阿尔泰南缘侧向增生过程中的VMS矿床：地质、地球化学特征与成矿机制

The Chinese Altai is one of the most important volcanogenic massive sulfide (VMS) deposit districts in China. All orebodies were lenticular or bedded and stratabounded by a suite of early Devonian volcanic-sedimentary rocks. Hydrothermal feeder zones developed under some of the orebodies. All the ores are massive or laminated, and show typical characteristics of VMS deposit. Based on the mineralizing time and the metal assembles, we divide 3 metallogenic stages: 1, Fe orefroming stage associated with basaltic and sedimentary rocks during very early Devonian; 2, Cu-Pb-Zn oreforming stage associated with rhyolitic and sedimentary rocks during early Devonian; 3， Cu-Zn oreforming stage in the dacitic and basaltic rocks during mid. Devonian. The hosting rocks for all orebodies are different, but they show very similar geochemical and isotopic characteristics. All the felsic rocks show enriched lighted rare earth elements (REE) patterns (La/Yb>5), and with an obvious Eu negative anomalies (Eu/Eu*<0.6). In the meanwhile, all the mafic rocks show flat REE pattern and no Eu anomalies. The Ashele basalt show an apparent Ce negative anomalies (Ce/Ce* <0.76), All the volcanic roks in Chinese Altai show the decoupled property between the high field strength elements (HFSE) and large ion lithophile elements (LILE). The negative Nb, Ta characteristics with respect to adjacent elements indicate that subduction-modified source. The Nd(t) of the hosting rocks for all orebodies changed in a small range (-1.5~5), and the (87Sr/86Sr)i change in a big range. The initial Sr value of the hosting rocks in Mengku and Tiemuerte are obviously affected by the seawater (0.705~0.710), and initial Sr values of hosting rocks Ashele change in a small range (0.704~0.706). All Sr-Nd isotopes of ores have the same range with the hosting rocks, indicating that both the ores and volcanic rocks have the same island arc source. The mean sulfur isotopes of sulfides from Ashele and Mengku are 6.2‰ and 3.4‰, respectively, indicating a deep magmatic source. However, the sulfur isotopes of sulfides from Keketale, Tiemuerte and Keyinbulake changed in -15.8‰~9.9‰, -23.5‰~1.87‰, -8.3‰~1.6‰, respectively. And the big sulfur isotope range indicated that the sulfur of the ores was a combination biogenic and magmatic source. All volcanic rocks from the VMS deposits in the southern Chinese Altai show a typical subduction related environments. Based on the regional and locally geological evidence, here we propose that the southern Chinese Altai is an island arc system, and all VMS deposits formed during the lateral accretion process. No VMS deposit formed during the formation of the island arc during Silurian; Fe VMS deposit formed during the beginning of the opening of the backarc basin in very early Devonian; Cu-Pb-Zn VMS deposits formed during the mature stage of the backarc basin in early Devonian; at last the Cu-Zn VMS deposit formed during the rifted stage of the island arc itself.

西南极南设得兰群岛中新生代火山岩基底沉积学及其大地构造制约

Livingston Island, the second island of South Shetland Island, constains Mesozoic-Cenozoic basement, Mesozoic-Cenozoic volcanic sequences, plutonic intrusions and post-subduction volcanic rocks, which document the history and evolution of an important part of the South Shetland Islands magmatic arc. The sedimentary sequence is named the Miers Bluff Formation (MBF) and is interpreted as turbidite since the first geological study on South Shetland Islands, and is interpreted as turbidite. It base and top are not exposed, but a thickness of more than 3000m has been suggested and seems plausible. The turbidite is overlain by Mid - Cretaceous volcanic rocks and intruded by Eocene tonalites. The age of the Miers Bluff Formation is poorly constrained Late Carboniferous -Early Triassic. Sedimentary Environment, tectonic setting and forming age of sedimentary rocks of the Miers Bluff Formation were discussed by means of the methods of sedimentology, petrography and geochemistry, combinig with the study of trace fossils and microfossil plants. The following conclusions are obstained. A sedimentary geological section of Johnsons Dock is made by outside measuring and watching, and then according the section, the geological map near the Spanish Antarctic station was mapped. Four pebbly mudstone layers are first distinguished, which thickness is about 10m. The pebbly mudstone is the typical rock of debris flow, and the depostional environment of pebbly mudstone may be the channel of mid fan of submarine fan. The sedimentsry structural characteristics and size analysis of sandstones show the typical sedimentary feature of turbidity flow and the Miers Bluff Formation is a deep-water turbidite (include some gravity-flow sediments). The materials of palaeocurrents suggest the continental slope dip to southeast, and indicate the provenance of turbidity sediment in the northwest area. By facies analysis, six main facies which include seven subfacies were recognized, which are formed in mid-fan and lower-fan of submarine, meanwhile, the sedimentary features of each facies and subfacies are summarized. The study of clastic composition, major elements, trace elements and rare earth elements indicates the forming setting of the Miers Bluff Formaton is active continental margin and continental island arc and the provenance is dissected magmatic arc which main composition is felsic gneiss. Many trace fossils of the whole succession were found in the turbidites of the Miers Bluff Formation. All these trace fossils are deep sea ichnofossils. There are fifteen ichnogenus, sixteen ichnospecies. Moreover, a new trace fossil was found and a new ichnogenus and new ichnospecies was proposed - Paleaichnus antarctics ichnogen, et ichnosp, nov.. Except the new ichnogenus and ichnospecies, others had been found in deep-sea flysch turbidites. Some are in mudstone and are preserved in the cast convex of overlying sandstone sole, they formed before turbidity flows occurred and belong to the high-different Graphoglyptida of fiysch mudstone. Others as Fucusopsis and Neonereites are preserved in sandstones and stand for trace assemblages after turbidity sedimentation. These trace fossils are typical members of abyssal "Nereites" ichnofacies, and provide for the depositional environment of the Miers Bluff Formation. Fairly diverse microfossil plants have been recovered from the Miers Bluff Formation, Livingston Island, including spores, pollen, acritarchs, wood fragments and cuticles. Containing a total of about 45 species (forms) of miospores, the palynofiora is quantitatively characterized by the dominance of non-striate bisaccate pollen, but spores of pteridophytes and pollen of gymnosperms are proportionate in diversity. It is somewhat comparable to the subzone C+D of the Alisporites zone of Antarctica, and the upper Craterisporites rotundus zone and the lower Polycingulatisporites crenulatus zone of Australia, suggesting a Late Triassic (possibly Norian-Rhaetian) age, as also evidenced by the sporadic occurrence of Aratrisporites and probable Classopollis as well as the complete absence of bisaccate Striatiti. The parent vegetation and paleoclimate are preliminarily deduced. At last, the paper prooses the provenance of sedimentary rocks of the Miers Bluff Formation locates in the east part to the southern Chile(or Southern South American). In the Triassic period, contrasting with New Zealand, Australia and South American of the Pacific margin of Gondwanaland, the Miers Bluff Formation is deposited in the fore-arc basin or back-arc basin of magmatic arc.

胶东地区金矿床成矿时代及其成矿地球动力学背景-兼论壳幔相互作用与成岩成矿

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

大别山岩石圈有效弹性厚度初步研究

As powerful tools to study the lithosphere dynamics, the effective elastic thickness (Te) as well as the envelope of yielding stress of lithosphere have been attracted great attention of geoscientists in the past thirty years. The oceanic lithosphere, contrary to the continental lithosphere, has more fruits for its simple structures and evolution process. In continent, the lithosphere commonly is complex and variable in the rheological, thermal structures, and has a complicated history. Therefore, the application of the effective elastic thickness in continent is still a subject to learn in a long time. Te, with the definition of the thickness of an elastic plate in theory flexured by the equal benging of the real stress in the lithosphere plate (Turcotte, 1982), marks the depth of transition between elastic and fluid behaviors of rocks subjected to stress exceeding 100 MPa over the geological timescales (McNutt, 1990). There are three methods often adapted: admittance or isostatic response function, coherence and forwarding. In principle, the models of Te consist of thermal-rheological, non-linear Maxwell, non-linear work hardening and rheological layered models. There is a tentative knowledge of Te that it is affected by the following factors: crustal thickness, crust-mantle decoupling, plate bending, boundary conditions of plate (end forces and bending moments), stress state, sedimentary layer, faulting effect, variation in the mountain belts' strike, foreland basin, inheritance of tectonic evolution, convection of mantle, seismic depth and lithosphere strength. In this thesis, the author introduces the geological sketch of the Dabie collisional orogenic belt and the Hefei Basin. The Dabie Mts. is famous for the ultra-high pressure metamorphism. The crustal materials subducted down to the depth of at least 100 km and exhumed. So that the front subjects arise such as the deeply subduction of continent, and the post-collisional crust-mantle interaction. In a geological journey at June of 1999, the author found the rarely variolitic basaltic andesite in the Dabie Mts. It occurs in Susong Group, near Zhifenghe Countryside, Susong County, Anhui Province. It is just to the south of the boundary between the high-grade Susong melange and the ultra-high grade South Dabie melange. It has a noticeable knobby or pitted appearance in the surface. The size of the varioles is about 1-4 mm. In hand-specimen and under microscope, there are distinct contacts between the varioles and the matrice. The mineralogy of the varioles is primarily radiate plagioclase, with little pyroxene, hornblende and quartz. The pyroxene, hornblende and quartz are in the interstices between plagioclase. The matrix is consisted of glass, and micro-crystals of chlorite, epidote and zoisite. It is clearly subjected and extensive alteration. The andesite has an uncommon chemical composition. The SiO_2 content is about 56.8%, TiO_2 = 0.9%, MgO = 6.4%, (Fe_2O_3)_(Total) = 6.7% ～ 7.6%, 100 Mg/(Mg+Fe) = 64.1 ～ 66.2. Mg# is significantly high. The andesite has higher abundances of large-lithophile trace elements (e.g. K, Ba, Sr, LREE), e.g. La/Nd = 5.56-6.07, low abundances of high-strength-field elements (HFSE, e.g. Ta, Nb, P, Ti), particularly Ta and Nb strongly depleted. These are consistent with the characteristics of subducted-related magmas (Pearcce, 1982; Sun and McDonaugh, 1989). In the spider diagram of trace elements, from Ce to right hand, the abundances of elements decrease quickly, showing a characteristic of the continental margins (Pearce, 1982). There has a strongly enrichment of light-rare-earth elements, with a significant diffraction of REEs (the mean value of (La/Yb)_N is 32.84). No Eu anomaly, but there are anomaly high (La/Yb)_N = 28.63-36.74, (La/Y)_N = 70.33 - 82.84. The elements Y and Yb depleted greatly, Y < 20 ppm, Y_N = 2.74-2.84, Yb_N = 2.18 - 2.35. From the La-(La/Sm) diagram, the andesite is derived from partial melting. But the epsilone value of Nd is -18.7 ～ -19.2, so that the material source may be the mantle materials affected by the crustal materials. The Nd model age is 1.9 Ga indicating that the basaltic andesite was resulted from the post-collisional crust-mantle interaction between the subducted Yangze carton and the mantle of Sino-Korea carton. To obtain the Te of the lithosphere beneath the Dabie Mts. and the Hefei Basin, the author applies the coherence method in this thesis. The author makes two topography-gravity profiles (profiles 7~(th) and 9~(th)) across the Dabie Mts. and the Hefei Basin, and calculates the auto-coherence, across coherence, power spectrum, across power spectrum of the topography and gravity of the two profiles. From the relationships between the coherence and the wave-number of profiles. From the relationships between the coherence and the wave-number of profiles 7~(th) and 9~(th), it is obtained that the characteristic wavelengths respectively are 157 km and 126 km. Consequently the values of effective elastic thickness are 6.5 km and 4.8 km, respectively. However, the Te values merely are the minimum value of the lithosphere because the coherencemethod in a relative small region will generate a systemic underestimation. Why there is a so low Te value? In order to check the strength of the lithosphere beneath the Dabie Mts., the authore tries to outline the yielding-stress envelope of the lithosphere. It is suggested that the elastic layers in the crust and upper mantle are 18 km and 35 km, respectively. Since there exist a low viscosity layer about 3-5 km thickness, so it is reasonable that the decoupling between the crust and mantle occurred. So the effective thickness of the lithosphere can be estimated from the two elastic layers. Te is about 34 km. This is the maximum strength of the lithosphere. We can make an approximately estimation about the strength of the lithosphere beneath the Dabie Mts.: Te is about 20-30 km. The author believes that the following factors should be responsible for the low Te value: (1) the Dabie Mts. has elevated strongly since K_3-J_1. The north part of the Dabie Mts. elevates faster than the south part today; (2) there occur large active striking faults in this area. And in the east, the huge Tan-Lu striking fault anyway tends to decrease the lithosphere strength; (3) the lithosphere beneath the Dabie Mts. is heter-homogeneous in spatio-temporal; (4) the study area just locates in the adjacent region between the eastern China where the lithosphere thickness is significantly reduced and the normal western China. These factors will decrease the lithosphere strength.

攀西地区红格、新街岩体的岩石地球化学特征

The mafic-ultramafic layered intrusions in the Panxi, China contain large V-Ti-magnetite deposits. These layered intrusions are related with the Emeishan continental flood basalts in space and time. Two layered intrusions, Hongge and Xinjie have clear PGE mineralization at the base of the intrusions. Thus the detailed investigations of these two intrusions not only have a geological but also have an economic significance. This thesis aims to characterize the elemental and Sr-Nd isotopic features of diverse rock zones within the intrusion on the basis of systematic studies of the major, trace element and isotope ratios, therefore to constrain the petrogenesis, mantle source and evolution of the Hongge and Xinjie intrusions. Generally, both Hongge and Xinjie intrusions show the same Fe-Ti-rich and Si-M-poor characteristics. They are also enriched in rare-earth elements (REE) and large-ion lithophile elements (LILE) as well as in Sr-Nd isotope ratios (Hongge: initial Sr = 0.7056-0.7076, ε_(Nd)(t) and (Nd/Sm)_N-ε_(Nd)(t) plots, the Hongge intrusion has a similar elemental and isotopic features to the Emeishan low-Ti (LT) basalts, whereas the Xinjie intrusion was close to the Emeishan high-Ti (HT) basalt. Therefore, the Hongge intrusion may be co-genetic with the LT basalt, formed by the partial melting of the spinel-garnet transition mantle that had a slight enriched isotope character. In contrast, the Xinjie intrusion and the HT basalts are probably derived from the garnet-phases mantle with a primitive isotope character. The involvement of the components of mantle wedge into the source is considered to be the major reason of the REE and LILE enrichment and Nd isotope depletion in the Xinjie intrusion. In contrast with the systematic variations in TiO_2 content, Mg#, transition elements (Ni, Cu, Co), REE concentrations, and La/Yb, La/Sm ratios from the lower zone to upper zone, the different rock zones of the Hongge intrusion have no clear Sr-Nd isotope variations. This suggests that the Hongge intrusions were formed by the crystal fractionation from the same magma source. The rhythm may be formed by slow injection of the co-genetic magma during the crystal fractionation. The increase in K_2O and Al_2O_3 contents, REE abundance, and the degree of the REE fractionation in the base of the intrusion, together with the relatively low ε_(Nd)(t) value, may imply that the base of the Hongge intrusion was contaminated with the local crust rocks. Xinjie intrusion shows the clearly elemental and isotopic differences in diverse cumulus cycles. The observation of the systematic variations in TiO_2 content, Mg# value, transition elements (Ni, Cu, Co), REE concentrations, and La/Yb, La/Sm ratios in first cycle was not occurred in second cumulus cycle. In addition, the ε_(Nd)(t) value in second cumulus cycle is apparently higher than that of the first one. Thus the abruptly elemental and isotopic changes at the base of second cycle demonstrate that there is considerable new and depleted magma addition to the residue magma after the crystallization of the first cycle. These features are very similar to those of the well-known PGE-rich Bushveld and Stillwater layered intrusions. The PGE mineralization in Xinjie intrusion is much better than in Hongge intrusion. Therefore, the layered intrusion similar to the Xinjie in Panxi area posses the better prospects for the PGE deposits.

西江流域环境河水地球化学研究

River is a major component of the global surface water and CO2 cycles. The chemistry of river waters reveals the nature of weathering on a basin-wide scale and helps us understand the exogenic cycles of elements in the continent-river-ocean system. In particular, geochemical investigation of large river gives important information on the biogeochemical cycles of the elements, chemical weathering rates, physical erosion rates and CO2 consumption during the weathering of the rocks within the drainage basin. Its importance has led to a number of detailed geochemical studies on some of the world's large and medium-size river systems. Flowing in the south of China, the Xijiang River is the second largest river in the China with respect to its discharge, after the Yangtze River. Its headwaters drain the YunGui Plateau, where altitude is approximately 2000 meters. Geologically, the carbonate rocks are widely spread in the river drainage basin, which covers an area of about 0.17xl06 km2, i.e., 39% of the whole drainage basin. This study focuses on the chemistry of the Xijiang river system and constitutes the first geochemical investigation into major and trace elements concentrations for both suspended and dissolved loads of this river and its main tributaries, and Sr isotopic composition of the dissolved load is also investigated, in order to determine both chemical weathering and mechanical erosion rates. As compared with the other large rivers of the world, the Xijiang River is characterized by higher major element concentration. The dissolved major cations average 1.17, 0.33, 0.15, and 0.04 mmol I"1 for Ca, Mg, Na, and K, respectively. The total cation concentrations (TZ+) in these rivers vary between 2.2 and 4.4 meq I'1. The high concentration of Ca and Mg, high (Ca+Mg)/(Na+K) ratio (7.9), enormous alkalinity and low dissolved SiO2/HCO3 ratio (0.05) in river waters reveal the importance of carbonate weathering and relatively weak silicate weathering over the river drainage basin. The major elements in river water, such as the alkalis and alkaline-earths, are of different origins: from rain water, silicate weathering, carbonate and evaporite weathering. A mixing model based on mass budget equation is used in this study, which allows the proportions of each element derived from the different source to be calculated. The carbonate weathering is the main source of these elements in the Xijiang drainage basin. The contribution of rainwater, especially for Na, reaches to approximately 50% in some tributaries. Dissolved elemental concentration of the river waters are corrected for rain inputs (mainly oceanic salts), the elemental concentrations derived from the different rock weathering are calculated. As a consequence, silicate, carbonate and total rock weathering rates, together with the consumption rates of atmospheric CO2 by weathering of each of these lithologies have been estimated. They provide specific chemical erosion rates varying between 5.1~17.8 t/km2/yr for silicate, 95.5~157.2 t/km2/yr for carbonate, and 100.6-169.1 t/km2/yr for total rock, respectively. CO2 consumptions by silicate and carbonate weathering approach 13><109and 270.5x10 mol/yr. Mechanical denudation rates deduced from the multi-year average of suspended load concentrations range from 92-874 t/km2/yr. The high denudation rates are mainly attributable to high relief and heavy rainfall, and acid rain is very frequent in the drainage basin, may exceed 50% and the pH value of rainwater may be <4.0, result from SO2 pollution in the atmosphere, results in the dissolution of carbonates and aluminosilicates and hence accelerates the chemical erosion rate. The compositions of minerals and elements of suspended particulate matter are also investigated. The most soluble elements (e.g. Ca, Na, Sr, Mg) are strongly depleted in the suspended phase with respect to upper continent crust, which reflects the high intensity of rock weathering in the drainage basin. Some elements (e.g. Pb, Cu, Co, Cr) show positive anomalies, Pb/Th ratios in suspended matter approach 7 times (Liu Jiang) to 10 times (Nanpan Jiang) the crustal value. The enrichment of these elements in suspended matter reflects the intensity both of anthropogenic pollution and adsorption processes onto particles. The contents of the soluble fraction of rare earth elements (REE) in the river are low, and REE mainly reside in particulate phase. In dissolved phase, the PAAS-normalized distribution patterns show significant HREE enrichment with (La/Yb) SN=0.26~0.94 and Ce depletion with (Ce/Ce*) SN=0.31-0.98, and the most pronounced negative Ce anomalies occur in rivers of high pH. In the suspended phase, the rivers have LREE-enriched patterns relative to PAAS, with (La/Yb) SN=1 -00-1 .40. The results suggest that pH is a major factor controlling both the absolute abundances of REE in solution and the fractionation of REE of dissolved phase. Ce depletion in river waters with high pH values results probably from both preferential removal of Ce onto Fe-Mn oxide coating of particles and CeC^ sedimentation. This process is known to occur in the marine environment and may also occur in high pH rivers. Positive correlations are also observed between La/Yb ratio and DOC, HCO3", PO4", suggesting that colloids and (or) adsorption processes play an important role in the control of these elements.

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.

Sedimentary-volcanic tufts formed during the early Middle Triassic volcanic event in Guizhou Province and their stratigraphic significance

The sedimentary-volcanic tuff （locally called ＂green-bean rock＂） formed during the early Middle Triassic volcanic event in Guizhou Province is characterized as being thin, stable, widespread, short in forming time and predominantly green in color. The green-bean rock is a perfect indicator for stratigraphic division. Its petrographic and geochemical features are unique, and it is composed mainly of glassy fragments and subordinately of crystal fragments and volcanic ash balls. Analysis of the major and trace elements and rare-earth elements （ REE）, as well as the related diagrams, permits us to believe that the green-bean rock is acidic volcanic material of the calc-alkaline series formed in the Indosinian orogenic belt on the Sino-Vietnam border, which was atmospherically transported to the tectonically stable areas and then deposited as sedimentary-volcanic rocks there. According to the age of green-bean rock, it is deduced that the boundary age of the Middle-Lower Triassic overlain by the sedimentary-volcanic tuff is about 247 Ma.

Preparation of lanthanide hydrides of nanometric size by the catalytic method

Rare-earth metals were hydrogenated in the presence of TiCl4 catalyst in tetrahydrofuran (THF) at 45 degreesC under normal pressure. Transmission electron micrographs showed that the re. sulting lanthanide hydrides were in the form of nanoparticles. The rate of hydrogenation decreased with increasing atomic number of the rare-earth elements.