (CuO) nanoparticles. CuO nanoparticle solution, which consisted of CuO nanoparticles, ethylene glycol as a reductant agent, and polyvinylpyrrolidone as a dispersant, was spin-coated on poly(dimethylsiloxane) (PDMS) substrates and was irradiated by focused femtosecond laser pulses to fabricate Cu-based micropatterns. When the laser pulses were raster-scanned onto the solution, CuO nanoparticles were reduced and sintered. Cu-rich and copper (I)-oxide (Cu2O)-rich micropatterns were formed at laser scanning speeds of 15 mm/s and 0.5 mm/s, respectively, and at a pulse energy of 0.54 nJ. Cu-rich electrically conductive micropatterns were obtained without significant damages on the substrates. On the other hand, Cu2O-rich micropatterns exhibited no electrical conductivity, indicating that microcracks were generated on the micropatterns by thermal expansion and shrinking of the substrates. We demonstrated a direct-writing of Cu-rich micro-temperature sensors on PDMS substrates using the foregoing laser irradiation condition. The resistance of the fabricated sensors increased with increasing temperature, which is consistent with that of Cu. This direct-writing technique is useful for fabricating Cu-polymer composite microstructures.

Exhibition of veiled features in diffusion bonding of titanium alloy and stainless steel via copper

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Laha, Tapas; Roy, Deb; Chatterjee, Subrata

2017-11-01

An investigation was carried out to know the extent of influence of bonding-time on the interface structure and mechanical properties of diffusion bonding (DB) of TiA|Cu|SS. DB of Ti6Al4V (TiA) and 304 stainless steel (SS) using pure copper (Cu) of 200-μm thickness were processed in vacuum using 4-MPa bonding-pressure at 1123 K from 15 to 120 min in steps of 15 min. Preparation of DB was not possible when bonding-time was less than 60 min as the bonding at Cu|SS interface was unsuccessful in spite of effective bonding at TiA|Cu interface; however, successful DB were produced when the bonding-time was 60 min and beyond. DB processed for 60 and 75 min (classified as shorter bonding-time interval) showed distinctive characteristics (structural, mechanical, and fractural) as compared to the DB processed for 90, 105, and 120 min (classified as longer bonding-time interval). DB processed for 60 and 75 min exhibited layer-wise Cu-Ti-based intermetallics at TiA|Cu interface, whereas Cu|SS interface was completely free from reaction products. The layer-wise structure of Cu-Ti-based intermetallics were not observed at TiA|Cu interface in the DB processed for longer bonding-time; however, the Cu|SS interface had layer-wise ternary intermetallic compounds (T1, T2, and T3) of Cu-Fe-Ti-based along with σ phase depending upon the bonding-time chosen. Diffusivity of Ti-atoms in Cu-layer (DTi in Cu-layer) was much greater than the diffusivity of Fe-atoms in Cu-layer (DFe in Cu-layer). Ti-atoms reached Cu|SS interface but Fe-atoms were unable to reach TiA|Cu interface. It was observed that DB fractured at Cu|SS interface when processed for shorter bonding-time interval, whereas the DB processed for longer bonding-time interval fractured apparently at the middle of Cu-foil region predominantly due to the existence of brittle Cu-Fe-Ti-based intermetallics.

Development of Chalcopyrite Crystals for Nonlinear Optical Applications

DTIC Science & Technology

1974-12-01

write the expansion ol the homopolar and the heteropolar part of the mean energy gap in the following way. £.(«) - £. + (a«», + (a.)’*, + (Ha) C...a nearly linear relation over a wide 7 —12-um spectral range. We therefore used a 1 stepping motor and synchronously rotated the AgGaSe, crystal

Electrochemical treatment of aqueous solutions of organic pollutants by electro-Fenton with natural heterogeneous catalysts under pressure using Ti/IrO2-Ta2O5 or BDD anodes.

PubMed

Ltaïef, Aziza Hadj; Sabatino, Simona; Proietto, Federica; Ammar, Salah; Gadri, Abdellatif; Galia, Alessandro; Scialdone, Onofrio

2018-07-01

The treatment of toxic organic pollutants by electro-Fenton (EF) presents some drawbacks such as the necessity to work at low pH and the low solubility of oxygen in water contacted with air or oxygen at room pressure that results often in slow and relatively low abatements. Here, the coupled adoption of natural heterogeneous catalysts and of relatively high pressure was proposed in order to improve the performances of EF for the treatment of organic pollutants. Caffeic acid (CA) and 3-chlorophenol were used as model resistant organic pollutants. EF process was performed using both conventional homogeneous FeSO 4 and natural heterogeneous catalysts (pyrite, chalcopyrite, Fe 2 O 3 and Fe 3 O 4 ) as iron catalysts and oxygen at various pressures in the absence or in the presence of BDD anode. The effect of the nature of the catalyst, the oxygen pressure, the current density and the catalyst load was widely investigated in order to optimize the process. It was shown that the coupled utilization of a natural heterogeneous catalyst such as chalcopyrite and a relatively high pressure allows to obtain the total removal of CA and a high removal of the TOC (about 75%) in short times (2 h) with relatively high current efficiencies using an Iridium based anode. In the case of 3-chlorophenol, the utilization of a BDD anode was necessary to achieve a high removal of the pollutant and the TOC. It was shown that the removal of 3-chlorophenol can be effectively performed in different water bodies and with different initial concentrations of 3-chlorophenol. Copyright © 2018 Elsevier Ltd. All rights reserved.

Modified sulfur isotopic compositions of sulfides in the nakhlites and Chassigny

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

Greenwood, J.P.; Riciputi, L.R.; McSween, H.Y. Jr.

Variable sulfur isotopic ratios of sulfide minerals in the nakhlites and Chassigny have been measured by ion microprobe. The ranges and means of {delta}{sup 34}S values of pyrrhotite and pyrite in nakhlites become more negative in the sequence Nakhla > Governador Valadares > Lafayette. This is also the sequence of increasing degrees of subsolidus re-equilibration, suggesting that {sup 32}S enrichment may be related to the subsolidus thermal history. A chalcopyrite vein cross cutting a pyrrhotite in Nakhla, coupled with chalcopyrite having slightly lighter {delta}{sup 34}S values, suggests that subsolidus fluids may have become isotopically lighter (with respect to sulfur) inmore » Nakhla with time. Pyrite has replaced pyrrhotite in Lafayette, suggesting that {line_integral}O{sub 2} and/or {line_integral}S{sub 2} increased after pyrrhotite crystallization. A model involving subsolidus hydrothermal modification of igneous sulfide minerals (with {delta}{sup 34}S {approximately} 0{degree}) due to late-stage oxidation of fluids provides a reasonable explanation for the sulfur isotopic systematics of the nakhlites and Chassigny. Sulfur isotopic alteration is believed to have occurred during the waning stages of nakhlite magmatism, rather than during a much later low-temperature (<100 C) iddingsite formation event, based on the ineffectiveness of abiogenic sulfur isotopic fractionation below 200 C. Variable mixing of two isotopically different fluids also could have produced the observed fractionations, although an isotopically light reservoir of sulfur is problematic. Other possible mechanisms evaluated to explain the sulfur isotopic values of the sulfide minerals include martial mantle heterogeneity, possible influence of martial biological processes, and magmatic degassing of SO{sub 2}.« less

Geology, mineralization, and fluid inclusion characteristics of the Kashkasu W-Mo-Cu skarn deposit associated with a high-potassic to shoshonitic igneous suite in Kyrgyzstan, Tien Shan: Toward a diversity of W mineralization in Central Asia

NASA Astrophysics Data System (ADS)

Soloviev, Serguei G.; Kryazhev, Sergey G.

2018-03-01

The Kashkasu deposit is part of the subduction-related Late Paleozoic (Late Carboniferous) metallogenic belt of Tien Shan. It is associated with a multiphase monzodiorite-monzonite-granodiorite-granite pluton of the magnetite-series high-K calc-alkaline to shoshonitic igneous suite. The deposit contains zones of W-Mo-Cu oxidized prograde and retrograde skarns, with abundant andraditic garnet, magnetite, locally scapolite and K-feldspar, as well as scheelite, chalcopyrite, and molybdenite. Skarns are overprinted by quartz-carbonate-sericite (phyllic alteration) zones with scheelite and sulfides. Prograde calcic skarn and initial retrograde skarns were formed from a high temperature (650 °C to 450-550 °C), high pressure (2000 bars to 600-900 bars) magmatic-hydrothermal low- to high-salinity aqueous chloride fluid. The gradual fluid evolution was interrupted by the intrusion of granodiorite and likely associated release of low-salinity (∼7-8 wt% NaCl equiv.) fluid. Ascent of this fluid to shallower levels and/or its cooling to 400-500 °C has resulted in phase separation into low-salinity (2.1-3.1 wt% NaCl equiv.) vapor and coexisting brine (35-40 wt% NaCl equiv.). The boiling was coincident with most intense scheelite deposition in retrograde skarn. Later retrograde skarn assemblages were formed from a gaseous, low- to moderate-salinity (3.4-8.1 wt% NaCl equiv.) fluid and then from high salinity (37-42 wt% NaCl equiv.) aqueous chloride fluids, the latter being enriched in Ca (17-20 wt% CaCl2) that could also affect scheelite deposition. Another cycle of fluid exsolution from crystallizing magma corresponded to quartz-carbonate-sericite-scheelite-sulfide (phyllic) alteration stage, with the early low-salinity (5.3-8.4 wt% NaCl-equiv.) fluid followed by later high-salinity (33.5-38.2 wt% NaCl-equiv.) fluid. The sulfur isotope data (δ34S = +5.1 to +9.0) suggest significant sulfur sourcing from sedimentary rocks enriched in seawater sulfate, possibly evaporites.

Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

PubMed

Albo, Jonathan; Vallejo, Daniel; Beobide, Garikoitz; Castillo, Oscar; Castaño, Pedro; Irabien, Angel

2017-03-22

The electrocatalytic reduction of CO 2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu 3 (μ 6 -C 9 H 3 O 6 ) 2 ] n ; (2) CuAdeAce MOF, [Cu 3 (μ 3 -C 5 H 4 N 5 ) 2 ] n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C 2 H 2 N 2 S 2 )] n ; and (4) CuZnDTA MOA, [Cu 0.6 Zn 0.4 (μ-C 2 H 2 N 2 S 2 )] n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO 2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO 2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm -2 , an electrolyte-flow/area ratio of 3 mL min cm -2 , and a gas-flow/area ratio of 20 mL min cm -2 . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-Nitrogen-Doped Graphene Hybrid as an Electrochemical Sensing Platform for Distinguishing DNA Bases.

PubMed

Sun, Shu-Wen; Liu, Hai-Ling; Zhou, Yue; Wang, Feng-Bin; Xia, Xing-Hua

2017-10-17

An electrochemical sensor using ultralight and porous copper-nitrogen-doped graphene (CuNRGO) nanocomposite as the electrocatalyst has been constructed to simultaneously determine DNA bases such as guanine (G) and cytosine (C), adenine (A), and thymine (T). The nanocomposite is synthesized by thermally annealing an ice-templated structure of graphene oxide (GO) and Cu(phen) 2 . Because of the unique structure and the presence of Cu 2+ -N active sites, the CuNRGO exhibits outstanding electrocatalytic activity toward the oxidation of free DNA bases. After optimizing the experimental conditions, the CuNRGO-based electrochemical sensor shows good linear responses for the G, A, T, and C bases in the concentration ranges of 0.132-6.62 μM, 0.37-5.18 μM, 198.2-5551 μM, and 270.0-1575 μM, respectively. The results demonstrate that CuNRGO is a promising electrocatalyst for electrochemical sensing devices.

Structural and electronic properties of Cu2Q and CuQ (Q = O, S, Se, and Te) studied by first-principles calculations

NASA Astrophysics Data System (ADS)

Zhao, Ting; Wang, Yu-An; Zhao, Zong-Yan; Liu, Qiang; Liu, Qing-Ju

2018-01-01

In order to explore the similarity, difference, and tendency of binary copper-based chalcogenides, the crystal structure, electronic structure, and optical properties of eight compounds of Cu2Q and CuQ (Q = O, S, Se, and Te) have been calculated by density functional theory with HSE06 method. According to the calculated results, the electronic structure and optical properties of Cu2Q and CuQ present certain similarities and tendencies, with the increase of atomic number of Q elements: the interactions between Cu-Q, Cu-Cu, and Q-Q are gradually enhancing; the value of band gap is gradually decreasing, due to the down-shifting of Cu-4p states; the covalent feature of Cu atoms is gradually strengthening, while their ionic feature is gradually weakening; the absorption coefficient in the visible-light region is also increasing. On the other hand, some differences can be found, owing to the different crystal structure and component, for example: CuO presents the characteristics of multi-band gap, which is very favorable to absorb infrared-light; the electron transfer in CuQ is stronger than that in Cu2Q; the absorption peaks and intensity are very strong in the ultraviolet-light region and infrared-light region. The findings in the present work will help to understand the underlying physical mechanism of binary copper-based chalcogenides, and available to design novel copper-based chalcogenides photo-electronics materials and devices.

Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

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

Zhang, Jinfang, E-mail: zjf260@jiangnan.edu.cn; Wang, Chao; Wang, Yinlin

2015-11-15

The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{supmore » 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties. - Highlights: • Reaction variables affecting Mo(W)/S/Cu cluster-based CPs is firstly explored. • Replacing central metal atom had a pronounced effect on W/S/Cu cluster-based CPs. • Photocatalytic activities of Mo(W)/S/Cu cluster-based CPs are firstly investigated.« less

Electrochemical properties of copper-based compounds with polyanion frameworks

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

Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota

The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed basedmore » on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.« less

A novel extended architecture with 4 6·6 4 topology based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(I) units

NASA Astrophysics Data System (ADS)

Tong, Ruizhan; Ren, Xiaoyu; Li, Zuoxi; Liu, Bin; Hu, Huaiming; Xue, Ganglin; Fu, Feng; Wang, Jiwu

2010-09-01

A novel inorganic-organic hybrid compound based on mixed-valence Wells-Dawson arsenotungstate and mixed-ligand Cu(I) units, Cu 8I(imi) 4(bpy) 6(H 2O)[As 2VW 2VW 16VlO 62]·2H 2O ( 1) (bpy=4,4'-bipydine; imi=imidazole), has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, luminescent spectrum and single crystal X-ray diffraction. Single-crystal X-ray diffraction revealed that four terminal and three bridging oxygen atoms of the Wells-Dawson cluster are coordinated to Cu(I) ions and form an unprecedented hepta-supporting polyoxometalate. The functionalized arsenotungstates are further connected by two kinds of tridentate linkers, Imi-Cu-(bpy)-Cu-(bpy)-Cu-(bpy)-Cu-Imi and Imi-Cu-(bpy)-Cu-(bpy)-Cu-H 2O, to construct a 3D framework with 4 6·6 4 topology. The hybrid material has an intense emission at about 397 nm.

Retention modeling for ultra-thin density of Cu-based conductive bridge random access memory (CBRAM)

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

Aga, Fekadu Gochole; Woo, Jiyong; Lee, Sangheon

We investigate the effect of Cu concentration On-state resistance retention characteristics of W/Cu/Ti/HfO{sub 2}/Pt memory cell. The development of RRAM device for application depends on the understanding of the failure mechanism and the key parameters for device optimization. In this study, we develop analytical expression for cations (Cu{sup +}) diffusion model using Gaussian distribution for detailed analysis of data retention time at high temperature. It is found that the improvement of data retention time depends not only on the conductive filament (CF) size but also on Cu atoms concentration density in the CF. Based on the simulation result, better datamore » retention time is observed for electron wave function associated with Cu{sup +} overlap and an extended state formation. This can be verified by analytical calculation of Cu atom defects inside the filament, based on Cu{sup +} diffusion model. The importance of Cu diffusion for the device reliability and the corresponding local temperature of the filament were analyzed by COMSOL Multiphysics simulation.« less

Soldering-induced Cu diffusion and intermetallic compound formation between Ni/Cu under bump metallization and SnPb flip-chip solder bumps

NASA Astrophysics Data System (ADS)

Huang, Chien-Sheng; Jang, Guh-Yaw; Duh, Jenq-Gong

2004-04-01

Nickel-based under bump metallization (UBM) has been widely used as a diffusion barrier to prevent the rapid reaction between the Cu conductor and Sn-based solders. In this study, joints with and without solder after heat treatments were employed to evaluate the diffusion behavior of Cu in the 63Sn-37Pb/Ni/Cu/Ti/Si3N4/Si multilayer structure. The atomic flux of Cu diffused through Ni was evaluated from the concentration profiles of Cu in solder joints. During reflow, the atomic flux of Cu was on the order of 1015-1016 atoms/cm2s. However, in the assembly without solder, no Cu was detected on the surface of Ni even after ten cycles of reflow. The diffusion behavior of Cu during heat treatments was studied, and the soldering-process-induced Cu diffusion through Ni metallization was characterized. In addition, the effect of Cu content in the solder near the solder/intermetallic compound (IMC) interface on interfacial reactions between the solder and the Ni/Cu UBM was also discussed. It is evident that the (Cu,Ni)6Sn5 IMC might form as the concentration of Cu in the Sn-Cu-Ni alloy exceeds 0.6 wt.%.

Reactions in Electrodeposited Cu/Sn and Cu/Ni/Sn Nanoscale Multilayers for Interconnects

PubMed Central

Chia, Pay Ying; Haseeb, A. S. M. A.; Mannan, Samjid Hassan

2016-01-01

Miniaturization of electronic devices has led to the development of 3D IC packages which require ultra-small-scale interconnections. Such small interconnects can be completely converted into Cu-Sn based intermetallic compounds (IMCs) after reflow. In an effort to improve IMC based interconnects, an attempt is made to add Ni to Cu-Sn-based IMCs. Multilayer interconnects consisting of stacks of Cu/Sn/Cu/Sn/Cu or Cu/Ni/Sn/Ni/Sn/Cu/Ni/Sn/Ni/Cu with Ni = 35 nm, 70 nm, and 150 nm were electrodeposited sequentially using copper pyrophosphate, tin methanesulfonic, and nickel Watts baths, respectively. These multilayer interconnects were investigated under room temperature aging conditions and for solid-liquid reactions, where the samples were subjected to 250 °C reflow for 60 s and also 300 °C for 3600 s. The progress of the reaction in the multilayers was monitored by using X-ray Diffraction, Scanning Electron Microscope, and Energy dispersive X-ray Spectroscopy. FIB-milled samples were also prepared for investigation under room temperature aging conditions. Results show that by inserting a 70 nanometres thick Ni layer between copper and tin, premature reaction between Cu and Sn at room temperature can be avoided. During short reflow, the addition of Ni suppresses formation of Cu3Sn IMC. With increasing Ni thickness, Cu consumption is decreased and Ni starts acting as a barrier layer. On the other hand, during long reflow, two types of IMC were found in the Cu/Ni/Sn samples which are the (Cu,Ni)6Sn5 and (Cu,Ni)3Sn, respectively. Details of the reaction sequence and mechanisms are discussed. PMID:28773552

A novel nonenzymatic amperometric hydrogen peroxide sensor based on CuO@Cu2O nanowires embedded into poly(vinyl alcohol).

PubMed

Chirizzi, Daniela; Guascito, Maria Rachele; Filippo, Emanuela; Tepore, Antonio

2016-01-15

A new, very simple, rapid and inexpensive nonenzymatic amperometric sensor for hydrogen peroxide (H2O2) detection is proposed. It is based on the immobilization of cupric/cuprous oxide core shell nanowires (CuO@Cu2O-NWs) in a poly(vinyl alcohol) (PVA) matrix directly drop casted on a glassy carbon electrode surface to make a CuO@Cu2O core shell like NWs PVA embedded (CuO@Cu2O-NWs/PVA) sensor. CuO nanowires with mean diameters of 120-170nm and length in the range 2-5μm were grown by a simple catalyst-free thermal oxidation process based on resistive heating of pure copper wires at ambient conditions. The oxidation process of the copper wire surface led to the formation of a three layered structure: a thick Cu2O bottom layer, a CuO thin intermediate layer and CuO nanowires. CuO nanowires were carefully scratched from Cu2O layer with a sharp knife, dispersed into ethanol and sonicated. Then, the NWs were embedded in PVA matrix. The morphological and spectroscopic characterization of synthesized CuO-NWs and CuO@Cu2O-NWs/PVA were performed by transmission electron microscopy (TEM), selected area diffraction pattern (SAD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis. Moreover a complete electrochemical characterization of these new CuO@Cu2O-NWs/PVA modified glassy carbon electrodes was performed by Cyclic Voltammetry (CV) and Cronoamperometry (CA) in phosphate buffer (pH=7; I=0.2) to investigate the sensing properties of this material against H2O2. The electrochemical performances of proposed sensors as high sensitivity, fast response, reproducibility and selectivity make them suitable for the quantitative determination of hydrogen peroxide substrate in batch analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Textural and stable isotope studies of the Big Mike cupriferous volcanogenic massive sulfide deposit, Pershing County, Nevada.

USGS Publications Warehouse

Rye, R.O.; Roberts, R.J.; Snyder, W.S.; Lahusen, G.L.; Motica, J.E.

1984-01-01

The Big Mike deposit is a massive sulphide lens entirely within a carbonaceous argillite of the Palaeozoic Havallah pelagic sequence. The massive ore contains two generations of pyrite, a fine- and a coarse-grained variety; framboidal pyrite occurs in the surrounding carbonaceous argillite. Coarse grained pyrite is largely recrystallized fine-grained pyrite and is proportionately more abundant toward the margins of the lens. Chalcopyrite and sphalerite replace fine-grained pyrite and vein-fragmented coarse-grained pyrite. Quartz fills openings in the sulphide fabric. S-isotope data are related to sulphide mineralogy and textures. Isotopically light S in the early fine-grained pyrite was probably derived from framboidal biogenic pyrite. The S-isotope values of the later coarse-grained pyrite and chalcopyrite probably reflect a combination of reduced sea-water sulphate and igneous S. Combined S- and O-isotope and textural data accord with precipitation of fine-grained pyrite from a hydrothermal plume like those at the East Pacific Rise spreading centre at lat. 21oN. The primary material was recystallized and mineralized by later fluids of distinctly different S-isotope composition. -G.J.N.

Integration of chemical and toxicological tools to assess the bioavailability of copper derived from different copper-based fungicides in soil.

PubMed

Wang, Quan-Ying; Sun, Jing-Yue; Xu, Xing-Jian; Yu, Hong-Wen

2018-06-20

Because the extensive use of Cu-based fungicides, the accumulation of Cu in agricultural soil has been widely reported. However, little information is known about the bioavailability of Cu deriving from different fungicides in soil. This paper investigated both the distribution behaviors of Cu from two commonly used fungicides (Bordeaux mixture and copper oxychloride) during the aging process and the toxicological effects of Cu on earthworms. Copper nitrate was selected as a comparison during the aging process. The distribution process of exogenous Cu into different soil fractions involved an initial rapid retention (the first 8 weeks) and a following slow continuous retention. Moreover, Cu mainly moved from exchangeable and carbonate fractions to Fe-Mn oxides-combined fraction during the aging process. The Elovich model fit well with the available Cu aging process, and the transformation rate was in the order of Cu(NO 3 ) 2 > Bordeaux mixture > copper oxychloride. On the other hand, the biological responses of earthworms showed that catalase activities and malondialdehyde contents of the copper oxychloride treated earthworms were significantly higher than those of Bordeaux mixture treated earthworms. Also, body Cu loads of earthworms from different Cu compounds spiked soils were in the following order: copper oxychloride > Bordeaux mixture. Thus, the bioavailability of Cu from copper oxychloride in soil was significantly higher than that of Bordeaux mixture, and different Cu compounds should be taken into consideration when studying the bioavailability of Cu-based fungicides in the soil. Copyright © 2018 Elsevier Inc. All rights reserved.

One-Step Catalytic Synthesis of CuO/Cu2O in a Graphitized Porous C Matrix Derived from the Cu-Based Metal-Organic Framework for Li- and Na-Ion Batteries.

PubMed

Kim, A-Young; Kim, Min Kyu; Cho, Keumnam; Woo, Jae-Young; Lee, Yongho; Han, Sung-Hwan; Byun, Dongjin; Choi, Wonchang; Lee, Joong Kee

2016-08-03

The hybrid composite electrode comprising CuO and Cu2O micronanoparticles in a highly graphitized porous C matrix (CuO/Cu2O-GPC) has a rational design and is a favorable approach to increasing the rate capability and reversible capacity of metal oxide negative materials for Li- and Na-ion batteries. CuO/Cu2O-GPC is synthesized through a Cu-based metal-organic framework via a one-step thermal transformation process. The electrochemical performances of the CuO/Cu2O-GPC negative electrode in Li- and Na-ion batteries are systematically studied and exhibit excellent capacities of 887.3 mAh g(-1) at 60 mA g(-1) after 200 cycles in a Li-ion battery and 302.9 mAh g(-1) at 50 mA g(-1) after 200 cycles in a Na-ion battery. The high electrochemical stability was obtained via the rational strategy, mainly owing to the synergy effect of the CuO and Cu2O micronanoparticles and highly graphitized porous C formed by catalytic graphitization of Cu nanoparticles. Owing to the simple one-step thermal transformation process and resulting high electrochemical performance, CuO/Cu2O-GPC is one of the prospective negative active materials for rechargeable Li- and Na-ion batteries.

CuS-Based Theranostic Micelles for NIR-Controlled Combination Chemotherapy and Photothermal Therapy and Photoacoustic Imaging.

PubMed

Chen, Guojun; Ma, Ben; Wang, Yuyuan; Xie, Ruosen; Li, Chun; Dou, Kefeng; Gong, Shaoqin

2017-12-06

Cancer remains a major threat to human health due to low therapeutic efficacies of currently available cancer treatment options. Nanotheranostics, capable of simultaneous therapy and diagnosis/monitoring of diseases, has attracted increasing amounts of attention, particularly for cancer treatment. In this study, CuS-based theranostic micelles capable of simultaneous combination chemotherapy and photothermal therapy (PTT), as well as photoacoustic imaging, were developed for targeted cancer therapy. The micelle was formed by a CuS nanoparticle (NP) functionalized by thermosensitive amphiphilic poly(acrylamide-acrylonitrile)-poly(ethylene glycol) block copolymers. CuS NPs under near-infrared (NIR) irradiation induced a significant temperature elevation, thereby enabling NIR-triggered PTT. Moreover, the hydrophobic core formed by poly(acrylamide-acrylonitrile) segments used for drug encapsulation exhibited an upper critical solution temperature (UCST; ∼38 °C), which underwent a hydrophobic-to-hydrophilic transition once the temperature rose above the UCST induced by NIR-irradiated CuS NPs, thereby triggering a rapid drug release and enabling NIR-controlled chemotherapy. The CuS-based micelles conjugated with GE11 peptides were tested in an epidermal growth factor receptor-overexpressing triple-negative breast cancer model. In both two-dimensional monolayer cell and three-dimensional multicellular tumor spheroid models, GE11-tagged CuS-based micelles under NIR irradiation, enabling the combination chemotherapy and PTT, exhibited the best therapeutic outcome due to a synergistic effect. These CuS-based micelles also displayed a good photoacoustic imaging ability under NIR illumination. Taken together, this multifunctional CuS-based micelle could be a promising nanoplatform for targeted cancer nanotheranostics.

Metallicity of Ca 2Cu 6P 5 with single and double copper-pnictide layers

DOE PAGES

Li, Li; Parker, David; Chi, Miaofang; ...

2016-02-16

We report thermodynamic and transport properties, and also theoretical calculations, for Cu-based compound Ca 2Cu 6P 5 and compare with CaCu 2-δP 2. Both materials have layers of edge-sharing copper pnictide tetrahedral CuP 4, similar to Fe–As and Fe–Se layers (with FeAs 4, FeSe 4) in the iron-based superconductors. Despite the presence of this similar transition-metal pnictide layer, we find that both Ca 2Cu 6P 5 and CaCu 2-δP 2 have temperature-independent magnetic susceptibility and show metallic behavior with no evidence of either magnetic ordering or superconductivity down to 1.8 K CaCu 2-δP 2 is slightly off-stoichiometric, with δ =more » 0.14. Theoretical calculations suggest that unlike Fe 3d-based magnetic materials with a large density of states (DOS) at the Fermi surface, Cu have comparatively low DOS, with the majority of the 3d spectral weight located well below Fermi level. The room-temperature resistivity value of Ca 2Cu 6P 5 is only 9 μΩ-cm, due to a substantial plasma frequency and an inferred electron-phonon coupling λ of 0.073 (significantly smaller than that of metallic Cu). Also, microscopy result shows that Cu–Cu distance along the c-axis within the double layers can be very short (2.5 Å), even shorter than metallic elemental copper bond (2.56 Å). The value of dρ/dT for CaCu 2-δP 2 at 300 K is approximately three times larger than in Ca 2Cu 6P 5, which suggests the likelihood of stronger electron-phonon coupling. Lastly, this study shows that the details of Cu–P layers and bonding are important for their transport characteristics. In addition, it emphasizes the remarkable character of the DOS of ‘122’ iron-based materials, despite much structural similarities.« less

Development of Cu Clad Cu-Zr Based Metallic Glass and Its Solderability

NASA Astrophysics Data System (ADS)

Terajima, Takeshi; Kimura, Hisamichi; Inoue, Akihisa

Soldering is a candidate technique for joining metallic glasses. It can be processed far below the crystallization temperatures of the various metallic glasses so that there is no possibility of crystallization. However, wettability of Cu-Zr based metallic glass by Pb free solder is poor because a strong surface oxide film interferes direct contact between them. To overcome the problem, Cu thin film clad metallic glass was developed. It was preliminary produced by casting a melt of Cu36Zr48Al8Ag8 pre-alloy into Cu mold cavity, inside which Cu thin film with 2 mm in thickness was set on the wall. Cu36Zr48Al8Ag8 metallic glass, whose surface Cu thin film was welded to, was successfully produced. From the microstructure analyses, it was found that reaction layer was formed at the interface between Cu and Cu36Zr48Al8Ag8 metallic glass, however, there was no oxide in the Cu clad layer. Solderability to the metallic glass was drastically increased. The Cu clad layer played an important role to prevent the formation of surface oxide film and consequently improved the solderability.

Low thermal budget photonic processing of highly conductive Cu interconnects based on CuO nanoinks. Potential for flexible printed electronics

DOE PAGES

Rager, Matthew S.; Aytug, Tolga; Veith, Gabriel M.; ...

2015-12-31

The developing field of printed electronics nanoparticle based inks such as CuO show great promise as a low-cost alternative to other metal-based counterparts (e.g., silver). In particular, CuO inks significantly eliminate the issue of particle oxidation, before and during the sintering process, that is prevalent in Cu-based formulations. We report here the scalable and low-thermal budget photonic fabrication of Cu interconnects employing a roll-to-roll compatible pulse-thermal-processing (PTP) technique that enables phase reduction and subsequent sintering of inkjet-printed CuO patterns onto flexible polymer templates. Detailed investigations of curing and sintering conditions were performed to understand the impact of PTP system conditionsmore » on the electrical performance of the Cu patterns. Specifically, the impact of energy and power of photonic pulses on print conductivity was systematically studied by varying the following key processing parameters: pulse intensity, duration and sequence. Through optimization of such parameters, highly conductive prints in < 1 s with resistivity values as low as 100 n m has been achieved. We also observed that the introduction of an initial ink-drying step in ambient atmosphere, after the printing and before sintering, leads to significant improvements in mechanical integrity and electrical performance of the printed Cu patterns. Moreover, the viability of CuO reactive inks, coupled with the PTP technology and pre ink-drying protocols, has also been demonstrated for the additive integration of a low-cost Cu temperature sensor onto a flexible polymer substrate.« less

Electrodeposition mechanism and characterization of Ni-Cu alloy coatings from a eutectic-based ionic liquid

NASA Astrophysics Data System (ADS)

Wang, Shaohua; Guo, Xingwu; Yang, Haiyan; Dai, JiChun; Zhu, Rongyu; Gong, Jia; Peng, Liming; Ding, Wenjiang

2014-01-01

The electrodeposition mechanism, microstructures and corrosion resistances of Ni-Cu alloy coatings on Cu substrate were investigated in a choline chloride-urea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChCl-urea IL) containing nickel and copper chlorides. Cyclic voltammetry showed that the onset reduction potentials for Cu (∼-0.32 V) and for Ni (∼-0.47 V) were close to each other, indicating that Ni-Cu co-deposition could be easily achieved in the absence of complexing agent which was indispensable in aqueous plating electrolyte. Chronoamperometric investigations revealed that Ni-Cu deposits followed the three-dimensional instantaneous nucleation/growth mechanism, thus producing a solid solution. The compositions, microstructures and corrosion resistances of Ni-Cu alloy coatings were significantly dependent on the deposition current densities. Ni-Cu alloy coatings were α-Ni(Cu) solid solutions, and the coating containing ∼17.6 at.% Cu exhibited the best corrosion resistance because of its dense and crack-free structure.

Wetting reaction of Sn-Ag based solder systems on Cu substrates plated with Au and/or Pd layer

NASA Astrophysics Data System (ADS)

Liu, C. Y.; Li, Jian; Vandentop, G. J.; Choi, W. J.; Tu, K. N.

2001-05-01

The wetting behavior of SnAg based Pb-free solders on Cu and Cu substrates plated with Au, Pd, and Au/Pd thin films have been studied. The wetting angle and kinetics of interfacial reaction were measured. The Au-plated substrates exhibit better wetting than the Pd-plated substrates. In the case of SnAg on Pd-plated Cu, SEM observation revealed that the solder cap was surrounded by an innerring of Cu-Sn compound and an outer ring of Pd-Sn compound. This implies that the molten SnAg solder had removed the Pd and wetted the Cu directly in the equilibrium state. The effects of pre-doping Cu in the SnAg solder on wetting behavior were also investigated. We found that wettability decreases with increasing Cu content in the solder. We also observed that the SnAgCu solders have a lower Cu consumption rate than the SnAg solder.

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Characteristics of Catalytic Gasification of Natural Coke with H2O in a Fluidized Bed

NASA Astrophysics Data System (ADS)

Lin, L. S.; Zhao, C. S.; Wang, S.; Zhu, G.; Xiang, W. G.

The experimental investigation on gasification characteristics of natural coke from Peicheng, Jiangsu with steam were conducted in a fluidized bed gasifier setup. The effects of several parameters, in terms of the catalyst type, the catalyst mixed manner and the dosage of catalyst over coke on the yield, the components, the heating value of fuel gas and the carbon conversion rate were examined. Results indicate that the fluidized bed gasification technology could overcome the shortcomings of natural coke. Ca-, Fe- and Cu-based nitrates could improve the gasification reaction effectively with a little difference, they could be listed in a descending sequence as follows: Cu-based>Fe-based>Ca-based according to their catalytic effect. The influences of Fe/Ca ratio and Cu/Ca ratio on gasification are similar, gas yield, carbon conversion rate and gas heating value per hour increase as Fe/Ca ratio or Cu/Ca ratio increases, but all of them go up first and then drop with decrease in Fe/Cu ratio. When the dosage of Ca-, Fe- and Cu-based nitrates mixed with the ratio of Ca/Fe/Cu= 10/35/55 is 3%, the best catalytic effect is achieved.

The electric and thermoelectric properties of Cu(II)-Schiff base nano-complexes

NASA Astrophysics Data System (ADS)

Ibrahim, E. M. M.; Abdel-Rahman, Laila H.; Abu-Dief, Ahmed M.; Elshafaie, A.; Hamdan, Samar Kamel; Ahmed, A. M.

2018-05-01

The physical properties, such as electric and optical properties, of metal-Schiff base complexes have been widely investigated. However, their thermoelectric (TE) properties remain unreported. This work presents Cu(II)-Schiff base complexes as promising materials for TE power generation. Therefore, three Cu(II)-Schiff base complexes (namely, [Cu(C32H22N4O2)].3/2H2O, [Cu(C23H17N4O7Br)], and [Cu(C27H22N4O8)].H2O) have been synthesized in nanosized scale. The electric and TE properties have been studied and comprehensive discussions have been presented to promote the nano-complexes (NCs) practical applications in the field of TE power generation. The electrical measurements confirm that the NCs are semiconductors and the electrical conduction process is governed by intermolecular and intramolecular transfer of the charge carriers. The TE measurements reveal that the Cu(II)-Schiff base NCs are nondegenerate P-type semiconductors. The measured Seebeck coefficient values were higher compared to the values reported in previous works for other organic materials indicating that the complexes under study are promising candidates for theremoelectric applications if the electrical conductivity could be enhanced.

Structure dependent selective efficacy of pyridine and pyrrole based Cu(II) Schiff base complexes towards in vitro cytotoxicity, apoptosis and DNA-bases binding in ground and excited state.

PubMed

Koley Seth, Banabithi; Saha, Arpita; Haldar, Srijan; Chakraborty, Partha Pratim; Saha, Partha; Basu, Samita

2016-09-01

This work highlights a systematic and comparative study of the structure-dependent influence of a series of biologically active Cu(II) Schiff base complexes (CSCs) on their in vitro cytotoxicity, apoptosis and binding with polymeric DNA-bases in ground and photo-excited states. The structure-activity relationship of the closely resembled CSCs towards in vitro cytotoxicity and apoptosis against cervical cancerous HeLa and normal human diploid WI-38 cell lines has been investigated by MTT assay and FACS techniques respectively. The steady-state and time-resolved spectroscopic studies have also been carried out to explore the selective binding affinities of the potential complexes towards different polymeric nucleic acid bases (poly d(A), poly d(T), poly d(G), poly d(C), Poly d(G)-Poly d(C)), which enlighten the knowledge regarding their ability in controlling the structure and medium dependent interactions in 'ground' and 'excited' states. The pyridine containing water soluble complexes (CuL(1) and CuL(3)) are much more cytotoxic than the corresponding pyrrole counterparts (CuL(2) and CuL(4)). Moreover the acidic hydrogens in CuL(1) increase its cytotoxicity much more than methyl substitution as in CuL(3). The results of MTT assay and double staining FACS experiments indicate selective inhibition of cell growth (cell viability 39% (HeLa) versus 85% (WI-38)) and occurrence of apoptosis rather than necrosis. The ground state binding of CuL(1) with polymeric DNA bases, especially with guanine rich DNA (Kb=6.41±0.122×10(5)), that enhances its cytotoxic activity, is further confirmed from its binding isotherms. On the other hand the pyrrole substituted CuL(4) complex exhibits the structure and medium dependent selective electron-transfer in triplet state as observed in laser flash photolysis studies followed by magnetic field (MF) effect. Copyright © 2016 Elsevier B.V. All rights reserved.

Mineralogical and Geochemical Characterization of the Kimmeria Intrusion-Related Deposit, Xanthi, NE Greece

NASA Astrophysics Data System (ADS)

Theodoridou, Stella; Melfos, Vasilios; Voudouris, Panagiotis; Miskovic, Aleksandar

2016-04-01

Although intrusion-related systems have not been previously recognized in the European segment of the Tethyan Metallogenic Belt, the Rhodope metallogenic province of SE Balkan peninsula hosts numerous such occurrences. The Kimmeria hydrothermal system incorporates two styles of ore mineralization: i) a massive Au-bearing magnetite-pyrrhotite skarn and ii) a Mo-Cu-Bi-W quartz vein-hosted mineralization, both of which are related to the Oligocene Xanthi pluton (25.5±1.2 to 30±1 My, K-Ar in hornblende and biotite). The Xanthi pluton, consisting of I-type gabbros, monzonites and amphibole-biotite granodiorites, intrudes the basement gneisses, mica schists, amphibolites and marbles of the Southern Rhodope Core Complex; a dome that has gradually exhumed from Paleocene/mid Eocene to Miocene (starting between 65 and >42 to 10 My). The Xanthi pluton emplacement and the magmatically derived hydrothermal fluid circulation were controlled by two major regional structures: the low-angle Kavala-Xanthi-Komotini detachment fault and the Nestos thrust fault. The Kimmeria Au-Cu-Fe skarn mineralization features a well-preserved aureole at the contact between the granodiorite and the surrounding marbles. It consists of two paragenetic stages comprising magnetite and pyrrhotite-rich assemblages. Alteration minerals comprise chlorite and sericite. Bulk chemical analyses of the skarn mineralization revealed relatively high concentration of Cu (1 wt.%), Pb (288 ppm) and Zn (0.74 wt.%). The mineralization is also enriched in As (< 75.8 ppm), W (< 82.1 ppm), Bi (<10.1 ppm), Sb (<331.9 ppm), Ag (< 15.9 ppm), and Sn (< 50 ppm). Te and Au are found in low concentrations of less than 2 ppm and 0.4 ppm, respectively. The Kimmeria Mo-Cu-Bi-W vein-type mineralization comprises a system of cross-cutting and sheeted quartz veins within the granodiorite, with pyrite, chalcopyrite and molybdenite as dominant sulfides. Minor sphalerite, tetrahedrite-tennantite, galena and rutile are also present, while sericite and chlorite as the alteration minerals. The Cu and Mo content of the vein type mineralization exceed 1.0 and 0.2 wt.% respectively, along with < 2.7 ppm Au, 1.3 to 79.5 ppm W and 0.6 to 456 ppm Bi. A first approach fluid study has revealed small variations in δ34S values of sulfides (0 - 2.3 ‰ VCDT) from both types of mineralization suggesting a magmatic source of sulfur. Silicate δ18O values of quartz show a narrow range between 10.3 and 11.2 ‰ (VSMOW) suggesting similar quartz formation for both mineralization types, at relatively low temperatures and probably from the same fluid. Oxygen isotopes values in calcite from the unmineralized marbles and ore specimens are scattered over a wide range from 12.1 to 41.7 ‰ (V-SMOW). They have relatively low carbon isotopic values (-4.8 to 2.1 ‰ V-PDB), indicative of a magmatic δ13C signature and a restricted isotopic exchange with hydrothermal fluids. Primary fluid inclusion studies have revealed the presence of CO2 in the ore fluid, which might have played an important role during the ore genesis irrespective of the mineralization style. This work was financially supported by the Western Tethyan Metallogeny Project (MDRU - The University of British Columbia).

New observations on the Ni-Co ores of the southern Arburese Variscan district (SW Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Naitza, Stefano; Secchi, Francesco; Oggiano, Giacomo; Cuccuru, Stefano

2015-04-01

Among the European Variscan regions, the Arburese district, located in the Paleozoic basement of SW Sardinia (Italy) is remarkable for its metallogenic complexity, and offers good opportunities to investigate time/space and genetic links between post-collisional Variscan intrusive magmatism and mineral deposits. The district hosts a large variety of mineral deposits and occurrences, which include the Pb-Zn (Cu, Ag) mesothermal veins of the Montevecchio Lode System, one of the largest and richest Variscan hydrothermal ore deposit of Europe, now exhausted. Ore deposits are genetically related to the emplacement of the Late Variscan (304±1 Ma) Arbus Pluton, a granitoid composite intrusion ranging from monzogabbroic to granodioritic and to peraluminous leucogranitic rock-types. After more than a century of geological studies in the area, several metallogenic issues are still unresolved; among them, the occurrence in the southern sectors of little known polymetallic Ni-Co-(Pb-Zn-Cu-Ag-Bi) veins, a kind of mineralization quite unusual for the Sardinian basement. These hydrothermal deposits are hosted by very low-grade metamorphic rocks at short distance from the intrusion, where contact effect generate also hornfels. Spatial, structural and textural characters of the hydrothermal system are coherent and in apparent continuity with those of the Montevecchio Lode System. Ni-Co ores are hosted by a system of parallel, 1-2 m thick high-angle veins that discontinuously follow the southwestern and southern contacts of the Arbus Pluton for about 7 km. They constantly dip SSW, sideways with respect to the pluton contact, and show a prevalence of fracture infilling (banded and brecciated) textures, with alternating quartz and siderite bands, cockades and frequent inclusions of wallrock fragments. Wallrocks are usually silicified, bleached and/or sericitized. Systematic studies of ore textures and parageneses from different veins along the system have been performed by standard ore microscopy and SEM-EDS. Ore minerals associations include Ni-Co (Fe, Sb) arsenides/sulfoarsenides (nickeline, rammelsbergite, skutterudite, safflorite, gersdorffite, breithauptite, lollingite, cobaltite), Pb-Zn-Cu-Ag-Bi sulfides (galena, sphalerite, chalcopyrite, tetrahedrite/freibergite, bismuthinite, proustite/pyrargirite, stephanite), native Bi and native Ag. Ore textures and mineral phases relationships allow to envisage the following paragenetic sequence: 1) deposition of quartz (I) and a Ni monoarsenide (nickeline), and antimonide (breithauptite) followed by 2) Ni-,Ni-Co, Co- and Fe- di-, tri- arsenides and sulfoarsenides (rammelsbergite, skutterudite, safflorite, löllingite, cobaltite), with bismuthinite and native Bi; 3) deposition of abundant siderite, with quartz (II), Pb-Zn-Cu-Ag sulfides and sulfosalts and rare native Ag, followed at last by 4) calcite. This sequence depicts a polyphased evolution with alternating gradual and abrupt changes of the physicochemical parameters of a mesothermal fluid initially characterized by Ni-As-(Sb) contents, subsequently evolved to higher contents of As, Co and Bi, and, finally, enriched in S, allowing Pb, Zn, Cu deposition as sulfides and sulfosalts.Thus, the fine alternating rims of pure nickeline (NiAs) and breithauptite (NiSb) in nickeline individuals, detected by SEM-EDS, may be explained by repeated compositional re-equilibrations due to variable As and Sb contents of the fluids; increases in As, and, moreover, the sudden appearance of siderite and sulfides after brecciations indicate further re-opening of the system, related to hydrothermal fracturing and syn-depositional tectonics.

Copper nanoparticles/compounds impact agronomic and physiological parameters in cilantro (Coriandrum sativum).

PubMed

Zuverza-Mena, Nubia; Medina-Velo, Illya A; Barrios, Ana C; Tan, Wenjuan; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

2015-10-01

The environmental impacts of Cu-based nanoparticles (NPs) are not well understood. In this study, cilantro (Coriandrum sativum) was germinated and grown in commercial potting mix soil amended with Cu(OH)2 (Kocide and CuPRO), nano-copper (nCu), micro-copper (μCu), nano-copper oxide (nCuO), micro-copper oxide (μCuO) and ionic Cu (CuCl2) at either 20 or 80 mg Cu per kg. In addition to seed germination and plant elongation, relative chlorophyll content and micro and macroelement concentrations were determined. At both concentrations, only nCuO, μCuO, and ionic Cu, showed statistically significant reductions in germination. Although compared with control, the relative germination was reduced by ∼50% with nCuO at both concentrations, and by ∼40% with μCuO, also at both concentrations, the difference among compounds was not statistically significant. Exposure to μCuO at both concentrations and nCu at 80 mg kg(-1) significantly reduced (p≤ 0.05) shoot elongation by 11% and 12.4%, respectively, compared with control. Only μCuO at 20 mg kg(-1) significantly reduced (26%) the relative chlorophyll content, compared with control. None of the treatments increased root Cu, but all of them, except μCuO at 20 mg kg(-1), significantly increased shoot Cu (p≤ 0.05). Micro and macro elements B, Zn, Mn, Ca, Mg, P, and S were significantly reduced in shoots (p≤ 0.05). Similar results were observed in roots. These results showed that Cu-based NPs/compounds depress nutrient element accumulation in cilantro, which could impact human nutrition.

Demonstration of Ultra High-Strength Nanocrystalline Copper Alloys for Military Applications

DTIC Science & Technology

2012-01-22

Powder Processing vi Acknowledgements The development of these Cu -Ta alloys was accomplished with assistance from the following...nanostructured Cu -Ta based alloy powders with a unique ability to retain their ultrahigh strength properties to temperatures nearing the melting point of the Cu ...nanostructured Cu -Ta based alloy powders with the unique ability to retain their ultrahigh strength properties to temperatures

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.

Susceptibility of 169 USA300 methicillin-resistant Staphylococcus aureus isolates to two copper-based biocides, CuAL42 and CuWB50.

PubMed

Luna, Vicki Ann; Hall, Tony J; King, Debbie S; Cannons, Andrew C

2010-05-01

To test the activity of two copper-based biocides, CuAL42 and CuWB50, and benzalkonium chloride against 169 isolates of methicillin-resistant Staphylococcus aureus (MRSA) pulsotype USA300, a virulent, multiply resistant, widespread clone in the USA. Tests including MIC, MBC and time-kill studies were performed multiple times. The MIC range, MIC(50) and MIC(90) (0.59-18.75, 4.69 and 4.69 ppm, respectively) and the MBC range, MBC(50) and MBC(90) (1.17-18.75, 4.69 and 9.38 ppm, respectively) for CuAL42 were identical with those obtained with CuWB50, except that the MBC range for CuWB50 was wider (0.59-37.5 ppm). In time-kill studies, a 6 log(10) reduction of cfu was achieved within 1 h (150 ppm) and 0.5 h (300 ppm) for CuAL42, and 1.5 h (150 ppm) and 0.75 h (300 ppm) for CuWB50. Both copper-based biocides can effectively kill USA300 MRSA and may facilitate the eradication of the organism from healthcare settings.

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

PubMed

Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

2014-02-01

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

Effects of soil properties on copper toxicity to earthworm Eisenia fetida in 15 Chinese soils.

PubMed

Duan, Xiongwei; Xu, Meng; Zhou, Youya; Yan, Zengguang; Du, Yanli; Zhang, Lu; Zhang, Chaoyan; Bai, Liping; Nie, Jing; Chen, Guikui; Li, Fasheng

2016-02-01

The bioavailability and toxicity of metals in soil are influenced by a variety of soil properties, and this principle should be recognized in establishing soil environmental quality criteria. In the present study, the uptake and toxicity of Cu to the earthworm Eisenia fetida in 15 Chinese soils with various soil properties were investigated, and regression models for predicting Cu toxicity across soils were developed. The results showed that earthworm survival and body weight change were less sensitive to Cu than earthworm cocoon production. The soil Cu-based median effective concentrations (EC50s) for earthworm cocoon production varied from 27.7 to 383.7 mg kg(-1) among 15 Chinese soils, representing approximately 14-fold variation. Soil cation exchange capacity and organic carbon content were identified as key factors controlling Cu toxicity to earthworm cocoon production, and simple and multiple regression models were developed for predicting Cu toxicity across soils. Tissue Cu-based EC50s for earthworm cocoon production were also calculated and varied from 15.5 to 62.5 mg kg(-1) (4-fold variation). Compared to the soil Cu-based EC50s for cocoon production, the tissue Cu-based EC50s had less variation among soils, indicating that metals in tissue were more relevant to toxicity than metals in soil and hence represented better measurements of bioavailability. Copyright © 2015 Elsevier Ltd. All rights reserved.

Microstructure, Mechanical and Wear Behaviors of Hot-Pressed Copper-Nickel-Based Materials for Diamond Cutting Tools

NASA Astrophysics Data System (ADS)

Miranda, G.; Ferreira, P.; Buciumeanu, M.; Cabral, A.; Fredel, M.; Silva, F. S.; Henriques, B.

2017-08-01

The current trend to replace cobalt in diamond cutting tools (DCT) for stone cutting has motivated the study of alternative materials for this end. The present study characterizes several copper-nickel-based materials (Cu-Ni; Cu-Ni-10Sn, Cu-Ni-15Sn, Cu-Ni-Sn-2WC and Cu-Ni-Sn-10WC) for using as matrix material for diamond cutting tools for stone. Copper-nickel-based materials were produced by hot pressing, at a temperature of 850 °C during 15 min and under an applied pressure of 50 MPa. The mechanical properties were evaluated though the shear strength and hardness values. The microstructures and fracture surfaces were analyzed by SEM. The wear behavior of all specimens was assessed using a reciprocating ball-on-plate tribometer. The hot pressing produced compacts with good densification. Sn and WC promoted enhanced mechanical properties and wear performance to Cu-Ni alloys. Cu-Ni-10Sn and Cu-Ni-10Sn-2WC displayed the best compromise between mechanical and wear performance.

A Cell-Adhesive Plasma Polymerized Allylamine Coating Reduces the In Vivo Inflammatory Response Induced by Ti6Al4V Modified with Plasma Immersion Ion Implantation of Copper

PubMed Central

Walschus, Uwe; Hoene, Andreas; Patrzyk, Maciej; Lucke, Silke; Finke, Birgit; Polak, Martin; Lukowski, Gerold; Bader, Rainer; Zietz, Carmen; Podbielski, Andreas; Nebe, J. Barbara; Schlosser, Michael

2017-01-01

Copper (Cu) could be suitable to create anti-infective implants based on Titanium (Ti), for example by incorporating Cu into the implant surface using plasma immersion ion implantation (Cu-PIII). The cytotoxicity of Cu might be circumvented by an additional cell-adhesive plasma polymerized allylamine film (PPAAm). Thus, this study aimed to examine in vivo local inflammatory reactions for Ti6Al4V implants treated with Cu-PIII (Ti-Cu), alone or with an additional PPAAm film (Ti-Cu-PPAAm), compared to untreated implants (Ti). Successful Cu-PIII and PPAAm treatment was confirmed with X-ray Photoelectron Spectroscopy. Storage of Ti-Cu and Ti-Cu-PPAAm samples in double-distilled water for five days revealed a reduction of Cu release by PPAAm. Subsequently, Ti, Ti-Cu and Ti-Cu-PPAAm samples were simultaneously implanted into the neck musculature of 24 rats. After 7, 14 and 56 days, peri-implant tissue was retrieved from 8 rats/day for morphometric immunohistochemistry of different inflammatory cells. On day 56, Ti-Cu induced significantly stronger reactions compared to Ti (tissue macrophages, antigen-presenting cells, T lymphocytes) and to Ti-Cu-PPAAm (tissue macrophages, T lymphocytes, mast cells). The response for Ti-Cu-PPAAm was comparable with Ti. In conclusion, PPAAm reduced the inflammatory reactions caused by Cu-PIII. Combining both plasma processes could be useful to create antibacterial and tissue compatible Ti-based implants. PMID:28726761

Evaluation of Die-Attach Bonding Using High-Frequency Ultrasonic Energy for High-Temperature Application

NASA Astrophysics Data System (ADS)

Lee, Jong-Bum; Aw, Jie-Li; Rhee, Min-Woo

2014-09-01

Room-temperature die-attach bonding using ultrasonic energy was evaluated on Cu/In and Cu/Sn-3Ag metal stacks. The In and Sn-3Ag layers have much lower melting temperatures than the base material (Cu) and can be melted through the heat generated during ultrasonic bonding, forming intermetallic compounds (IMCs). Samples were bonded using different ultrasonic powers, bonding times, and forces and subsequently aged at 300°C for 500 h. After aging, die shear testing was performed and the fracture surfaces were inspected by scanning electron microscopy. Results showed that the shear strength of Cu/In joints reached an upper plateau after 100 h of thermal aging and remained stable with aging time, whereas that of the Cu/Sn-3Ag joints decreased with increasing aging time. η-Cu7In4 and (Cu,Au)11In9 IMCs were observed at the Cu/In joint, while Cu3Sn and (Ag,Cu)3Sn IMCs were found at the Cu/Sn-3Ag joint after reliability testing. As Cu-based IMCs have high melting temperatures, they are highly suitable for use in high-temperature electronics, but can be formed at room temperature using an ultrasonic approach.

Microstructure and Interfacial Reactions During Vacuum Brazing of Stainless Steel to Titanium Using Ag-28 pct Cu Alloy

NASA Astrophysics Data System (ADS)

Laik, A.; Shirzadi, A. A.; Sharma, G.; Tewari, R.; Jayakumar, T.; Dey, G. K.

2015-02-01

Microstructural evolution and interfacial reactions during vacuum brazing of grade-2 Ti and 304L-type stainless steel (SS) using eutectic alloy Ag-28 wt pct Cu were investigated. A thin Ni-depleted zone of -Fe(Cr, Ni) solid solution formed on the SS-side of the braze zone (BZ). Cu from the braze alloy, in combination with the dissolved Fe and Ti from the base materials, formed a layer of ternary compound , adjacent to Ti in the BZ. In addition, four binary intermetallic compounds, CuTi, CuTi, CuTi and CuTi formed as parallel contiguous layers in the BZ. The unreacted Ag solidified as islands within the layers of CuTi and CuTi. Formation of an amorphous phase at certain locations in the BZ could be revealed. The -Ti(Cu) layer, formed due to diffusion of Cu into Ti-based material, transformed to an -Ti + CuTi eutectoid with lamellar morphology. Tensile test showed that the brazed joints had strength of 112 MPa and failed at the BZ. The possible sequence of events that led to the final microstructure and the mode of failure of these joints were delineated.

Te-Rich argyrodite occurrence in Roşia Montană ore deposit, Apuseni Mountains, Romania

NASA Astrophysics Data System (ADS)

Bailly, Laurent; Tămaş, Călin-Gabriel; Minuţ, Adrian

2005-06-01

A new argyrodite occurrence has been discovered in the Roşia Montană ore deposit located in the South Apuseni Mountains, Romania. Argyrodite is associated with common base metal sulfides and sulfosalts (galena, sphalerite, chalcopyrite, tetrahedrite ± alabandite, pyrite, and marcasite), tellurides (hessite, altaite, sylvanite) and rare electrum grains in the Ag-rich Cârnicel vein hosted by an extracraterial phreatomagmatic breccia within the Cârnic massif. SEM and EPMA analyses revealed that this argyrodite is Te-rich and a mean Ag 8.04Ge 0.9Te 2.07S 3.77 formula was calculated. This phase could be the germaniferous equivalent of the previously-described Te-rich canfieldite. To cite this article: L. Bailly et al., C. R. Geoscience 337 (2005).

Orbital frustration induced unusual ordering in semiconductor alloys

NASA Astrophysics Data System (ADS)

Liu, Kai; Yin, Wanjian; Chen, Shiyou; Gong, Xingao; Wei, Suhuai; Xiang, Hongjun

It is well known that ternary zinc-blende semiconductors are always more stable in the chalcopyrite (CH) structure than the Cu-Au (CA) structure because CH structure has large Coulomb interaction and reduced strain energy. Surprisingly, an experimental study showed that ZnFeSe2 alloy takes the CA order as the ground state structure, which is consistent with our density function theory (DFT) calculations showing that the CA order has lower energy than the CH order for ZnFeSe2. We reveal that the orbital degree of freedom of high-spin Fe2+ ion (d6) in the tetrahedral crystal field plays a key role in stabilizing the CA order. First, the spin-minority d electron of the Fe2+ ion tends to occupy the dx2-y 2 -like orbital instead of the d3z2 -r2 -like orbital because of its large negative Coulomb energy. Second, for a nearest-neighboring Fe2+ pair, two spin-minority d electrons with occupied dx2-y 2 -like orbitals in the plane containing the Fe-Fe bond has lower electronic kinetic energy. Both conditions can be satisfied in the CA ordered ZnFeSe2 alloy, while there is an orbital frustration in the CH structure. Our results suggest that orbital degree of freedom provides a new way to manipulate the structure and properties of alloys. Work at Fudan was supported by NSFC (11374056), the Special Funds for Major State Basic Research (2012CB921400, 2015CB921700), Program for Professor of Special Appointment (Eastern Scholar), and Fok Ying Tung Education Foundation.

Alteration Mineralogy and Geochemical Characteristics of Porphyry Cu-Mo Mineralization in Domaniç (Kütahya) Area

NASA Astrophysics Data System (ADS)

Sariiz, K.; Sendir, H.

2012-04-01

The study area is located at 30 km northwest of Domaniç (Kütahya) and covers on approximately 250 square kilometers. The Devonian (Paleozoic) schists which are composed of gneiss, mica schist and chlorite schist is the oldest unit of the study area. This units are overlain unconformably by the Permian Allıkaya Marbles. Eocene granodioritic intrusives cut other rock series and located as a batholite. Magmatic units present porphyric and holocrystalline textures. Granodioritic intrusions are represented by tonalite, tonalite porphyr, granodiorite, granodiorite porphyr, granite, diorite, diorite porphyries. Potassic, phyllitic and prophyllitic hydrothermal alteration zones are determined in host rocks and wallrocks. Mineralizations are observed as disseminated, and stockwork types within the granodioritic rocks. Ore minerals are pyrotine, pyrite, chalcopyrite, molybdenite, rutile, bornite, sphalerite, marcasite and limonite. Geochemically, it is of sub-alkaline affinity, belongs to the high-K, calc-alkaline series and displays features of typical I-type affinity. They show enrichment in large-ion lithophile elements (LIL) and depletion Nb and Ti indicating a subduction zone related magmatic signature for their origin. δ18O (quartz) values range from 8,8 to 12,1 ‰. δ18O (biotite) and δD (biotite) values range from 2,6 to 6,1 ‰ and -87 - -125 (SMOW). These values indicate that mixture magmatic-meteoric of hydrothermal solutions origin which are potassic to propylitic zones. δ13C (calcite) values range from 1,9 to 3,3 ‰ (PDB). Calcite values within the marine carbonates in the study area.

Textures and trace element composition of pyrite from the Bukit Botol volcanic-hosted massive sulphide deposit, Peninsular Malaysia

NASA Astrophysics Data System (ADS)

Basori, Mohd Basril Iswadi; Gilbert, Sarah; Large, Ross Raymond; Zaw, Khin

2018-06-01

The Bukit Botol volcanic-hosted massive sulphide (VHMS) deposit is located in the Central Belt of Peninsular Malaysia. The deposit occurs in a package of Permian-aged coherent felsic volcanic and volcaniclastic rocks which have a geochemical signature indicative of a volcanic arc tectonic setting. Mineralisation shows distinct ore zonation, forming a stringer to massive sulphide zone at the footwall followed by barite lenses and exhalite layers (Fe-Mn ore) at the top. Mineralogy is characterised by pyrite as the major sulphide mineral, with minor chalcopyrite, sphalerite, and rare galena; traces of gold, silver- and tin-bearing minerals also occur in the massive sulphide and barite ores. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis combined with the textural characteristics of pyrite provides evidence for significant variations of trace elements in different pyrite types at Bukit Botol, having three types of pyrite in the paragenetic sequence. The concentrations of As, Se, Te, Cu, Zn and Pb decrease from the early pyrite 1 to the late stage pyrite 3, and the Co/Ni ratios vary for the three pyrite types. The combined textural and compositional data of pyrite suggest that the hydrothermal fluid responsible for mineralisation evolved from an early, high temperature, reduced, low pH and desulphurized fluid to more S-rich, oxidized, high pH and cooler fluid. Available sulphur isotope data from the Bukit Botol deposit point to reduced seawater, along with a possible magmatic contribution, as the most probable sources for the ore-forming fluids.

Eco-friendly graphene synthesis on Cu foil electroplated by reusing Cu etchants

PubMed Central

Kwon, Ki Chang; Ham, Juyoung; Kim, Sungjun; Lee, Jong-Lam; Kim, Soo Young

2014-01-01

Graphene film grown by chemical vapor deposition using Cu substrate is promising for industrial applications. After etching the Cu substrate, which is essential step in graphene transfer process, the etchant solution must be chemically treated to prevent water pollution. Here we investigated that a method of reusing Cu etchant used to synthesize graphene, the synthesis of graphene on the resulting reused Cu films (R-G), and the application of R-G to organic light-emitting diodes (OLEDs) and organic photovoltaic cells (OPVs). The turn-on voltage of OLEDs based on the R-G electrode was 4.2 V, and the efficiencies of OPVs based on the R-G electrode were 5.9–5.95%, that are similar to or better than those of the indium-tin-oxide-based devices. These results suggest that the reusing of Cu foil by the electroplating method could reduce the cost of graphene synthesis, thus opening a wide range of applications in graphene electronics. PMID:24777344

Enhanced Oxidation-Resistant Cu@Ni Core-Shell Nanoparticles for Printed Flexible Electrodes.

PubMed

Kim, Tae Gon; Park, Hye Jin; Woo, Kyoohee; Jeong, Sunho; Choi, Youngmin; Lee, Su Yeon

2018-01-10

In this work, the fabrication and application of highly conductive, robust, flexible, and oxidation-resistant Cu-Ni core-shell nanoparticle (NP)-based electrodes have been reported. Cu@Ni core-shell NPs with a tunable Ni shell thickness were synthesized by varying the Cu/Ni molar ratios in the precursor solution. Through continuous spray coating and flash photonic sintering without an inert atmosphere, large-area Cu@Ni NP-based conductors were fabricated on various polymer substrates. These NP-based electrodes demonstrate a low sheet resistance of 1.3 Ω sq -1 under an optical energy dose of 1.5 J cm -2 . In addition, they exhibit highly stable sheet resistances (ΔR/R 0 < 1) even after 30 days of aging at 85 °C and 85% relative humidity. Further, a flexible heater fabricated from the Cu@Ni film is demonstrated, which shows uniform heat distribution and stable temperature compared to those of a pure Cu film.

Advanced Cu chemical displacement technique for SiO2-based electrochemical metallization ReRAM application.

PubMed

Chin, Fun-Tat; Lin, Yu-Hsien; You, Hsin-Chiang; Yang, Wen-Luh; Lin, Li-Min; Hsiao, Yu-Ping; Ko, Chum-Min; Chao, Tien-Sheng

2014-01-01

This study investigates an advanced copper (Cu) chemical displacement technique (CDT) with varying the chemical displacement time for fabricating Cu/SiO2-stacked resistive random-access memory (ReRAM). Compared with other Cu deposition methods, this CDT easily controls the interface of the Cu-insulator, the switching layer thickness, and the immunity of the Cu etching process, assisting the 1-transistor-1-ReRAM (1T-1R) structure and system-on-chip integration. The modulated shape of the Cu-SiO2 interface and the thickness of the SiO2 layer obtained by CDT-based Cu deposition on SiO2 were confirmed by scanning electron microscopy and atomic force microscopy. The CDT-fabricated Cu/SiO2-stacked ReRAM exhibited lower operation voltages and more stable data retention characteristics than the control Cu/SiO2-stacked sample. As the Cu CDT processing time increased, the forming and set voltages of the CDT-fabricated Cu/SiO2-stacked ReRAM decreased. Conversely, decreasing the processing time reduced the on-state current and reset voltage while increasing the endurance switching cycle time. Therefore, the switching characteristics were easily modulated by Cu CDT, yielding a high performance electrochemical metallization (ECM)-type ReRAM.

Electronic structure of PrBa2Cu3O7: A local-spin-density approximation with on-site Coulomb interaction

NASA Astrophysics Data System (ADS)

Biagini, M.; Calandra, C.; Ossicini, Stefano

1995-10-01

Electronic structure calculations based on the local-spin-density approximation (LSDA) fail to reproduce the antiferromagnetic ground state of PrBa2Cu3O7 (PBCO). We have performed linear muffin-tin orbital-atomic sphere approximation calculations, based on the local-spin-density approximation with on-site Coulomb correlation applied to Cu(1) and Cu(2) 3d states. We have found that inclusion of the on-site Coulomb interaction modifies qualitatively the electronic structure of PBCO with respect to the LSDA results, and gives Cu spin moments in good agreement with the experimental values. The Cu(2) upper Hubbard band lies about 1 eV above the Fermi energy, indicating a CuII oxidation state. On the other hand, the Cu(1) upper Hubbard band is located across the Fermi level, which implies an intermediate oxidation state for the Cu(1) ion, between CuI and CuII. The metallic character of the CuO chains is preserved, in agreement with optical reflectivity [K. Takenaka et al., Phys. Rev. B 46, 5833 (1992)] and positron annihilation experiments [L. Hoffmann et al., Phys. Rev. Lett. 71, 4047 (1993)]. These results support the view of an extrinsic origin of the insulating character of PrBa2Cu3O7.

Single-phase and well-dispersed Cu1.75S nanocrystals by ambient pressure diethylene glycol solution synthesis

NASA Astrophysics Data System (ADS)

Zheng, Xuerong; Jin, Zhengguo; Liu, Hui; Wang, Yueqiu; Wang, Xin; Du, Haiyan

2013-02-01

Single-phase, well-dispersed Cu1.75S nanocrystals were synthesized by an ambient pressure, hydrazine hydrate and ethylenediamine co-assisted diethylene glycol based solution chemical process using copper chloride and thioacetamide as precursors at the temperature range from 180 to 210 °C. Influence of hydrazine hydrate and ethylenediamine adding amounts, synthetic temperature on crystal growth, size distribution and optical properties of the synthesized Cu1.75S nanocrystals were investigated by XRD, TEM, HRTEM, EDX and UV-vis measurements. The synthetic reaction at above 200 °C grew flaky-shaped nanocrystals with relatively narrow size distribution. The formation of single-phase Cu1.75S nanocrystals in the diethylene glycol based solution process might be involved in the presence of intermediate [Cu(en)n]1+ and [Cu(NH3)4]2+ complexes in reaction solution, providing a stable Cu(I) and Cu(II) valent-mixed precursor.

Sensory determinants of valve rhythm dynamics provide in situ biodetection of copper in aquatic environments.

PubMed

Jou, Li-John; Chen, Bo-Ching; Chen, Wei-Yu; Liao, Chung-Min

2016-03-01

This study successfully applied an improved valvometry technique to measure waterborne copper (Cu), based on valve activity dynamics of the freshwater clam Corbicula fluminea. The improved valvometry technique allows the use of free-range bivalves and avoids causing stresses from experimental artifacts. The proposed daily valve rhythm models and a toxicodynamics-based Hill model were linked to predict valve dynamic responses under different Cu exposures with a circadian valve rhythm endpoint. Cu-specific detection threshold was 5.6 (95 % CI 2.1-9.3) and 19.5 (14.6-24.3) μg L(-1) for C. fluminea, based on response times of 300 and 30 min, respectively. Upon exposure to Cu concentrations in excess of 50 μg L(-1), the alteration of valve rhythm behavior was correlated with Cu concentration within 30 min, indicating notable sensing ability. This study outlines the feasibility of an in situ early warning dynamic biomonitoring system for detection of waterborne Cu based on circadian valve activities of C. fluminea.

Elastocaloric effect in CuAlZn and CuAlMn shape memory alloys under compression

PubMed Central

Qian, Suxin; Wang, Yi; Pillsbury, Thomas E.; Hada, Yoshiharu; Yamaguchi, Yuki; Fujimoto, Kenjiro; Hwang, Yunho; Radermacher, Reinhard; Cui, Jun; Yuki, Yoji; Toyotake, Koutaro; Takeuchi, Ichiro

2016-01-01

This paper reports the elastocaloric effect of two Cu-based shape memory alloys: Cu68Al16Zn16 (CuAlZn) and Cu73Al15Mn12 (CuAlMn), under compression at ambient temperature. The compression tests were conducted at two different rates to approach isothermal and adiabatic conditions. Upon unloading at a strain rate of 0.1 s−1 (adiabatic condition) from 4% strain, the highest adiabatic temperature changes (ΔTad) of 4.0 K for CuAlZn and 3.9 K for CuAlMn were obtained. The maximum stress and hysteresis at each strain were compared. The stress at the maximum recoverable strain of 4.0% for CuAlMn was 120 MPa, which is 70% smaller than that of CuAlZn. A smaller hysteresis for the CuAlMn alloy was also obtained, about 70% less compared with the CuAlZn alloy. The latent heat, determined by differential scanning calorimetry, was 4.3 J g−1 for the CuAlZn alloy and 5.0 J g−1 for the CuAlMn alloy. Potential coefficients of performance (COPmat) for these two alloys were calculated based on their physical properties of measured latent heat and hysteresis, and a COPmat of approximately 13.3 for CuAlMn was obtained. This article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’. PMID:27402936

Application Of Ti-Based Self-Formation Barrier Layers To Cu Dual-Damascene Interconnects

NASA Astrophysics Data System (ADS)

Ito, Kazuhiro; Ohmori, Kazuyuki; Kohama, Kazuyuki; Mori, Kenichi; Maekawa, Kazuyoshi; Asai, Koyu; Murakami, Masanori

2010-11-01

Cu interconnects have been used extensively in ULSI devices. However, large resistance-capacitance delay and poor device reliability have been critical issues as the device feature size has reduced to nanometer scale. In order to achieve low resistance and high reliability of Cu interconnects, we have applied a thin Ti-based self-formed barrier (SFB) using Cu(Ti) alloy seed to 45nm-node dual damascene interconnects and evaluated its performance. The line resistance and via resistance decreased significantly, compared with those of conventional Ta/TaN barriers. The stress migration performance was also drastically improved using the SFB process. A performance of time dependent dielectric breakdown revealed superior endurance. These results suggest that the Ti-based SFB process is one of the most promising candidates for advanced Cu interconnects. TEM and X-ray photoelectron spectroscopy observations for characterization of the Ti-based SFB structure were also performed. The Ti-based SFB consisted of mainly amorphous Ti oxides. Amorphous or crystalline Ti compounds such as TiC, TiN, and TiSi formed beneath Cu alloy films, and the formation varied with dielectric.

The effect of Ti-B on stabilization of Cu-Zn-Al martensite

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

Stipcich, M.; Romero, R.

1998-10-05

The application of shape memory effect in devices requires, in many cases, stable and reliable transformation temperatures. However, as a consequence of diffusional processes, in Cu-based shape memory alloys, reverse transformation temperature significantly rises after aging at temperatures above room temperature. This generally unwanted behavior is usually referred to as the stabilization of martensite. Numerous investigations have been carried out on this subject as reviewed by Ahlers and Chandrasekaran et al. Within the Cu-based alloys the Cu-Zn-Al are claimed to be more prone to stabilization than Cu-Al-Ni on aging. It has been proposed that in the Cu-Zn-Al the stabilization ismore » due to the interchange of Cu and Zn atoms assisted by vacancies, changing, consequently, the long range order inherited from the {beta} phase. In the present work, the authors investigate the stabilization behavior of polycrystalline samples of stress induced Cu-Zn-Al and Cu-Zn-Al-B martensite.« less

Ordered PdCu-Based Nanoparticles as Bifunctional Oxygen-Reduction and Ethanol-Oxidation Electrocatalysts

DOE PAGES

Jiang, Kezhu; Wang, Pengtang; Guo, Shaojun; ...

2016-06-02

Here, the development of superior non-platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen-reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells,but still agreat challenge.Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu-based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo.Under the dual tuning on the composition and intermetallic phase,the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol-oxidation reaction (EOR)than those of disordered PdCuM NPs,the commercial Pt/Cand Pd/C catalysts.The density functional theory (DFT)calculations reveal that themore » improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on thePd surface owing to the smaller atomic size of Cu, Co,and Ni.« less

A new rhodamine-based colorimetric chemosensor for naked-eye detection of Cu2 + in aqueous solution

NASA Astrophysics Data System (ADS)

Hu, Yang; Zhang, Jing; Lv, Yuan-Zheng; Huang, Xiao-Huan; Hu, Sheng-li

2016-03-01

A new colorimetric probe 1 based on rhodamine B lactam was developed for naked-eye detection of Cu2 +. The optical feature of 1 for Cu2 + was investigated by UV-vis absorption spectroscopy. Upon the addition of Cu2 +, the 1 displayed a distinct color change from colorless to pink, which can be directly detected by the naked eye. The stoichiometry of 1 to Cu2 + complex was found to be 1:1 and the naked-eye detection limit was determined as low as 2 μM. The results suggest that the probe 1 may provide a convenient method for visual detection of Cu2 + with high sensitivity.

Theoretical Investigation of the Thermodynamic Properties of η'-(Cu, Co)6Sn5 Alloys

NASA Astrophysics Data System (ADS)

Wu, Heng; Zhang, Xuechao; Zheng, Bing; Zhao, Xiuchen; Liu, Ying; Li, Hong; Cheng, Jingwei

2018-02-01

We perform theoretical investigations on the structures of η'-Cu6Sn5-based intermetallic compounds (IMCs) with different Co doping concentration (0-12.2 wt.%) based on density functional theory (DFT). The variations of the structural, elastic and thermodynamic properties of (Cu, Co)6Sn5 IMCs with pressure (0-18 GPa) and temperature (0-500 K) are obtained with the application of quasi-harmonic Debye model for the non-equilibrium Gibbs free energy. It is found that the volume of (Cu, Co)6Sn5 shrinks with Co concentration increasing in the range of imposed pressure and temperature. At the same time, the bulk modulus of Cu4Co2Sn5 is the largest among those of Cu6Sn5, Cu5Co1Sn5 and Cu4Co2Sn5. By calculating the Debye temperature of Cu6Sn5, we find that it is higher than that of Cu5Co1Sn5 and Cu4Co2Sn5 when the pressure is higher than 2 GPa. Meanwhile, heat capacities of all three Cu6Sn5, Cu5Co1Sn5, and Cu4Co2Sn5 converge to a near-constant value at about 1090 J/mol K in the range of the imposed pressures.

Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

NASA Astrophysics Data System (ADS)

Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

2017-09-01

Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

Theoretical prediction of the electronic transport properties of the Al-Cu alloys based on the first-principle calculation and Boltzmann transport equation

NASA Astrophysics Data System (ADS)

Choi, Garam; Lee, Won Bo

Metal alloys, especially Al-based, are commonly-used materials for various industrial applications. In this paper, the Al-Cu alloys with varying the Al-Cu ratio were investigated based on the first-principle calculation using density functional theory. And the electronic transport properties of the Al-Cu alloys were carried out using Boltzmann transport theory. From the results, the transport properties decrease with Cu-containing ratio at the temperature from moderate to high, but with non-linearity. It is inferred by various scattering effects from the calculation results with relaxation time approximation. For the Al-Cu alloy system, where it is hard to find the reliable experimental data for various alloys, it supports understanding and expectation for the thermal electrical properties from the theoretical prediction. Theoretical and computational soft matters laboratory.

Design, properties and application of a facile fluorescence switch for Cu(II).

PubMed

Diao, Haipeng; Niu, Weiping; Liu, Wen; Feng, Liheng; Xie, Jun

2017-01-05

A facile fluorescence switch based on Schiff base 2,2'-[1,3-phenylenbis- (methylidynenitrilo)]bis[benzenethiol] (PMBB) has been developed and used to sensing metal ions. UV-vis absorption and fluorescence emission spectra show that the PMBB receptor has high selectivity and sensitivity for Cu(II) ions. Based on the photoinduced electron transfer (PET) and chelation enhanced fluorescence (CHEF) mechanisms, the receptor exhibits an fluorescence "turn-on" switch signal for Cu(II). The 1:1 binding mode of PMBB and Cu (II) ions can be obtained by the Job-plot and ESI-Mass spectra data. Noticeably, the color changes (from colorless to yellow) of PMBB solutions for Cu(II) sensing can be observed by naked eyes in the sunlight. The detection limit of the receptor for Cu(II) may reach 10(-7)mol/L with a good linear relation in the lower concentrations of Cu(II). To develop the practical application, the Cu(II) ions in swimming pool water samples were detected. Results show that PMBB receptor as a fluorescent probe can use to detect the trace level of Cu(II) in the environmental samples. This work contributes to providing a facile strategy for designing efficient probes and developing their practical application value. Copyright © 2016 Elsevier B.V. All rights reserved.

Copper-tuned magnetic order and excitations in iron-based superconductors Fe1+yTe1-xSex

NASA Astrophysics Data System (ADS)

Wen, Jinsheng; Xu, Zhijun; Xu, Guangyong; Lumsden, Mark; Matsuda, Masaaki; Valdivia, Patrick; Bourret, Edith; Lee, Dunghai; Gu, Genda; Tranquada, John; Birgeneau, Robert

2012-02-01

We report neutron scattering results on the Cu-substitution effects in the iron-based superconductors, Fe1+yTe1-xSex. In the parent compound, it is found that Cu drives the low-temperature magnetic ground state from long-range commensurate antiferromagnetic order in Fe1.06TeCu0.04 to short-range incommensurate order in FeTeCu0.1. In the former sample, the structural and magnetic ordering temperature is 40 K; in FeTeCu0.1, the structural phase transition is not obvious and a transition to the spin-glass state is found at 22 K. Cu suppresses superconductivity in FeTe0.5Se0.5---Tc is reduced to 7 K with a 2% Cu doping, and no superconductivity is found in the 10% Cu-doped sample. In the meantime, the intensity and energy of the resonance mode are suppressed in the 2% Cu-doped sample, while there is no resonance in the non-superconducting sample. Besides, the low-temperature magnetic excitation spectra are distinct for these two samples, with the superconducting one having an ``hour-glass" shape and the other one having a ``waterfall" shape. Our results provide further insights on the interplay between magnetism and superconductivity in the iron-based superconductors.

Copper Nanoparticle Induced Cytotoxicity to Nitrifying Bacteria ...

EPA Pesticide Factsheets

With the inclusion of engineered nanomaterials in industrial processes and consumer products, wastewater treatments plants (WWTPs) will serve as a major sink for these emerging contaminants. Previous research has demonstrated that nanomaterials are potentially toxic to microbial communities utilized in biological wastewater treatment (BWT). Copper-based nanoparticles (CuNPs) are of particular interest based on their increasing use in wood treatment, paints, household products, coatings, and byproducts of semiconductor manufacturing. A critical step in BWT is nutrient removal via denitrification. This study examined the potential toxicity of bare and polyvinylpyrrolidone (PVP) coated CuO, and Cu2O nanoparticles, as well as Cu ions to microbial communities responsible for nitrogen removal in BWT. Inhibition was inferred from changes to the specific oxygen uptake rate (sOUR) in the absence and presence of Cu ions and CuNPs. X-ray absorption fine structure spectroscopy, with Linear Combination Fitting (LCF), was utilized to track changes to Cu speciation throughout exposure. Results indicate that the dissolution of Cu ions from CuNPs drive microbial inhibition. The presence of a PVP coating on CuNPs has little effect on inhibition. LCF fitting of the biomass combined with metal partitioning analysis supports the current hypothesis that Cu-induced cytotoxicity is primarily caused by reactive oxygen species formed from ionic Cu in solution via catalytic reaction inter

Mineralogical, stable isotope, and fluid inclusion studies of spatially related porphyry Cu and epithermal Au-Te mineralization, Fakos Peninsula, Limnos Island, Greece

NASA Astrophysics Data System (ADS)

Fornadel, Andrew P.; Voudouris, Panagiotis Ch.; Spry, Paul G.; Melfos, Vasilios

2012-05-01

The Fakos porphyry Cu and epithermal Au-Te deposit, Limnos Island, Greece, is hosted in a ~20 Ma quartz monzonite and shoshonitic subvolcanic rocks that intruded middle Eocene to lower Miocene sedimentary basement rocks. Metallic mineralization formed in three stages in quartz and quartz-calcite veins. Early porphyry-style (Stage 1) metallic minerals consist of pyrite, chalcopyrite, galena, bornite, sphalerite, molybdenite, and iron oxides, which are surrounded by halos of potassic and propylitic alteration. Stage 2 mineralization is composed mostly of quartz-tourmaline veins associated with sericitic alteration and disseminated pyrite and molybdenite, whereas Stage 3, epithermal-style mineralization is characterized by polymetallic veins containing pyrite, chalcopyrite, sphalerite, galena, enargite, bournonite, tetrahedrite-tennantite, hessite, petzite, altaite, an unknown cervelleite-like Ag-telluride, native Au, and Au-Ag alloy. Stage 3 veins are spatially associated with sericitic and argillic alteration. Fluid inclusions in quartz from Stage 1 (porphyry-style) mineralization contain five types of inclusions. Type I, liquid-vapor inclusions, which homogenize at temperatures ranging from 189.5°C to 403.3°C have salinities of 14.8 to 19.9 wt. % NaCl equiv. Type II, liquid-vapor-NaCl, Type III liquid-vapor-NaCl-XCl2 (where XCl is an unknown chloride phase, likely CaCl2), and Type IV, liquid-vapor-hematite ± NaCl homogenize to the liquid phase by liquid-vapor homogenization or by daughter crystal dissolution at temperatures of 209.3 to 740.5 °C, 267.6 to 780.8 °C, and 357.9 to 684.2 °C, respectively, and, Type V, vapor-rich inclusions. Stage 2 veins are devoid of interpretable fluid inclusions. Quartz from Stage 3 (epithermal-style) veins contains two types of fluid inclusions, Type I, liquid-vapor inclusions that homogenize to the liquid phase (191.6 to 310.0 °C) with salinities of 1.40 to 9.73 wt. % NaCl equiv., and Type II, vapor-rich inclusions. Mixing of magmatic fluids with meteoric water in the epithermal environment is responsible for the dilution of the ore fluids that formed Stage 3 veins. Eutectic melting temperatures of -35.4 to -24.3 °C for Type I inclusions hosted in both porphyry- and epithermal-style veins suggest the presence of CaCl2, MgCl2, and/or FeCl2 in the magmatic-hydrothermal fluids. Sulfur isotope values of pyrite, galena, sphalerite, and molybdenite range from δ34S = -6.82 to -0.82 per mil and overlap for porphyry and epithermal sulfides, which suggests a common sulfur source for the two styles of mineralization. The source of sulfur in the system was likely the Fakos quartz monzonite for which the isotopically light sulfur isotope values are the result of changes in oxidation state during sulfide deposition (i.e., boiling) and/or disproportionation of sulfur-rich magmatic volatiles upon cooling. It is less likely that sulfur in the sulfides was derived from the reduction of seawater sulfate or leaching of sulfides from sedimentary rocks given the absence of primary sulfides in sedimentary rocks in the vicinity of the deposit. Late-stage barite (δ34S = 10.5 per mil) is inferred to have formed during mixing of seawater with magmatic ore fluids. Petrological, mineralogical, fluid inclusion, and sulfur isotope data indicate that the metallic mineralization at Fakos Peninsula represents an early porphyry system that is transitional to a later high- to intermediate-sulfidation epithermal gold system. This style of mineralization is similar to porphyry-epithermal metallic mineralization found elsewhere in northeastern Greece (e.g., Pagoni Rachi, St. Demetrios, St. Barbara, Perama Hill, Mavrokoryfi, and Pefka).

Enhanced electrochemical performances with a copper/xylose-based carbon composite electrode

NASA Astrophysics Data System (ADS)

Sirisomboonchai, Suchada; Kongparakul, Suwadee; Nueangnoraj, Khanin; Zhang, Haibo; Wei, Lu; Reubroycharoen, Prasert; Guan, Guoqing; Samart, Chanatip

2018-04-01

Copper/carbon (Cu/C) composites were prepared through the simple and environmentally benign hydrothermal carbonization of xylose in the presence of Cu2+ ions. The morphology, specific surface area, phase structure and chemical composition were investigated. Using a three-electrode system in 0.1 M H2SO4 aqueous electrolyte, the Cu/C composite (10 wt% Cu) heat-treated at 600 °C gave the highest specific capacitance (316.2 and 350.1 F g-1 at 0.5 A g-1 and 20 mV s-1, respectively). The addition of Cu was the major factor in improving the electrochemical performance, enhancing the specific capacitance more than 30 times that of the C without Cu. Therefore, the Cu/C composite presented promising results in improving biomass-based C electrodes for supercapacitors.

Materials science and integration bases for fabrication of (BaxSr1-x)TiO3 thin film capacitors with layered Cu-based electrodes

NASA Astrophysics Data System (ADS)

Fan, W.; Kabius, B.; Hiller, J. M.; Saha, S.; Carlisle, J. A.; Auciello, O.; Chang, R. P. H.; Ramesh, R.

2003-11-01

The synthesis and fundamental material properties of layered TiAl/Cu/Ta electrodes were investigated to achieve the integration of Cu electrodes with high-dielectric constant (κ) oxide thin films for application to the fabrication of high-frequency devices. The Ta layer is an excellent diffusion barrier to inhibit deleterious Cu diffusion into the Si substrate, while the TiAl layer provides an excellent barrier against oxygen diffusion into the Cu layer to inhibit Cu oxidation during the growth of the high-κ layer in an oxygen atmosphere. Polycrystalline (BaxSr1-x)TiO3 (BST) thin films were grown on the Cu-based bottom electrode by rf magnetron sputtering at temperatures in the range 400-600 °C in oxygen, to investigate the performance of BST/Cu-based capacitors. Characterization of the Cu-based layered structure using surface analytical methods showed that two amorphous oxide layers were formed on both sides of the TiAl barrier, such that the oxide layer on the free surface of the TiAl layer correlates with TiAlOx, while the oxide layer at the TiAl/Cu interface is an Al2O3-rich layer. This double amorphous barrier layer structure effectively prevents oxygen penetration towards the underlying Cu and Ta layers. The TiAlOx interfacial layer, which has a relatively low dielectric constant compared with BST, reduced the total capacitance of the BST thin film capacitors. In addition, the layered electrode-oxide interface roughening observed during the growth of BST films at high temperature, due to copper grain growth, resulted in large dielectric loss on the fabricated BST capacitors. These problems were solved by growing the BST layer at 450 °C followed by a rapid thermal annealing at 700 °C. This process significantly reduced the thickness of the TiAlOx layer and interface roughness resulting in BST capacitors exhibiting properties suitable for the fabrication of high-performance high-frequency devices. In summary, relatively high dielectric constant (280), low dielectric loss (0.007), and low leakage current (<2×10-8 A/cm2 at 100 kV/cm) were achieved for BST thin film capacitors with Cu-based electrodes.

A new rhodamine-based colorimetric chemosensor for naked-eye detection of Cu(2+) in aqueous solution.

PubMed

Hu, Yang; Zhang, Jing; Lv, Yuan-Zheng; Huang, Xiao-Huan; Hu, Sheng-Li

2016-03-15

A new colorimetric probe 1 based on rhodamine B lactam was developed for naked-eye detection of Cu(2+). The optical feature of 1 for Cu(2+) was investigated by UV-vis absorption spectroscopy. Upon the addition of Cu(2+), the 1 displayed a distinct color change from colorless to pink, which can be directly detected by the naked eye. The stoichiometry of 1 to Cu(2+) complex was found to be 1:1 and the naked-eye detection limit was determined as low as 2 μM. The results suggest that the probe 1 may provide a convenient method for visual detection of Cu(2+) with high sensitivity. Copyright © 2015 Elsevier B.V. All rights reserved.

Ten Years Development of Metallurgical Research and Technology in Communist China

DTIC Science & Technology

1960-01-15

milling problems. The methods are magnetic separa- tion combined with flotation , roasting followed by magnetic separation in S’GteS -. ..o . *tPeca...combination with flotation , and reverse flotation . In each process, the iron concentrate made contains 60 Fe or better, recovery is more than 80", and...extracted. For example, from tungsten ores, we are recovering molybdaniti, bismuthinite, chalcopyrite, cassiter- ite, scheelite, pyrite , and other useful

Atomistic and Ab Initio Calculations or Ternary II-IV-V2 Semiconductors

DTIC Science & Technology

1999-12-07

consisting of two- and three-body terms is developed reproducing crystal lattice constants, elastic and dielectric constants very well. The calculated...the lattice . This difference may well be due to defect-induced lattice distortion which plays a key role in stabilizing the hole states in the... lattice . 15. SUBJECT TERMS Chalcopyrites, Defects, Atomistic and AB Initio Calculations 16. SECURITY CLASSIFICATION OF: a. REPORT u b. ABSTRACT U

Invisible gold in Colombian auriferous soils

NASA Astrophysics Data System (ADS)

Bustos Rodriguez, H.; Oyola Lozano, D.; Rojas Martínez, Y. A.; Pérez Alcázar, G. A.; Balogh, A. G.

2005-11-01

Optic microscopy, X-ray diffraction (XRD), Mössbauer spectroscopy (MS), Electron microprobe analysis (EPMA) and secondary ions mass spectroscopy (SIMS) were used to study Colombian auriferous soils. The auriferous samples, collected from El Diamante mine, located in Guachavez-Nariño (Colombia), were prepared by means of polished thin sections and polished sections for EPMA and SIMS. Petrography analysis was made using an optical microscope with a vision camera, registering the presence, in different percentages, of the following phases: pyrite, quartz, arsenopyrite, sphalerite, chalcopyrite and galena. By XRD analysis, the same phases were detected and their respective cell parameters calculated. By MS, the presence of two types of pyrite was detected and the hyperfine parameters are: δ 1 = 0.280 ± 0.01 mm/s and Δ Q 1 = 0.642 ± 0.01 mm/s, δ 2 = 0.379 ± 0.01 mm/s and Δ Q 2 = 0.613 ± 0.01 mm/s. For two of the samples MS detected also the arsenopyrite and chalcopyrite presence. The mean composition of the detected gold regions, established by EPMA, indicated 73% Au and 27% Ag (electrum type). Multiple regions of approximately 200 × 200 μm of area in each mineral sample were analyzed by SIMS registering the presence of “invisible gold” associated mainly with the pyrite and occasionally with the arsenopyrite.

Evolution of Size and Chemical Composition of Copper Concentrate Particles Oxidized Under Simulated Flash Smelting Conditions

NASA Astrophysics Data System (ADS)

Pérez-Tello, Manuel; Parra-Sánchez, Víctor R.; Sánchez-Corrales, Víctor M.; Gómez-Álvarez, Agustín; Brown-Bojórquez, Francisco; Parra-Figueroa, Roberto A.; Balladares-Varela, Eduardo R.; Araneda-Hernández, Eugenia A.

2018-04-01

An experimental study was conducted to elucidate the evolution of size and chemical composition of La Caridad copper concentrate particles during oxidation under simulated flash smelting conditions. Input variables tested included particle size and oxygen concentration in the process gas. The response variables included the size distributions, chemical composition, and morphology of the reacted particles at seven locations along a laboratory reactor. Particles with initial size < 45 µm contained mostly chalcopyrite, they increased their mean size and decreased the amount of dust in the population during oxidation. This was explained by a reaction path involving rapid melting followed by collision and coalescence of reacting droplets during flight. Particles with sizes > 45 µm contained varying amounts of chalcopyrite and pyrite, and tended to either maintain or decrease their mean size upon oxidation. When size reduction was observed, dust was produced because of fragmentation, and the particles showed no evidence of collisions during flight. The main oxidation products detected in the particles consisted of matte, cuprospinel, and magnetite. A plot of the mean size divided by the mean size in the feed against the fraction of sulfur eliminated generalized the experimental data so far reported in the literature, and helped identify the reaction path followed by the particles.

Facile one-pot synthesis of cellulose nanocrystal-supported hollow CuFe2O4 nanoparticles as efficient catalyst for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Sufeng; Zhao, Dongyan; Hou, Chen; Liang, Chen; Li, Hao

2018-06-01

A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s-1 g-1, which was higher than H-CuFe2O4 NPs (0.50 s-1 g-1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.

Using new hetero-spectral two-dimensional correlation analyses and synchrotron-radiation-based spectromicroscopy to characterize binding of Cu to soil dissolved organic matter.

PubMed

Sun, Fusheng; Li, Yaqing; Wang, Xiang; Chi, Zhilai; Yu, Guanghui

2017-04-01

Understanding the binding characteristics of copper (Cu) to different functional groups in soil dissolved organic matter (DOM) is important to explore Cu toxicity, bioavailability and ultimate fate in the environment. However, the methods used to explore such binding characteristics are still limited. Here, two-dimensional correlation spectroscopy (2DCOS) integrated with Fourier transform infrared (FTIR), 29 Si nuclear magnetic resonance (NMR), 27 Al NMR, and synchrotron-radiation-based FTIR spectromicroscopy were used to explore the binding characteristics of Cu to soil DOM as part of a long-term (23 years) fertilization experiment. Compared with no fertilization and inorganic fertilization (NPK), long-term pig manure fertilization (M) treatment significantly increased the concentration of total and bioavailable Cu in soils. Furthermore, hetero-spectral 2DCOS analyses demonstrated that the binding characteristics of Cu onto functional groups in soil DOM were modified by fertilization regimes. In the NPK treatment, Cu was bound to aliphatic C, whereas in the manure treatment SiO groups had higher affinity toward Cu than aliphatic C. Also, the sequence of binding of functional groups to Cu was modified by the fertilization treatments. Moreover, synchrotron-radiation-based FTIR spectromicroscopy showed that Cu, clay minerals and sesquioxides, and C functional groups were heterogeneously distributed at the micro-scale. Specifically, clay-OH as well as mineral elements had a distribution pattern similar to Cu, but certain (but not all) C forms showed a distribution pattern inconsistent with that of Cu. The combination of synchrotron radiation spectromicroscopy and 2DCOS is a useful tool in exploring the interactions among heavy metals, minerals and organic components in soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

X-ray crystal structure and theoretical study of a new dinuclear Cu(II) complex with two different geometry centers bridged with an oxo group

NASA Astrophysics Data System (ADS)

Golbedaghi, Reza; Azimi, Saeid; Molaei, Atefeh; Hatami, Masoud; Notash, Behrouz

2017-10-01

A new Schiff base ligand HL, 1,3-bis(2-((Z)-(2-aminoethylimino)methyl)phenoxy)ethylene di amine, has been synthesized from the reaction of a new aldehyde and ethylenediamine. After preparation the Schiff base, a new dinuclear Cu(II) complex with two different geometry for each metal ion was synthesized. Single crystal X-ray structure analysis of the complex Cu(II) showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. The crystal structure studying shows, a perchlorate ion has been coordinated to the two Cu(II) metal centers as bridged and another perchlorate coordinated to the one of Cu(II) ion as terminal. However, two interesting structures square pyramidal and distorted octahedral Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, we had a theoretical study to have a comparison of experimental and theoretical results we determined the HOMO and LUMO orbitals.

Evaluation of Copper-1,3,5-benzenetricarboxylate Metal-organic Framework (Cu-MOF) as a Selective Sorbent for Lewis-base Analytes

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

Harvey, Scott D.; Eckberg, Alison D.; Thallapally, Praveen K.

2011-09-01

The metal-organic framework Cu-BTC was evaluated for its ability to selectively interact with Lewis-base analytes, including explosives, by examining retention on GC columns packed with Chromosorb W HP that contained 3.0% SE-30 along with various loadings of Cu-BTC. SEM images of the support material showed the characteristic Cu-BTC crystals embedded in the SE-30 coating on the diatomaceous support. Results indicated that the Cu-BTC-containing stationary phase had limited thermal stability (220°C) and strong general retention for analytes. Kováts index calculations showed selective retention (amounting to about 300 Kováts units) relative to n-alkanes for many small Lewis-base analytes on a column thatmore » contained 0.75% Cu-BTC compared to an SE-30 control. Short columns that contained lower loadings of Cu-BTC (0.10%) were necessary to elute explosives and related analytes; however, selectivity was not observed for aromatic compounds (including nitroaromatics) or nitroalkanes. Observed retention characteristics are discussed.« less

Investigation of thin film solar cells based on Cu2S and ternary compounds such as CuInS2

NASA Technical Reports Server (NTRS)

Loferski, J. J.

1975-01-01

Production and characterization in thin film form of Cu2S and related Cu compounds such as CuInS2 for photovoltaic cells are examined. The low cost process technology being reported, namely the sulfurization method, is capable of producing films on various substrates. Cathodoluminescence is being used as a diagnostic tool to identify Cu(x)S and CuInS2 compounds. Also, single crystals of CuInS2 are being prepared and it is contemplated that p-n junctions will be made in such crystals.

Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

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

Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com; Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id

2015-09-30

One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) andmore » LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.« less

Highly Efficient Oxygen-Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion-Based CO2 Capture.

PubMed

Imtiaz, Qasim; Kurlov, Alexey; Rupp, Jennifer Lilia Marguerite; Müller, Christoph Rüdiger

2015-06-22

Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are emerging thermochemical CO2 capture cycles that allow the capture of CO2 with a small energy penalty. Here, the development of suitable oxygen carrier materials is a key aspect to transfer these promising concepts to practical installations. CuO is an attractive material for CLC and CLOU because of its high oxygen-storage capacity (20 wt %), fast reaction kinetics, and high equilibrium partial pressure of oxygen at typical operating temperatures (850-1000 °C). However, despite its promising characteristics, its low Tammann temperature requires the development of new strategies to phase-stabilize CuO-based oxygen carriers. In this work, we report a strategy based on stabilization by co-precipitated ceria (CeO2-x ), which allowed us to increase the oxygen capacity, coke resistance, and redox stability of CuO-based oxygen carriers substantially. The performance of the new oxygen carriers was evaluated in detail and compared to the current state-of-the-art materials, that is, Al2 O3 -stabilized CuO with similar CuO loadings. We also demonstrate that the higher intrinsic oxygen uptake, release, and mobility in CeO2-x -stabilized CuO leads to a three times higher carbon deposition resistance compared to that of Al2 O3 -stabilized CuO. Moreover, we report a high cyclic stability without phase intermixing for CeO2-x -supported CuO. This was accompanied by a lower reduction temperature compared to state-of-the-art Al2 O3 -supported CuO. As a result of its high resistance towards carbon deposition and fast oxygen uncoupling kinetics, CeO2-x -stabilized CuO is identified as a very promising material for CLC- and CLOU-based CO2 capture architectures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

(1)H NMR and GC-MS Based Metabolomics Reveal Defense and Detoxification Mechanism of Cucumber Plant under Nano-Cu Stress.

PubMed

Zhao, Lijuan; Huang, Yuxiong; Hu, Jerry; Zhou, Hongjun; Adeleye, Adeyemi S; Keller, Arturo A

2016-02-16

Because copper nanoparticles are being increasingly used in agriculture as pesticides, it is important to assess their potential implications for agriculture. Concerns have been raised about the bioaccumulation of nano-Cu and their toxicity to crop plants. Here, the response of cucumber plants in hydroponic culture at early development stages to two concentrations of nano-Cu (10 and 20 mg/L) was evaluated by proton nuclear magnetic resonance spectroscopy ((1)H NMR) and gas chromatography-mass spectrometry (GC-MS) based metabolomics. Changes in mineral nutrient metabolism induced by nano-Cu were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that nano-Cu at both concentrations interferes with the uptake of a number of micro- and macro-nutrients, such as Na, P, S, Mo, Zn, and Fe. Metabolomics data revealed that nano-Cu at both levels triggered significant metabolic changes in cucumber leaves and root exudates. The root exudate metabolic changes revealed an active defense mechanism against nano-Cu stress: up-regulation of amino acids to sequester/exclude Cu/nano-Cu; down-regulation of citric acid to reduce the mobilization of Cu ions; ascorbic acid up-regulation to combat reactive oxygen species; and up-regulation of phenolic compounds to improve antioxidant system. Thus, we demonstrate that nontargeted (1)H NMR and GC-MS based metabolomics can successfully identify physiological responses induced by nanoparticles. Root exudates metabolomics revealed important detoxification mechanisms.

Catalytic combustion of styrene over copper based catalyst: inhibitory effect of water vapor.

PubMed

Pan, Hongyan; Xu, Mingyao; Li, Zhong; Huang, Sisi; He, Chun

2009-07-01

The effects of water vapor on the activity of the copper based catalysts with different supports such as CuO/gamma-Al2O3, CuO/SiO2 and CuO/TiO2 for styrene combustion were investigated. The catalytic activity of the catalysts was tested in the absence of and presence of water vapor and the catalysts were characterized. Temperature programmed desorption (TPD) experiments and diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) measurements were conducted in order to estimate and explain the water effects. Results showed that the existence of water vapor had a significant negative effect on the catalytic activity of these copper based catalysts due to the competition adsorption of water molecule. DRIFTS studies showed that the catalyst CuO/gamma-Al2O3 had the strongest adsorption of water, while the catalyst CuO/TiO2 had the weakest adsorption of water. H2O-TPD studies also indicated that the order of desorption activation energies of water vapor on the catalysts or the strength of interactions of water molecules with the surfaces of the catalysts was CuO/gamma-Al2O3>CuO/SiO2>CuO/TiO2. As a consequence of that, the CuO/TiO2 exhibited the better durability to water vapor, while CuO/gamma-Al2O3 had the poorest durability to water vapor among these three catalysts.

Melting Point Depression and Fast Diffusion in Nanostructured Brazing Fillers Confined Between Barrier Nanolayers

NASA Astrophysics Data System (ADS)

Kaptay, G.; Janczak-Rusch, J.; Jeurgens, L. P. H.

2016-08-01

Successful brazing using Cu-based nanostructured brazing fillers at temperatures much below the bulk melting temperature of Cu was recently demonstrated (Lehmert et al. in, Mater Trans 56:1015-1018, 2015). The Cu-based nano-fillers are composed of alternating nanolayers of Cu and a permeable, non-wetted AlN barrier. In this study, a thermodynamic model is derived to estimate the melting point depression (MPD) in such Cu/AlN nano-multilayers (NMLs) as function of the Cu nanolayer thickness. Depending on the melting route, the model predicts a MPD range of 238-609 K for Cu10nm/AlN10nm NMLs, which suggests a heterogeneous pre-melting temperature range of 750-1147 K (476-874 °C), which is consistent with experimental observations. As suggested by basic kinetic considerations, the observed Cu outflow to the NML surface at the temperatures of 723-1023 K (450-750 °C) can also be partially rationalized by fast solid-state diffusion of Cu along internal interfaces, especially for the higher temperatures.

In vitro bioactivity, tribological property, and antibacterial ability of Ca-Si-based coatings doped with cu particles in-situ fabricated by laser cladding

NASA Astrophysics Data System (ADS)

Hou, Baoping; Yang, Zhao; Yang, Yuling; Zhang, Erlin; Qin, Gaowu

2018-03-01

The present study aimed to in-situ fabricate Ca-Si-based coatings doped with copper particles (Cu-CS coatings) to enhance in vitro bioactivity, tribological property, and antibacterial ability of Ti-6Al-4V alloy. The effects of copper addition on the multiple properties were evaluated. Our results showed that Ca2SiO4, CaTiO3, and Cu2O were in-situ fabricated after laser processing. The Cu-CS coatings exhibited an excellent wear resistance and enhanced wettability. Regarding the in vitro bioactivity, after soaking in simulated body fluid, Cu-CS coatings developed an apatite surface layer that was reduced in the coatings with higher weight percent Cu addition. The Cu-CS coatings enhanced the inhibitory action against E. coli strains, especially for the coating with a higher concentration of Cu in it. Hence, the synthesized Cu-CS coatings present excellent tribological properties, enhanced bioactivity, and antibacterial property, and, therefore, would be used to modify the surface properties of Ti-6Al-4V implants for bone tissue engineering applications.

Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

NASA Astrophysics Data System (ADS)

Shao, Min; Li, Ming-Xing; Lu, Li-Ruo; Zhang, Heng-Hua

2016-09-01

Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250-350 °C. Complexes 1-3 show similar orange emission band at 602 nm originating from LMCT mechanism.

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

Srivastava, Himanshu; Ganguli, Tapas; Deb, S. K.

The in-situ growth of CuO nanowires was studied by Energy Dispersive X-ray Diffraction (EDXRD) to observe the mechanism of growth. The study was carried out for comparison at two temperatures—at 500 °C, the optimum temperature of the nanowires growth, and at 300 °C just below the temperature range of the growth. The in situ observation revealed the successive oxidation of Cu foil to Cu{sub 2}O layer and finally to CuO layer. Further analysis showed the presence of a compressive stress in CuO layer due to interface at CuO and Cu{sub 2}O layers. The compressive stress was found to increase withmore » the growth of the nanowires at 500 °C while it relaxed with the growth of CuO layer at 300 °C. The present results do not support the existing model of stress relaxation induced growth of nanowires. Based on the detailed Transmission Electron Microscope, Scanning Electron Microscope, and EDXRD results, a microstructure based growth model has been suggested.« less

Evaluation of the Pulmonary Toxicity of a Fume Generated from a Nickel-, Copper-Based Electrode to be Used as a Substitute in Stainless Steel Welding.

PubMed

Antonini, James M; Badding, Melissa A; Meighan, Terence G; Keane, Michael; Leonard, Stephen S; Roberts, Jenny R

2014-01-01

Epidemiology has indicated a possible increase in lung cancer among stainless steel welders. Chromium (Cr) is a primary component of stainless steel welding fume. There is an initiative to develop alternative welding consumables [nickel (Ni)- and copper (Cu)-based alloys] that do not contain Cr. No study has been performed to evaluate the toxicity of fumes generated from Ni- and Cu-based consumables. Dose-response and time-course effects on lung toxicity of a Ni- and Cu-based welding fume (Ni-Cu WF) were examined using an in vivo and in vitro bioassay, and compared with two other well-characterized welding fumes. Even though only trace amounts of Cr were present, a persistent increase in lung injury and inflammation was observed for the Ni-Cu WF compared to the other fumes. The difference in response appears to be due to a direct cytotoxic effect by the Ni-Cu WF sample on lung macrophages as opposed to an elevated production of reactive oxygen species (ROS).

Evaluation of the Pulmonary Toxicity of a Fume Generated from a Nickel-, Copper-Based Electrode to be Used as a Substitute in Stainless Steel Welding

PubMed Central

Antonini, James M; Badding, Melissa A; Meighan, Terence G; Keane, Michael; Leonard, Stephen S; Roberts, Jenny R

2014-01-01

Epidemiology has indicated a possible increase in lung cancer among stainless steel welders. Chromium (Cr) is a primary component of stainless steel welding fume. There is an initiative to develop alternative welding consumables [nickel (Ni)- and copper (Cu)-based alloys] that do not contain Cr. No study has been performed to evaluate the toxicity of fumes generated from Ni- and Cu-based consumables. Dose–response and time-course effects on lung toxicity of a Ni- and Cu-based welding fume (Ni–Cu WF) were examined using an in vivo and in vitro bioassay, and compared with two other well-characterized welding fumes. Even though only trace amounts of Cr were present, a persistent increase in lung injury and inflammation was observed for the Ni–Cu WF compared to the other fumes. The difference in response appears to be due to a direct cytotoxic effect by the Ni–Cu WF sample on lung macrophages as opposed to an elevated production of reactive oxygen species (ROS). PMID:25392698

A copper-based layered coordination polymer: synthesis, magnetic properties and electrochemical performance in supercapacitors.

PubMed

Liu, Qi; Liu, Xiuxiu; Shi, Changdong; Zhang, Yanpeng; Feng, Xuejun; Cheng, Mei-Ling; Su, Seng; Gu, Jiande

2015-11-28

A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles.