北祁连与块状硫化物矿床有关的早古生代火山岩的地球化学研究

Different conclusions from previous work are made from the geochemical study for the early Paleozoic volcanic rocks hosting massive sulfide deposits in the north Qilian Orogen. The main points are: (1)The geochemical characteristics of the basalts and rhyolites from the Baiyin deposit are not consistent with that of the volcanic rocks in the continental rift setting, but show the relationship with subduction. The basalts and rhyolites from the Baiyin deposit are probably individual tectonic slice piled by subduction, and there is no bimodal volcanic rock suite occurred in the Baiyin deposit. Zircon U-Pb dating constrains the magmatic emplacement of basalts and rhyolites at 475±10Ma and 453±12Ma, respectively. The basalts are characterized by enriched Th and Sr, and depleted Nb, Ta and Ti. They have relatively high Th/Nb ratios between 0.9 and 1.3. Their εNd(T) values vary from -1.2 to +3.4. The chemical and isotopic compositions display a typical subduction-related signature, and they suggest that an enriched component with the isotopic composition of EMII might have contributed to the generation of the Baiyin basalts. The basalts were likely formed in a mature island-arc or a volcanic arc built on comparatively young or thin continental crust in an active continental margin. The rhyoIites have low concentrations of LILE compared to the basalts. They do not seen to have a relationship with the basalts, because of their significantly higher εNd(T) values (+4.3～+7.7). The high and positive εNd(T) values also rule out their derivation from anatexis of the continental crust. A modeling study suggests that the source.of the Zhe-Huo and Xiaotieshan rhyolites is similar to boninite and IAT (island-arc tholeiite), and hence indicating an intra-oceanic arc environment. (2) The formation of the Shangliugou volcanic rocks from .Qilian area is also related to subduction. The basaltic andesite have low TiO_2(0.45～0.63%) and P_2O_5(0.04～0.09) content, and high Th/Nb ratios (0.3～0.6). They show flat REE patterns. Their εNd(T) values vary in a narrow range from +4.8 to +6.4. The chemical and isotopic compositions indicate that they are derived from a slightly depleted mantle source and are fromed in intra-island arc setting. The rhyolites show calc-alkaline trend. They show enriched LREE and fiat HREE patterns with obvious negative Eu anomaly. They have high Th/Ta ratios (5.0 ～ 11.7) and large negative εNd(T) values (-2.6 ～ -8.4). The rhyolites are formed in active continental margin and result from a mixed process of two endmembers, or crust assimilation. (3) The metal elements of the volcanic-hosted massive sulfide deposit have two sources, the copper and zinc are derived from rhyolitic magmas whereas the lead are probably related to old sediments overlying the rhyolites. (4) It is suggested here that the volcanic rocks hosting massive sulfide deposit in the north Qilian orogen, which are previously considered as a bimodal suite of Neo-proterozoic to middle Cambrian age in a continental rift, are virtually related to subduction magmatism in Ordovician age, and there might have no continental rift magmatism of Neo-proterozoic to middle Cambrian in the north Qilian.

塔里木盆地塔中地区寒武-奥陶系烃源岩古地温及成烃演化史研究

The present maturity of Cambrian and Ordovician source rocks in Tazhong area, Tarim basin, is studied using several organic petrology methods and conodont CAI method. The highest palaeotemperature that the Cambrian-Ordovician undergone is revealed by Laser Roman Microprobe (LRM) analysis and by simulating experiment of the kerogen chemical kinetics. In according to all above study, the thermal history of Cambrian and Ordovician is reconstructed based on numerical simulating approaches. The characteristics of secondary hydrocarbon generating are studied by inclusions analysis. The reflectances of the samples in the drills located in Tazhong area show that the maturities of Cambrian source rocks are in the stages of condense oil-dry gas, and that of Ordovician source rocks range from peak of oil generating to wet gas stage. The palaeotemperature data of Cambrian-Orovician source rocks from well Tacan 1, based on LRM analysis, are in coincidence with that from other methods. Also are the palaeotemperature data of Cambrian-Orovician source rocks in well Tacan 1 based on the simulating experiments of kerogen pyrolysis, similar to the homogenization temperatures of inclusions in the source rocks. Aaccording to the vitrinite inflectance data of the TZ12 well and Tacan 1 well, the paleotemperature gradients are analysized and reconstructed. These data show that the paleotemperature gradient in Tazhong area was the highest during Cambrian-Ordovician period, it was up to 3.5°C/100m. Following, the temperature gradient descended gradually and it reached to the lowest at present (2.2°C/100m). The histories of maturation and hydrocarbon generation of Cambrian and Ordovician source rocks in Tazhong area are researched systematically and quantitatively, the results show that periods of oil generation from Cambrian and Ordovician source rocks lasted for a long time from Ordovician to Carbonferious periods because the central Cambrian stratum in the north slope of Tazhong area is buried differently in depth. The top of the Cambrian entered into the peak of oil generation in middle-late Ordovician, and most area of the north slope of Tazhong area entered into the peak of oil generation in Carbonferious period, and on the uplift belt some of source rocks entered into the peak of oil generation in Permian period. In early Devonian, the central of the Lower Ordovician source rocks near the Manjiaer depression reached the peak of oil generation and near the top of the Tazhong uplift did not reached the peak of oil generation until early Cretaceous. The middle-upper Ordovician entered into the peak of oil generation in early-middle Jurassic. The time of the middle-upper Ordovician in the top of the uplift belt entering into the peak of oil generation was delayed, because the source rock was buried shallowly, and it did not reached the peak of oil generation until middle Cretaceous. Middle-upper Ordovician in the top of the north slope has been in the peak of oil generation now, it is consistent with the maturity (1.0-1.2%Ro) of the source rocks. The characteristics of the inclusions formed by kerogens are different from that by crystal-enclosed organic matters(OM) during secondary hydrocarbon generation of Cambrian and Ordovician source rocks. The secondary hydrocarbon generation mainly occurred in Mesozoic-Cenozoic period, in an area of about 9000km2 in the north slope. The intensity of the secondary hydrocarbon generation of Cambrian and Ordovician is up to 21kg/torg and 36kg/torg) respectively. Using the staged gas chromatography, the high-over maturated carbonate source rocks are analysized to release the adsorbed OM, inclusions OM and crystal-enclosed OM, respectively, and to evaluate their relative contributions to secondary hydrocarbon generation. The three periods of oil and gas migration and petroleum pools formation in Tazhong area are determined according to organic inclusions and solid bitumen.

华南震旦纪-寒武纪两期成磷事件及其地球动力学意义

Phosphorus is an important biological and ecological element that to a certain degree constrains ecological environment and nutrient (including carbon) cycling. Marine sedimentary phosphorites are the principal phosphorus supply of the mankind. In the eastern to southern margins of the Yangtze Craton, South China, there are two phosphogenetic events at the Doushantuo stage of the Late Sinian and the Meishucun stage of the Early Cambrian respectively, corresponding two explosion events of life across the Precambrian\Cambrian boundary. Phosphorus ores from the Sinian and Cambrian phosphate in South China can be classified roughly into two categories, namely, grained and non-grained phosphorites. Grained phosphorites, hosted in dolostone type of phosphogenetic sequences and with larger industrial values, occur mainly in margins of the Upper Yangtze Platform, formed in shallow-water environments with high hydraulic energy and influenced by frequent sea-level change. Non-grained phosphorites, hosted principally in black-shale type of phosphogenetic sequences and with smaller industrial values, are distributed mainly in the Jiangnan region where deeper-water sub-basins with low hydraulic energy were prevailing at the time of phosphogenesis. Secular change ofδ~(13)C, δ~(18) O, ~(86)Sr/~(87)Sr values of carbonates from Sinian and Cambrian sequences were determined. A negative abnormal ofδ~(13)C, δ~(18)O values and positive abnormal of 86Sr/87Sr values from the fossiliferous section of the Lowest Cambrian Meishucun Formation implies life depopulation and following explosion of life across the PrecambriamCambrian boundary. Based on a lot of observations, this paper put forward a six-stage genetic model describing the whole formational process of industrial phosphorites: 1) Phosphorus was transported from continental weathering products and stored in the ocean; 2) dissolved phosphates in the seawater were enriched in specific deep seawater layer; 3) coastal upwelling currents took this phosphorus-rich seawater to a specific coastal area where phosphorus was captured by oceanic microbes; 4) clastic sediments in this upwelling area were enriched in phosphorus because of abundant phosphorus-rich organic matters and because of phosphorus absorption on grain surfaces; 5) during early diagenesis, the phosphorus enriched in the clastic sediments was released into interstitial water by decomposition and desorption, and then transported to the oxidation-reduction interface where authigenic phosphates were deposited and enriched; 6) such authigenic phosphate-rich layers were scoured, broken up, and winnowed in shallow-water environments resulting in phosphate enrichment. The Sinian-Cambrian phosphorites in South China are in many aspects comparable with coastal-upwelling phosphorites of younger geological ages, especially with phosphorites from modern coastal upwelling areas. That implies the similarities between the Sinian-Cambrian ocean and the modern ocean. Although Sinian-Cambrian oceanic life was much simpler than modern one, but similar oceanic planktons prevail, because oceanic planktons (particularly phytoplanktons) are crucial for phosphate enrichment related to coastal upwelling. It implies also a similar seawater-layering pattern between the Sinian-Cambrian ocean and the modern ocean. The two global phosphate-forming events and corresponding life-explosion events at the Sinian and Cambrian time probably resulted from dissolved-phosphate accumulation in seawater over a critical concentration during the Earth's evolution. Such an oceanic system with seawater phosphorus supersaturation is evidently unstable, and trends to return to normal state through phosphate deposition. Accordingly, this paper put forward a new conception of "normal state <=> phosphorus-supersaturation state" cycling of oceanic system. Such "normal state <=> phosphorus-supersaturation state" cycling was not only important for the three well-known global phosphate-forming events, also related to the critical moments of life evolution on the Earth. It might be of special significance. The favorable paleo-oceanic orientation in regard to coastal-upwelling phosphorite formation suggests a different orientation of the Yangtze Craton between the Sinian time and the present time (with a 135° clockwise difference), and a 25° anti-clockwise rotation of the Yangtze Craton from late Sinian to early Cambrian. During the Sinian-Cambrian time, the Yangtze Craton might be separated from the Cathaysia Block, but might be still associated with the North China Craton.

中-新元古代海洋的硫和碳同位素的演化

Data on seawater carbon isotope in the Mesoproterozoic and Neoproterozoic is abundant. However, the sulfur isotopic age curve of seawater sulfates determined through the analysis of sulfur isotopic composition of marine evaporite is uncertain in the Mesoproterozoic and Neoproterozoic since evaporites are generally rare in Precambrian. The Mesoproterozoic and Neoproterozoic Carbonate Formations preserve not only the carbon isotopic records, but also the sulfur isotopic records of coeval seawater in the Huabei Platform and the Yangtze Platform, China. Sulfur isotopic composition can be determined by the extraction of trace sulfate from carbonate samples. Successive measurements of sulfur and carbon isotopic compositions of carbonate samples from the Mesoproterozoic and Neoproterozoic strata in the Huabei Platform and the Yangtze Platform was accomplished through the extracting of trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were obtained from analytical results of sulfur and carbon isotopes of the same sample without diagenetic alteration. The high-resolution age curve of sulfur isotope given in this paper may reflect the trend of variations in sulfur isotope composition of seawater sulfates during the Mesoproterozoic and Neoproterozoic. It can be correlated with the characteristics of variation in age curve of carbon isotope of coeval seawater carbonates. The δ34S values of seawater varied from +10.3-37.0‰ during the Mesoproterozoic, which took on oscillated variation on the whole. The δ34S values took on high values in the Mesoproterozoic Chuanlinggou stage, Tuanshanzi stage Tieling stage and in Neoproterozoic Jing'eryu stage. The average of those was about +30‰. The sulfates have low δ34S values in the Mesoproterozoic Yangzhuang stage and Hongshuizhuang stage, The average of those was all lower than +20‰. There occured large-amplitude changs in δ34S values of seawater during the Mesoproterozoic. Large-amplitude oscillate of 534S values occured in the intervals of 1600~1400Ma and 1300~1200Ma. The δ13C values of seawater are mostly negative in Changcheng stage of late Paleoproterozoic, -0 ± 1‰ range in Jixian stage of Mesoproterozoic , and the positive 2±2‰ commonly in early Neoproterozoic Jing'eryu stage. From 1000 Ma to 900 Ma, about 108 years interval of oceanic 513C record is shortage. At the end of Paleoproterozoic (1700 - 1600 Ma), the oceanic 813C values change from -3‰ to 0‰, but strongly oscillate near 1600 Ma. Two larger variations of seawater 513C values occur in the Mesoproterozoic: one is a cycle of about 4%o happens at ca. 1400 Ma; another is rise from >2‰ to>5‰ at ca. 1250 Ma and then become stable at the near 1000 Ma. There appears a large positive excursion over +20‰ in 534S value of ancient seawater sulfates in the early Doushantuo stage. Simultaneously, 8 C values of ancient seawater occur a positive excursion reaching 10‰. These allow δ4S values and 513C values to reach high values of+51.7‰ and +6.9‰, respectively. The range of variation in 834S values of seawater is relatively narrow and 513C values are quite high in the middle Doushantuo stage. Then, δ34S values of seawater become oscillating, the same happens in δ13C values. Negative excursions in 834S values and 813C values occur simultaneously at the end of the Doushantuo stage, and the minimum of δ34S values and δ13C values dropped to -11.3‰ and -5.7‰, respectively. The ancient seawater in the Dengying stage has high δS values and δ13C values. Most of the δ34S values of the trace sulfate samples varied between +23.6‰ and +37.9‰ except two boundaries of the Dengying Formation, and the S13C values of the carbonate samples of the Dengying Formation varied between +0.5‰ and +5.0‰. There appeared large negative excursion in 834S values and δ13C values of ancient seawater at the bounder of Precambrian-Cambrian. The isotopic characteristics of sulfur and carbon implicated that the organic productivity and isotopic fractionation caused by biology were low and the palaeoceanic environment was quite unstable during the Mesoproterozoic. The increase and subsequent oscillation of seawater δ13C value occurred from 1700 to 1600 Ma and near 1300 Ma may be responsible to the two global tectonic events happened at coeval time. The characteristics of variation in sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment, which became beneficial to inhabitation and propagation of organism. The organic production and the burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable that means the global climate and the environment possibly were fluctuating and reiterating after the global glaciation. The negative excursions of S34S values and δ13C values occurring at the end of the Doushantuo stage represent a global event, which might be relative to the oxidation of deep seawater. The isotopic characteristics of sulfur and carbon implicated that there were a high organic productivity and a high burial rate of organic carbon in the Dengying stage. It is obvious that the palaeoceanic environment in Dengying stage was stable corresponding and beneficial for biology to inhabit and propagate except for the two boundaries. The tendency of sulfur and carbon isotopic variations maybe resulted from the gradual oxygenation of ocean environment during the Dengying stage. It has been reported that the secular variations of the sulfur isotopic compositions in seawater was negative correlated with that of carbon isotopic compositions. However, our results show that it is not the case. They were negatively correlated in some intervals and positively in some other intervals of the Mesoproterozoic and Neoproterozoic. The difference in correlation may be associated with the changes in conditions of redox in oceanic environment, e.g. sharp change of the oxidation-reduction interface. The strong changes in global environment may induce the abnormality to occur in the biogeo chemical S and C cycles in the ocean and accordingly sharp Variations in isotopic composition of seawater sulfur and carbon during the Mesoproterozoic and Neoproterozoic. Simultaneously, the global tectonism caused large changes of 87Sr/86Sr ratios. The leading factor that causes the variation in isotopic composition is different in the different intervals of the Mesoproterozoic and Neoproterozoic. Thus, there may exist different models of the biogeochemical S and C cycles in the ocean during the Mesoproterozoic and Neoproterozoic.

句容海安区块热史、成烃史与二次生烃

Jurong -Hai'an block of lower Yangtz area is one of the important petroleum exploration area among the residual marine basins in the south China. In the history of the basin's evolution, the strongly compressing, napping, folding and deforming during Indosinian to Yanshan epoch resulted in destruction of the early formed petroleum pool. Therefore, the strategy exploration of the secondary hydrocarbon generation and later formation of petroleum pool was brought forward for petroleum exploration and planning in the study area..On the basis of tectonic and sedimentary as well as present-day thermal regime evolution, using vitrinite reflectance and apatite fission track data and the paleo-heat flow based method, the basin's thermal history is reconstructed and hence the strata's temperature history are obtained. In addition, the maturation histories of the main four sets of marine hydrocarbon source rocks in the block are calculated. Furthermore, taking the maturity in the end of early Cretaceous as the original maturity and according to the formulas fitted by the secondary hydrocarbon generation model, the secondary hydrocarbon generation potential of the four sets of source rock is evaluated.The results of thermal history reconstruction show that Jurong-Hai'an block was under an uniform thermal setting during the Caledonian to Hercynian period and characterized by middle heat flow (52~57rnW/ m2). The uniform thermal setting was divided during and after Indosinian to Yanshan epoch. Wuwei area of southern Anhui province was under the high heat flow setting(~90 mW/m2)between 236Ma and 137Ma; Jurong area of southern Jiangsu ,Huangqiao area and Subei basin reached its maximum heat flow of 90,84 and 78-82 mW/m2 at 101Ma,157Ma and 56Ma respectivelyThe study of secondary hydrocarbon generation shows that the upper Paleozoic and Triassic source rocks have excellent secondary hydrocarbon generation potential. Silurian source rock posses some secondary hydrocarbon generation. Cambrian source rock, however, nearly has no secondary hydrocarbon generation. Overall there are no advantages of secondary hydrocarbon generation in the southern area of Jiansu. The intensity of secondary hydrocarbon generation in North Jiangsu basin is definitely better than that in the southern area of Jiangsu.

Isotope geochronology of Dapingzhang spilite-keratophyre formation in Yunnan Province and its geological significance

On the basis of the geological field investigations and isotope geochronological studies the Sm-Nd isochron age (513 Ma?0 Ma), Rb-Sr isochron age (511 Ma? Ma) and K-Ar age (312-317 Ma) of the Dapingzhang spilite-keratophyre formation in Yunnan Province are presented. From these geochronological data it is evidenced that this suite of volcanic rocks was formed in the Cambrian and the parent magma was derived from a depleted mantle, which was influenced by crustal contamination and/or seawater hydrothermal

贵州遵义早寒武世黑色岩系地球化学研究

华南早寒武世黑色岩系赋存Ni-Mo-PGE、V-U、Se、磷块岩、重晶石（毒重石）、石煤等多种矿产，富含As、Se、Hg、Gd、Pb等多种对生态环境有害的元素，产出小壳、海绵骨针、大型双壳节肢动物等多种古生物化石，因而它在矿产勘查、环境保护、地史古生物等方面具有重要的研究意义。然而，目前这些方面的研究还处于积累阶段，许多科学问题还没有得到很好地解决，一方面是因为华南早寒武世地层划分不统一，缺乏精确的年代学数据；另一方面是因为沉积地球化学研究程度不高。为了深入认识早寒武世古海洋的环境特征和演化历史，促进统一的早寒武世地层的建立，本论文选择了扬子地台上的贵州遵义早寒武世中南村黑色岩系剖面为对象，进行了系统的沉积地质学和地球化学研究，取得了如下几个方面的重要认识： （1）中南村黑色岩系剖面从下到上由磷块岩层、富黄铁矿粘土岩层、“破碎层”、硅质(页)岩层、钒矿层、含粉砂黑色页岩层、镍钼矿层、含化石黑色页岩层、黑色页岩层和粉砂质页岩层10个岩层组成，具有两个明显的特征，一是沉积环境发生了变化，从剖面底部远岸的、砂质输入较少的远海环境逐渐过渡到剖面顶部近岸的、砂质输入较多的近海环境；二是剖面下部的地质活动相对较丰富，除了火山成因“破碎层”和热水成因硅质岩外，还含有三个重要的硫化物矿化层：富黄铁矿粘土岩层、钒矿层和镍钼矿层。 （2）磷块岩主要由碳氟磷灰石和自生石英组成，含少量自生重晶石和含钒伊利石；磷灰石具有“老磷块岩”型REE配分曲线：∑REE高，Ce明显负异常，MREE富集，HREE亏损；磷灰石的硫酸盐硫同位素较大，平均为38.1‰。由此可推测，磷块岩是在分层海洋的上升洋流区的氧含量最小带的沉积物-水界面上形成的，沉积、成岩过程中吸收了海水中的硫酸盐和REE；磷块岩中磷灰石所记录的早寒武世海水硫酸盐的硫同位素组成为36.6±1.6‰。 （3）黑色硅、泥质岩中，微量元素Ba、Ni、U、V和Mo含量总体上较高，元素/Sc值与有机碳/Sc值之间的相关性明显；有机碳同位素组成较低，为-34.3‰～-31.2‰，表明早寒武世海洋可能为具有分层结构、古生产力水平较高、静海缺氧环境等特点的古海洋。剖面上，元素/Sc值向上逐渐降低，13Corg向上变大，有机质中的REE组成向上变为海水型，表明从早期到晚期古生产力水平和缺氧程度在不断减弱。 （4）微量元素U/Sc值、Mo/Sc值，有机碳同位素组成，有机质中的REE特征等参数在硅质岩、“破碎层”、钒矿层、镍钼矿层中均显示明显的异常，暗示它们的形成与热水/热液活动有关。镍钼矿层处的地球化学异常与古海洋历史性调整有关，可作为“前三叶虫统”分阶的标志，其它层位的异常特征可以作为区域地层对比的标志。

贵州遵义地区早寒武世黑色岩系中镍钼多金属富集层的矿物学和地球化学研究

在新元古代-寒武纪交替阶段（~544Ma）的短短几百万年间，生物种类和数量剧增，这一事件被称之为“寒武纪生物大爆发”（Cambrian Exploration），同时在这一时期，也发生了全球的海洋缺氧事件（Ocean Anoxic Event，OAE）。这些事件造成了在世界范围内的寒武系底部普遍发育了一套富有机质的黑色岩系。在中国南方，从皖南、浙江经赣北、湘西北、贵州至云南一线，下寒武统黑色岩系的分布近2000公里。这些黑色岩系的发育程度在全球背景中很具特色，是全球背景中研究黑色岩系及其相关科学问题的理想场所。 我国南方大陆早寒武世黑色岩系广泛分布且层位稳定，并伴有Mo、Ni、Se、V、Ag、Au、PGE等多种元素富集层。由于其处在特殊的地球演化背景及地质条件，成为目前国内外研究的一个热点区域。基于此，本文在前人工作的基础上，以贵州遵义地区早寒武世黑色岩系中镍钼多金属富集层为研究对象，通过矿物学、元素地球化学、同位素地球化学等研究手段，探讨中国南方早寒武世黑色岩系中镍钼多金属富集层的成因机制。通过研究，取得以下几点认识： (1) 下寒武统镍钼多金属富集层中SiO2含量较低，MgO、Na2O、K2O、MnO、TiO2在炭质页岩和镍钼层中含量差别不大。镍钼多金属富集层中Fe、Ca、P的含量明显高于碳质页岩，这与镍钼层中硫化物、方解石和磷质的显著增加有关。 (2) 镍钼多金属富集层中微量元素Se、Mo、Cd、Ag、Tl、U、Ni，、Bi、Zn、Cu、V等均有较大富集，富集系数为n到n×103。其中尤以Se、Mo最为富集，两者的富集系数均超过30000，其中Mo元素的富集系数大于50000。 (3)通过多种地球化学指标判别，如Se在黑色岩系中超常赋存，U/Th比值远大于1，黑色页岩和镍钼多金属富集层的Ce具有负异常、Eu有微弱的正异常，多种成矿元素的相关关系等这些特征，都暗示了海底喷流热液和生物的共同作用。此外，黑色岩系中V/(V+Ni)的比值反映了它的沉积环境为缺氧环境。 (4)研究区下寒武统黑色岩系中镍钼多金属富集层的矿物组合以黄铁矿、白铁矿、针镍矿、辉砷镍矿、铁辉砷镍矿、紫硫镍矿、赫硫镍矿和碳硫钼矿为主。 矿物生成大多经历了两个成矿阶段：沉积－早期热液阶段和热液－生物阶段。 (5)根据电子探针分析，对于主要富集元素Ni、Mo而言，Ni以出现大量的镍矿物为特征。镍钼多金属富集层中Mo元素主要以“碳硫钼矿”（MoSC）的形式赋存。Se与As元素在硫化物中含量变化十分特征，如在黄铁矿中Se元素较少而As元素含量较高，在碳硫钼矿中情况相反，推测这是由于Se与As元素不同的地球化学性质以及上述两种矿物不同的形成期次造成的。 (6)同位素研究表明，镍钼多金属富集层的硒同位素的分布范围较窄，δ82/76Se范围为-1.56‰- +1.85‰,平均值+0.25‰。根据目前所测得的硒同位素数据，不支持从海水中还原金属元素沉积富集的机制。我们认为当硒通过海底喷流作用释放后，首先以类质同象的方式结合到硫化物相中，这一过程不会造成硒同位素的大的分馏。流体中剩余的少部分硒与海水混合，并且为藻类吸附而沉淀下来，这一过程会造成约1-2‰的硒同位素分馏。这一模式可较好的解释遵义地区下寒武统Ni-Mo-Se富集层的硒同位素组成特征和硒在不同物相中的分配形式。 (7) 镍钼多金属富集层和围岩的有机碳含量为1.75%～13.9%，平均9.16%，有机碳同位素组成为（δ13Corg）-30.6‰～-32.2‰,这一负偏移可能是由于寒武纪早期的海侵作用造成的。

华南下寒武统层序框架的初步构建―以遵义松林地区为例

华南下寒武统保存着国际著名的生物群（如澄江生物群），同时蕴藏着磷块岩、重晶石、稀土及Ni-Mo-PGE等丰富的矿产资源，因此，它一直为地质科学家们持续关注的热点之一。关于华南下寒武统的研究，前人在古生物学方面已经取得了卓著的成就，主要表现在国际权威期刊上（如期刊《Science》和《Nature》）已发表大量的关于澄江生物群的研究成果，对早期生命演化研究具有重要而广泛的影响。然而，华南下寒武统年代学及国际对比研究方面已明显滞后，公开发表的华南下寒武统的高精度、可靠的锆石U-Pb年龄数据至本研究论文截稿时止仍然仅有唯一的一个，即Jenkins et al. (2002)报道的国际前寒武系-寒武系界线层型候选剖面―云南晋宁梅树村剖面的朱家菁组中谊村段中部（第5层）钾质斑脱岩锆石SHRIMP U-Pb年龄（538.2 ± 1.5 Ma）。因而，华南下寒武统中的重要生物群、矿床及具全球对比意义的C同位素漂移事件缺乏地层精确年龄的约束，进而制约了早期生命演化理论、矿床成因解释及地层国际对比等方面研究的发展。 近来，发现华南下寒武统赋存独特的钾质斑脱岩层，它们在横向上广泛分布于云南东部、四川峨眉麦地坪、贵州西部（如织金和金沙岩孔）及北部（如遵义松林）、湖北宜昌泰山庙和湖南张家界等地区，在地层序列垂向上主要产出于朱家菁组中谊村段中部、石岩头组底部以及它们的相当层位。这些钾质斑脱岩既是建立地层框架等时层潜在的物质基础，亦是获取地层精确锆石U-Pb年龄的具重要意义的研究对象之一。因此，对它们进行系统研究可望改观华南下寒武统年代学及国际对比研究方面的落后现状。 同时，华南下寒武统广泛产出的磷块岩既具有重要的资源价值，另一方面，任一磷块岩层代表着一次独立的成磷事件，因而将华南地区下寒武统磷块岩进行区域上的对比研究，从而以磷块岩层作为等时层，对构建华南下寒武统地层框架具有重要的地层学意义。 此外，华南下寒武统产出的Ni-Mo多元素富集层广泛分布于扬子地台范围，西起云南东部，东部延至浙江诸暨地区，在NE-SW向延伸近1600 km，它既代 表了重要的成矿事件，亦为关键的地球化学异常层位。因此，对Ni-Mo多元素富集层进行区域上的对比研究，明确它在华南下寒武统各重要剖面的产出位置，对于构建华南下寒武统层序框架具有重要意义。 遵义松林地区的下寒武统因赋存Ni-Mo-PGE矿床及与滇东地区澄江生物群相当的遵义生物群而日益受到国内外地质学家们的广泛关注。该区牛蹄塘组底部产出磷块岩、钾质斑脱岩及Ni-Mo多元素富集层，与滇东地区梅树村剖面出露的地层具有潜在的可对比性。因此，本研究选取近年来日益受科学家们关注的遵义松林地区下寒武统作为研究对象，重点对该区牛蹄塘组底部的钾质斑脱岩开展矿物学、地球化学和年代学研究。同时，将遵义松林地区下寒武统剖面上磷块岩、钾质斑脱岩、Ni-Mo多元素富集层主要与滇东地区梅树村剖面的相应岩层进行地球化学对比研究。研究的目的在于通过对华南地区上述两条代表性的下寒武统剖面进行地层对比研究，初步构建华南下寒武统具时间、空间涵义的层序框架，从而约束华南下寒武统中的重要生物群、矿床及具全球对比意义的C同位素漂移事件的时间，进一步促进华南下寒武统的划分和全球对比。论文获得以下主要结论性认识： （1）滇东地区朱家菁组中谊村段中部钾质斑脱岩及其邻近的磷块岩可构成华南下寒武统层序框架的第一个标志层。这一标志层在贵州大部分地区（或华南地区的多数下寒武统剖面）缺失。该标志层的磷块岩稀土元素总量和Y含量高于新元古代陡山沱期磷块岩，低于遵义松林地区牛蹄塘组底部及其华南其它地区相当层位（石岩头组底部及戈仲伍组）的磷块岩。第一个标志层的钾质斑脱岩的原始岩浆为亚碱性系列的酸性岩浆，其典型特征为具有较低的Zr（变化范围144×10-6~291×10-6，平均196.4×10-6）、Nb（变化范围10×10-6~13×10-6，平均11.86×10-6）含量和较高的Zr/Nb比值（变化范围为12.63~24.24，平均值为16.55）。这一层钾质斑脱岩的锆石U-Pb年龄为538.2±1.5 Ma（Jenkins et al., 2002）。 （2）遵义松林地区牛蹄塘组底部钾质斑脱岩和磷块岩分别相当于滇东地区石岩头组底部钾质斑脱岩和磷块岩，它们构成华南下寒武统层序框架的第二个标志层。该标志层中钾质斑脱岩的原始岩浆性质为中性岩浆，其碱性程度高于朱家菁组中谊村段中部钾质斑脱岩的原始岩浆。相对于中谊村段中部钾质斑脱岩，该层位的钾质斑脱岩具有高的Zr(变化范围187.0910-6~391.5710-6，平均值318.4010-6)、Nb（49.6910-6~140.0010-6，平均值90.6810-6）含量和低的Zr/Nb（2.60~4.32，平均值3.61）比值。该钾质斑脱岩的年龄为518 ± 5 Ma。该标志层的磷块岩以极其富REE和Y为特征，其稀土元素总量平均值为636.01×10-6，Y含量平均值262.43×10-6，明显高于滇东地区中谊村段磷块岩（∑REE平均值为195.45×10-6，Y含量平均值为91.2310-6），它们代表早寒武世时期一次特殊的以极其富REE和Y为特征的成磷事件。 （3）Ni-Mo多元素富集层可以作为构建华南下寒武统层序框架中的第三个等时标志层。滇东地区梅树村剖面的Ni-Mo多元素富集层被重新校正在玉案山组底部（即13层，Ni、Mo含量分别为135×10-6和583×10-6）。Ni-Mo多元素地球化学标志层的典型特征为在剖面上具Ni、Mo等多种微量元素及贵金属元素的最高异常。该标志层的Re-Os年龄为537~542 Ma，可能代表的不是地层层序的年龄。 （4）初步建立华南下寒武统时间框架。约束了华南地区下寒武统Ni-Mo-PGE矿床的下限年龄应为518 ± 5 Ma。同时，该时间框架亦约束了滇东地区澄江生物群及最古老三叶虫的下限年龄（518 ± 5 Ma），考虑到石岩头组底部钾质斑脱岩的产出位置与玉案山组中部澄江生物群的产出层位存在相当的距离（大于80 m），因此，前人对澄江生物群的推测年龄（525~530 Ma）可能有些偏老。此外，初步约束了华南地区具全球对比意义的C同位素正漂移事件的年龄（538~518 Ma）。该时间框架是建立在两个相互支持的地层高精度锆石SHRIMP U-Pb年龄的基础之上，而国际前寒武系-寒武系界线年龄的最新研究成果为542 Ma，因此，它支持将华南地区的前寒武系-寒武系界线置于朱家菁组中谊村段中部钾质斑脱岩层（第5层）的下伏地层的方案。结合华南地区最新的地层古生物学研究成果（朱茂炎等，2001；Zhu et al., 2003），将这一界线置于朱家菁组中谊村段底界可作为一种合理的选择。

扬子地台晚震旦至早寒武世沉积碳同位素研究

震旦-寒武交变期是地史上一个重大转折期，从隐生宙向显生宙过渡，海、陆、空发生了显著不同的变化，是一个具有特殊意义的过渡时期。中国扬子地区广泛发育的海相沉积层序有效地记录了震旦一寒武交变期重要的地质事件，因此为研究该时期大气圈、生物圈、岩石圈和水圈的相互联系提供了独一无二的场所。在前寒武纪一寒武纪地质研究中，由于缺少标志性生物化石，行之有效的生物地层学方法在上前寒武系的划分和对比中受到很大限制，沉积有机，质干酪根和相应碳酸盐的稳定碳同位素分析已经成为全球对比和划分的一个极为重要的的研究方法。尽管一些学者对扬子地台进行了多年的地球化学研究，使用碳酸盐和与之共生的有机质碳同位素组成对广泛的扬子地台变化的沉积环境进行研究还很欠缺、对分析和探讨该时期的生命演化过程和环境变化的关系研究方面还不足。本研究是以中国扬子地区为研究范围，用沉积碳酸盐和与之共生的有机质碳同位素组成对广泛的扬子地台变化的沉积环境（台地相、盆地相、过渡地带）进行分析，初步建立了一个地球化学模型，用于解释震旦一寒武交变期沉积地球化学记录，分析和探讨区域扬子地台碳循环和环境变化与地质事件之间的内在和外在联系：（1）南沱期：有机碳同位素组成（瓮安剖面平均值在-35.0‰左右）表现为较强负异常。地球被称为雪球（Snow-ball）或部分冰雪覆盖球体（Slush-ball），水体滞留和水动力不强，原始产率较低，物源以深源为主；生物不发育，主要是细菌和低等的真核细胞生物；空气和海水的气体通过冰裂缝进行交换，促进了碳酸盐的溶解；有机碳循环主要通过厌氧过程，比如细菌硫酸盐还原作用进行。（2）陡山沱期和灯影期：南沱晚期一陡山沱早期，海水的碳酸盐碳同位素组成短期仍然较负（瓮安剖面的δl3Ccarb-avg为-2.8‰ 松桃剖面1、2的δ13Ccarb-avg分别是-3.5％0和-8.6％。）；有机质的碳同位素组成总体呈现正漂移（瓮安护3Corg－avg：-26.3‰；南明剖面的δ13Corg-avg高达-26.7‰），这正是全球分布的“帽”碳酸盐出现的时期：接近地表的火山去气作用释放出较之现代350倍的CO2，导致地球迅速变暖，冰雪融化，大陆风化作用加强，海平面上升，“雪球，，转化为“温室，大气中大量的CO2快速转化为碳酸钙沉入海水中。全球可能处于一个异常高的海洋沉积速率时期。随后陡山沱组的护3Ccarb值显著上升，暗示了这一时期生物作用加强，有机碳埋藏速率明显提高，有机碳和还原硫埋藏的增加，导致上层海水345的富集，硫同位素组成较高。热液作用和上升洋流作用促成了瓮安磷矿的形成和瓮安生物群的繁盛。在南沱冰期后的陡山沱期和灯影期，高的别3c的出现主要是由于进行光合作用的海洋植物群体产率的迅速增加、海洋沉积速率的升高、海洋深部水柱中缺氧层的存在、热液活动、上升洋流作用、海水分层结构引起的，而短期同位素组成的负漂移和生物产率的变化则可能是区域事件所造成。明显的碳同位素组成负漂移出现在前寒武／寒武界线附近，这反映了碳短期变化的翻覆，与震旦纪末生物绝灭、环境变化的地质事件相符合。（3）牛蹄塘期：本研究结果发现，在牛蹄塘组／郭家坝组底部黑色岩系中，有机碳、无机碳、有机硫、黄铁矿硫同位素组成值相对较低，有机碳和黄铁矿含量相对较高。δ3Corg-avg和δ3Ccarb-avg分别是-33.9士0.7‰和-2.5＝0.4‰；TOC＞0.5；黄铁矿平均含量为0.96％间变化；黄铁矿（δ4ScRs）和有机硫同位素组成（δ34SOBS）平均值分别为0.3士7.5‰和3.4土7.1‰。由于牛蹄塘初期的环境变化频繁和不稳定，扬子区处于一段特殊的时期，碳、硫同位素组成延续上震旦统的负漂移现象，海侵事件、还原环境、缺氧事件、裂谷作用火山喷发、、气液喷溢、热水作用等造成海水相刘较深，有机碳埋藏量增大，多金属富集成矿。在牛蹄塘中晚期碳同位素组成趋于稳定，碳同位素组成重化，有机碳和黄铁矿含量降低：碳酸盐和有机质的碳同位素组成平均值分别是0.31±1.0‰和-31．41．3％。（沙滩），呈现稳定的正漂移；TOC平均值是0.8％；沙滩剖面郭家坝组中上部样品的黄铁矿平均含量0.5％；δ34SCRS-avg和δ34SOBS-avg为17.8士2.0‰和16.9±1.8‰。在牛蹄塘中期，随着大气圈和水圈中CO2含量降低、环境稳定，促使寒武纪生物繁盛，可能与增加的寒武系生物产量和微生物作用有关。对牛蹄塘期的环境情况有如下分析：随着全球变暖、海平面迅速上升，上升洋流活跃，由于分层海水的存在，海水在氧化带附近及其上部具有较高的有机物生成率，使寒武纪初期成为形成植物繁衍和带壳动物爆发的重要时期。碳同位素组成由震旦一寒武交变期的不稳定负漂移变化到稳定正漂移，这与世界其它地区的变化相一致。下寒武统富有机碳和黄铁矿的黑色页岩沉积，暗示了早寒武世缺氧环境的存在。（4）凯里期：早中寒武世交变期有机碳和无机碳同位素组成规律的变化，出现在扬子地台台江剖面上。有机质埋藏的变化，与生物从下寒武到中寒武统的变化相联系。碳酸盐和有机碳同位素组成的变化规律，反映了震旦一寒武交变期沉积环境的多变和震旦一寒武交变期碳循环的波动，这与变化的古环境背景、环境条件和生物演化的变化相互联系。碳酸盐碳同位素组成反映了海水最初的同位素信息；海底热液作用和上升一洋流作用可能成为影响碳同位素组成的重要因素。然而，各一地区在同一时期存在相似性，也有很大的不同，所以针对区域和局部事件，还需要进一步研究和探讨。

扬子地块周边C、P硅岩建造中硒的富集机理对比研究-以渔塘坝、紫阳富硒区为例

在自然界中存在一套由硅质岩、泥质岩／页岩或板岩、碳酸盐岩和粉砂岩组成的沉积建造，并以富含有机质和菌藻微生物等为特征，沉积厚度较大，岩石类型以硅岩为主，称之为“硅岩建造”。硅岩建造中的硅质岩不仅是许多重要矿种（如金、硒、铀、钒、磷、锰、铂族元素、重晶石和黄铁矿等）的赋存层和含矿岩系的重要岩类，而且由于它形成于特定的地球化学条件下，能够反映出某些沉积相带特殊的地质背景，另外，硅质岩本身就是一种生物岩，对探讨生物成岩、成矿作用有重要意义。所以对硅岩建造及其内硅质岩研究具有十分重要的理论意义和实用价值。因此，本论文选择扬子地块周边寒武系（南秦岭紫阳硒富集区）、二叠系（湖北恩施双河渔塘坝硒矿床）富硒硅岩建造为研究对象。通过岩石地球化学、同位素地球化学、矿物学以及流体包裹体等方法从含硒规律、岩石成因、沉积环境、成矿流体性质等方面，分别对对两个不同时代或不同层位的富硒硅岩建造开展了系统的地球化学对比研究；并从矿物学、包裹体成分及物理化学条件等方面对渔塘坝硒矿床的成因作了探讨。通过研究，取得了以下主要认识：1渔塘坝硒矿区和紫阳硒富集区富硒硅岩建造岩石以硅质岩为主，硅质岩中5102含量范围分别为64.2％-95.84％和63.62％-95.24％。同时包括部分碳质硅质岩丫碳质页岩 和碳、硅板岩及含腐泥层的石煤；渔塘坝硒矿床硅质岩中Se含量大于80ug/g的样品均采自下二叠统茅口组的硅质岩段内，紫阳下寒武统硒富集体中硅质岩中硒的含量最高（可达278ppm）。2微量元素研究表明，两地区富硒硅质岩中均含有较高的Cu，Ni、V、As、Sb、Cr，且U／Th＞1。在U-Th、Zr-Cr和P2O5-Y相关图以及Fe-Mn-（Cu+Co+Ni）三角图上，两研究区内硅质岩样品点均落于热水沉积区。渔塘坝硒矿区硅质岩的REE总量较低，平均为38.9×10-6，紫阳硒富集区硅质岩REE总量除个别较高（达110×10-6以上）外，总体也较低（12.0-37.6）×l0-6；另外，从稀土元素配分模式看，两地区硅质岩均有较明显的Ce负异常，且Eu从无明显Eu异常到出现正Eu异常。都反映出热水沉积硅质岩的特征。从si和O同位素组成来看，两个地区硅质岩的δ3051和δ18O值也总体位于热水成因硅质岩区域内。根据隧石一水的氧同位素分馏方程计算得知，两研究区硅质岩的形成温度分别为46℃-72℃和78.6℃-126.20℃。地球化学特征表明，两地区富硒硅质岩均来自热水沉积作用。另外，渔塘坝硒矿区硅质岩中Cr含量较高，且存在腕足类生物化石；紫阳硒富集区硅质岩中Ba及有机质含量较高，且存在叶琳生物标志化合物。结合两地区碳同位素组成特征（渔塘坝地区δ13c为正值，可能和上扬子区早、晚二叠世之间多期次喷发的火山活动，造成地球史上二叠纪生物大灭绝有关；紫阳地区δ13C为负值，说明碳同位素来源于沉积有机物质），暗示两地区硅质岩的成因可能与火山沉积作用有关，且在成岩过程中有部分生物的参与。3渔塘坝赋矿硅质岩硫同位素组成具有较高的负值，表明矿床形成于缺氧的海盆内：紫阳硒富集区形成黄铁矿的硫主要来自海水硫酸盐。4系统研究了渔塘坝硒矿区硒的矿物学，显示硒以自然硒、独立矿物、类质同像及有机吸附四种形式赋存于矿床中。废弃石煤堆中的自然硒矿物，是自然因素和人为活动共同干预的结果，并非石煤的缓慢自燃的结果。5对研究区成矿流体中包裹体均一温度、盐度和密度进行了系统研究，结果显示：两地区的流体包裹体以原生包裹体为主，数量较多且形态复杂；研究区（渔塘坝硒矿和紫阳硒富集区）成矿流体处于中一低温（ 190-250）℃和（120-155）℃条件。渔塘坝硒矿区石英和方解石包裹体内的流体盐度分别为（5.9-10.l）B％和（3.9-4.5）WB％，紫阳硒富集区流体盐度为（1.2-2.8）WB％，后者流体盐度明显低于前者。流体密度经计算分别为0.79-0.79／cm3和0.69-0.969／cm3。重点对渔塘坝硒矿区的石英和方解石包裹体进行了拉曼光谱成分测试，结果显示：包裹体成分以H2O和N2为主，含少量 CH4、C2H4、C2H6、C3H5、C4H6、C4H4和C6H6等成分，说明成矿溶液介质主要为具有还原性质的水溶液，其成矿条件具还原性的特点。6渔塘坝硒矿区成矿物理化学条件的研究表明，即富硒成矿流体为中低温（190-250）℃、压力平均为60Mpa。成矿早期02、eZ相对较低，乃较高，且fS2/fSe2＞l，有利于硫化物沉淀在成矿主阶段，随着硫化物的沉淀，fS2和fSe2相应增大，且fO2较高。高的fO2阻止了硒进入硫化物，而有利于硒化物的形成。 7系统研究了富硒硅岩建造的沉积环境和构造环境特征，认为渔塘坝硒矿床中富硒硅质岩主要形成于浅海滞留的盆地沉积环境，紫阳下寒武统硅质岩沉积环境属于深水滞留沉积环境；渔塘坝硒矿床主要形成于拉张的断陷盆地中，紫阳硒富集体则形成于拉张的裂谷环境。

Ubuntu and the Obligation to Obey the Law

Nkiruka, M., Ubuntu and the Obligation to Obey the Law, Cambrian Law Review. Vol. 37. 2006. p. 17 RAE2008

The relevance and admissibility of prior sexual history with the defendant in sexual offence cases

Kibble, N, ?The Relevance and Admissibility of Prior Sexual History with the Defendant in Sexual Offence Cases? (2001) 32 Cambrian Law Review 27-63 (cited with approval by HL in R v A(2) [2002] AC 45) RAE2008

John Austin, H. L. A. Hart... Oh, And W. Jethro Brown!

Ireland, R. W., Cambrian Law Review, 34 pp.57-69 RAE2008

The date and authorship of Culhwch ac Olwen: a reassessment

Rodway, S. (2005). The date and authorship of Culhwch ac Olwen: a reassessment. Cambrian Medieval Celtic Studies. 49, pp.21-44. RAE2008