Lu-Hf同位素的MC-ICP-MS实验方法及其在华北克拉通典型火山岩研究中的应用

Over past ten years, a great development has been made in the Lu-Hf isotopic system with the advent of MC-ICP-MS. Based on a comprehensive review of available references in the related field, a novel analytical protocol of three exchange chromatographies after one mixed acid attacking geological samples was developed in this work, which not only avoids common multiple sample treatments for natural inhomegeneous samples, but also is useful for Rb-Sr, Sm-Nd and Lu-Hf isotopic system simultaneously, especially for the garnet- and apatite-bearing rocks for the Sm-Nd and Lu-Hf geochronology. An analytical procedure for the Lu and Hf concentration in geological samples determined by by ID-MC-ICP-MS was detailedly investigated. The Hf yield is > 90 % and total procedural blank is less than. 50 pg for Hf and 10 pg for Lu, respectively. The developed method was successfully applied to the determination of Lu and Hf concentrations for USGS geological materials. A one-column procedure for Hf purification in geological samples using common anion exchange chromatography and its isotopic analyses by MC-ICP-MS were also established. Multiple analyses of Standard Reference Materials demonstrate that this method was simple, time-saving, cheap and efficient, especially suitable for the Hf isotopic compositions of young samples. Finally, the measurements of Sr and Nd isotopic compositions using Neptune MC-ICP-MS were described briefly, which indicates that Neptune MC-ICP-MS can precisely measure Sr and Nd isotopic compositions as the TIMS does, even more efficient and less time-consuming than the TIMS method. The Hf isotopic characteristics of typical volcanic rocks (Cenozoic Changle-Linqu basalts, Mesozoic Fangcheng basalts, Mesozoic Jianguo basalts, Mesozoic Wulahada high-Mg andesite, Cenozoic Fanshi, Zuoquan and Xiyang-Pingding basalts of the Taihang Mountains, Paleozoic diamondiferous Menyin and Fuxian Kimblites) from the North China Craton were firstly studied in this work. Coupled with Nd isotopic compositions, it shows that the Hf isotopes could be a better tracer for mantle sources than the Nd isotopes. Individual kimberlite fields from both the Mengyin and Fuxian regions have quite uniform Hf isotopic compositions, similar to the situation for the Nd isotopes.

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.

松辽盆地长岭断陷火山岩气藏的形成条件与分布规律

Changling fault depression is a compound fault depression complicated by interior fault, with faults in the west and overlap in the west. North of Changling fault depression show NNE strike while south is NW strike. Changling fault depression has undergone twochasmic stage which control the development and distribution of volcanic rock, one depression stage, later inversion and uplift stage which control the formation of natural gas reservoir, and basin atrophic stage. The main boundary faults and main faults in Changling fault depression control three volcanic cycles and the distribution of volcanic rock. Seismic reflection characteristic and logging response characteristic of volcanic rock in study area are obvious, and the distribution characteristic, volcanic cycle and active stage of volcanic rock can be revealed by seismic attribute, conventional logging data can distinguish clastic rock from volcanic rock or distinguish partial different types of volcanic rock. The reservoir property of rhyolite and volcanic tuff are the best. Favorable volcanic reservoir can be preserved in deep zone. Imaging logging and frequency decompostion technology of seismic data act as effective role in the study of reservoir physical property and gas-bearing properties of volcanic rock.. Hydrocarbon gas in study area is high and over mature coal type gas, the origin of CO2 is complex, it is either inorganic origin or organic origin, or mixing origin. Hydrocarbon gas is mainly originate from Shahezi formation and Yingcheng formation source rocks, CO2 is mainly mantle source gas. Hydrocarbon has the characteristics of continuous accumulation with two charging peak. The first peak represent liquid hydrocarbon accumulation time, The second peak stand for the accumulation time of gaseous hydrocarbon.CO2 accumulate approximately in Neocene. The source rock distribution range, volcanic rock and favorable reservoir facies, distribution characteristic of deep fault (gas source fault) and late inversion structure are the major factors to control gas reservoir formation and distribution. All the results show that these traps that consist of big inherited paleo uplift(paleo slope), stratigraphic overlap and thinning out, volcanic rock, are the most advantageous target zone.

大兴安岭北段晚中生代火山岩地球化学特征及其地质意义

This thesis mainly concentrates on the geochronology, prtrology, elemental geochemistry and Sr-Nd-Pb-Hf isotopic geochemistry of the volcanic rocks in north Da’Hinggan Mountain. By analyzing the data obtained in this study and data from other people, this thesis explored the age distribution, petrology and mineralogy and geochemistry characteristics of the volcanic rocks in north Da’Hinggan Mountain. Furthermore, this thesis speculated upon the source characteristics of these volcanic rocks and their implications for the tectonic evolution and crust accretion. According to the twenty Ar-Ar ages, four zircon U-Pb SHRIMP ages and two Zircon U-Pb LA-ICP-MS ages, the duration of the eruption of the Late Mesozoic volcanic rocks in north Da’Hing Mountain was about 160Ma-106Ma. Most of these volcanic rocks belong to early Cretaceous and the late Jurassic volcanic rocks are only restricted in Manzhouli. The bulk of the late Mesozoic volcanic rocks are high-K calc-alkaline rocks. Only a small portion of these volcanic rocks are shoshonites. These rocks are mainly intermediate or acid and the basic rocks usually have higher alkaline contents. Rock types are very complex in this region. These volcanic rocks have a large TiO2 variation and the Al2O3 and alkaline contents are high. From the point of mineralogy, the plagioclases in these volcanic rocks are oligoclases, andesines and labradorites, and the labradorites are more common. Most pyroxenes in these volcanic rocks are augites which belong to clinopyroxene. The source of the Late Mesozoic volcanic rocks was an enriched lithospheric mantle. When the magma en route to the surface it was contaminated by crust material slightly and had some fractional crystallization. These rocks which mainly belong to high-K calc-alkaline series were one of the results of postorogenic tectonic-magmatic activities. The upwelling in late Mesozoic supplied heat to melt the enriched lithospheric mantle which was resulted from the subduction of paleo-Asian Ocean and/or Mengol-Okhotsk ocean. These late Mesozoic volcanic rocks are also important to the upper crustal accretion of north Da’Hinggan Mountain since the late Mesozoic. These volcanics and the contemporary emplacement of granites and the basaltic underplating in combination fulfilled the crust accretion history in north Da’Hinggan Mountain in Late Mesozoic.

西天山造山带古生代构造演化与地壳增生—来自花岗岩和蛇绿岩的证据

The Central Asian Orogen Belt (CAOB), which is different from the subductional orogen and the collisional orogen, is known as the most important site of crustal growth in the Phanerozoic, and it has been a ‘hot spot’ for studying the orogenic belts. The Chinese West Tianshan Orogen is occupying the west-southern part of the CAOB and is of great importances to understand the orogenic processes and the continental growth in the Central Asia. The West Tianshan Orogen had undergone complex tectonic evolutional processes in Paleozoic times and large volumes granitic rocks have recorded important information about these processes. Litter is known about Phanerozoic continental growth in the Western Tianshan area so far, compared with the other areas of the CAOB, such as eastern Junggar, western Junggar, Altai and Alakol. The aim of this dissertation is to set up the chronology frame of granitoids in western Tianshan, provide new evidence for the tectonic evolution and discuss the Paleozoic continental growth in this area, on the basis of the studies on the isotopic chronology, major element, trace element and Nd-Sr isotopic geochemistry of granitoids and the isotopic chronology and geochemistry of the ophiolites in this area, especially the Kule Lake ophiolites. 25 precise SHRIMP U-Pb zircon and LA-ICPMS U-Pb zircon ages have been obtained in this dissertation. The granitic rocks in western Tianshan had been formed during two periods: the granitic gneiss with an age of 896Ma, possibly representing the forming age of the Precambrian basement; the granitic rocks with ages varying from 479Ma to 247Ma, recording the Paleozoic orogenic process of western Tianshan. The granitoids in western Tianshan are composed of intermediate-basic rocks, intermediate rocks, intermediate-acid rocks and acid rocks, mainly intermediate-acid rocks and acid rocks. They are mostly granite, granodiorite, quartz syenite and monzodiorite. Different types of granitic rocks are exposed in different tectonic units. The granitoids on the northern margin of the Yili Plate mainly formed in late Paleozoic (413Ma ~ 281Ma), those with ages varying from 413Ma to 297Ma show continental arc affinities and the magnesian calc-alkalic metaluminous diorite of 281Ma display the geochemical characteristics similar to those of granites formed during the post-orogenic period. The granitiods on the southern margin of the Yili Plate include the adakite diorite of 470Ma which was formd by partial melting of thickened lower crust, the post-collisional alkali-feldspar granite of 430Ma, the volcanic arc granite of 348Ma and the Triassic post-collisional granite. The granitoids in the Central Tianshan Plate formed in 479Ma ~ 247Ma, mainly in 433Ma ~ 321Ma. The granitic rocks with ages of 479Ma ~ 321Ma are magnesian calc-alkalic to alkalic rocks with continental arc affinities. A few post-collisional granitoids of 276Ma ~ 247Ma may have inherited the geochemical characteristics of pre-existing arc magma. The granitic rocks in Southern Tianshan (northern margin of the Tarim plate) formed two stages, 420Ma ~ 411Ma and ca. 285Ma. The magnesian calcic to alkalic granites of 420Ma ~ 411Ma may formed during the extension process of the continental margin. The granite of 285Ma includes mostly ferroan calc-alkalic to alkali-calcic rocks with high SiO2 and high alkaline contents, and obviously negative anomaly of Eu, Ba, Sr, P, Ti, similar to the geochemical characteristics of the A-type granite which is formed during post-collisional extension. The Kule Lake ophiolite in southern Tianshan shows the affinity of N-MORB. A SHRIMP zircon U-Pb age of 425±8Ma has obtained for gabbros. Some zircons have given another group of 206Pb/238U age 918Ma, which may indicate the information of the pre-exist old basement rock. The small oceanic basin represented by Kule Lake ophiolite probably developed on the split northern margin of Tarim block. A model for Paleozoic tectonic evolution of the West Tianshan Orogen has been proposed here on the basis of the new results obtained in this dissertation and the previous published data. In Early Cambrian, the Terskey Ocean occurred along the North Nalati fault (NNF), and it separated the Yili plate from the Central Tianshan plate which was probably connected with the Tarim plate. The Terskey Ocean probably subducted towards south under the Central Tianshan plate and towards north under the Yili plate simultaneously. In the early stage of Late Ordovician, the Terskey Ocean had been closed, and the Yili and Central Tianshan plates collided. Meanwhile, extension happened within the joint Central Tianshan and Tarim plates gradually and the Paleo-South Tianshan Ocean had been formed. In Early Silurian, the Paleo-South Tianshan Ocean began to subduct beneath the composite Yili-Central Tianshan plate, which was intruded by volcanic arc granitoids. In Middle Silurian, the Paleo-South Tianshan Ocean, which had reached a certain width, was subducting strongly. And this subduction may have produced voluminous granitoids in the Central Tianshan plate. In the latest stage of Carboniferous, the Paleo-South Tianshan ocean closed, and the Yili-Central Tianshan plate and Tarim plate collided. In Late Cambrian, Paleo-Junggar Ocean occurred to north of the Yili plate; and started to subduct towards south under the Yili plate in Ordovician. This subduction may have produced a magma arc on the northern margin of the Yili plate. In Late Carboniferous, the Paleo-Junggar Ocean had been closed. The Yili-Central and Junggar plates amalgamated together. The West Tianhan Orogen may undergo a post-collisional collapse since Permian. And the magmatic activities may continue to early Triassic. The initial 87Sr/86Sr ration of the granitic rocks in the western Tianshan Mountains varies from 0.703226 to 0.716343, and Nd（t）from -6.50 to 2.03. The characteristics of Sr-Nd isotope indicate that the source of granitic material is not a sole source, which may be produced by mantle-crust magma mixing. In Paleozoic time, lateral growth of the continental crust along active continental margins was dominant, whereas the vertical growth of continental crust resulted from post- collisional mantle derived magmas was not obvious.

辽河盆地西部凹陷深部流体的地球化学特征与成藏效应

The main research area of this thesis is the Western Depression in the Liaohe Basin. Based on the drilling core observation and mud logging data, the features of the mantle–derived fluids and their effects on oil/gas generation in the Western Depression of the Liaohe Basin,was studied with comprehensive methods of volcanic petrology, sediment petrology, fluid geochemistry, sedimentlogy, and structural geology, and use of polarized light microscope, fluorescence microscope, electron microscope, fluid and melt inclusion test, and isotopic test of nature gas etc. The observation of drill cores in study area and other studies reveal that the main passageway of the volcanic eruption in the Cenozoic was the Xibaqian-Gaosheng fault, and the volcanic rocks of each stage were distributed around it. Mantle-derived fluid which affected on oil/gas generation formed later than the volcanic spew and those fluids entered into the depression through the Taian-Dawa fault and the Central fault. The volatile fraction analysis of the melt inclusion reveals the presence of two kinds of mantle fluids; they are hydrogen-rich fluid and carbon dioxide-rich fluid. These the two kinds of fluids were mainly distributed in olivine and pyroxene respectively. The hydrothermal veins development have multiple stages, from high temperature quartz vein to low temperature calcite vein and analcime vein, in which the fluid inclusion extremity component are methane and carbon dioxide, which indicate that when mantle-derived fluids ascended and entered into the basin, most of these fluids interacted with the organic matter in the basin even though some of these entered into atmosphere. The present isotopic test of the nature gas reveals the high 3He/4He value between the region of the Taian-Dawa fault and the Central fault, which also imply the feature of origin in mantle. This phenomenon indicates that the Mesozoic basement faults and the main Cenozoic faults had connected crust and the mantle during the basin evolution, so the mantle derived fluids could enter the basin along those faults. The main source rocks of the ES3 and ES4 members of the Shahejie Formation began to expel hydrocarbon at the end period of the ES1 member of the Shahejie Formation, and reached its peak during the period of the Dongying Formation deposition. During these periods, the mantle derived-fluids entered the basin constantly along the main faults, and supplied lots of hydrogen for hydrocarbon generation. Though the volcanic rocks and the mantle-derived fluids in the Eastern Depression were more developed than in the Western Depression, the source rocks and the deep fluids were not interacted better than the Western Depression because of the affection of structural evolution. In the Eocene, the Eastern Depression did not deposit the ES4 member of the Shahejie Formation, furthermore, the mantle-fluid formed in the Fangshengpao stage escaped to the atmosphere, which confined the later stage hydrocarbon generation capability.

均衡重力异常计算与综合解释——以黄海地区为例

Petroleum and Natural Gas is an important strategic resources. The reserves of Petroleum and Natural Gas can’t meet the need of our country, which also blocks the development of economy and threatens the safety of national. Therefore, it makes a great sense to bring “the second round of oil & gas exploration” into effect and study the exploration of oil and gas of Pre-Cenozoic residual basins in China. The integrated geophysical exploration is the main way to research the Pre-Cenozoic residual basins. Gravity exploration is one of the most important exploration methods, which has played an important role in oil and gas prospecting, such as compartmentalizing geotectonic elements, delineating the distribution range of sedimentary basins, searching oil and gas structure, abstracting oil and gas information, and so on, from its naissance. The isostatic gravity anomalies is significant for exploration, which can help us research deep crustal structure, the equilibrium state of earth, the geologic structure of shallow crust, the basement shape of sedimentary basins and the genetic evolution of sedimentary basins. In the paper, we stress the implication and physical meanings systemically, and discuss the calculation theory. On the basis of previous work, we test different isostatic compensation models and parameters to find out their influences to the result of isostatic gravity anomalies. In addition, we improve the method of isostatic gravity anomalies calculation and give a system of isostatic gravity anomalies calculation which is proved has satisfying effect. From the research above, we find that the results of Platt model and Airy model are consistent, which have similar form and almost the same value. However, by contrast, the Airy model is proved has better adaptability than Platt model. The two main parameters——crust thickness and density difference of crust and mantle, both have influence to the isostatic gravity anomalies, but the latter have more. Finally, we adopt the regional field extending edge method to make the result more of actual geologic condition. On the methods above, we calculate the isostatic gravity anomalies field in Yellow Sea area from the Bouguer gravity anomalies and the water depth and altitude data. And then the isostatic gravity anomalies character is analyzed and the integrated geological-geophysical interpretation is made on the basis of summarizing the previous research result systemically and analyzing other geophysical data and geological information. From the research, we find that the Yellow Sea area belongs to continental type crust equilibrium regions, where the isostatic gravity anomalies field is placid and has less fluctuation values, which implies that the area is in equilibrium state to different extends.

地幔压力下CaSiO3 Perovskite状态方程和弹性常数的第一性原理研究

In the past decade density functional theory (DFT) has made its way from a peripheral position in quantum chemistry to center. Of course the often excellent accuracy of the DFT based methods has provided the primary driving force of this development. This dissertation is devoted to the study of physical and chemical properties of planetary materials by first-principle calculation. The concerned properties include the geometry, elastic constants and anisotropy. In the first chapter, we give a systematic introduction to theoretical background and review its progress. Development of quantum chemistry promotes the establishment of DFT. Theorem of Hohenberg-Kohn is the fundament of DFT and is developed to Kohn-Sham equation, which can be used to perform real calculations. Now, new corrections and extensions, together with developed exchange-correlation, have made DFT more accurate and suitable for larger systems. In the second chapter, we focus on the calculational methods and technical aspects of DFT. Although it is important to develop methods and program, external package are still often used. At the end of this chapter, we briefly some widely used simulation package and the application of DFT. In the third chapter, we begin to focus on properties of real materials by first principles calculation. We study a kind of minerals named Ca perovskite, investigate its possible structure and anisotropy at Earth’s mental condition. By understanding and predicting geo-physically important materials properties at extreme conditions, we can get the most accurate information to interpret seismic data in the context of likely geophysical processes.

西秦岭新生代火山岩中的地幔捕虏体和捕虏晶研究

Western Qinling, a conjunction region of the North China Craton, the Yangtze Craton and the Tibetan Plateau, has very complicated history of geologic and tectonic evolution. Previous studies mainly focus on tectonics and petrology of volcanic rocks in the western Qinling. Therefore, little is known about the Cenozoic lithospheric mantle beneath the western Qinling. Mafic, ultramafic and/or alkaline volcanic rocks and their entrained mantle peridotitic xenoliths and xenocrysts are known as samples directly from the lithospheric mantle. Their petrological and geochemical characteristics can reflect the nature and deep processes of the lithospheric mantle. Cenozoic volcanic rocks in the western Qinling contain abundant mantle xenoliths and xenocrysts, which provide us an opportunity to probe the lithospheric mantle beneath this region and a new dimension to insight into geologic evolution. Cenozoic volcanic rocks (7-23 Ma) from the western Qinling are sparsely distributed in the Lixian-Dangchang-Xihe Counties, Gansu Province, China. Volcanic rocks contain plenty of mantle-derived xenoliths, including spinel lherzolites with subordinate wehrlite, dunite, olivine websterite, clinopyroxenite and garnet lherzolite, and few olivine, clinopyroxene and spinel xenocrysts. These peridotitic xenoliths show clear deformed textures and their major minerals show excellent orientation. Thus, these peridotites are typical deformed peridotites. Olivine xenocrysts have clearly-zoned textures. The peridotitic xenoliths can be divided into two groups based on their compositions, namely, the H-type and L-type. The H-type peridotites are characterized by high Fo (>90) in olivines in which fine-grained ones have higher Fo than the coarse grains, low CaO (<20 %) in clinopyroxenes, high Cr# (>40) in spinels and high equilibration temperatures. They may represent the refractory lithospheric mantle. In contrast, the L-type peridotites contain low Fo (<90) olivines (with lower Fo in fine-grained olivines), high CaO (>20 %) clinopyroxenes, low Cr# (<20) spinels and low equilibration temperatures. They experienced low degree of partial melting. The Cenozoic lithospheric mantle beneath the western Qinling was refractory in major element compositions based on the mineral compositions of xenoliths and xenocrysts and experienced complicated deep processes. The lithospheric mantle was modified by shear deformation due to the diapirism of asthenosphere and strong tectonic movements including the collision between North China Craton and Yangze Craton and the uplift of Tibetan Plateau, and then underwent metasomatism with a hydrous, Na, Ti and Cr enriched melt.

利用台阵面波资料研究华北克拉通北缘燕山褶皱带及其邻区的地壳与上地幔结构

The continent of eastern China, especially the North China Craton (NCC), has endured intensive tectonic renovation during Mesozoic and Cenozoic, with the presence of widespread magmatism, high heat flow and development of large sedimentary basins and mountain ranges. The cratonic lithosphere of the region has been destroyed remarkably, which is characterized by not only a significant reduction in thickness but also complex modifications in physical and chemical properties of the lithosphere. As for the tectonic regime controlling the evolution of the NCC, various models have been put forward, including the impingement of mantle plumes (“mushroom cloud” model), the collision of south China block and north China block, the subduction of the Pacific plate, etc. Lithosphere delamination and thermal erosion were proposed as the two end-member mechanisms of the lithospheric thinning. However, given the paucity of the data, deep structural evidence is currently still scarce for distinguishing and testifying these models. To better understand the deep structure of the NCC, from 2000 to the present, temporary seismic array observations have been conducted in the NCC by the Seismological Laboratory of the Institute of the Geology and Geophysics, Chinese Academy of Sciences under the North China Interior Structure Project (NCISP). Many arrays extend from the North China Craton and the off-craton regions, and traverse a lot of main tectonic boundaries. A total of more than 300 broadband seismic stations have been deployed along several profiles that traversed the major tectonic units within the craton’s interior, at the boundary areas and in the neighboring off-craton regions. These stations recorded abundant high-quality data, which provides an unprecedented opportunity for us to unravel the deep structural features of the NCC using seismological methods. Among all the seismological methods, the surface wave method appears to be an efficient and widely adopted technique in studying the crustal and upper mantle structures. In particular, it can provide the absolute values of S-wave velocity that are difficult to obtain with other methods. Benefiting from the deployment of dense seismic arrays, progresses have been made in improving the spatial resolution of surface wave imaging, which makes it possible to resolve the fine-scale velocity structures of the crust and upper mantle based on surface wave analysis. Meanwhile, the differences in the S-wave velocities derived from Rayleigh and Love wave data can provide information on the radial anisotropy beneath the seismic arrays. In this thesis, using the NCISP-III broadband data and based on phase velocity dispersion analysis and inversion of fundamental mode Rayleigh and Love waves, I investigated the lateral variations in the S-wave velocity structure of the crust and uppermost mantle beneath the Yanshan Belt and adjacent regions at the northeastern boundary of the NCC. Based on the constructed structural images, I discussed possible deep processes of the craton destruction in the study region.

地震层析成像与天山地区的壳幔深部结构研究

The Tien Shan is the most prominent intracontinental mountain belt on the earth. The active crustal deformation and earthquake activities provide an excellent place to study the continental geodynamics of intracontinental mountain belt. The studies of deep structures in crust and upper mantle are significantly meaningful for understanding the geological evolution and geodynamics of global intracontinental mountain belts. This dissertation focuses on the deep structures and geodynamics in the crust and upper mantle in the Tien Shan mountain belt. With the arrival time data from permanent and temporal seismic stations located in the western and central Tien Shan, using seismic travel time tomographic method, we inversed the P-wave velocity and Vp/Vs structures in the crust and uppermost mantle, the Pn and Sn velocities and Pn anisotropic structures in the uppermost mantle, and the P-wave velocity structures in the crust and mantle deep to 690km depth beneath the Tien Shan. The tomographic results suggest that the deep structures and geodynamics have significant impacts not only on the deformations and earthquake activities in the crust, but also on the mountain building, collision, and dynamics of the whole Tien Shan mountain belt. With the strongly collision and deformations in the crust, the 3-D P-wave velocity and Vp/Vs ratio structures are highly complex. The Pn and Sn velocities in the uppermost mantle beneath the Tien Shan, specially beneath the central Tien Shan, are significantly lower than the seismic wavespeed beneath geological stable regions. We infer that the hot upper mantle from the small-scale convection could elevate the temperature in the lower crust and uppermost mantle, and partially melt the materials in the lower crust. The observations of low P-wave and S-wave velocities, high Vp/Vs ratios near the Moho and the absences of earthquake activities in the lower crust are consistent with this inference. Based on teleseismic tomography images of the upper mantle beneath the Tien Shan, we infer that the lithosphere beneath the Tarim basin has subducted under the Tien Shan to depths as great as 500 km. The lithosphere beneath the Kazakh shield may have subducted to similar depths in the opposite direction, but the limited resolution of this data set makes this inference less certain. These images support the plate boundary model of converge for the Tien Shan, as the lithospheres to the north and south of the range both appear to behave as plates.

中祁连花岗岩年代学、地球化学及其构造意义

The Qilian Orogenic Belts had undergone very complicated evolutional histories and play an important role in understanding the tectonic evolutions of old terrains in northwestern China, in which granitiods formed during Proterozoic-early Mesozoic are widely outcropped. Detailed studies of these granitiods can shed some light on the tectonic evolution of this region. In this thesis, we have conducted geochronological and geochemical studies on eight selected granitic plutons to unravel their emplacement ages and petrogenesis. Furthermore, their tectonic implications were also discussed based on these results. In Neo-Proterozoic, our results suggest that two stages of magmatic activities were taken place in Central Qilian Block, GroupⅠ(750-790Ma) and Group Ⅱ(845－ 930Ma). In Neo-Paleozoic, most granitic plutons were emplaced from Ordovician to Devonian, whereas granitiods with Triassic ages have also been discovered in South Qilian Belt. Inherited zircons with old ages of 1.7Ga, 2.1Ga and 2.7Ga have also been obtained in our study. Geochemical studies suggest that the Proterzoic granites were produced under high pressures and low temperatures from metamorphosed protolith rocks with compostions from basic to intermediate. This implies that some hot sources were underplated beneath lithosophere via mantle-derived magmatism. In combination with regional geological data, we propose that the Cental Qilian block was an old arc terrene during Precambrian, and two stage granitoids were formed under a back-arc extensional setting. Granitic rocks emplaced in early Paleozoic belong to strong peraluminous S-type granites, which were derived from metagreywacke having strong relationships with collisional process. Together with previous data, our results indicate that granitoids in Qilian Orogenic Belt formed during early Paleozoic have different petrogenesis and emplaced ages, which reflect that Qilian Orogenic Belt had underwent complicated multi-stage subduction-collusional processes in early Paleozoic. On the other hand, granitic rocks in South Qilian Belt with Triassic ages were formed by subduction of East Kulun during early Paleozoic-Late Mesozoic, which represent another orogenic episode in the northern margin of Tibetan Plateau.

长白山火山成因—物理机制和化学演化

This thesis is one of the contributions to NSFC project, “The Changbaishan Volcanism and its Links to the Northeast Asia Tectonic System”. The thesis presents our most recent works on Changbaishan Volcanism, on two aspects as (1) the chemical evolution of the Cenozoic volcanism and the physical links of magma genesis, (2) the Holocene activity of the Tianchi Volcano and risks of potential eruption. 1. Chemical evolution and physical links to the Changbaishan Volcanism Physical links to the Chanbaishan Volcanism, just like origins of most of the volcanisms in eastern China, has long been an enigma. A large scale of volcanic activity has dominated many places of eastern China in Meso-Cenozoic. Activity of these volcanisms in eastern China covers several quite different blocks, covers variety of tectonics, and covers a period of time over 200 million years. Such a large-scale and long-lived volcanism in a continental area challenges our knowledge on dynamics of the Earth’s interior. Some works on “Diwa” hypothesis and “lithospheric thinning” hypothesis present possible links between volcanisms and dynamic evolutions of the earth’s interior, but still cannot interpret where are the sources of the heat and fluid, which are essential to the volcanisms. Based on the study of this thesis, we suggest that dynamics of the deep subduction of western Pacific Plate is the critical factor to the Changbaishan Volcanism and volcanisms in NE China, and maybe even essential to most of the Meso-Cenozoic volcanisms in eastern China. In NE China, stagnant slabs flatted in the mantle transition zone (MTZ, ca. 660 km deep) transport and release significant hydrous fluid to the upper mantle. Metamorphism of the deep-subducted slabs and hence a series of mineral phases play an important role in the water transport, exchange, restore, and release. Dehydrated fluid of the wet slab ascending from the MTZ fertile the upper mantle, and also provide upward heat flow which is essential to the magma genesis. Then magma and volcanism occur with the deep subduction from Mesozoic to mordern time in eastern China. To discribe the exact chemical characteristics of the deep subduction releated volcanics is very difficult, because few researches has contributed to the chemical behaviors of fluid and trace elments in the very deep interior of the Earth, such 660 km deep, 410km or 350km where the fluid may ascend and react. However we can still find some chemical characteristics of oceanic subduction. Basalts of the Changbaishan Volcanism have siginficant characteristics of potassium rich, and even can be called a potassic igneous province. If there are only two possible ways, recycled continentical crust or oceanic crust, to fertile the mantle potossium element as we know now, it’s easy to attribute this to the deep-subducted of the west Pacific Plate. To the eastern China, fluid inclusions in mantle xenoliths from the Cenozic basalts also reveal potassium-rich characteristics. This reveals that the same potassium feritle agents may occur in the mantle sources of eastern China. 2. Holocene activiy of the Tianchi Volcano As one of the large volcanic center and complex volcanic cone, the Tianchi Volcano is a dangerous active volcano, with several Holocene eruptions. Among these eruptions, the Millennium Eruption is regardede as one of the biggist eruptions in the world in the last 2000 years. To estimate the potential danger of volcanic eruption, we discuss two essential factors, as (i) volcanic history of Holocene eruptions, including volcanic geolgy, chronnology and chemistry, (ii) state, evolution and relationship of the magma chambers in mantle and crust beneath the Tianchi Volcano.

华北克拉通新生代玄武岩携带的地幔橄榄岩Fe同位素地球化学及含金云母地幔岩岩石学研究

In recent years, thanks to the improvement of analytical methods and the use of MC-ICP-MS, Fe isotope can be measured precisely. Fe isotope shows considerable variation both in biological and inorganic processes (from low T to high T) in nature, Therefore, Fe isotope has become one of the exciting frontier sciences and has favorable prospects of the application to the geosciences and life sciences. Based on a comprehensive review of available references in the related field, this study focuses on the development of techniques for high-precision measurement of iron isotope using MC-ICP-MS, and application of the techniques developed to study the Fe isotopes as well as major and trace element compositions of minerals (Ol, Opx, Cpx and Sp) from spinel peridotitic xenoliths from Cenozoic alkaline basalts to investigate Fe isotopic features of the lithospheric mantle beneath the North China Craton. The minerals from these xenoliths are similar to those off-cratonic peridotites world-wide, but are remarkably different from those on-cratonic peridotites and clinopyroxenes from these spinel lherzolites exhibit two types of chondrite-normalized REE patterns i.e. LREE-depleted and flat or spoon-shaped. It is noted that total abundances of REE in clinopyroxenes from these peridotites show a broad negative correlation with Cr# numbers of Cpx and Sp. The Fe isotope results show that the spinel peridotitic xenoliths have small but distinguishable Fe isotopic variations in minerals (generally Ol < Opx < Cpx) and samples, and the isotopic range in spinel is relatively large. Positive linear relationship with the ε57Fecpx/ε57Feopx ratio close to one unit has been observed between Fe isotopes of coexistent Opx and Cpx, indicating that the Cpx and Opx have generally reached Fe isotopic equilibrium. However, Fe isotopes between the Ol and Sp show apparent disequilibrium. The broadly negative correlation between mineral Fe isotopes and oxygen fugacity (fo2), metasomatic indexes such as spinel Cr#, (La/Yb) N and (La/Sm) N ratios of clinopyroxenes suggest that Fe isotopic variations in different minerals and peridotites were probably produced by melt-peridotite interaction. This study further confirms the previous observation that the lithospheric mantle has distinguishable and heterogeneous Fe isotopic variations at a scale of xenoliths. Mantle metasomatism that induces the interaction of the lithospheric mantle peridotite with metasomatic agent is a most potential mechanism for the Fe isotope fractionation in mantle peridotites. Therefore, Fe isotope could be a new and powerful tool to probe the evolution of the lithospheric mantle. We also report mineral compositions, clinopyroxene trace element concentrations and Sr-Nd isotopes for newly-discovered phlogopite-bearing spinel lherzolite and olivine clinopyroxenite xenoliths from three different localities （Hannuoba, Hebei Province; Jining Sangyitang, Inner Mongolia; Hebi, Henan Province）of the North China Craton. Systematic comparisons with phlogopite-free spinel lherzolite xenolith from the same locality reveals that the phlogopite-bearing peridotitic xenoliths have relatively higher Al2O3, CaO, Na2O, K2O, TiO2 contents and lower MgO contents than those phogopite-free counterparts. The former also has higher LREE concentrations, but relatively less radiogenic Sr-Nd isotopic ratios. This demonstrates that mantle metasomatism can not only enrich the basaltic components and trace element concentrations, but also make a decrease in Mg# of the peridotites and olivines and a relative depletion in Sr-Nd isotopes. 87Rb/86Sr-87Sr/86Sr isochrons of the phlogopite-bearing xenoliths indicate that mantle metasomatism happened in the Mesozoic and/or Cenozoic time. The metasomatic agent was derived from the asthenosphere. The result also manifests that the widespread similarity of the geochemical features such as major and trace elements and isotopic compositions in the Cenozoic lithospheric mantle beneath the North China Craton to those “oceanic” lithospheric mantle could be as a result of the ubiquitous presence of the interaction between the old refractory peridotites and the infiltrated asthenospheric melt, rather than the actually newly-accreted lithospheric mantle.

北大别黄土岭麻粒岩变质演化：对大别造山带演化进程的指示意义

Granulites from Huangtuling in the North Dabie metamorphic core complex in eastern China preserve rare mineralogical and mineral chemical evidence for multistage metamorphism related to Paleoproterozoic metamorphic processes, Triassic continental subduction-collision and Cretaceous collapse of the Dabieshan Orogen. Six stages of metamorphism are established, based on detailed mineralogical and petrological studies: (I) amphibolite facies (6.3–7.0 kbar, 520–550 °C); (II) high-pressure/high-temperature granulite facies (12–15.5 kbar, 920–980 °C); (III) cooling and decompression (4.8–6.0 kbar, 630-700 °C); (IV) medium-pressure granulite facies (7.7–9.0 kbar, 690–790 °C); (V) low-pressure/high-temperature granulite facies (4.0–4.7 kbar, 860–920 °C); (VI) retrograde greenschist facies overprint (1–2 kbar, 340–370 °C). The P–T history derived in this study and existing geochronological data indicate that the Huangtuling granulite records two cycles of orogenic crustal thickening events. The earlier three stages of metamorphism define a clockwise P–T path, implying crustal thickening and thinning events, possibly related to the assembly and breakup of the Columbia Supercontinent ca. 2000 Ma. Stage IV metamorphism indicates another crustal thickening event, which is attributed to the Triassic subduction/collision between the Yangtze and Sino–Korean Cratons. The dry lower crustal granulite persisted metastable during the Triassic subduction/collision due to lack of hydrous fluid and deformation. Stage V metamorphism records the Cretaceous collapse of the Dabieshan Orogen，possibly due to asthenosphere upwelling or removal of the lithospheric mantle resulting in heating of the granulite and partial melting of the North Dabie metamorphic core complex. Comparison of the Huangtuling granulite in North Dabie and the high-pressure (HP)–ultrahigh-pressure (UHP) metamorphic rocks in South Dabie indicates that the subducted upper (South Dabie) and lower (North Dabie) continental crusts underwent contrasting tectonometamorphic evolution during continental subduction–collision and orogenic collapse. High-pressure granulites are generally characterized by the absence of orthopyroxene. However, the Huangtuling felsic granulite rarely preserves the high-pressure granulite facies assemblage of garnet + orthopyroxene + biotite + plagioclase + K-feldspar + quartz. To investigate the effects of bulk rock composition on the stability of orthopyroxene-bearing, high-pressure granulite facies assemblages in the NCKFMASHTO (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3) system, we constructed a series of P–T–X pseudosections based on the melt-reintegrated composition of the Huangtuling felsic high-pressure granulite. Our calculations demonstrate that the orthopyroxene-bearing, high-pressure granulite facies assemblages are restricted to low XAl [Al2O3/(Na2O + CaO + K2O + FeO + MgO + Al2O3) < 0.35, mole proportion] or high XMg [MgO/(MgO + FeO) > 0.85] felsic–metapelitic rock types. Our study also reveals that the XAl values in the residual felsic–metapelitic, high-pressure granulites could be significantly reduced by a high proportion of melt loss. We suggest that orthopyroxene-bearing high-pressure granulites occur in residual overthickened crustal basement under continental subduction–collision zones and arc–continent collision belts.