Estimation of surface free energy of pyrites by contact angle measurements

The surface properties of coal-pyrite play a major role in determining its separation from coal in processes such as flotation. The solution pH is an important parameter in determining the surface properties of both coal and coal-pyrite such as surface free energy and zeta-potential. In the present investigation, the effect of pH on the surface free energy of pyrites from different sources was studied. The surface free energy of solids is made up of two components, i.e. the dispersive surface free energy and the acid-base interaction energy. Various methods have been used by previous researchers to evaluate these two components for different solids. In the present study, a new approach was developed and used to study the surface free energy of pyrite surfaces. Results indicate that the dispersion surface free energy of various pyrites is independent of pH while the acid-base interaction energy is strongly dependent on the pH. The acid-base interaction energy is different for each pyrite sample and also the change with pH varies with the type of pyrite. Coal-pyrite was found to be more hydrophobic than ore-pyrite which may be attributed to the presence of carbon in coal-pyrites. The acid-base interaction energy varied little with pH for coal pyrites than ore-pyrite. Comparison of acid-base interaction energy with zeta-potential measurements shows a good correlation between the minimum in acid-base interaction energy and the pHpzc.

Thallium isotope composition in pyrites

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.

The mineral industry of the British Empire and foreign countries. Statistics, 1920-1922. Pyrites.

At head of title: Imperial Mineral Resources Bureau.

The mineral industry of the British Empire and foreign countries. Statistics, 1919-1921. Pyrites.

At head of title: Imperial Mineral Resources Bureau.

Multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the Teutonic Bore volcanic complex, Yilgarn Craton, Western Australia

We report sensitive high mass resolution ion microprobe, stable isotopes (SHRIMP SI) multiple sulfur isotope analyses (32S, 33S, 34S) to constrain the sources of sulfur in three Archean VMS deposits—Teutonic Bore, Bentley, and Jaguar—from the Teutonic Bore volcanic complex of the Yilgarn Craton, Western Australia, together with sedimentary pyrites from associated black shales and interpillow pyrites. The pyrites from VMS mineralization are dominated by mantle sulfur but include a small amount of slightly negative mass-independent fractionation (MIF) anomalies, whereas sulfur from the pyrites in the sedimentary rocks has pronounced positive MIF, with ∆33S values that lie between 0.19 and 6.20‰ (with one outlier at −1.62‰). The wall rocks to the mineralization include sedimentary rocks that have contributed no detectable positive MIF sulfur to the VMS deposits, which is difficult to reconcile with the leaching model for the formation of these deposits. The sulfur isotope data are best explained by mixing between sulfur derived from a magmatic-hydrothermal fluid and seawater sulfur as represented by the interpillow pyrites. The massive sulfide lens pyrites have a weighted mean ∆33S value of −0.27 ± 0.05‰ (MSWD = 1.6) nearly identical with −0.31 ± 0.08‰ (MSWD = 2.4) for pyrites from the stringer zone, which requires mixing to have occurred below the sea floor. We employed a two-component mixing model to estimate the contribution of seawater sulfur to the total sulfur budget of the two Teutonic Bore volcanic complex VMS deposits. The results are 15 to 18% for both Teutonic Bore and Bentley, much higher than the 3% obtained by Jamieson et al. (2013) for the giant Kidd Creek deposit. Similar calculations, carried out for other Neoarchean VMS deposits give value between 2% and 30%, which are similar to modern hydrothermal VMS deposits. We suggest that multiple sulfur isotope analyses may be used to predict the size of Archean VMS deposits and to provide a vector to ore deposit but further studies are needed to test these suggestions.

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.

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.

胶东地区金矿床成矿时代及其成矿地球动力学背景-兼论壳幔相互作用与成岩成矿

Jiaodong Peninsula is the largest repository of gold in China. Varieties of studies have been involved in the mechanism of metallogenesis. This thesis is a part of the project "Study of basic geology related to the prespecting of the supra-large deposits" which supported by National Climbing Program of China to Prof. Zhou. One of the key scientific problems is to study the age and metallogenic dynamics of ore deposit and to understand how interaction between mantle and crust constrains on metallogenesis and lithogenesis. As Jiaodong Peninsula to be study area, the Rb-Sr, Sm-Nd and Pb isotopic systematics of pyrite and altered rocks are measured to define the age and origin of gold. The elemental and Sr-Nd-Pb isotopic compositions of dikes and granites was studied to implicate the source and lithogenesis of the dike and granite and removal of lithosphere and the interaction between mantle and crust in the Jiaodong Peninsula. Considering the tectonic of Jiaodong Peninsula, basic on the time and space, this thesis gives a metallogenic dynamics of gold mineralization and discusses the constraints of the interaction between mantle and crust on the metallogenesis and lithogenesis. This thesis reports the first direct Rb-Sr dating of pyrites and ores using sub-sampling from lode gold deposit in Linglong, Jiaodong Peninsula and the results demonstrate this as a useful geochronological technique for gold mineralization with poor age constraint. The Rb-Sr data of pyrites yields an isochron age of (121.6-122.7) Ma, whereas, those of ore and ore-pyrite spread in two ranges from 120.0 to 121.8 Ma and 110.0-111.7 Ma. Studies of characteristic of gold deposit, microscopy of pyrite and quartz indicate that the apparent ages of ore and ore-pyrite are not isochron ages, it was only mixed by two end members, i.e., the primitive hydrothermal fluids and wall rocks. However, the isochron age of pyrite samples constrains the age of gold mineralization, i.e., early Cretaceous, which is in good consistence with the published U-Pb ages of zircon by using the SHRIMP technique. The whole rock Rb-Sr isochron age of altered rocks indicates that the age of gold mineralizing in the Xincheng gold deposit is 116.6 ± 5.3 Ma. The Sr, Nd and Pb isotopic compositions of pyrite and altered rocks indicate that the gold and relevant elements were derived from multi-sources, i.e. dikes derived from enriched lithospheric mantle and granites, granodiorites and metamorphic rocks outcropped on the crust. It also shows that the hydrothermal fluids derived from mantle magma degassing had play an important role in the gold mineralizing. The major and trace elements, Sr-Nd-Pb isotopic data of granites and granodiorites suggest that the Linglong Granite and Kunyushan Granite were derived from partial melting of basement rocks in the Jiaodong Peninsula at post-collision of North China Craton with South China Craton. Guojialing Granodiorite was considered to be derived from a mixture source, that is, mixed by magmas derived from an enriched lithospheric mantle and crust during the delamination of lithosphere induced by the subduction of Izanagi Plate and the movement of Tancheng-Lujiang Fault. There are kinds of dikes occurred in the Jiaodong Peninsula, which are accompanying with gold mineralization in time and space. The dikes include gabrro, diabase, pyroxene diorite, gabrrophyre, granite-porphyry, and aplite. The whole rock K-Ar ages give two age intervals: 120-124 Ma for the dikes that erupted at the gold mineralizing stage, and <120 Ma of the dikes that intruded after gold mineralizing. According to the age and the relationship between the dikes and gold mineralizing, the dikes could be divided into two groups: Group I (t = 120-124 Ma) and Group II (t < 120Ma). Group I dikes show the high Mg and K, low Ti contents, negative Nb anomalies and positive Eu anomalies, high ~(87)Sr/~(86)Sr and negative εNd(t) values and an enrichment in light rare earth elements, large ion lithosphile elements and a depletion in high field strength elements. Thus the elemental and isotopic characteristics of the Group I dikes indicate that they were derived from an enriched lithospheric mantle perhaps formed by metasomatism of the melt derived from the recycled crustal materials during the deep subduction of continent. In contrast, the Group II dikes have high Ti, Mg and K contents, no negative Nb anomalies, high ~(87)Sr/~(86)Sr and positive or little negative εNd(t) values, which indicate the derivation from a source like OIB-source. The geochemical features also give the tectonic constraints of dikes, which show that Group I dikes were formed at continental arc setting, whereas Group II dikes were formed within plate background. Considering the tectonic setting of Jiaodong Peninsula during the period of gold mineralizing, the metallogenic dynamics was related to the subduction of Izanagi Plate, movement of Tancheng-Lujiang Fault and removal of lithopheric mantle during Late Mesozoic Era.

山西堡子湾金矿角砾岩带控矿规律、成矿时代及隐伏矿体定位预测

The Puziwan gold deposit is located at the northern boundary of the North China platform where there are very favorable ore-forming conditions. The deposit is a medium-sized gold deposit associated with silver and copper polymetallic minerallization which were closely related to cryptoexplosive processes and fluidization and underwent multi-epoch superposition of mineralization. The mineralization consists of cryptoexplosive breccia-type, fluidizing-type, porphyry-type, quartz vein-type, etc. The ore-controlling law of ore-bearing brecciated zone is systematically studied in the paper. The shape, scale and attitude of ore bodies are dominat in the upper, the ore bodies of fluidizing breccia-type are dominant in the upper and the middle part, the porphyry-type ore bodies are dominant in the bottom. The quartz vein-type ore bodies are impenetrated in all the brecciated zone. The metallogenic epoch of Puziwan gold deposit is collated and stipulated. The Rb-Sr isochron age of quartz porphyry (wall rock) is 233 Ma, refering to the Ar-Ar age of gold-bearing quartz, excluded the former conclusion that the so-called metallogenic epoch (245.9Ma) is in Indosinian epoch. The nonage metallogenic age of Buziwan gold deposit shoule be in the Yanshanian epoch (142.5Ma). By applying the sub-specimen sampling technique, the Rb-Sr isochron age of gold-bearing pyrites in late mineralization epoch is dated to be 64 Ma. In conclusion, the metallogenetic epoch of Puziwan gold deposit is in late Yanshanian-early Himalayan epoch. On the above basis, the metallogenic model of the "train type" and new texture model of ore deposit are established. by applying the methods of geology, shallow seismic exploration, remote sensing, partial geochemical extraction and the study of inclusions in the late granite porphyry, the author has made the metallogenic progosis in the depth and the prephery of Puziwan gold deposit and eight prospecting targets are proposed.