Speciation Analysis of Organotin Compounds in Shellfish by Hyphenated Technique of High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds in the shellfish samples. Agilent TC-C-18 column was selected, mobile phase of the HPLC was CH3CN:H2O: CH3COOH = 65:23:12 (V/V), 0. 05% TEA, pH = 3.0 at flow rate 0.4 mL/min. Five mixed organotin standards from 100 mu g/L to 0. 5 mu g/L was used for the method evaluation. The experimental results indicate that the linearity (R-2) for each compound was over 0.998. The shellfish samples were treated by supersonic extraction with mobile phase for 30min. Four organotin compounds including dibutyltin (DBT), tributyltin (TBT), diphenyltin (DphT) and triphenyltin (TPhT) in shellfish samples were detected with method mentioned above. It was found that the domain compounds in the samples were tributyltin (TBT) and triphenyltin (TPhT). The recoveries test from the standard addition for trimethyltin (TMT tributyltin (TBT), and triphenyltin (TPhT) were, over 80%. However, the recoveries for diphenyltin (DPhT) and dibutyltin (DBT) were relatively low, 37.3% and 75.2% respectively. The reason might be attributed to the decomposition of those compounds during the extraction procedure. The further study on this subject is under the progress.

塔里木盆地塔中—巴楚地区早二叠世岩浆岩地球化学特征及其成因

Tazhong-Bachu region is located in the Western Tarim basin.The early Permian magmatic rocks occur in the earth surface of Tazhong-Bachu region are mainly distributed in Kepintag,Mazhartag and Wajilitag region. There are a lot of wells, in which researchers found the early Permian magmatic rocks,in desert cover area.Most magmatic rocks are basic rocks, a few of which are ultrabasic rocks and intermediate-acid magmatic rocks.The ultrabasic rocks are are mainly occur in the Cryptoexplosive Breccia Pipes ,which is located in the volcanic complex body of Wajilitag region.The basic rocks can be divided into three rock types：The first type of the magmatic rocks in Tazhong-Bachu region is volcanic rock ,which occurs in the Lower Permian Kupukuziman Formation and Kaipaizileike Formation. Most Volcanic rocks are basalts,a few of which are volcanic breccias and pyroclastic rocks.The basalts are distributed in stratiform occurrences and interbeded the clastic rocks in Kepintag region.The attitudes of the basalts are nearly horizontal.Columnar Joints, gas pore textures and amygdaloidal structure are to develop in basalts.The second type of the magmatic rocks in Tazhong-Bachu region is diabase,which occurs in Mazhartag region.Diabase dike swarms occur in the stratums of Silurian, Devonian, Carboniferous and Lower Permian.They make from NNW direction to SSE direction, the obliquity of stratum is greater than 60°, and the dike thickness is form several cm to several meters. Diabasic texture is found in the rocks .The first type of the magmatic rocks in Tazhong-Bachu region are gabbro- pyroxenite rocks ,which occur in the Wajilitag igneous complex body. The intermediate-acid magmatic rocks, which are mainly syenites, are located in Mazhartag and Wajiltag region. But they are small in the whole Tazhong-Bachu region.There are intermediate-acid magmatic rocks,which are mainly dacite,in the northeast part of the wells in Tazhong-Bachu region.But ,it is not found in earth surface.Through systematical geochemical research of early Permian magmatic rocks,which are distributed in Kepintag,Mazhartag, Wajilitag region and the wells such as F1 well、Z1 well、Z13 well、TZ18 well、H3 well、H4 well et al., the focus on the geochronologic characteristics, the main element,trace element and REE geochemistry, the mineralogic characteristics, the Sr-Nd and Pb isotopic characteristics are put forward. The main points are: 1、A combined study of CL imaging and LA-ICP-MS U-Pb dating were carried out for zircon grains of the magmatic rocks in the Tazhong-Bachu region from the Tarim basin.The results of the systematic zircon LA-ICP-MS U-Pb dating reveal 272±6Ma to 291±10Ma for the magamatic rocks. It indicated that Early Permian is an important period of magmatic acvivity in the Tazhong-Bachu region. 2、There are a big hunch in the curves of primitive mantle-normalized trace element concentrations in the early Permian magmatic rocks from Kepintag, Mazhartag, Wajilitag region and the 14 wells. Light rare earth elements are comparatively rich and heavy rare earth elements are comparatively poor. The slope rates are same between light rare erath elements and heavy rare earth elements. It is not like the curves of the basalts in the convergent margin of plate , in which the slope rates of light rare erath elements is bigger than the alope rates of heavy rare erath elements, and the curves of heavy rare earth elements are comparatively flat. The magmatic rocks of Tazhong-Bachu region rarely have the characteristics of the basalts in the convergent margin of plate, which is that Tantalum, Niobium and Titanium are much poor, and Zirconium, Hafnium and Phosphorus are moderately poor. The magamatic rocks are mostly alkaline, which is indicated by the dots of the (Na2O+K2O)-SiO2 identification diagram. All of these indicate that the early Permian magmatic rocks were formed in an extension environment of intraplate. 3、The Thorium abundance is high and Tantalum abundance is low in most magmatic rocks from Tazhong-Bachu reguion, which is formed for crustal contamination.In the Th/Yb-Ta/Yb identification diagram，most dots are in the region, which means active continental margin, but a few dots are in the region, which means mantle source. It indicated the feeding of continental crust materials. 4、The magnesium content of the olvines from Wagilitag region is richest, and the olvines from Kepintag region is poorest in the tree region. 5、Through the the Sr-Nd and Pb isotopic study of the basalts and diabases from the F1 well core, Z1 well core, Z13 well core,TZ18 well core, and the basalts，gabbros, diabases(diabase-prophyrites) and pl-peridotites from Kepintag,Mazhartag, Wajilitag region , it indicated that all isotopic data is similar and close to enriched mantle.

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.

化德群和土门群沉积岩碎屑锆石研究：对华北克拉通基底及元古宙盆地演化的指示意义

The Huade Group, consisting of low-grade and un-metamorphosed sedimentary rocks with no volcanic interlayer, is located at the northern margin of the North China craton and adjoining the south part of the Central Asian Orogenic Belt. It is east to the Paleo- to Meso-Proterozoic Bayan Obo and Zhaertai-Langshan rifts and northwest to the Paleo- to Neo-proterozoic Yanshan aulacogen, in which the typical Changcheng, Jixian and Qingbaikou systems are developed. The Huade Group are mainly composed of pebbly sandstones, sandstones, greywackes，shales，calc-silicate rocks and limestones, partly undergoing low-grade metamorphism and being changed to meta-sandstones, schists, phyllites, slates and crystalline limestones or marbles. The stratigraphic sequences show several cycles of deposition. Each of them developed coarse clastic rocks – interbedded fine clastic rocks and pelites from bottom upward or from coarse clastic rocks to interbedded fine clastic rocks and pelites to carbonate rocks. The Tumen Group outcrop sporadically around or west to the Tanlu faults in western Shandong. They are mainly composed of pebbly sandstones, sandstones, shales and limestones. This thesis deals with the characteristics of petrology, geochemistry and sedimentary of the Huade Group and the Tumen Group, and discusses the LA-ICP-MS and SIMS U-Pb ages, Hf isotope and trace element composition of the detrital zircons from 5 meta-sandstone samples of the Huade Group and 3 sandstone samples of the Tumen Group. The age populations of the detrital zircons from the Huade Group are mainly ~2.5 Ga and ~1.85 Ga, and there are also minor peaks at ~2.0 Ga, ~1.92 Ga and ~1.73 Ga. Most of the detrital zircon grains of 2.47-2.57 Ga and a few of 1.63-2.03 Ga have Hf crust model ages of 2.7-3.0 Ga, and most of the detrital zircon grains of 1.63-2.03 Ga have Hf crust model ages of 2.35-2.7 Ga, with a peak at 2.54 Ga. The main age peaks of the detrital zircons from the Tumen Group are ~2.5 Ga、~1.85 Ga, 1.57 Ga, 1.5 Ga, 1.33 Ga and 1.2 Ga. Different samples from the Tumen Group have distinct Hf isotopic characteristics. Detrital zircon grains of ~2.52 Ga from one sandstone sample have 2.7-3.2 Ga Hf crust model ages, whereas zircon grains of 1.73-2.02 Ga and 2.31-2.68 Ga from another sample have Hf crust model ages of 2.95-3.55 Ga. Detrital zircon grains of Mesoproterozoic ages have Paleoproterozoic (1.7-2.25 Ga) crust model ages. Through detailed analyses of the detrital zircons from the Huade and Tumen Group and comparison with those from the sedimentary rocks of similar sedimentary ages, the thesis mainly reaches the following conclusions: 1. The youngest age peaks of the detrital zircons of 1.73 Ga constrains the sedimentary time of the Huade Group from late Paleoproterozoic to Mesoproterozoic. 2. The age peaks of detrital zircons of the Huade Group correspond to the significant Precambrian tectonic-thermal events of the North China craton. The basement of the North China craton is the main provenance of the Huade Group, of which the intermediate to high grade metamorphic sedimentary rocks are dominant and provide mainly 1.85-1.92 Ga sediments. 3. The Huade basin belongs to the North China craton and it is suggested that the northern boundary of the North China craton should be north to the Huade basin. 4. The stratigraphic characteristics indicate the Huade Group formed in a stable shallow-hypabyssal sedimentary basin. The rock association and sedimentary time of the Huade Group are similar to those of the Banyan Obo Group and the Zhaertai Group, and they commonly constitute late Paleoproterozoic to Mesoproterozoic continental margin basins along the northern margin of the North China craton. 5. The continental margin basins would have initiated coeval with the Yanshan and Xiong’er aulacogens. 6. The ages of the detrital zircons from the Tumen Group and the Penglai Group at Shandong peninsula and the Yushulazi Group at south Liaoning are similar, so their sedimentary time is suggested to be Neoproterozoic，coeval with the Qingbaikou system. The detrital zircon ages of 1.0-1.2 Ga from the Tumen Group, the Penglai Group and the Yushulazi Group indicate that there have being 1.0-1.2 Ga magmatic activities at the eastern margin of the North China craton. 7. The U-Pb age populations of the detrital zircons from the late Paleoproterozoic to Neoproterozoic sedimentary rocks suggest that the main Precambrian tectonic-thermal events of the North China craton happened at ~2.5 Ga and ~1.85 Ga. But the events at 2.7 Ga and 1.2 Ga are also of great significance. Hf isotope characteristics indicate that the significant crust growth periods of the North China craton are 2.7-3.0 Ga and ~2.5 Ga.

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.

内蒙古白云鄂博地区元古宙构造-岩浆演化史与超大型REE-Nb-Fe矿床成因

Bayan Obo giant REE-Nb-Fe deposit in the northen margin of the North China Craton (NCC) is well known in the world for its abundant rare earth element resources. There is nearly one hundred year of studying history in substance component, chronology and geochemistry of the ore deposit, since the main ore body was found in 1927. However, there still exist remarkable divergences in genesis, mineralized age and material origin. Especially the REE enrichment mechanism leaves us a secret. Recent research shows that the Bayan Obo ore deposit likely resulted from the carbonatite magma activity, which is a favorable factor for REE accumulation. Based on the analysis of tectonic evolution history of north margin of NCC this thesis mainly discussed the formation background of cratonic margined rifts in Bayan Obo, and presented the analytical results of formation environment, intrusion age and deep origin of Proterozoic carbonatite magma. These research results can provide evidence for ore genesis. LA ICP-MS U-Pb dating on zircon shows that the Neoarchean basement was mainly composed of calc-alkaline TTG gneisses (2588±16Ma). The collision orogeny movement of the northen margin of the NCC between 2.0 Ga to 1.9 Ga brought the swarm of diorite-granodiotite magma (2023±16Ma) and intense regional metamorphism event (1906.3±7.7 Ma to 1892.7±6.7 Ma). In the sequent super continent break up background, intense metamorphic and deformed basement complex was uplifted to the surface suffered denudation, forming Mesoproterozoic Bayan Obo group in the contemporary continental margin rifts. The uplift of basement complex and formation of continental rifts were likely related with mantle plume activity. Evidence from petrological and geochemical data suggests that abundant alkaline-basic magma resulted from enhancement of continental breakup activity, that separated into carbonatite veins and mafic dykes by melt immiscibility mechanism, intruded in Bayan Obo margin rifts at the late stage of extension movement. Carbonatite veins can be divided into three main types by mineral composition: dolomite carbonatite, dolomite-calcite coexistent carbonatite and calcite carbonatite. Intrusion relationship between different types of carbonatite veins show that the calcite carbonatite veins were formed latter than the dolomite type as well as the coexistent type. Moreover, geochemical data also reveals successive and evolutive character between them. The content of REE increases together with the calcite minerals component. That is to say that REE gradually accumulated as the evolution of carbonatite magma. High precision Sm-Nd isochron data shows that the intrusion age of carbonatite veins was at 1319±48Ma. Moreover, the REE mineralization age in calcite carbonatite veins was around 1275±87Ma that is consistent with the intrusion age in error range. According to these data the abundant REE already existed in the carbonatite magma before intrusion and result in the earlier ore mineralization. The average age of mineralized dolomite was at 1353±100Ma, and the mineralization age of apatite in coarse grain dolomite was around 1329±150Ma. These data is consistent with carbonatite. Considering the coincident rare, trace element and isochron composition between them, it is presumed that mineralized dolomite was also the carbonatite intrusion and was the mainly factor for huge REE enrichment.

山东莒南地区韧性剪切带的变形特征与形成演化

Ju Nan of Shandong province is located at southwest of Sulu UHP (ultrahigh-pressure) metamorphic terrane. It is composed of gneiss, paragneiss, eclogites, ultramafic rocks, marble and quartzite. A large ductile shear zone extends east-west has been found at the Zhubian, The south of Junan county. The Zhubian ductile shear zone is composed of high srain rock and mylonites. The mylonites fall into 3 types: Initial gneiss mylonite, mylonite and altramylonit.obvious lineation of penetration,foliation,S-Cfabrics,porphyroclasts,folds,irregularundulatory,extinction,subgrain boundary, dynamic recrystallization microstructure, core-mantle structure and are common in the ductile shear zone. Based on field work and microstructural analyse, a conclution is arrived: The ductile shear zone is an approximately SE trending faults. The Zhubian ductile shear zone formed at Ep ―Hb facies conditions which could be proved by deformaed and metamorphosed mineral aggregates, Deformation behavior, Ternary-feldspar geothermometry and so on. Zircon MC―ICP―MS U-Pb analysis is performed on the mylonite and have an average age ―835.9±13.9Ma, it’s the primary rocks formed age. The Zhubian ductile shear zone maybe formed at 224-242Ma.

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.

东天山后碰撞镁铁-超镁铁岩镍铜硫化物矿床PGE地球化学示踪与富集规律研究

Eastern Tianshan area, a Paleozoic complex trench-arc-basin system, experienced multi-period sudbuction and collision in geological history. A large number of Early Permian mafic-ultramafic intrusions emplaced along deep faults in post-collision extension tectonic stage and hosted a series of magmatic Cu-Ni sulfide deposits. This paper sets newly-discovered Tianyu magmatic Cu-Ni sulfide deposit related to small intrusion as an example. On basis of the study of ore-forming mechanism of Cu-Ni deposit, we compared PGE content and discussed enrichment mechanism and regularity of mafic-ultramafic rocks and ores in Jueluotage tectonic belt and Central Tianshan Massif. PGE and Cu, Ni, S contents correlate with each other. PGE is mainly controlled by S content.Samilar PGE distribution patterns of mafic-ultramafic show that complex originated from the same parental magma; Pd/Ir and Ni/Cu ratios indicate that high-Mg basaltic magma and deep sulfide segregation happened during magma evolution process. PGE and Cu-Ni ores are enriched in liquid sulfide and only individual samples completely control by monosulfide solid solution. Comparison of all control factors, early segregation of sulfide and quality of supply of magma may be the key factors leading to the Eastern Tianshan magmatic copper-nickel sulfide deposits don’t reach PGE grade, but we do not rule out the possibility of occurrence continuous mafic-ultramafic rocks and PGE-rich layer in deep.

内蒙古中部道郎和都格铜多金属矿的地质特征矿床类型及找矿模式研究

Daolangheduge copper polymetallic deposit is located on east edge of Ondor Sum-Bainaimiao metallogenic belt, which is a prospective area of porphyry copper deposit, in Xianghuangqi of central Inner Mongolia. Geotectonically, it occurred in the continental margin accretion belt along the north margin of North China Plate, south of the suture zone between North China Plate and Siberian Plate. The intrusive rocks in this area mainly consist of intermediate-acid magmatic rocks, and the quartz veins, tourmaline veins and the transitional phase are comparatively developed. According to our research, the ore-bearing rock body is mainly quartz diorite while the surrounding rock is mainly biotite granite. Besides, the wall rock alteration are mainly propylitization, pyritization and silicification, which consist of epidotization, actinolitization, chloritzation and so on. The metallic minerals are mainly chalcopyrite and pyrite. In addition, the primary ore is mainly of quartz-chalcopyrite-pyrite type. Above all, Daolangheduge copper polymetallic deposit is suggested to be categorized in the porphyry copper type. With isotopic dating and geochemical research on quartz diorite of ore-bearing rock body, the zircon LA-ICP-MS U-Pb dating of two samples yields an age of 266±2 Ma, falling into the range of late Permian Epoch. It is the first accurate age data in Xianghuangqi area, so it should play a key role in the research of deposit and magmatic rocks in this area. With the major elements and trace elements analysis of 14 samples, the quartz diorite should be among the calc-alkaline series, the geochemical characteristics show higher large-ion lithophile elements of Rb, Sr and LREE, low high-field strength elements of Nb, Ta and high transition elements of Cu, Cr . Also, the REE patterns have negative Eu anomalies. With the same analysis of 4 sample for the biotite granite, the geochemical characteristics show higher Rb, Th,, Zr, Hf and LREE, low Nb, Sm and HREE and Eu has no anomaly. It should be among the calc-alkaline series, over aluminum quality and has characteristics of Adakites. According to isotopic dating and geochemical characteristics of ore-bearing rock body, it is suggested that its materials mainly derived from upper mantle that had fractional crystallization and its magma source region may be affected by fluid metasomatism of paleo-asian ocean. It should be an extensional process of post-orogeny according to regional tectonic evolution. Consequently, because of the decrease of temperature and pressure, the ore forming fluid was raised to surface and mineralized accompanied by magmatic activity which might occur in south of the suture zone. By geological survey, further geophysical and geochemical work is needed. In this area, we have accomplished high precision magnetic prospecting, high density electrical survey, gravity prospecting, soil geochemical prospecting, X-ray fluorescence analyzer prospecting and so on. According to geophysical and geochemical abnormal and surface occurrence, 11 drills are arranged to verification. The type of ores are mainly quartz-chalcopyrite-pyrite ores within 3 drills by drill core logging. Although the grade as well as the scale of already-found Cu deposits are insufficient for industrial exploitation, the mineralization prospect in this region is supposed to be great and the potential in mineral exploration at depth is excellent.

碎屑锆石年龄和Nd-Hf同位素组成对扬子基底演化的制约

The South China craton was formed by the collision of the Yangtze and Cathaysia blocks during the Neoproterozoic Jiangnan orogeny (also termed as the Jingnin or Sibao orogeny in Chinese literature). Basement rocks within the Yangtze block consist mainly of Proterozoic sediments of the Lengjiaxi and Banxi Groups. U-Pb ages of detrital zircons obtained by the LA-ICP-MS dating technique imply that the deposition of the Lengjiaxi Group continued until the Neoproterozoic. The youngest detrital zircons suggest a maximum deposition age of ~830 Ma for the Lengjiaxi Group, consistent with the initiation time of the deposition of the overlying Banxi Group, likely indicating continuous deposition of these two groups and a short temporal hiatus (~10 Ma) between the Neoproterozoic sedimentary rocks distributed in the South China craton. Detrital zircons from both the Lengjiaxi and Banxi Groups have a wide range of εHf(t) values from -12 to 14.2 and a continuous Nd and Hf model age spectrum from ~820 Ma to 2200 Ma. Some grains have model ages ranging up to ca. 2.9-3.5 Ga, indicating that both juvenile mantle material and ancient crust provided sedimentary detritus. This is also consistent with the Nd isotopic signature of sedimentary rocks recorded in the Lengjiaxi Group, suggesting a back-arc tectonic setting. The Banxi Group has slightly enriched Nd isotopic signatures relative to the Lengjiaxi Group, implying a higher percentage of old continental material in the sedimentary source. Combined with previously published data, new results can help us to reconstruct the Neoproterozoic tectonic evolution of the South China craton. The age spectrum of detrital zircons and Nd-Hf isotopic composition suggests a two-stage collision: Between 1000 Ma to 870 Ma, a continental magmatic arc was build up along the eastern margin of the Yangtze block. Convergence led to continent-based back-arc extension, subsidence and formation of a back-arc basin. Detritus originating from arc-related magmatic and old basement rocks was transported into this back-arc basin resulting in formation of the Lengjiaxi Group and its equivalents. At around 870 Ma, a second (oceanic) arc was formed by extension of an inter-arc basin, subduction subsequently led to the first collision and the emplacement of the blueschist mélange. Accretion of the magmatic arc lasted until the closure of an oceanic basin between the Yangtze and Cathaysia blocks at about 830 Ma. Shortly after the collision, subsequent uplift, further extension of the former back-arc basin and post-collisional granitoid magmatism caused a tilting of the Lengjiaxi sediments. Between 830 Ma and 820 Ma, subsequent closure of the oceanic back-arc basin and formation of the Jiangnan orogen took place, leaving a regional unconformity above the Lengjiaxi Group. Above this unconformity the Banxi Group was immediately deposited during the post-tectonic stage.

新疆东昆仑蛇绿岩岩石学、地球化学特征及其大地构造意义

The East Kunlun area of Xinjiang (briefly EKAX) is the western part of broadly speaking East Kunlun orogenic zone. The absence of geological data (especially ophiolites) on this area has constrained our recognition to its geology since many years. Fund by National 305 Item (96-915-06-03), this paper, by choosing the two ophiolite zones (Muztag and Southwestern Margin of Aqikekule Lake ophiolite zones) exposed at EKAX as the studied objects and by the analysis of thin section, electron probe, XRF, ICP-MS, SEM and Sm-Nd isotope, totally and sys ematically dealt with the field geological, petrological, minerological, petrochemical and geochemical characteristics (including trace, rare earth element and Sm-Nd isotope) and the tectonic setting indicated by them for each ophilite zone. Especially, this paper discussed the trace and rare earth element patterns for metamorphic peridotites, their implications and related them to the other components of ophiolite in order to totally disclose ophiolite origins. Besides, this paper also studied the petrological, geochemical and paleobiological characteristics for the cherts coexsisted with the Muztag ophiolite and the tectonic setting indicated by them. Based on these, the author discussed the tectonic evolution from Proterozoic to Permian for this area. For Muztag ophiolite, their field geological, petrological, minerological, petrochemical and geochemical characteristics show that: ① outcropped along the Muztag-Jingyuhu fault with west-to-east strike, the ophiolite is composed of such three components as metamorphic peridotites, cumulates and volcanic rocks; ② metamophic peridotites consist of such types as lherzolites, serpentinized lherzolites and serpentinites, only pyroxenites is seen of cumulates and volcanic rocks include basalts, basaltic andesites and andesites; ③ mineralogical data on this ophiolite suggest it formed in supra-subduction zone (SSZ)environment, and its mantle wedge is heterogeneous; ④ whole-rock TiO_2 and Al_2O_3 of metamorphic peridotites indicate their original environment with the MORB and SSZ characteristics; ⑤ metamorphic peridotites have depleted LREE and flat REE patterns and volcanic rocks have enriched LREE patterns; ⑥ trace element characteristics of metamorphic peridotites imply that they had undergone Nb and Ta enrichment event after partial melting; ⑦ trace element characteristics of volcanic rocks and their tectonic diagrams show they are formed in the spreading and developed island arc environment with back-arc basin, such as rifted island arc, which is supported by the ε_(Nd)(t) -2.11～+3.44. In summary, the above evidence implies that Muztag ophiolite is formed in SSZ environment, where heterogeneous mantle wedge was metasomatised by the silica-enriched melt from subducted sediments and/or oceanic crust, which makes the mantle wedge enriched again, and this enriched mantle wedge later partially melted to form the volcanic rocks. For Southwestern Margin of Aqikekule Lake ophiolite, their field geological, petrological, minerological, petrochemical and geochemical characteristics show that: ① it outcropped as tectonic slices along the near west-to-east strike Kunzhong fault and is composed of metamorphic perodotties, cumulates and volcanic rocks, in which, chromites are distributed in the upper part of metamorphic peridotites as pods, or in the lower part of cumulates as near-strata; ② metamorphic peridotites include serpentinites, chromite-bearing serpentinites, thlorite-epidote schists and chromitites, of which, chromitites have nodular and orbicular structure, and cumulates include pyroxenits, serpentinites, chromite-bearing serpentinites, chromites and metamorphically mafic rocks and only basalts are seen in volcanic rocks; ③ Cr# of chromites suggest that they formed in the SSZ and Al_2O_3 and TiO_2 of metamorphic peridotites also suggest SSZ environment; ④metamorphic peridotites have V type and enriched LREE patterns, cumulates have from strongly depleted LREE, flat REE to enriched LREE patterns with universally striking positive Eu anomalies and basalts show flat REE or slight enriched LREE patterns with no Eu anomalies; ⑤ trace element and Sm-Nd isotope characteristics of metamorphic peridotites imply their strikingly heterogeneous mantle character(ε_(Nd)(t)+4.39～+26.20) and later Nb, Ta fertilization; ⑥ trace element characteristics of basalts and their tectonic diagrams show they probably formed in the rifted island arc or back-arc basin enviromnent. In summary, the above evidence shows that this ophiolite formed in the SSZ environment and melts from subudcted plate are joined during its formation. Rare earth element, whole-rock and sedimentary characteristics of cherts with the Muztag ophiolite show that they formed in the continental margin environment with developed back-arc basin, and radiolarias in the cherts indicate that the upper age of Muztag ophiolite is early carboniferous. Based on the accreted wedge models of Professor Li Jiliang for Kunlunshan Mountain and combined with study on the two typical ophiolite profiles of EKAX, the author discussed the tectonic evolution of EKAX from Proterzoic to Permian.

铂族元素分析方法研究及其在有关地质问题中的应用

Characterization of Platinum Group Elements (PGE) has been applied to earth, space and environmental sciences. However, all these applications are based on a basic prerequisite, i.e. their concentration or ratio in the research objects can be accurately and precisely determined. In fact, development in these related studies is a great challenge to the analytical chemistry of the PGE because their content in the geological sample (non-mineralized) is often extremely low, range from ppt (10~(-12)g/g) to ppt (10~(-9)g/g). Their distribution is highly heterogeneous, usually concentrating in single particle or phase. Therefore, the accurate determination of these elements remains a problem in analytical chemistry and it obstructs the research on geochemistry of PGE. A great effort has been made in scientific community to reliable determining of very low amounts of PGE, which has been focused on to reduce the level of background in used reagents and to solve probable heterogeneity of PGE in samples. Undoubtedly, the fire-assay method is one of the best ways for solving the heterogeneity, as a large amount of sample weight (10-50g) can be hold. This page is mainly aimed at development of the methodology on separation, concentration and determination of the ultra-trace PGE in the rock and peat samples, and then they are applied to study the trace of PGE in ophiolite suite, in Kudi, West Kunlun and Tunguska explosion in 1908. The achievements of the study are summarized as follows: 1. A PGE lab is established in the Laboratory of Lithosphere Tectonic Evolution, IGG, CAS. 2. A modified method of determination of PGE in geological samples using NiS Fire-Assay with inductively coupled plasma-mass spectrometry (ICP-MS) is set up. The technical improvements are made as following: (1) investigating the level of background in used reagents, and finding the contents of Au, Pt and Pd in carbonyl nickel powder are 30, 0.6 and 0.6ng/g, respectively and 0.35, 7.5 and 6.4ng, respectively in other flux, and the contents of Ru, Rh, Os in whole reagents used are very low (below or near the detection limits of ICP-MS); (2) measuring the recoveries of PGE using different collector (Ni+S) and finding 1.5g of carbonyl nickel is effective for recovering the PGE for 15g samples (recoveries are more than 90%), reducing the inherent blank value due to impurities reagents; (3) direct dissolving nickel button in Teflon bomb and using Te-precipitation, so reducing the loss of PGE during preconcentration process and improving the recoveries of PGE (above 60% for Os and 93.6-106.3% for other PGE, using 2g carbonyl nickel); (4) simplifying the procedure of analyzing Osmium; (5)method detection limits are 8.6, 4.8, 43, 2.4, 82pg/g for 15g sample size ofRu, Rh, Pd, Ir, Pt, respectively. 3. An analytical method is set up to determine the content of ultra-trace PGE in peat samples. The method detection limits are 0.06, 0.1, 0.001, 0.001 and 0.002ng/mL for Ru, Rh, Pd, Ir and Pt, respectively. 4. Distinct anomaly of Pd and Os are firstly found in the peat sampling near the Tunguska explosion site, using the analytical method. 5. Applying the method to the study on the origin of Tunguska explosion and making the following conclusions: (1) these excess elements were likely resulted from the Tunguska Cosmic Body (TCB) explosion of 1908. (2) The Tunguska explosive body was composed of materials (solid components) similar to C1 chondrite, and, most probably, a cometary object, which weighed more than 10~7 tons and had a radius of more than 126 m. 6. The analysis method about ultra-trace PGE in rock samples is successfully used in the study on the characteristic of PGE in Kudi ophiolite suite and the following conclusions are made: (1) The difference of the mantle normalization of PGE patterns between dunite, harzburgite and lherzolite in Kudi indicates that they are residual of multi-stage partial melt of the mantle. Their depletion of Ir at a similar degree probably indicates the existence of an upper mantle depleted Ir. (2) With the evolution of the magma produced by the partial melt of the mantle, strong differentiation has been shown between IPGE and PPGE; and the differentiation from pyroxenite to basalt would have been more and more distinct. (3) The magma forming ophiolite in Kudi probably suffered S-saturation process.

内陆湖沼相和近海沼泽相沉积环境煤中微量元素和矿物的对比研究—以辽宁北票、江西建新和桥头煤研究为例

Using knowledge of geology, geochemistry, coal petrology, mineralogy, by means of a variety of advanced measuring methods such as inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRD), scanning electron microscopy with energy-dispersive spectrometer(SEM-EDS), sequential chemical extract and density fractions, the characteristics of trace elements and minerals in Jurassic Beipiao coal mine under inland limnetic sedimentary environment and in late Permian Jianxin and Qiaotou coal mines under paralic swamp sedimentary environment were studied. Compared with the average concentration in the world bituminous coals, the Beipiao coal was characterized by relatively high contents of Sc, Ti, Cr, Co, Ni, Zn, Se, Sr, Zr, Y, Ba, REE and Th, and lower contents of V, Rb, Cd, Sn, Pb, Bi and U; while the Jianxin coal was relatively enriched in Li, Sc, Ga, Sr, Y, Nb, Sb, Th and U, with low concentration of Be, Co, Ni, Cu, Ge, Zr, Mo, Cd, Cs, Ba, Pb and Bi; and the Qiaotou coal was enriched in Li, Sc, Sr, Nb, Ta, Zr, REE, Hf, Th and U, with low concentration of Be, V, Co, Ni, Cu, Ge, Mo, Cd, Cs, Ba, Tl, Pb and Bi. The concentrations of Ca, Mg and K in Beipiao coal are higher than those in Jianxin coal and Qiaotou coal, while Fe, S and Ti in Beipiao coal are lower than those in Jianxin coal and Qiaotou coal. The proximate analysis of coal samples was carried out, which indicated that Beipiao coal was medium- to high- ash (5.92-60.68%) with low sulphur coal, and Jianxin coal and Qiaotou coal was medium to high ash (8.85-46.33%) with high sulphur. The reflectivity was measured, which explained that Beipiao coal belonged to high volatile bituminous coal, Jianxin coal was low volatile bituminous coal and Qiaotou coal was low volatile anthracite. Quantitative maceral analyses were studied. The characteristics of rare earth elements (REE) were investigated, which showed that the total contents of REE were higher than that of the world's average content. With the increase of coal's metamorphic grade, the total contents of REE decreased from 98.5 X 10"6 of Beipiao coal to 94.2 X 10"6 of Jianxin coal, and to 75.9 X 10"6 of Qiaotou coal, and 5Eu reduced which indicated that the element Eu depleted. The characteristics of REE was controlled by the metamorphic grade of coal. And REE were mainly absorbed in clay minerals in Beipiao coal samples, while in Jianxin and Qiaotou coal mines, REE were primarily related to clay mineral and pyrite. The variation of trace elements in vertical direction of coal seams was studied, and the results showed that different trace elements differed greatly. The correlation between trace elements and ash were determined. Four major trace elements (aluminium-silicates, sulphide, carbonate and phosphate) accounted for the occurrence and distribution of most elements studied were determined. Coal samples were separated by density fraction, which showed that Cr, Cu, Mo and Pb were closely related to inorganic matters mainly distributed in P >2.6 and dropped remarkably in the density fractions P <2.3 . The occurrences of Co, Cr, Ni, As, Se, Mo, U were studied directly and quantitatively using sequential chemical extract with six steps, which showed that Co. Ni, Mo and U were mainly in the form of mineral, and As, Se chiefly in the form of organic state, while Cr mostly in the form of organic state and mineral. Major mineral phases presented in the Beipiao coal were Kaolinite, illite, quartz, calcite, and small amount of siderite, barite. While major mineral phases in Jianxin and Qiaotou coal were pyrite, kaolinite, and small amount of marcasite, rutile, sphalerite. This is the first time that the chromite in the coal was discovered in China, which indicates that Cr occurrence appeared in the form of chromite. The ratio of Sr/Ba, Sr/Ca and V/Ni in Beipiao coal mine under inland limnetic is smaller than that of in Jianxin and Qiaotou coal mines under paralic swamp. The ratio of K/Na and Th/U of Beipiao coal mine is higher than that of Jianxin and Qiaotou coal mine, which proved that Beipiao coal was not affected by sea water and Jianxin and Qiaotou coal were affected by sea water. Trace elements such as Cr, Ni, Mo in minerals were analyzed by SEM-EDS. The factors controlling the enrichment of trace elements can be divided into syngenetic stage factors and epigenetic stage factors.

石笋微层序列的断代和信号研究

Based on chronological and climatologic analysis of many young stalagmites in Shihua Cave at Beijing and Water Cave in Benxi, Liaoning Province, this dissertation aims to discuss some key points on quantitative reconstruction of high resolution climate change from micro bands time series in young stalagmites. On chronological aspect of micro bands time series in young stalagmite, the uppermost micro bands were testified formed in the sampling year or the year before sampling from long term and in situ experiment in Shihua Cave at Beijing. Have been observed detailed under microscope, the micro bands were counted and compared with high resolution TIMS-230Th or ICP-MS U series dating, the results show that the micro bands are annual bands. The microscopic characteristics of annual bands in North China is as follows after studying lots of young stalagmites: the interface appears to be carved, and there is a light line adjacent to it, which moves back and forth slightly when adjusting the microscope slide. The cross dating of annual bands from different stalagmites is experimented in this thesis. On climatologically aspect of micro bands times series in young stalagmites, one significant problem is that the deposition trend resulting from the variation of the stalagmite shape. Various deposition trends have been discussed and corrected before climatologically analysis of micro bands series. And the whole year in situ observation and analysis of dripping water in Shihua Cave provide us new evidence for climate information reserved in stalagmites micro bands. The stalagmites in the same cave may contain different climate information due to the micro hydrological condition. The annual bands of young stalagmites collected from North China can be used to reconstruct past climate changes quantitatively. The warm season temperature (May, June, July, August) is reconstructed using two annual bands time series from Shihua Cave, Beijing, which corresponds to the warm/cool periods very well in Chinese history documents. The precipitation record of past 500 years is reconstructed using two stalagmite annual bands series from Shihua Cave, which is consistent to the dryness/wetness records derived from historical documents too.