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.

A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, alpha-PbO2-type, and pyrite-type for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase. (C) 2014 AIP Publishing LLC.

Local disorder investigation in NiS2-xSex using Raman and Ni K-edge x-ray absorption spectroscopies

We report on Raman and Ni K-edge x-ray absorption investigations of a NiS2-xSex (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS2-xSex Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS2-xSex pyrites.

Oxygen isotopes and volatiles in martian meteorites

Oxygen isotopes were measured in mineral separates from martian meteorites using laser fluorination and were found to be remarkably uniform in both δ18O and Δ17O, suggesting that martian magmas did not assimilate aqueously altered crust regardless of any other geochemical variations.

Measurements of Cl, F, H, and S in apatite from martian meteorites were made using the SIMS and NanoSIMS. Martian apatites are typically higher in Cl than terrestrial apatites from mafic and ultramafic rocks, signifying that Mars is inherently higher in Cl than Earth. Apatites from basaltic and olivine-phyric shergottites are as high in water as any terrestrial apatite from mafic and utramafic rocks, implying the possibility that martian magmas may be more similar in water abundance to terrestrial magmas than previously thought. Apatites from lherzolitic shergottites, nakhlites, chassignites, and ALH 84001 (all of which are cumulate rocks) are all lower in water than the basaltic and olivine-phyric shergottites, indicating that the slow-cooling accumulation process allows escape of water from trapped melts where apatite later formed. Sulfur is only high in some apatites from basaltic and olivine-phyric shergottites and low in all other SNCs from this study, which could mean that cumulate SNCs are low in all volatiles and that there are other controlling factors in basaltic and olivine-phyric magmas dictating the inclusion of sulfur into apatite.

Sulfur Kα X-rays were measured in SNC apatites using the electron probe. None of the peaks in the SNC spectra reside in the same position as anhydrite (where sulfur is 100% sulfate) or pyrite (where sulfur is 100% sulfide), but instead all SNC spectra peaks lie in between these two end member peaks, which implies that SNC apatites may be substituting some sulfide, as well as sulfate, into their structure. However, further work is needed to verify this hypothesis.

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.

The Early Diagenetic Formation of Organic Sulfur in the Sediments of Mangrove Lake, Bermuda

Due to a low mineral content, the sapropelic sediments depositing in Mangrove Lake, Bermuda, provide an excellent opportunity to explore for possible additions of sulfur to organic matter during the early stages of diagenesis. We evaluated early diagenetic organic sulfur transformations by monitoring the concentrations and stable isotopic compositions of a number of inorganic and organic sulfur pools, thereby accounting for all of the sulfur in the sediments. We have identified and quantified the following sulfur pools: porewater sulfate, porewater sulfide, elemental sulfur, pyrite sulfur, hydrolyzable organic sulfur (HYOS), chromium-reducible organic sulfur (CROS), and nonchromium-reducible organic sulfur (Non-CROS). Of the organic sulfur pools, the Non-CROS pool is by far the largest, followed by CROS, and finally HYOS. By 60 cm depth these pools contribute, respectively, to 85, 7.9, and 3.6% of the total solid phase sulfur. The HYOS pool is probably of biological origin and shows no interaction with the sulfur compounds produced during diagenesis. By contrast, CROS is produced, most likely, from the diagenetic addition of polysulfides to functionalized lipids in the upper, H2S-poor, elemental sulfur-rich, region of the sediment. A portion of this sulfur pool is unstable and decomposes on contact with the H2S-rich porewaters. The portion of CROS that remains in the sulfidic waters appears to readily exchange sulfur isotopes with H2S. While some of the Non-CROS pool is of biological origin, some is also formed by the diagenetic addition of sulfur to organic compounds in the upper H2S-poor region of the sediment. By contrast with CROS, Non-CROS is not diagenetically active in the H2S-rich porewaters. Overall, somewhere between 27 and 53 % of the organic sulfur buried in Mangrove Lake sediments is of diagenetic origin, with the remaining organic sulfur derived from biosynthesis. We extrapolate our Mangrove Lake results and calculate that in typical coastal marine sediments between 11 and 29 μmol g−1 of organic sulfur will form during early diagenesis, of which 2–5 μmol g−1 will be chromium reducible.

Distribution of organic and reduced sulfur forms in marsh soils of coastal Louisiana

Soil samples from a Louisiana Barataria Basin brackish marshes were fractionated into acid-volatile sulfides (AVS), HCl-soluble sulfur, elemental sulfur, pyrite sulfur, ester-sulfate sulfur, and carbon-bonded sulfur. Inorganic sulfur composed 13% of total sulfur in brackish marsh soil with HCl-soluble sulfur representing 63–92% of the inorganic sulfur fraction. AVS represented less than 1% of the total sulfur pool. Pyrite sulfur and elemental sulfur together accounted for 8–33% of the inorganic sulfur pool. Organic sulfur, in the forms of ester-sulfate sulfur and carbon-bonded sulfur, was the most dominant pool representing the majority of total sulfur in brackish marsh. Results were compared to values reported for fresh and salt marshes. Reported inorganic sulfur fractions were greater in adjacent marshes, constituting 24% of total sulfur in salt marsh, and 22% in freshwater marshes. Along a salinity gradient, HCl-soluble sulfur represented 78–86% of the inorganic sulfur fraction in fresh, brackish, and salt marsh. Organic sulfur in the forms of ester-sulfate sulfur and carbon-bonded sulfur was the major constituent (76–87%) of total sulfur in all marshes. Reduced sulfur species, except elemental sulfur, increased seaward along the salinity gradient. Accumulation of reduced sulfur forms through sedimentation processes was significant in marsh energy flow in fresh, brackish and salt marshes.

3D Fe3S4 flower-like microspheres: high-yield synthesis via a biomolecule-assisted solution approach, their electrical, magnetic and electrochemical hydrogen storage properties

Well-defined 3D Fe3S4 flower-like microspheres were synthesized via a simple biomolecule-assisted hydrothermal process for the first time. On the basis of a series of contrast experiments, the probable growth mechanism and fabrication process of the products were proposed. The electrical conductivity property of the as-synthesized Fe3S4 sample exhibited a rectifying characteristic when a forward bias was applied for the bottom-contacted device. The magnetic properties of the products were studied as well and the results demonstrated that the products presented ferromagnetic properties related to the corresponding microstructure. In addition, we first verified that the Fe3S4 flower-like microspheres could store hydrogen electrochemically, and a discharge capacity of 214 mA h g(-1) was measured without any activation under normal atmospheric conditions at room temperature.

Sedimentary changes during the Holocene in the Bohai Sea and its paleoenvironmental implication

Samples of two cores, Cores M5-5 and M7-4 in the Bohai Sea were analyzed in isotopes, grain size, heavy minerals, chemical compositions, and 14 C dating to reconstruct the sedimentation during the Holocene. Abrupt change in carbon and oxygen stable isotopes was recognized at Core M5-5 at about 6400 a BP, which was likely due to the intrusion of the Yellow Sea Warm Current (YSWC) extension into the Bohai Sea. At Core M7-4, sediments between 5900 and 6600 a BP (150-260 cm depth) became coarse-grained, containing rich garnet, high manganese content, and nil autogenic pyrite, indicating a very dynamic sedimentary event during which the ambience was transformed from reductive to oxidative, and sedimentation boosted. Meanwhile, the YSWC had invaded into the Bohai Sea indicated by rich planktonic foraminifera in this event. (c) 2008 Elsevier Ltd. All rights reserved.

Authigenic sulfide minerals and their sulfur isotopes in sediments of the northern continental slope of the South China Sea and their implications for methane flux and gas hydrate formation

This is a report of the study of the authigenic sulfide minerals and their sulfur isotopes in a sediment core (NH-1) collected on the northern continental slope of the South China Sea, where other geophysical and geochemical evidence seems to suggest gas hydrate formation in the sediments. The study has led to the findings: (1) the pyrite content in sediments was relatively high and its grain size relatively large compared with that in normal pelagic or hemipelagic sediments; (2) the shallowest depth of the acid volatile sulfide (AVS) content maximum was at 437.5 cm (> 2 mu mol/g), which was deeper than that of the authigenic pyrite content maximum (at 141.5-380.5 cm); (3) delta S-34 of authigenic pyrite was positive (maximum: +15 parts per thousand) at depth interval of 250-380 cm; (4) the positive delta S-34 coincided with pyrite enrichment. Compared with the results obtained from the Black Sea sediments by Jorgensen and coworkers, these observations indicated that at the NH-1 site, the depth of the sulfate-methane interface (SMI) would be or once was at about 437.5-547.5 cm and the relatively shallow SMI depth suggested high upward methane fluxes. This was in good agreement with the results obtained from pore water sulfate gradients and core head-space methane concentrations in sediment cores collected in the area. All available evidence suggested that methane gas hydrate formation may exist or may have existed in the underlying sediments.

博兴洼陷新生代构造-沉积演化及其对鲁西隆起的响应

The West Shandong Uplift and its adjacent basins, with same evolutional history before Mesozoic, are an important basin-orogenic systems in North China. After late Mesozoic, tectonic differentiation between basin and orogenic belt gradually displayed in the study area. The Boxing sag is a part of Jiyang Depression near to West Shandong Uplift, in which the whole Mesozoic and Cenozoic strata are preserved. Based on the analysis of sedimentary records in the Boxing sag, the Cenozoic structural and sedimentary evolutions in Boxing Sag and its response to Western Shandong uplift are discussed in this dissertation. The main conclusions in this research are presented as follows. Based on Seismic and well logging profile interpretation, fault growth index, thickness difference between bottom wall and top wall and fault activity rate from Eocene to Pliocene are studied. Boxing sag had three main faults, NE, NW and NEE trending faults. Research shows that the activity of the NW trending fault in the Boxing sag became weaken from E1-2S4 to N2m gradually. The evolution of NE and the NEE trending fault can be divided into three episodes, from E1-2k to E2s4, from E2s3 to E3s1, from N2m to E3d. The analysis of Paleogene samples of heavy mineral assemblages shows that metamorphic rocks represented by garnet, intermediate-acid igneous rocks represented by the assemblage of apatite, zircon and tourmaline became less from E1-2k to N2g, and sedimentary rocks represented by the assemblage of pyrite, barite and limonite also became less. Intermediate-basic igneous rocks represented by the assemblage of leucoxene, rutile and ilmenite and metamorphic rocks represented by epidote became more and more. Electronic microprobe analysis shows that glaucophane and barroisite are existed in Kongdian Formation and the 4th member of Shahejie Formation, and they demonstrate that Western Shandong and Eastern Shandong are all the source regions of the Boxing Sag, and they also indicate that oceanic crust existed before the collision between the Yangtze and North China continent. The fact that Eastern Shandong is the source region of Boxing Sag also indicates that Western Shandong was not high enough to prevent sediment from Eastern Shandong at E1-2k and E2s4. The results of the dating of five detrital zircons of Boxing Sag show Kongdian Formation and the 4th member of Shahejie Formation have the age peaks of 2800Ma and 700-800. It means that Eastern Shandong is the source region of Boxing Sag at early Paleogene and Western Shandong is not high enough to prevent the sediment from Eastern Shandong. The ages of 160-180 and 220-260 Ma, which exist in the Guantao Formation and Paleogene, are common in Eastern Shandong and rare in Western Shandong,and it implied that Western Shandong is a low uplift at 24Ma. The Paleogene strata have almost same age groups, while the Guantao Formation has significant variations of age groups, and this indicates that Boxing Sag and Western Shandong uplift had taken place tremendous changes. The results of apatite fission track in Boxing sag show that three times uplifts happened at the source region at 60 Ma, 45Ma and 15Ma respectively, and the Boxing sag experienced two subsidences at 60Ma, 45Ma and one uplift at 20Ma.

油气、微生物与砂岩型铀矿形成关系研究——以东胜铀矿床和钱家店铀矿床为例

Sandstone-type uranium deposits are frequently found close to oil fields or uraniferous sandstones contain bitumen or petroleum. However, few evidence has been presented to indicate the association of uranium mineralization with petroleum oxidation. Thus, Dongsheng uranium deposit in Ordos Basin and Qianjiadian deposit in Kailu Basin are taken for examples to solve the puzzle. Integration data from sedimentary petrology, mineralogy, race elements geochemistry, isotope geochemistry and organic geochemistry, the uranium and petroleum sources, and diagenetic paragenesis of the host sandstone are analyzed, and then the genetic relationship between microbes, petroleum and uranium deposits are discussed. The observation under microscope shows that the host sandstone samples from Middle Jurassic Zhiluo Formation in the Dongsheng deposit contained different kinds of metamorphic rock fragments, which should have been derived form outcrops north to this basin. The LREE/HREE ratios of gneiss and amphibolite sampled from outcrops were close to the highest and the lowest LREE/HREE ratios of the sandstones with well-compared chondrite-normalized REE patterns, respectively. So these results consistently indicated that parent rocks of sandstones were mainly contributed from these two kinds of metamorphic rocks. There was very high Th/U ratio for granite gneiss, which was a mainly potential U resource. Hydrocarbon inclusions and adsorbed hydrocarbons are observed under fluorescence microscope in the host sandstone of Dongsheng uranium deposit, suggesting that the sandstones may have been utilized as oil migration pathways. Based on biomarker parameters, it is indicated that the inclusion oils and adsorbed hydrocarbons were marginally mature to mature, and were derived from humic-sapropel type organic matter under poor reducing freshwater to semi-saline environment. The features are similar to those of organic matter extracted from Triassic sandstone and source rock, but are different from that of cretaceous sandstone. Thus, it can be concluded that the inclusion oils and adsorbed hydrocarbons were mainly derived from Triassic lacustrine facies source rock. Observation results under Scanning Electron Microscopy and Electron Microprobe with Energy Spectrum Analysis show that, in Dongsheng area, the main uranium ore mineral is coffinite. The coffinite is intimately intergrown or coexists with pyrite and calcite, thus, the solution during mineralization stage is inferred to be alkaline. The alkaline environment is not favored for uranium to be pre-concentrated by absorption, and then be reduced abiogenetically. δ34S of pyrite and δ13C of calcite indicate that pyrite was formed by bacterial sulfate reduction (BSR) and part of the carbon of calcite has been dirived from oxidation of petroleum, respectively. Additionally, petroleum is found biodegraded. All the lines of evidence consistently indicate that petroleum was involved in uranium mineralization. Coffinite with microbe-like structures is found in the high U sandstone samples and is composed of nanoparticles, indicating the coffinite is biogenic. The conclusion are also supportted by laboratory experiment studies, which have shown that SRB are capable of utilizing U(VI) as the preferred electron acceptor for respiration and reduce U(VI) to U(IV) directly, coupled the oxidaton of organic matter and sulfate reduction. Based on the research results mentioned above, in the Dongsheng area, coffinite is likely to have formed by mixing of brine containing petroleum derived from Triassic with uranium-bearing meteoric water from outcrops north to Ordos Basin. SRB utilize hydrocarbon as carbon source, and directly reduce U(VI) resulting in precipitation of coffinite. The product of metabolism, H2S and CO2, was precipitated as pyrite and calcite during mineralization stage. Petroleum in fluid inclusions and adsorbed type in host sandstone from Lower Cretaceous Yaojia Formation in Qianjiadian uranium deposit, Kailu Basin, are derived from Jurassic Jiufotang Formation in this basin and the uranium mineral consists mainly of pitchblende. The δ34S and δ13C values of pyrite and calcite during mineralization stage indicate SRB have likely degraded petroleum, which is similar to that of Dongsheng deposit. The alkaline environment as indicated by the diagenetic mineral assemblage calcite, Fe dolomite, pyrite and pitchblende deposit suggests that U ore in the Qiangjiajiadian has a similar origin, i.e., direct reduction by SRB. However, less part of pitchblende is intergrown with kaolinite, suggesting the solution during mineralization stage is acidic. The environment is favorable for U(VI) to be adsorded on quartz or other mineral, and then reduced by H2S produced by SRB. Thus, it can be concluded that U(VI) reduction with petroleum oxidation by SRB and other microbes is an important ore-forming mechanism in petroleum-related sandstone-type uranium deposits. The finding is significant in that it provides a theoretical basis for exploration of both uranium and petroleumr.

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.

黄铁矿热转变过程的岩石磁学研究

Pyrite is the most stable iron-sulfide in reduced environment, and plays an important role in geochemical iron-sulfur cycling of sediments. Thus, the presence of pyrite in sediments and rocks is an important indicator of sedimentary environments. Previous studies on the thermal products of pyrite showed that all of the products (e.g., pyrrhotite, magnetite, hematite) have strong capability of carrying remanence. To deepen our understanding of the environmental and paleomagnetic significances of pyrite, the mineral transformation processes of pyrite upon heating were systematically investigated in this study using intergrated rock magnetic experiments (in both argon and air atmospheres) and X-ray diffraction analysis. The room temperature susceptibility of the paramagnetic pyrite is about 2.68×10-5 SI. In argon atmosphere (reducing environment), pyrite was transformed into monoclinic stable single domain (SD) pyrrhotite above 440 C. The corresponding coercive force and remanence coercivity are about 20 mT and 30 mT, respectively. In contrast, in air atmosphere (oxidation environment), the intermediate thermal products of pyrite are magnetite and pyrrhotite, which were quickly further oxidated to SD hematite, which has coercivity of about 1400 mT. In addition, the hematite particles gradually grow from SD to PSD grain size region by multiple heating runs. The transformation processes of pyrite in oxidation atomosphere can be interpreted by three possible pathways: (1) pyrite→magnetite→hematite; (2) pyrite→pyrrhotite→magnetite→hematite; and (3) pyrite→pyrrhotite→hematite. Low-temperature magnetic experiments show no transitions for pyrite. Despite that low-temperature magnetic method is not suitable for identification of pyrite, it is clear in this study that the high-temperature thermomagnetic measurements (e.g.,  -T and J-T curves) are very sensitive to the presence of pyrite in sediments and rocks. Nevertheless, for the thermal treatment products, low-temperature magnetic measurements showed the 34 K transition of pyrrhotite and the 250 K Morine transition of hematite. Iron-sulfide has also been found on Martian meteorolites by other workers. Therefore, systematic study of rock magnetism of pyrite (and other iron-sulfides) and their products will have great significances for both paleomagnetism and planetary magnetism.

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.