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.

山东西部中生代碳酸岩和火山岩的地球化学特征及其成因研究

On account of some very peculiar features, such as extremely high Sr and Nd contents which can buffer their primary isotopic signatures against crustal contamination, deep-seated origin within mantle, and quick ascent in lithosphere, carbonatites are very suitable for deciphering the nature of sub-continental lithospheric mantle(SCLM) and receiving widespread attentions all around the world. The Mesozoic carbonatites located in western Shandong was comprehensively investigated in this dissertation. The extremely high REE concentrations, similar spider diagrams to most other carbonatites around the world and high Sr. low Mn contents of apatite from carbonatites confirm their igneous origin. The K depletion of carbonatites from this studies reflect the co-existing of carbonatite melts with pargasite+phlogopite lherzolite rather than phlogopite lherzolite. Geological characteristics and their occumng without associated silicate rocks argue against their origin of fractionation of or liquid immisibility with carbonated silicate melts. In contrast to the low S7Sr/86Sr and high l43Nd/l44Nd of other carbonatites in the world, carbonatites of this studies show EMU features with high S7Sr/86Sr and low l4jNd/144Nd ratios, which imply that this enriched nature was formed through metasomatism of enriched mantle preexisted beneath the Sino-korean craton by partial melts of subducted middle-lower crust of Yangtze craton. In addition to carbonatites, the coeval Mesozoic volcanic rocks from western Shandong were also studied in this dissertation. Mengyin and Pingyi volcanic rocks, which located in the south parts of western Shandong are shoshonite geochemically. while volcanic rocks cropped out in other places are high-K calc-alkaline series. All these volcanic rocks enriched in LREE and LILE. depleted in HFSE, and show TNT(strong negative anomalies in Ta, Nb. Ti) patterns in spider diagrams which are common phenomena in arc-related volcanic rocks. The Sr-Nd-Pb isotopic systematics reveal that the volcanic rocks decrease gradually in 87Sr/86Sr, 206Pb/204Pb, 20SPb/204Pb and increase in TDM from south to north, suggesting the distinction of SCLM beneath Shandong in Mesozoic is more explicit in south-north trending than in east-west trending. The variable features of SCLM can be attributed to the subduction of Yangtze craton beneath Sino-Korean craton, and subsequent metasomatism of SCLM by partial melts of Yangtze lower crust in different extent.

鲁西临朐地区中生代铁寨杂岩体的岩石化学与地球化学特征及其成因研究

The Tiezhai intrusive complex is located in the north of the Luxi block, Shandong province, eastern China. It lies ～30 km west of the Tanlu fault, and is at the cross of the Wujing and Jiushan faults. The Tiezhai complex was formed about 120～130 Ma, when large-scale magmatism was active in eastern part of North China. This paper carries out petrochemical and geochemical study on the Tiezhai intrusive complex, and discusses its genesis in detail. The Tiezhai intrusive complex can be subdivided into three rock series. The first is the gabbro-diorite series formed in early stage. Its composition variation shows 01 and Cpx fractional crystallization trend. The second is the porphyritic diorite and monzonite series, showing dominating Hb fractional differentiation. Their composition variation shows Hb fractional crystallization trend. The third is the porphyritic quartz monzonite with K-feldspar megacrysts, showing weakly Hb and Bi fractional crystallization trend. All types of rocks in the Tiezhai complex are belonging to the high-K cac-alkaline series. They have elevated Sr (450-1660 ppm), Ba (210-1780 ppm) and relatively low Rb (30-100 ppm). For the gabbro-dioritic rocks in the early stage, the abundances of Ni (20-250 ppm), Cr (50-350 ppm), V(l30-250 ppm) and Co (20-40 ppm) are high, indicating a mantle origin. All rocks have negative anormalies of Nb, Ta, Ti and P, and enriched LREE and strong differentiated REE patterns. The porphyritic monzonites and quartz monzonites have very low HREE, Yb and Y contents and positive Eu anormalies, similar to adakite. Most rocks have lowε_(Nd)(t) of-1.5～-10.9, and high (~(87)Sr/~(86)Sr)_i of 0.704～0.709. The data have characters of enriched lithosphere mantle (EMI). In summary, the Tiezhai intrusive complex was inferred to be generated by a mantle derived magma through fractional crystallization. When the primary magma gathered in some place between crust and mantle, the crystallization started and causing magma evolution. The remaining / evolved magma ascended and emplaced again and again in the upper crust in Tiezhai area. Then Tiezhai complex formed. The porphyritic monzonites and quartz monzonites have major and trace element characters of typical adakite, but they are likely to be generated by Hb fractional crystallization.

安多地区早中侏罗世岩浆岩岩石地球化学和同位素年代学研究及其对构造演化的制约

Anduo area is located in the Central Tibet, the middle segment of the Bangonghu-Nujiang suture. Anduo Block is the northern part of Lhasa terrane. The relationships among the different geological bodies were determined during the 1: 250000 regional geological surveying. Petrography, petrologic geochemistry, isotopic geochemistry and geochronology of igneous rocks from the suture and granitoids from Anduo Block were analyzed systematically as a whole for the first time. Then, their tectonic setting and history are discussed.Anduo ophiolitic melange consists of metamorphic peridotites, cumulates, plagiogranites, sheeted dykes swarm, pillow lava and radiolarian cherts. The concentration of Cr and Ni in the metamorphic peridotites is very high, with Mg# about 0.94 ~ 0.97, higher 87Sr/86Sr and Pb isotopic ratios, and lower 143Nd/i44Nd ratio. LREE is enriched relative to HREE and positive Eu anomaly is very clear. The REE distribution curve is U shape. Nb and Ta anomalies from cumulate gabbro and sheeted dyke swarm are not clear, while that are slightly negative from pillow lava. Plagiogranite belongs to strong calc-alkaline series with high Si, middle Al, low Fe, Mg and low K contents. Eu anomaly (~ 1.23) from plagiogranites is slightly positive. The character of all components of ophiolite is similar to that of the MORB, while to some extent the ophiolite was influenced by crustal material. Anduo ophiolite formed in a mature back-arc basin. Additionally, intermediate acidity volcanic rocks within Anduo phiolite melange are island arc calc-alkline rocks related to ocean subduction.The early-middle Jurassic plutonic rocks are tonalite, granodiorite bearing-phenocryst, magaporphyritic hornblende monzogranite, magaporphyritic monzogranite, monzogranite bearing-phenocryst and syenogranite in turn. They belong to calc-alkaline series which developed from middle K to high K series temporally. REE distribution curves of all plutonic rocks are similar and parallel to each other. SREE and negative Eu anomaly values decrease. In the multi-element spider diagram, the curves of different plutons are similar to each other, but troughs of Nb, Sr, P and Ti from young plutons become more evident. This suggests that thereare some closely petrogenetic affinities among plutonic rocks which make up amagma plutonism cycle of the early-middle Jurassic. Magma source is mainly crustal,but abundant mafic microgranular enclaves within granitoids indicate that crastalmagma should be mixed with mantle-derived magma and the mantle-derived magmadecreased subsequently. Tonalite has features of I-type granite, magaporphyriticmonzogranite is transition type, and monzogranite bearing-phenocryst is S-typegranite. The characteristic of granitoids from Anduo Block suggest that the formingtectonic setting is active continental margin.Reliable zircon U-Pb SHRIMP ages are obtained in the study area firstly. Plagiogranite from the Anduo ophiolite of the Bangonghu-Nujiang suture is 175.1 Ma, and granitoids from Anduo Block is 172.6-185.4 Ma. Additionally, plagioclase from the plagiogranite dates a 40Ar/39Ar age of 144 Ma, while biotite and hornblend from granitoids of Anduo Block give a 163-165 Ma.Similar cooling ages of plagiogranite from the Anduo ophiolitic melange and granitoids from Anduo Block and the spatial distribution of the ophiolitic rocks between Anduo, Naqu, and Shainzha area suggest that bilateral subduction of the Bangonghu-Nujiang oceanic basin took place in the early-middle Jurassic. During this subduction, Anduo ophiolitic rocks were related to north subduction of the Bangonghu-Nujiang oceanic basin and Anduo back-arc basin spreading, while granitoids from Anduo Block were related to south subduction.

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。

碳酸盐岩上覆红色风化壳中风化组分确定的一种新模式

确定化学风化剖面的风化组分来源是一个重要而又困难的问题,通过对贵州省平坝白云岩风化剖面中Sr同位素组成的研究,揭示了典型就位白云岩风化剖面的Sr同位素特征,验证87Sr/86Sr与Nb/Sr比率的图解模式对碳酸盐岩风化剖面的适用性,提出了87Sr/86Sr与Nd/Sr比率的图解新模式.研究认为,该模式不仅对白云岩的化学风化具有明显的指示意义,也更好地补充和限定了87Sr/86Sr与Nb/Sr比率的图解所反映出的矿物组分和风化过程.这一研究结果将为风化剖面中Sr同位素的定量研究提供重要的区分指标.

层控夕卡岩型矿床成矿系统的元素活动性及质量迁移——以铜陵冬瓜山铜矿床为例

应用改善了的质量平衡方程研究冬瓜山层控夕卡岩型铜矿床成矿系统的元素活动性及质量迁移,结果表明:系统中Zr ,Hf ,Y和Nb 为不活动元素,其余均为活动元素。主量元素中仅CaO 为迁出组分,其质量迁移量为84 % ,其余均为带入组分,带入量最大的SiO2 的质量迁移量高达2384 %;稀土元素均为带入组分,其中,中稀土较轻稀土和重稀土的活动性更强;其它微量元素中,带入序列由强到弱为:Cr →Ta →Sn →Th ,迁出序列由强至弱依次为:U →Sb →Ni →Sr →Ba →Rb →Co →W;成矿元素Cu 和Ag 为带入组分,其中Cu 的带入量最大,质量迁移量高达1200 %。本文还得出两点具普适性认识: ①稀土元素较其它微量元素对体系条件的变化更为敏感,且往往表现出明显的规律性变化,能更好地示踪地质地球化学过程。②不同元素在不同体系中的行为特征差异极大,仅凭经验判定某一元素为不活动元素往往不可靠。因此,在开展质量平衡研究时,首先采用适当方法确认体系的不活动元素是一项不可或缺的前提工作。

大兴安岭中段二叠系大石寨组细碧岩的岩石学地球化学特征及其成因探讨

大兴安岭中段林西地区二叠纪大石寨组下部的细碧角斑岩建造记录了大石寨裂陷槽早期的发育历史，因而对其成因和构造环境的研究具有一定的意义。本文在详细地野外工作基础上，对二叠系大石组的细碧岩进行了较为系统的岩石学、元素地球化学及同位素地球化学研究。结果表明，细碧岩的岩石类型为玄武岩、玄武安山岩、安山岩、橄榄组安岩和粗安岩（或歪长粗面岩），属于拉斑玄武岩岩石系列；细碧岩的主量元素质量分数及变化范围类型似于N－MORB玄武岩；与正常洋中脊玄武岩相比较，细碧岩的LILE元素明显富集，HFSE元素的质量分数与大洋中脊玄武岩（N－MORB）相接近，Nb,Ta明显亏损；细碧岩的稀土元素分配模式具平坦型；（^87Sr/^86Sr)t为0．7013－0．7056。细碧岩形成于大石寨裂陷槽早期裂陷阶段弧后盆地局部扩张的构造环境；细碧岩是由拉斑玄武质岩浆在上升过程中热卤水的严重混染后喷出地表结晶而形成的。

可见光响应光催化剂K4Ce2Ta10O30、K4Ce2Nb10O30及其固溶体的电子结构

基于密度泛函理论（DFT），采用平面波赝势（PWP）DA及广义梯度近似（GGA）方法，对可见光响应的光催化剂K4Ce2Ta10O30、K4Ce2Nb10O30及其固溶体进行电子结构的第一性原理计算．结果表明，光催化剂K4Ce2Ta10O30和K4Ce2Nb10O30的导带分别主要由Ta5d和Nb4d组成，处于高能级的电子未占据态的Ce饷其有很明显的重迭，但由于其高度局域特性，不能很好地参与光生电子在导带中的传导，从而对光催化活性的贡献很小；而其价带则由O2p与Ta5d（Nb4d）的杂化轨道组成，同时电子占据态的Ce4f对价带也有一定的贡献，各个电子轨道对能带结构的贡献决定了该系列可见光响应光催化剂的物理化学和光催化特性．固溶体系列中随着Nb含量的增加，其吸收光谱依次红移，带隙变窄，导带底变低，光生电子的还原能力降低．在同溶体K4Ce2Ta10-xNbxO30（x=2，5，8）中，由于Ce4f仇道对价带顶的贡献相对较小，固溶体的价带顶低于K4Ce2Ta10O30、K4Ce2Nb10O30的价带顶，光生空穴的氧化能力相对较强．该系列光催化剂的电子结构分析结果与光催化水分解的活性实验结果有很好的一致性.

辽东五龙地区燕山期侵入岩类同源岩浆演化微量元素、同位素证据与金矿成矿

辽东五龙地区中生代燕山期侵入岩类在时空上与金矿关系密切。该类侵入岩具有接近的微量元素Th／U、Zr／Hf、Nb／Ta值。随着不同岩石类型中的SiO2、MgO的含量的变化，(^87Sr／^66Sr)i和(^143Nd／^144Nd)i值保持不变，说明岩浆在侵位过程中没有明显受到围岩物质混染，且该类侵入岩有着相同的岩浆源区。Sr、Nd同位素组成表明成岩物质以下地壳为主。三股流花岗岩和矿石有相似的Pb同位家组成，结合含金石英脉(矿体)切穿已固结三股流花岗岩的地质事实，暗示了三股流花岗岩不太可能是直接的矿质提供者，推测成矿物质与成岩物质主体来自深部的同一岩浆源区，金矿成矿是同一岩浆源区岩浆演化不同阶段的产物。

临沧锗矿床的微量元素地球化学

采用ICP—MS测定了临沧锗矿中51个含矿煤、5个无矿煤、9个硅质岩样品的微量元素含量，并与基底二云母花岗岩进行对比，探讨了含矿煤与无矿煤的微量元素地球化学及其与锗超常富集的关系，得出几点认识：a.含矿煤、无矿煤和硅质岩中的大多数微量元素来自基底的二云母花岗岩；b．热水携带了成矿所必需的锗；c．Nb可作为锗矿化的指示元素。

姚安和马厂箐富碱侵入岩体的地球化学特征

姚安岩体和马厂箐岩体属哀牢山-金沙江富碱侵入岩带的组成部分,位于NW-WNW向哀牢山-金沙江深大断裂东侧。姚安岩体主要为正长斑岩,马厂箐岩体主要为花岗斑岩两岩体化学成分上具有富碱、高钾的特点。岩石富轻稀土和Rb、Sr、Ba、Th、La等大离子亲石元素而亏损Nb、Ta和Ti等高场强元素。岩石的Rb/Sr、La/Nb和Ba/Nb以及LREE/HREE比值高,铕异常不明显,ISr值偏高,εNd值偏低。研究表明:(1)姚安岩体和马厂箐岩体形成于喜山期大陆弧伸展环境。两岩体的岩浆均起源于富集地幔(EMII),其壳幔混合特征,主要是俯冲带地幔楔内壳-幔物质源区混合的结果;(2)尽管姚安和马厂箐岩体在成岩构造背景、成岩时代、成岩方式和源区特征以及成分上高碱富钾等方面具相似性,但它们在岩性和组成上仍存在较大差异。这种差异可能是由源区物质部分熔融程度不同,以及岩浆结晶时温压和氧逸度等条件的不同所造成;(3)金矿化主要与相对高温、低压和高氧逸度的碱性系列岩浆活动有关,而铜矿化则主要与相对低温、高压和低氧逸度的碱性-亚碱性过度系列岩浆活动有关。

峨眉山大火成岩省太和花岗岩的成因及构造意义

攀西地区的太和花岗质岩体和赋存超大型钒钛磁铁矿矿床的辉长岩体在空间上共生,成因上均与峨眉山地幔柱头的上升密切相关。太和花岗质岩体主要由超碱质花岗岩和石英正长岩及少量正长岩组成;富含高场强元素并具高Ga/Al值（3.74~5.63）,显示典型A型花岗岩的特征。花岗岩、正长岩和辉长岩的Nb/Ta和Zr/Hf值与洋岛玄武岩（OIB）的相应比值近似。花岗质岩石具较低的87Sr/86Sr初始值（0.7025~0.7049）和正的εNd（t）值（1.9~3.5）,与辉长岩的值相近[（87Sr/86Sr）i=0.7049~0.7052;εNd（t）=2.4~3.3]。太和花岗质岩体的εNd（t）为正值,显示地幔柱来源的底侵玄武质岩浆对其形成起主要作用。辉长质和花岗质岩石具相似的钕同位素组成,表明其母岩浆来自于同一源区。我们认为太和花岗质侵入体主要由底侵于下地壳的玄武质岩浆分异出的花岗质熔体侵位及随后经结晶分异而形成。因此,晚古生代时幔源岩浆底侵造成的地壳增生在峨眉山大火成岩省中表现极为显著。

云南思茅大平掌矿区火山岩的地球化学特征及构造意义

大平掌矿区细碧岩-石英角斑岩建造为典型的双峰式火山岩组合,缺失SiO_2为52％～61％之间的中性火山岩。火山岩的TiO_2含量低及其它岩石化学特征、稀土元素地球化学特征均表明这套火山岩很可能形成于岛弧环境。不相容元素N-MORB标准化型式以Ba、Nd、Sm相对富集和Nb、Sr、Ti的相对亏损为特征,其中Ba 富集和Nb亏损更是岛弧火山作用的主要特征之一。大平掌矿区细碧岩具非常低的 Nb/Y(<0.15)和Zr/TiO_2(<0.01)比值,石英角斑岩的低Zr/TiO_2和Nb/Y特征以及Zr/Y比值(3.34～4.23)、(La/Yb)_N比值(0.47～2.50)变化范围都可以反映出火山岩形成于岛弧环境。大平掌火山岩的Sr、Nd同位素特征与世界上典型岛弧火山岩的Sr、Nd特征相似,其岩浆来源于亏损地幔,且经受地壳混染和(或)海水热液蚀变的影响。岩石中富含的放射成因铅也与岛弧环境密切相关。因此,大平掌铜多金属矿床的形成很可能受岛弧环境下的双峰式火山作用控制。

贵州修文小山坝铝土矿中镓等伴生元素分布规律研究

通过ICP-MS等分析方法对贵州小山坝铝土矿中伴生元素的研究，发现该矿床TiO2、Ga、Ge、Sc、Nb、Li和REE等有用伴生元素在铝土矿矿体中均有较高富集，其含量大多接近或超过了工业综合利用标准，具有较大的经济价值，特别是矿区富铁铝土矿石中Ga和Sc等含量异常高。贵州铝土矿资源丰富，其伴生元素在铝土矿冶炼过程中所产生的赤泥中更为富集，因此，贵州铝土矿综合利用前景十分巨大，这些元素潜在的经济价值，在某种程度上，甚至会超过主导产品氧化铝的价值。开展铝土矿中镓等伴生有用元素的分布及赋存状态的研究，对于镓等稀散元素在特殊地质地球化学环境中超常富集机制、矿产资源综合价值的重新认识评估和矿产资源的综合利用将十分重要，不仅可为铝工业注入新的活力，增加新的经济增长点，而且还可以解决大量赤泥堆放和利用问题，同时获得较大的社会效益与环境效益。