Ultrasonic spray pyrolysis of CZTS solar cell absorber layers and characterization studies

CZTS (Copper Zinc Tin Sulphide) is a wide band gap quartnery chalcopyrite which has a band gap of about 1.45 eV and an absorption coefficient of 10(4) cm(-1); thus making it an ideal material to be used as an absorber layer in solar cells. Ultrasonic Spray Pyrolysis is a deposition technique, where the solution is atomized ultrasonically, thereby giving a fine mist having a narrow size distribution which can be used for uniform coatings on substrates. An Ultrasonic Spray Pyrolysis equipment was developed and CZTS absorber layers were successfully grown with this technique on soda lime glass substrates using aqueous solutions. Substrate temperatures ranging from 523 K to 723 K were used to deposit the CZTS layers and these films were characterized using SEM, EDAX and XRD. It was observed that the film crystallized in the kesterite structure and the best crystallites were obtained at 613 K. It was observed that the grain size progressively increased with temperature. The optical band gap of the material was obtained as 1.54 eV.

Surface chemical characterisation of Paenibacillus polymyxa before and after adaptation to sulfide minerals

A heterotroph Paenibacillus polymyxa bacteria is adapted to pyrite, chalcopyrite, galena and sphalerite minerals by repeated subculturing the bacteria in the presence of the mineral until their growth characteristics became similar to the growth in the absence of mineral. The unadapted and adapted bacterial surface have been chemically characterised by zeta-potential, contact angle, adherence to hydrocarbons and FT-IR spectroscopic studies. The surface free energies of bacteria have been calculated by following the equation of state and surface tension component approaches. The aim of the present paper is to understand the changes in surface chemical properties of bacteria during adaptation to sulfide minerals and the projected consequences in bioflotation and bioflocculation processes. The mineral-adapted cells became more hydrophilic as compared to unadapted cells. There are no significant changes in the surface charge of bacteria before and after adaptation, and all the bacteria exhibit an iso-electric point below pH 2.5. The contact angles are observed to be more reliable for hydrophobicity assessment than the adherence to hydrocarbons. The Lifschitz–van der Waals/acid–base approach to calculate surface free energy is found to be relevant for mineral–bacteria interactions. The diffuse reflectance FT-IR absorbance bands for all the bacteria are the same illustrating similar surface chemical composition. However, the intensity of the bands for unadapted and adapted cells is significantly varied and this is due to different amounts of bacterial secretions underlying different growth conditions.

Surface chemical and adsorption studies using Thiobacillus ferrooxidans with reference to bacterial adhesion to sulfide minerals

Adhesion of Thiobacillus ferrooxidans to pyrite and chalcopyrite in relation to its importance in bioleaching and bioflotation has been studied. Electrokinetic studies as well as FT-IR spectra suggest that the surface chemistry of Thiobacillus ferrooxidans depends on bacterial growth conditions. Sulfur-,Pyrite- and chalcopyrite-grown Thiobacillus ferrooxidans were found to be relatively more hydrophobic. The altered surface chemistry of Thiobacillus ferrooxidans was due to secretion of newer and specific proteinaceous compounds. The adsorption density corresponds to a monolayer coverage in a horizontal orientation of the cells. The xanthate flotation of pyrite in presence of Thiobacillus ferrooxidans is strongly depressed where as the cells have insignificant effect on chalcopyrite flotation. This study demonstrate that: (a)Thiobacillus ferrooxidans cells can be used for selective flotation of chalcopyrite from pyrite and importantly at natural pH values. (b)Sulfur-grown cells exhibits higher leaching kinetics than ferrous ion-grown cells.

Growth of AgInS2 thin films by ultrasonic spray pyrolysis technique

Silver Indium Di-sulfide (AgInS2) thin films are deposited using ultrasonic spray pyrolysis technique and the effect of substrate temperature (T-s) on film growth is studied by varying the temperature from 250 to 400 degrees C. From the structural analysis, orthorhombic AgInS2 phase is identified with preferential orientation along (002) plane. Further analysis with Raman revealed the coexistence of Cu-Au ordered and chalcopyrite structures in the films. Stoichiometric films are obtained at T-s of 300 degrees C. Above 300 degrees C, the film conductivity changed from p to n-type and the grain size decreased. The band gap of AgInS2 films varied from 1.55 to 1.89 eV and absorption coefficient is found to be >10(4) cm(-1). The films have sheet resistance in the range of 0.05 to 1300 Omega/square Both p and n type films are prepared through this technique without any external doping. (C) 2013 Elsevier B.V. All rights reserved.

Cu(In,Al)Se-2 thin films by one-step electrodeposition for photovoltaics

Chalcopyrite Cu(In,Al)Se-2 (CIAS) thin films are grown on stainless steel substrate through one-step electrodeposition at room temperature. Indium is partially replaced with aluminum to increase the band gap of CuInSe2 without creating significant change in the original structure. The deposition potential is optimized at -0.8 V (vs. SCE) and annealing of the films is performed in vacuum to remove binary phases present in the as-deposited films. In/Al ratio is varied from 1/9 to 8/2, to find the suitability for solar cell fabrication. For In/Al ratio of less than 8/2, CuAlSe2 phase is formed in the film in addition to the CIAS phase. Depth profile X-ray photoelectron spectroscopy analysis of the CIAS sample prepared with In/Al ratio of 8/2 in the precursor solution confirmed the existence of single phase CIAS throughout the film. This film showed p-type conductivity while the rest of the samples with In/Al ratio less than 8/2 showed n-type conductivity. The band gap of the film varied from 1.06 to 1.45 eV, with variation in deposition potential. Structural, optical, morphological, compositional and electrical characterizations are carried out to establish the suitability of this film for solar cell fabrication. (C) 2013 Elsevier B.V. All rights reserved.

Solution Processed Cu2CoSnS4 Thin Films for Photovoltaic Applications

Earth abundant alternative chalcopyrite Cu2CoSnS4 (CCTS) thin films were deposited by a facile sol-gel process onto larger substrates. Temperature dependence of the process control of deposition and desired phase formations was studied in detail. Films were analyzed for complete transformation from amorphous to polycrystalline, with textured structures for stannite phase, as reflected from the X-ray diffraction and with nearly stoichiometric compositions of Cu:Co:Sn:S = 2:0:1:0:1:0:4:0 from EDAX analysis. Morphological investigations revealed that the CCTS films with larger grains, on the order of its thickness, were synthesized at higher temperature of 500 degrees C. The optimal band gap for application in photovoltaics was estimated to be 1.4 eV. Devices with SLG/CCTS/Al geometry were fabricated for real time demonstration of photoconductivity under A.M 1.5 G solar and 1064 rim infrared laser illuminations. A photodetector showed one order current amplification from similar to 1.9 X 10(-6) A in the dark to 2.2 x 10(-5) A and 9.8 X 10(-6) A under A.M 1.5 G illumination and 50 mW cm(-2) IR laser, respectively. Detector sensitivity, responsivity, external quantum efficiency, and gain were estimated as 4.2, 0.12 A/W, 14.74% and 14.77%, respectively, at 50 mW cm(-2) laser illuminations. An ON and OFF ratio of 2.5 proved that CCTS can be considered as a potential absorber in low cost photovoltaics applications.

Tailoring the Cu(In, Al)S-2 nanostructures for photonic applications

Solvent dependent and low temperature based Chalcopyrite CuIn1-xAlxS2 (CIAS) nano structures were synthesized by a simple one-pot solvothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible spectroscopy and micro-Raman spectroscopy were used to characterize the nanostructures structurally and optically. CIAS hollow spheres were constructed from the nanoplates. Detailed formation mechanism of the hollow spheres was explained. Tentative optical phonon vibrational modes have been discussed. Steady state room temperature IR photodectection have been demonstrated with all the CIAS nanostructures under IR lamp illumination. Photo current was amplified by two orders and one order in case of nano needle like structures and hollow spheres respectively, which was explained based upon the trap assisted space charge. Growth and decay constants lasted for few milli seconds.

Sulfurization of sputtered Ag-In precursors for AgInS2 solar cell absorber layers

Silver indium sulfide (AgInS2) thin films are deposited by sequential sputtering of metallic precursor Ag/In] followed by sulfurization. Effect of substrate temperature (Tsub) during sulfurization process on the film growth is studied by varying the substrate temperature from 350 to 500 degrees C. Films prepared above 350 degrees C showed a mixture of orthorhombic and tetragonal phases of AgInS2 with tetragonal phase being dominant. Better crystalline, nearly stoichiometric and p-type films are obtained at a substrate temperature of 500 degrees C. The characteristic A(1) mode of AgInS2 chalcopyrite structure is observed in the Raman spectra at 274 cm(-1) for the films prepared above 350 degrees C. The grain size of the film increases from 489 to 895 nm with the increase in substrate temperature. The binding energies of the constituent elements are determined using XPS. The band gap of AgInS2 films is in the range of 1.64-1.92 eV and the absorption coefficient is found to be >10(4) cm(-1). Preliminary studies on the AgInS2/ZnS solar cell showed an efficiency of 0.3%. (C) 2015 Elsevier B.V. All rights reserved.

Metallogenic Provinces of the Southwestern United States and Northern Mexico

Some of the metallogenic provinces of the southwestern United States and northern Mexico are defined by the geographic distribution of trace elements in the primary sulfide minerals chalcopyrite and sphalerite. The elements investigated include antimony, arsenic, bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, molybdenum, nickel, silver, tellurium, thallium, and tin. Of these elements, cobalt, gallium, germanium, indium, nickel, silver, and tin exhibit the best defined geographic distribution.

The data indicate that chalcopyrite is the preferred host for tin and perhaps molybdenum; sphalerite is the preferred host for cadmium, gallium, germanium, indium, and manganese; galena is the preferred host for antimony, bismuth, silver, tellurium, and thallium; and pyrite is the preferred host for cobalt, nickel, and perhaps arsenic. With respect to the two minerals chalcopyrite and sphalerite, antimony, arsenic, molybdenum, nickel, silver, and tin prefer chalcopyrite; and bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, and thallium prefer sphalerite. This distribution probably is the result of the interaction of several factors, among which are these: the various radii of the elements, the association due to chemical similarities of the major and trace elements, and the degree of ionic versus covalent and metallic character of the metal-sulfur bonds in chalcopyrite and sphalerite. The type of deposit, according to a temperature classification, appears to be of minor importance in determining the trace element content of chalcopyrite and sphalerite.

A preliminary investigation of large single crystals of sphalerite and chalcopyrite indicates that the distribution within a single crystal of some elements such as cadmium in sphalerite and indium and silver in chalcopyrite is relatively uniform, whereas the distribution of some other elements such as cobalt and manganese in sphalerite is somewhat less uniform and the distribution of tin in sphalerite is extremely erratic. The variations in trace element content probably are due largely to variations in the composition of the fluids during the growth of the crystals, but the erratic behavior of tin in sphalerite perhaps is related to the presence of numerous cavities and inclusions in the crystal studied.

Maps of the geographic distribution of trace elements in chalcopyrite and sphalerite exhibit three main belts of greater than average trace element content, which are called the Eastern, Central, and Western belts. These belts are consistent in trend and position with a beltlike distribution of copper, gold, lead, zinc, silver, and tungsten deposits and with most of the major tectonic features. However, there appear to be no definite time relationships, for as many as four metallogenic epochs, from Precambrian to late Tertiary, are represented by ore deposits within the Central belt.

The evidence suggests that the beltlike features have a deep seated origin, perhaps in the sub-crust or outer parts of the mantle, and that the deposits within each belt might be genetically related through a beltlike compositional heterogeneity in the source regions of the ores. Hence, the belts are regarded as metallogenic provinces.

PHOTOELECTROCHEMISTRY OF ELECTRODEPOSITED POLYCRYSTALLINE CUINSE2 THIN-FILMS .1. ELECTRODEPOSITION OF CUINSE2 FILMS

Electrodeposition of CuInSe2 was investigated in acidic solutions containing Cu2+, In3+ and HSeO2+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium substrate. The mechanism of the electrodeposition process is discussed. Structure analysis of the deposited film shows a typical polycrystalline chalcopyrite structure, good crystallinity and homogeneous dispersion. The photoelectrochemical cells made of these kinds of deposited films in polysulfide redox solution give distinct photoresponse.

东天山红山高硫型浅成低温铜-金矿床氧化带的形成机理和硫酸盐矿物的系列发现及意义

Located in the Paleozoic uplift along the southern margin of Tu-Ha basin in eastern Xinjiang, the newly discovered Hongshan Cu-Au deposit occurs in the superimposed Mesozoic volcanic basin upon the north section of later Paleozoic Dananhu-Tousuquan accretionary arc. Kalatage Cu-Au orebelt is controlled by NWW-trend faults, and includes Hongshan and Meiling Cu-Au deposits. The host rocks of Hongshan ore district are mainly rhyolitic-dacitic ignimbrites, whereas Cu-Au mineralization is closely related to quartz porphyry, rhyolitic porphyry and granitic porphyry. Mineralization styles are dominantly veinlet-disseminated and veinlet, occasionally stockwork. The mineral association is chalcopyrite, pyrite, bornite, chalcocite and sphalerite. The hydrothermal alteration consists of silicfication, sericitization, alunitization, pyrophylitization, illitization, hydromuscovitization, and chloritization. Hongshan Cu-Au deposit, on the edge of the desert, is one of the driest areas in eastrn Tianshan. Moreover， the highest temperature has been up to 60℃, and the average rainfall receives only 34.1mm/y. The light rainfall and rapid evaporation in the vicinity of this deposit have allowed the formation of a great variety of water-soluble sulfates. Oxidization zone of this deposit lies on the upper part of primary sulfide orebodies appearing with a depth of 50-60m, which is dominant in sulfate minerals. 1. Based on the field observation, the volcanic and sub-volcanic rock composition, hydrothermal alteration, ore structure and mineralization characteristics, this paper proposed that the Hongshan Cu-Au deposit belongs to a transitional type from high-sulfide epithermal to porphyry Cu-Au deposit, which corresponds with the typical HS-epithermal deposit such as Zijinshan Au-Cu deposit in Fujian Province, SE-China. 2. The Hongshan copper-gold deposit was controlled by the tectonic, stratum, magma activity and volcanic apparatus, whereas Au mineralization is closely related to quartz porphyry, rhyolitic porphyry and fine grained pyritization in hydrothermal activity, and Cu mineralization is closely related to quartz porphyry and hydrothermal explosive breccia. 3. Oxidation zone of Hongshan Cu-Au deposit lies on the upper part of primary sulfide orebodies deposit. 23 sulfate minerals were identified in this work. The results of samples XRD and chemical analysis were furthermore confirmed through thermal, infrared spectrum and mössbauer spectrum analysis. Among those, nine minerals as Ferricopiapite, Cuprocopiapite, Rhomboclase, Parabutlerite, Krausite, Yavapaiite, Metasideronatrite Kroehnkite and Paracoquimbite were founded in China for the first time. And Paracoquimbite was secondly reported in the world (first case reported at 1938 in Chile). 4. EPMA analysis shows that Al impurity in crystal lattice is important to polytype formation of paracoquimbite and coquimbite besides stack fault. 5. Compared with Meiling Cu-Au deposit in the same Kalatage ore belt from the characteristics of δ34S of barite, lithofacies, hydrothermal alteration and homogeneous temperature, Hongshan Cu-Au deposit belongs to the same metallogenic system of HS-epithermal type as Meiling Cu-Au deposit. But Hongshan Cu-Au deposit has less extensive alteration and shallower denudation. 6. Sulfur isotope analyses show that δ34S values of pyrites vary in the range of +1.86‰~+5.69‰, with an average of 3.70‰, mostly in the range of +1.86‰~+3.20‰, and δ34Scp<δ34Spy. Therefore ore-forming fluid of porphyry comes from mantle and was contaminated by the earth’s crust. Sulfur isotope has reached balance in ore-forming process. 7. Sulfur isotope analyses show that δ34S values of sulfates vary in the range of +2.15‰~+6.73‰, with an average of +3.74‰, mostly equals as δ34S values of primary sulfides in Hongshan Cu-Au deposit. So supergene sulfates inherit sulfur of primary sulfide. δ34S values are mostly same in different sulfates. As well as pyrite and chalcopyrite, volcanic hot spring and associated native sulfur underground also provide water medium and sulfur during the formation process of sulfate. 8. According to the EPMA of sample chalcopyrite and pyrite in Hongshan Cu-Au, the value of Cu/Ni is 0.98-34.72, mostly close to the value of 5, which shows that Hongshan deposit is a typical volcanogenic magmaic hypothermal deposit. Au and Ag, Zn, Te and Bi are positive correlation, Cu and Hg, Se, Sb are positive correlation, indicates Au and Cu don’t locate in the factor of mineralization of same mineralization groups. The reasons of gold concentration in the oxidation zone are: 1). Change of redox potential (Eh) makes gold to deposit from the liquid of mineralization zone; 2). PH is one of the most factors of gold’s deposition; 3). Soluble complex and colloid of gold can be adsorbed easily. 9. The biotite and hornblende K-Ar isotopic ages from the wall rock－quartz diorite, biotite granite and monzonite granite are 231.99±3.45Ma, 237.97±2.36Ma and 296.53±6.69Ma respectively. The ore-bearing rhyolitic breccia lava contains breccia of the biotite granite which indicates the volcanism and related Cu-Au mineralization occurred later than the granite, possibly in Mesozoic. K-Ar ages of granitoids in Sanya, Baishiquan and Hongliugou area and Molybdenite Re-Os age of Baishan Mo deposit all are in Triassic. Besides late Paleozoic magmatism, igneous magmatic event of Mesozoic was widespread in eastern Tianshan. 10. The K-Ar age dating indicates that the K-Ar age of Voltaite occurred below surface 1m is 56.02±3.98Ma, K-Ar age of Ferricopiapite occurred below surface 1.5m is 8.62±1.12Ma, K-Ar age of Yavapaiite occurred below surface 14 m is 4.07±0.39Ma, and K-Ar age of Voltaite occurred below surface 10 m is 14.73±1.73Ma. So the age interval of oxidation zone of Hongshan copper-golden bed is between 60 -3.38Ma. Oxidization occurred at Caenozoic era (from 65Ma), which can be identified through comparing with different deposits oxidation zone in other countries. The coupling between global tectonic event and climatic change event which occur from Caenozoic era has some effect on epigeosphere system, which can act on the surface of bed oxidation zone similarly. It induces that the age mentioned above coincide with collision of India-Asia and multistage uplifting of Qinhai-Tibet Plateau happened subsequently. Bed oxidation zone is the effect and record of collision and uplifting of Tibet Plateau. The strong chemical weathering of surface accumulation to which was leaded by PETM event occurred Paleocene and Eocene is the reason of Voltaite sharply rises. On the contrary, Ferricopiapite formed due to the global cold weather. The predecessor did much research through biota, isotopes, susceptibility, but this paper try to use different sulfate mineral instead of climatic change. So the research of sulfate minerals not only indicates a great deal of oxidized zone feature, but also the intergrowth of sulfate minerals may be used to trace paleoenviroment and paleoclimate of oxidation zone. 11. Analysis of the information of alteration and mineralization features of four bore cores, induced activity polarization well logging and Eh-4 geophysical section, deep mineralization anomaly objects of Hongshan ore districts shows low resistance, middle and high polarization, measurements of Eh-4 consecutive conductance section show the existing of concealed porphyry ore body deeper than 450m, on the top of and around rock body there are low resistance body ranged from 100-300Ω•m, this area may be the ore-bearing part. In a word, Hongshan Cu-Au deposit deposit is a combine of upper HS-style epithermal Au deposit and deeper porphyry mineralization system. It has great potential to find large HS-style epithermal-porphyry Au-Cu deposits. This paper consists of seven chapters and twenty seven sections. The geological character of deposit is basic condition in this work. Constitute of oxidation zone, research of sulfate mineral, relation between oxidation and primary zone, K-Ar ages of potassic sulfate are key parts of thesis. Genesis of ore deposit is the further expansion of this research. Analysis of ore-controlling factors is the penetration above basic. Analysis of potential is application of exploration.

班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

内蒙古中部道郎和都格铜多金属矿的地质特征矿床类型及找矿模式研究

Daolangheduge copper polymetallic deposit is located on east edge of Ondor Sum-Bainaimiao metallogenic belt, which is a prospective area of porphyry copper deposit, in Xianghuangqi of central Inner Mongolia. Geotectonically, it occurred in the continental margin accretion belt along the north margin of North China Plate, south of the suture zone between North China Plate and Siberian Plate. The intrusive rocks in this area mainly consist of intermediate-acid magmatic rocks, and the quartz veins, tourmaline veins and the transitional phase are comparatively developed. According to our research, the ore-bearing rock body is mainly quartz diorite while the surrounding rock is mainly biotite granite. Besides, the wall rock alteration are mainly propylitization, pyritization and silicification, which consist of epidotization, actinolitization, chloritzation and so on. The metallic minerals are mainly chalcopyrite and pyrite. In addition, the primary ore is mainly of quartz-chalcopyrite-pyrite type. Above all, Daolangheduge copper polymetallic deposit is suggested to be categorized in the porphyry copper type. With isotopic dating and geochemical research on quartz diorite of ore-bearing rock body, the zircon LA-ICP-MS U-Pb dating of two samples yields an age of 266±2 Ma, falling into the range of late Permian Epoch. It is the first accurate age data in Xianghuangqi area, so it should play a key role in the research of deposit and magmatic rocks in this area. With the major elements and trace elements analysis of 14 samples, the quartz diorite should be among the calc-alkaline series, the geochemical characteristics show higher large-ion lithophile elements of Rb, Sr and LREE, low high-field strength elements of Nb, Ta and high transition elements of Cu, Cr . Also, the REE patterns have negative Eu anomalies. With the same analysis of 4 sample for the biotite granite, the geochemical characteristics show higher Rb, Th,, Zr, Hf and LREE, low Nb, Sm and HREE and Eu has no anomaly. It should be among the calc-alkaline series, over aluminum quality and has characteristics of Adakites. According to isotopic dating and geochemical characteristics of ore-bearing rock body, it is suggested that its materials mainly derived from upper mantle that had fractional crystallization and its magma source region may be affected by fluid metasomatism of paleo-asian ocean. It should be an extensional process of post-orogeny according to regional tectonic evolution. Consequently, because of the decrease of temperature and pressure, the ore forming fluid was raised to surface and mineralized accompanied by magmatic activity which might occur in south of the suture zone. By geological survey, further geophysical and geochemical work is needed. In this area, we have accomplished high precision magnetic prospecting, high density electrical survey, gravity prospecting, soil geochemical prospecting, X-ray fluorescence analyzer prospecting and so on. According to geophysical and geochemical abnormal and surface occurrence, 11 drills are arranged to verification. The type of ores are mainly quartz-chalcopyrite-pyrite ores within 3 drills by drill core logging. Although the grade as well as the scale of already-found Cu deposits are insufficient for industrial exploitation, the mineralization prospect in this region is supposed to be great and the potential in mineral exploration at depth is excellent.

山东莱州金城金矿床构造-流体成矿特征

This paper studied the metallotectonics, altered rocks, altered minerals and fluid inclusions. The conclusions are: (1)The gold deposits in Jiaodong district were formed quickly uplifted tectonic setting which was induced by the Mantle doming in Mesozoic era. (2)Both Jiaojia-type and Linglong-type gold mineralizations were formed in the same tectonic-fluid system. (3) The Ar-Ar age of the earlier stage of the gold mineralization is 114～116Ma. (4)The development of the plaiting ore-control tectonic system underwent four stagesrcounterclockwise ductile compresso-shearing, clockwise brittle tenso-shearing and counterclockwise brittle compresso-shearing and brittle normal faulting after mineralization. (5)The mineralization has five stages: quartz and k-feldspar stage, quartz and ferro-carbonate and pyrite stage, quartz and chalcopyrite stage, pyrite and sericite and quartz stage and carbonate stage, and they make up four ore-types: red ore, vein ore, mottled ore and grey ore. (6) The features of mineralizations and ore-forming fluids in different stages are different. But the ore-forming fluids are rich in Si, Fe, P_2O_5, H_2O, CO_2, SO_4~(2-), K~+, Na~+, Ca~(2+) and Cl~- in general and their salinities are from 4 to 18 NaClwt%. (7) The ore-forming fluids came mainly from the Mantle in early stage, then mainly from magma, and mainly from meteoric water in the last stage. (8) Au in the ore-forming fluid was mainly carried in the form of complex of Au and S. (9)The temperature of ore-forming fluid is from 350℃ to 120℃and its pressure is from 20MPa to 38MPa. (10)The gold vein composed by quartz, ferro-carbonate, chalcopyrite and pyrite (vein ore) was filled in the tensional fracture in the top of the magma dome. The disseminated ore bodies composed by pyrite, sericite and quartz (grey ore) was metasomatized in the shearing fault which developed along the contact zone between Linglong intrusive body and Jiaodong Group, which is placed in the flank top of magma dome. In the joint and fracture induced by the shearing fault which developed along the contact zone between Linglong intrusive body and Jiaodong Group, veiniet and stockwork ore (red ore) and veinlet-disseminated ore (mottled ore) composed by quartz and pyrite was formed. (ll)Fluid boiling maybe one of the form of the ore-forming substances precipitation.

河北寿王坟铜矿成矿定年及同位素地球化学特征

Samples from carbonate wall-rocks, skarn, ore of skarn type, later calcite vein, and ore of porphyry type in Shouwangfen copper deposit district were collected. Systematic study was carried out on carbon, oxygen, rubidium, strontium and sulfur isotope compositions of carbonates and sulfides in these samples. The first Isochron dating by the Rb-Sr isotopes in chalcopyrite of ore sub-sample was done as well. The following conclusions were obtained. The age (113.6±4.3Ma), obtained by Rb-Sr isotope isochron dating of chalcopyrite and pyrite from sub-sample of skarn ores, probably represents the true mineralization age of skarn ores. That demonstrates the genetic relationship between granodiorite in Shouwangfen complex and skarn copper ores. On the other hand, the Rb-Sr isochron age (73±15Ma) of chalcopyrite from porphyry ores is a little incredible because of bad synthesizing evaluation. But combined with other age data of igneous rocks, it implies the possibility of hydrothermal mineralization in connection with magma activity during the fourth period of Yanshanian in Hebei Province, even in the whole northern edge of Huabei continental block. Together from structure analysis of sulfide sub-samples, from pretreating preccedure of Rb-Sr isotope isochron and its' valuating, we found out that Rb-Sr isotope isochron of sulfide sub-samples is influenced by the crystal structure of sulfides. That is, sulfide ores with very big crystals are not suitable for sub-sample isochron. Carbon, oxygen, sulfur and strontium compositions, of different minerals in these two kinds of ores, imply that the ore-forming hydrothermal fluids were probably derived from magma deep under the crust. The calcite ~(87)Sr/~(86)Sr ratios from the porphyry are consistent to the initial 87Sr/86Sr ratio of the Rb-Sr isochron of chalcopyrite and pyrite in the skarn ore, indicating that these two kinds of ores have the same source characteristic, although the porphyry deposit was formed probably 40 million years later than the skarn one according to our dating results. Skarn and skarn ores are usually considered as interaction product between carbonate wall-rocks and magmatic fluids, but the carbon of the sedimentary carbonate seems not involved in the skarn ores. Considering the connection of magmatic processes and hydrothermal ore formation in the Shouwangfen district, particularly, the spatial distribution of skarn-type and porphyry-type ores, it is possible that the Shouwangfen ore district corresponds to a hydrothermal ore-forming system, which was promoted by high-intruding magmatic rocks. Systematic stable isotopic research can help to reveal the upper part of this hydrothermal ore-forming system, which mainly related to heated and circulating meteoric water, and the lower part principally related to ascending magmatic fluids. Both skarn and porphyry ore-bodies are formed by up-intruding magmatic fluids (even more deep mantle-derived fluids).