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.

中国大中型气田天然气成藏物理化学模拟研究

Natural gas pays more important role in the society as clean fuel. Natural gas exploration has been enhanced in recent years in many countries. It also has prospective future in our country through "85" and "95" national research. Many big size gas fields have been discovered in different formations in different basins such as lower and upper Paleozoic in Erdos basin, Tertiary system in Kuche depression in Tarim basin, Triassic system in east of Sichuan basin. Because gas bearing basins had been experienced multiple tectogenesis. The characteristics of natural gases usually in one gas field are that they have multiple source rocks and are multiple maturities and formed in different ages. There has most difficult to research on the gas-rock correlation and mechanism of gas formation. Develop advanced techniques and methods and apply them to solve above problems is necessary. The research is focused on the critical techniques of geochemistry and physical simulation of gas-rock correlation and gas formation. The lists in the following are conclusions through research and lots of experiments. I 8 advanced techniques have been developed or improved about gas-rock correlation and gas migration, accumulation and formation. A series of geochemistry techniques has been developed about analyzing inclusion enclave. They are analyzing gas and liquid composition and biomarker and on-line individual carbon isotope composition in inclusion enclave. These techniques combing the inclusion homogeneous temperature can be applied to study on gas-rock correlation directly and gas migration, filling and formation ages. Technique of on-line determination individual gas carbon isotope composition in kerogen and bitumen thermal pyrolysis is developed. It is applied to determine the source of natural is kerogen thermal degradation or oil pyrolysis. Method of on-line determination individual gas carbon isotope composition in rock thermal simulation has being improved. Based on the "95"former research, on-line determination individual gas carbon isotope composition in different type of maceral and rocks thermal pyrolys is has been determined. The conclusion is that carbon isotope composition of benzene and toluene in homogenous texture kerogen thermal degradation is almost same at different maturity. By comparison, that in mixture type kerogen thermal pyrolysis jumps from step to step with the changes of maturity. This conclusion is a good proof of gas-rock dynamic correlation. 3. Biomarker of rock can be determined directly through research. It solves the problems such as long period preparing sample, light composition losing and sample contamination etc. It can be applied to research the character of source rock and mechanism of source rock expulsion and the path of hydrocarbon migration etc. 4. The process of hydrocarbon dynamic generation in source rock can be seen at every stage applying locating observation and thermal simulation of ESEM. The mechanism of hydrocarbon generation and expulsion in source rock is discussed according to the experiments. This technique is advanced in the world. 5. A sample injection system whose character is higher vacuum, lower leaks and lower blank has been built up to analyze inert gas. He,Ar,Kr and Xe can be determined continuously on one instrument and one injection. This is advanced in domestic. 7. Quality and quantity analysis of benzene ring compounds and phenolic compounds and determination of organic acid and aqueous gas analysis are applied to research the relationship between compounds in formation water and gas formation. This is another new idea to study the gas-rock correlation and gas formation. 8. Inclusion analysis data can be used to calculate the Paleo-fluid density, Paleo-geothermal gradient and Paleo-geopressure gradient and then to calculate the Paleo-fluid potential. It's also a new method to research the direction of hydrocarbon migration and accumulation. 9. Equipment of natural gas formation simulation is produced during the research to probe how the physical properties of rock affect the gas migration and accumulation and what efficiency of gas migrate and factors of gas formation and the models of different type of migration are. II study is focused on that if the source rocks of lower Paleozoic generated hydrocarbon and what the source rocks of weathered formation gas pool and the mechanism of gas formation are though many advanced techniques application. There are four conclusions. 1.The maturity of Majiagou formation source rocks is higher in south than that in north. There also have parts of the higher maturity in middle and east. Anomalous thermal pays important role in big size field formation in middle of basin. 2. The amount of gas generation in high-over maturity source rocks in lower Paleozoic is lager than that of most absorption of source rocks. Lower Paleozoic source rocks are effective source rocks. Universal bitumen exists in Ordovician source rocks to prove that Ordovician source rocks had generated hydrocarbon. Bitumen has some attribution to the middle gas pool formation. 3. Comprehensive gas-rock correlation says that natural gases of north, west, south of middle gas field of basin mainly come from lower Paleozoic source rocks. The attribution ratio of lower Paleozoic source rocks is 60%-70%. Natural gases of other areas mainly come from upper Paleozoic. The attribution ratio of upper Paleozoic source rocks is 70%. 4. Paleozoic gases migration phase of Erdos basin are also interesting. The relative abundance of gasoline aromatic is quite low especially toluene that of which is divided by that of methyl-cyclohexane is less than 0.2 in upper Paleozoic gas pool. The migration phase of upper Paleozoic gas may be aqueous phase. By comparison, the relative abundance of gasoline aromatic is higher in lower Paleozoic gas. The distribution character of gasoline gas is similar with that in source rock thermal simulation. The migration phase of it may be free phase. IH Comprehensive gas-rock correlation is also processed in Kuche depression Tarim basin. The mechanism of gas formation is probed and the gas formation model has been built up. Four conclusions list below. 1. Gases in Kuche depression come from Triassic-Jurassic coal-measure source rocks. They are high-over maturity. Comparatively, the highest maturity area is Kelasu, next is Dabei area, Yinan area. 2. Kerogen thermal degradation is main reason of the dry gas in Kuche depression. Small part of dry gas comes from oil pyrolysis. VI 3.The K12 natural gas lays out some of hydro-gas character. Oil dissolved in the gas. Hydro-gas is also a factor making the gas drier and carbon isotope composition heavier. 4. The mechanism and genesis of KL2 gas pool list as below. Overpressure has being existed in Triassic-Jurassic source rocks since Keche period. Natural gases were expulsed by episode style from overpressure source rocks. Hetero-face was main migration style of gas, oil and water at that time. The fluids transferred the pressure of source rocks when they migrated and then separated when they got in reservoir. After that, natural gas migrated up and accumulated and formed with the techno-genesis. Tectonic extrusion made the natural gas overpressure continuously. When the pressure was up to the critical pressure, the C6-C7 composition in natural gas changed. The results were that relative abundance of alkane and aromatic decreased while cycloalkane and isoparaffin increased. There was lots of natural gas filling during every tectonic. The main factors of overpressure of natural gas were tectonic extrusion and fluid transferring pressure of source rocks. Well preservation was also important in the KL2 gas pool formation. The reserves of gas can satisfy the need of pipeline where is from west to east. IV A good idea of natural gas migration and accumulation modeling whose apparent character is real core and formation condition is suggested to model the physical process of gas formation. Following is the modeling results. 1. Modeling results prove that the gas accumulation rule under cap layer and gas fraction on migration path. 2. Natural gas migration as free phase is difficult in dense rock. 3. Natural gases accumulated easily in good physical properties reservoirs where are under the plugging layer. Under the condition of that permeability of rock is more than 1 * 10~(-3)μm~(-1), the more better the physical properties and the more bigger pore of rock, the more easier the gas accumulation in there. On the contrary, natural gas canonly migrate further to accumulate in good physical properties of rock. 4. Natural gas migrate up is different from that down. Under the same situation, the amount of gas migration up is lager than that of gas migration down and the distance of migration up is 3 times as that of migration down. 5. After gas leaks from dense confining layer, the ability of its dynamic plug-back decreased apparently. Gas lost from these arils easily. These confining layer can confine again only after geology condition changes. 6. Water-wetted and capillary-blocking rocks can't block water but gases generally. The result is that water can migrate continuously through blocking rocks but the gases stay under the blocking rocks then form in there. The experiments have proved the formation model of deep basin gas.

卡林型金矿不可见金与超压流体（Overpressured fluid）关系探讨——以贵州贞丰水银洞金矿为例

贵州水银洞(岩上)微细浸染型金矿产于贵州省贞丰县境内，是目前我国第一个成功地从原生硫化物矿石中商业性生产出金的微细浸染型金矿矿山。该矿床的矿体产于灰家堡背斜东段核部的上二叠统龙潭组地层中及其与中二叠统茅口组灰岩的接触带，呈几层基本平行排布的似层状和透镜状产出。金矿化主要赋存于硅化白云石化生物碎屑灰岩和泥灰岩(85％)和强硅化角砾状粘土岩(14％)中。