SYNTHESIS, CHARACTERIZATION AND CATALYTIC BEHAVIOR OF LA2-XSRXCOO4+/-LAMBDA (X=0-2) IN COMPLETE OXIDATION

A series of mixed oxides La2-xSrxCoO4+/-lambda (x=0-2) with varying x values was synthesized. The crystal structure of this series of mixed oxides was studied by using XRD. The result showed that when x=0.25-1.5 the mixed oxides possessing K2NiF4 structure are formed. The valences of the transition metal Co and the relation between +/-lambda content and x value by using chemical analysis method have been measured, too. The redox property of this series of mixed oxides and different kinds of oxygen species were studied by IR, TPD, TPR, XPS and SEM methods. The catalytic activity in the complete oxidation of CO and CH4 was investigated and the relationships between the activity, composition and structure of the mixed oxides have been elucidated.

STUDIES ON THE PEROVSKITE-TYPE MIXED CATALYSTS OF TITANIUM SYSTEM FOR OXIDATIVE COUPLING OF METHANE - THE INFLUENCE OF CALCINATION TEMPERATURE

The correlations of the calcination temperature, structure and catalytic activity for the oxidative coupling of methane on the LiLa0.5Ti0.5O2+lambda catalysts whose main phase and major active phase is Perovskite-type ternary complex oxide LaTi1-yLiyO3-lambda have been studied. The surface and bulk structures of the catalysts were characterized by means of XRD, XPS, IR, BET and so on, The results cleary indicated that the effect of calcination temperature on the activity for the oxidative coupling of methane is twofold. On one hand, it is favorable for Li+ substitution for Ti3+ to enter into the lattice of LaTiO3 and produce more oxygen vacancies in which active oxygens are formed; however, excessively high calcination temperature make the amount of Li+ substitution for Ti3+ lower, due to a little change of structure or phases for the catalyst. On the other hand, the conversion of CH4 drops because of the decrease of surface area, when the calcination temperature is raised.

A STUDY OF SURFACE OXYGEN SPECIES FROM LA-ME-O (ME=MG, CA, SR, BA) CATALYSTS FOR METHANE OXIDATIVE COUPLING

CO2-TPD was used to study the surface basicity of La-Me-O mixed oxides and O-2-TPD, CH4-TPD were employed to study the surface active oxygen species. Comparing the CO2-TPD with O-2-TPD, we can see that the basicity of catalyst is in parallel with the catalystic activity. The stronger basicity is more profitable for the catalyst to adsorb oxygen to form active oxygen species and to activate CH4 by breaking a C-H bond, By comparing the catalytic activity, the results showed that La-Ba-O(La/Ba=7/3) catalyst had the strongest basicity, and it gave the highest CH4 conversion and C-2 selectivity, The results from the pulse reaction showed that the lattice oxygen participated in the OCM reaction without gas oxygen, and it was the selective oxygen species.

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的表面碱性和表面活性氧种

利用CO2-TPD方法考察了Ti-La-Li系多元氧化物催化剂的表面碱性,实验发现:C2 选择性与表面碱强度呈顺变关系,而CH4 转化率与CO2 的脱附峰面积呈顺变关系.同时,利用XPS,O2-TPD等方法对该体系催化剂的表面活性氧种进行了表征与研究,结果表明:催化剂的表面晶格氧与C2 选择性有关,表面吸附氧与甲烷转化(包括偶联和深度氧化)有关.O2 -TPD实验发现催化剂的表面存在三种氧:α( 100℃≤t≤450℃),β(450℃

COMPARISON OF THE SULFURIZATION OF COMOK/AL2O3 CATALYST WITH H2S AND CS2

Only H2S consumption and H2O formation was found in the sulfurization of CoMoK/Al2O3 water gas shift catalyst with H2S/H-2. but CO2 was formed first, then CH4, H2O and H2S appeared in the later part of TPS with CS2/H-2. Carbon deposition on the catalyst during the sulfurization with CS2/H-2 caused a lower activity than the catalyst sulfurized with H2S but could be removed in the run of WGS reaction.

祁连山海北高寒湿地植物群落结构及生态特征

海北高寒湿地系沼泽型和湖泊型湿地相并存．海北高寒湿地植物种类组成较少，从湿地中央到边缘植物优势种组成不同，群落结构变化明显．中部以帕米尔苔草为主要植物建群种的沼泽草甸，边缘地带以藏嵩草为主要建群种的沼泽化草甸，从中央到边缘地带主要有25种植物组成，隶属10科20属．高寒湿地植物有较高的地上生物量（349．373g•m^-2）和地下生物量（仅1～40cm层次最高可达10769．301g•m^-2），而且地下部分远高于地上部分，地下生物量从表层到深层基本均匀下降，与矮嵩草草甸和金露梅灌丛草甸区的地下生物量分布截然不同．因湿地帕米尔苔草、藏嵩草、黑褐苔草、华扁穗草等为主的植物粗纤维高，牲畜利用率下降，不论地上还是地下对土壤有机物的补给均较高，多年的积累使其海北高寒湿地有深达2～3m的泥炭层，使湿地形成一个非常重要的碳库．在气候变暖的条件下，这些未分解或半分解的土壤有机物质（或残体）将加速分解，对大气有更多的CO2、CH4等温室气体的排放．

Methane emissions by alpine plant communities in the Qinghai-Tibet Plateau

For the first time to our knowledge, we report here methane emissions by plant communities in alpine ecosystems in the Qinghai-Tibet Plateau. This has been achieved through long-term field observations from June 2003 to July 2006 using a closed chamber technique. Strong methane emission at the rate of 26.2 +/- 1.2 and 7.8 +/- 1.1 mu g CH4 m(-2) h(-1) was observed for a grass community in a Kobresia humilis meadow and a Potentilla fruticosa meadow, respectively. A shrub community in the Potentilla meadow consumed atmospheric methane at the rate of 5.8 +/- 1.3 mu g CH4 m(-2) h(-1) on a regional basis; plants from alpine meadows contribute at least 0.13 Tg CH4 yr(-1) in the Tibetan Plateau. This finding has important implications with regard to the regional methane budget and species-level difference should be considered when assessing methane emissions by plants.

Effects of forage composition and growing season on methane emission from sheep in the Inner Mongolia steppe of China

Understanding the effects of dietary composition on methane (CH4) production of sheep can help us to understand grassland degradation resulting in an increase of CH4 emission from ruminant livestock and its resulting significance affecting CH4 source/sink in the grazing ecosystem. The objective of this study was to investigate the effect of forage composition in the diet of sheep in July and August on CH4 production by sheep in the Inner Mongolia steppe. The four diet treatments were: (1) Leymus chinensis and Cleistogenes squarrosa (LC), (2) Leymus chinensis, Cleistogenes squarrosa and concentrate supplementation (LCC), (3) Artemisia frigida and Cleistogenes squarrosa (AC), and (4) Artemisia frigida, Cleistogenes squarrosa and concentrate supplementation (ACC). CH4 production was significantly lower in July than in August (31.4 and 36.2 g per sheep-unit per day, respectively). The daily average CH4 production per unit of digestive dry matter (DM), organic matter (OM) and neutral detergent fiber (NDF) increased by 10.9, 11.2 and 42.1% for the AC diet compared with the LC diet, respectively. Although concentrate supplementation in both the AC and LC diets increased total CH4 production per sheep per day, it improved sheep productivity and decreased CH4 production by 14.8, 12.5 and 14.8% per unit of DM, OM and NDF digested by the sheep, respectively. Our results suggested that in degraded grassland CH4 emission from sheep was increased and concentrate supplementation increased diet use efficiency. Sheep-grazing ecosystem seems to be a source of CH4 when the stocking rate is over 0.5 sheep-units ha(-1) during the growing season in the Inner Mongolia steppe.

Short-term effects of sheep excrement on carbon dioxide, nitrous oxide and methane fluxes in typical grassland of Inner Mongolia

Excrement patches of grazing animals play an important role in greenhouse gas (GHG) fluxes due to the high nitrogen (N) and available carbon (C) deposited in small areas, but little information is available for the effect of excrement in the Inner Mongolian grassland (43 26 degrees N, 116 degrees 40'E). To elucidate the effect of grazing sheep urine, fresh dung and compost on fluxes of methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O), a short-term field study (65 days) was carried out in the typical grassland of Inner Mongolia with the optimised closed chamber/GC technique. Compared with the control, cumulative net CH4 consumption decreased 36, 31, and 18% from urine, fresh dung, and compost plots, respectively; net CO2-C output increased by 6.5, 1.5, and 1.2% from urine, fresh dung, and compost treated soil, respectively; about three times as much N2O-N was emitted from urine and the fresh dung treatments during 65 days. Nitrous oxide emission was positively correlated with CO, emission (R = 0.691, P < 0.01) and water-filled pore space (R = 0.698, P < 0.01). The percentages of N2O-N loss of applied-N were 0.44 and 1.05% for urine and fresh dung, respectively. Our results suggest that in autumn in the degraded grassland of Inner Mongolia, the effect of sheep excrement may be ignored when evaluating the total GHG emissions.

The potential importance of grazing to the fluxes of carbon dioxide and methane in an alpine wetland on the Qinghai-Tibetan Plateau

To assess the impact of livestock grazing on the emission of greenhouse gases from grazed wetlands, we examined biomass growth of plants, CO2 and CH4 fluxes under grazing and non-grazing conditions on the Qinghai-Tibetan Plateau wetland. After the grazing treatment for a period of about 3 months, net ecosystem CO2 uptake and aboveground biomass were significantly smaller, but ecosystem CH4 emissions were remarkably greater, under grazing conditions than under non-grazing conditions. Examination of the gas-transport system showed that the increased CH4 emissions resulted from mainly the increase of conductance in the gas-transport system of the grazed plants. The sum of global warming potential, which was estimated from the measured CO2 and CH4 fluxes, was 5.6- to 11.3-fold higher under grazing conditions than under non-grazing conditions. The results suggest that livestock grazing may increase the global warming potential of the alpine wetlands. (c) 2005 Elsevier Ltd. All rights reserved.

Methane emissions from different vegetation zones in a Qinghai-Tibetan Plateau wetland

We measured methane (CH4) emissions in the Luanhaizi wetland, a typical alpine wetland on the Qinghai-Tibetan Plateau, China, during the plant growth season (early July to mid-September) in 2002. Our aim was to quantify the spatial and temporal variation of CH4 flux and to elucidate key factors in this variation. Static chamber measurements of CH4 flux were made in four vegetation zones along a gradient of water depth. There were three emergent-plant zones (Hippuris-dominated; Scirpus-dominated; and Carex-dominated) and one submerged-plant zone (Potamogeton-dominated). The smallest CH4 flux (seasonal mean = 33.1 mg CH4 m(-2) d(-1)) was, observed in the Potamogeton-dominated zone, which occupied about 74% of the total area of the wetland. The greatest CH4 flux (seasonal mean = 214 mg CH4 m(-2) d(-1)) was observed in the Hippuris-dominated zone, in the second-deepest water area. CH4 flux from three zones (excluding the Carex-dominated zone) showed a marked diurnal change and decreased dramatically under dark conditions. Light intensity had a major influence on the temporal variation in CH4 flux, at least in three of the zones. Methane fluxes from all zones increased during the growing season with increasing aboveground biomass. CH4 flux from the Scirpus-dominated zone was significantly lower than in the other emergent-plant zones despite the large biomass, because the root and rhizome intake ports for CH4 transport in the dominant species were distributed in shallower and more oxidative soil than occupied in the other zones. Spatial and temporal variation in CH4 flux from the alpine wetland was determined by the vegetation zone. Among the dominant species in each zone, there were variations in the density and biomass of shoots, gas-transport system, and root-rhizome architecture. The CH4 flux from a typical alpine wetland on the Qinghai-Tibetan Plateau was as high as those of other boreal and alpine wetlands. (C) 2004 Elsevier Ltd. All rights reserved.

水-盐-气天然流体的物理化学性质模拟与流体包裹体应用研究

Natural fluids with water-salt-gas are often found in every sphere of the Earth, whose physicochemical properties and geochemical behaviors are complicated. To study these properties and behaviors turns out to be one of the challenging issues in geosciences. Traditional approaches mainly depend on experiments and observations. However, it is impossible to obtain a large number of data covering a large T-P space of the Earth by experimental methods in the near future, which will hinder the advance of the theoretical study. Therefore, it is important to model natural fluids by advanced theoretical methods, by which limited experimental data can be extended to a large temperature-pressure-composition space. Physicochemical models developed in this dissertation are not only more accurate, but also extend the applied T-P-m region of the experimental data of the multi-fluid systems by about two times. These models provide the new and accurate theoretical tools for the geochemical research, especially for the water-rock interactions and the study of the fluid inclusions. The main achievements can be summarized as follows: (1) A solubility model on components of natural gases is presented. The solubility model on the systems of CH4-H2O-NaCl, C2H6-H2O-NaCl or N2-H2O-NaCl takes advantage of modern physicochemical theory and methods, and is an improvement over previous models whose prediction and precision are relatively poor. The model can predict not only the gas solubility in liquid phase but also water content in the gas phase. In addition, it can predict gases (methane or nitrogen) solubility in seawater and brine. Isochores can be determined, which are very important in the interpretation of fluid inclusions. (2) A density model on common aqueous salt solutions is developed. The density models with high precision for common aqueous salt solutions (H2O-NaCl, H2O-LiCl, H2O-KCl, H2O-MgCl2, H2O-CaCl2, H2O-SrCl2 or H2O-BaCl2) are absent in the past. Previous density models are limited to the relatively small range of experimental data, and cannot meet the requirement of the study of natural fluids. So a general density model of the above systems is presented by us based on the international standard density model of the water. The model exceeds the other models in both precision and prediction. (3) A viscosity model on common aqueous alkali-chloride solutions is proposed. Dynamic viscosity of water-salt systems, an important physics variable, is widely used in three-dimension simulation of the fluids. But in most cases, due to the lack of viscosity models with a wide T-P range, the viscosity of aqueous salt solutions is replaced by that of the water, giving rise to a relatively large uncertainty. A viscosity model with good prediction for the systems (H2O-NaCl, H2O-LiCl or H2O-KCl) is presented on the base of the international standard viscosity model of water and the density model developed before. (4) Equation of State applied in fluid inclusions. The best Equations of State in the world developed by others or us recently are applied in the study of the fluid inclusions. Phase equilibria and isochores of unitary system (e.g. H2O, CO2, CH4, O2, N2, C2H6 or H2S), binary H2O-NaCl system and ternary H2O-CH4-NaCl system are finished. From these programs and thermodynamic equations of coexisting ores, the physicochemical conditions before or after the deposits form can be determined. To some extent, it is a better tool.

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.

湘西地区上震旦统上部－下寒武统底部黑色岩系沉积学及地球化学

Widespread black chert-shales occur in the Ediacaran-Cambrian(E-C) boundary successions along the flank of Yangtze Platform, South China, remarkable changes in sedimentology, geochemistry and biology were recorded. Although extensive studies were carried out upon this boundary succession, the origin of black chert-shales still remain controversial. This paper focuses on the E-C black chert-shales in western Hunan, South China, upon which detailed depositional and geochemical changes are documented, accordingly a depositional model for black chert-shales is proposed. Stratigraphic anatomy across the depositional strike demonstrates that the shallow-water Dengying dolostone along the platform margin sharply pass basinward into the Liuchapo chert successions, which indicate syndepositional extensional faulting at depth could have occurred along the platform margin. The deep-water Niutitang phosphorite-rich black shales are either underlain by the Dengying dolostones on the platform margin toward platform interior or directly by the Liuchaopo chert successions farther basinwards. By detailed investigation, silica chimneys are firsly identified approximately in the chert along platform margin; two types of silica chimneys, including mounded and splayed/funnelized chert(generally brecciated) bodies are further sorted out. The mounded chert are exitbited by domed or hummocky surfaces on the top and irregular spongy to digitiform internal fabrics; within the silica mounds, abundant original vesicles/voids and/or channels were mostly plugged by initial chalcedony, quartze crystals with minor dolomite and bladed barite crystals. Splayed/funnelized brecciated chert “intrusion” cross-cut the uppermost dolostones capping to the horizon underneath, and are directly overlain by the Niutitang phosphorite-rich black shales. Their similarities to the silica chimneys reported from the oceanic spreading centres suggest a similar origin responsible for these unique silica bodies which is also supported by the microthermonmetric data and element geochemistry. High P, Ba, Fe contents and positive correlation between Fe and TOC concentrations in the Niutitang black shales indicate a high palaeo-productivity in the Early Cambrian ocean. The low Th/U and the high V/Cr, V/Sc, V/(V+Ni) ratios in the black shales suggest an anoxic water condition during this interval. Furthermore, Positive Eu anomalies and high Ba contents in the sediments also imply a hydrothermal influence on the formation of Niutitang black shales. To better constrain the placement of deep-water successions straddling the E-C boundary and the timing of hydrothermal silica chimneys, sensitive high-resoluton ion microprobe(SHRIMP) U-Pb dating of zircon grains from tuffs within the chert succession of Liuchapo Formation at Ganziping was conducted and yields a weighted-mean 206Pb/238Pb age at 536.6±5.5Ma, younger than E-C boundary age(542.0±0.3Ma). This age combined with carbon isotopic data is then proposed to correspond to the U-Pb age of zircons(538.2±1.5Ma) from the Zhongyicun member of Meishucun Formation at Meishucun in eastern Yunna, thus, the E-C boundary in Gazngziping was placed between the Dengying formations and Liuchapo formatioms. therefore, the silica chimneys took place at the beginning of the Cambrian period. The temporal coincidence of silica chimneys and negative excursions of δ13C and δ34Spy pairs suggest hydrothermal activities were likely responsible for the isotopic changes. Under such a circumstance, vast amounts of greenhouse gases(CO2, CH4, H2S), with highly 13C-depleted carbon and 34S-depleted sulfur would be released into the ocean and atmosphere. A positive shift in δ34Scas and Δ34S values from the late Ediacaran to the Early Cambrian could be a reflection of enhanced bacterial sulfate reduction(BSR), strengthened by the intensified oceanic anoxia stimulated by hydrothermal activities. Based on the analyses of sedimentology and geochemistry, a model- “oceanic anoxia induced by hydrothermal–volcanic activies” was proposed to responsible for the formation of black chert-shales during this E-C transition. Under this case, hydrothermal-volcanic activies could release large large amount of greenhouse into atmosphere and metal micronutrients into the ocean, which may lead to global warming, stratified ocean, thereby a high palaeoproductivity; on the other hand, the massive releasing of reduced hydrothermal fluids with abundant H2S, could have in turn enhanced the ocean anoxia. All of these were favourable the for preservation of organic matter, and subsequent extensive deposition of black silica-shales.

东天山地区金矿床成矿流体地球化学及其成矿机制

The mechanism of gold ore formation in the eastern Tianshan Mountains, Xinjiang Uygur Autonomous Region, that has been dealt with from various aspects, remains unclear. On the basis of investigations of regional geology, ore deposit geology, and microscopic observations of ores and related rocks of the Jinwozi, the 210, and the Mazhuangshan gold ore deposits, this thesis made a systematic research on the microthermometry of gangue quartz-hosted fluid inclusions, gas, liquid ion and rare earth element compositions and hydrogen, oxygen isotope compositions of sulfide- and quartz-hosted fluid inclusions, and sulfur and lead isotope compositions of sulfide ore minerals from the major ores in the three deposits. On the basis of the above synthetic studies, sources of ore-forming fluids and metals, and mechanism of gold ore formation in the region were discussed. Gas compositions of pyrite- and sphalerite-hosted fluid inclusions were first analyzed in this thesis. Compared with gangue quartz-hosted fluid inclusions, the sulfide-hosted ones are richer in gaseous species CO2, CO, and CH4 etc. Both gas and liquid CO2 are commonly observed in fluid inclusions, whereas halite daughter minerals rarely occur. Ore-forming fluids for the three gold ore deposits are characteristically of medium to low temperatures, medium to low salinities, are rich in CO2 and Na+, K+, Cl" ions. Gas covariation diagrams exhibit linear trends that are interpreted as reflecting mixing between the magamtic fluid and meteoric-derived groundwater. Regarding rare earth element compositions, the Jinwozi and the 210 deposits show moderate to strong LREE/HREE fractionations with negative Eu anomalies. However, the Mazhuangshan deposit shows little LREE/HREE fractionation with positive Eu anomalies. Hydrogen and oxygen isotope compositions of pyrite-hosted fluid inclusions that were first analyzed in this thesis indicate the presence of magmatic water. Hydrogen and oxygen isotope compositions of pyrite- and quartz-hosted fluid inclusions suggest mixing between magmatic water and meteoric-derived groundwater. Sulfur and lead isotope compositions of sulfide ore minerals indicate multi-sources for the metallogenetic materials that range from the crust to the mantle. On the basis of the above synthetic studies, genesis of the gold ore deposits in the eastern Tianshan Mountains was approached. From the Middle-Late Hercynian to Early Indosinian, geodynamic regime of the region was changing from the collisional compression to the post-collisional extension. During the period, magmas were derived from the crust and the mantle and carried metallogenetic materials. Magma intrusion in the upper crust released the magmatic fluids, and drove circulation of groundwater. Mixing of magmatic fluid with groundwater, and extraction of metallogenetic materials from the country rocks are the mechanism for the gold ore formation in the eastern Tianshan Mountains.