Influence of nature of support on the catalytic activity of supported molybdenum-oxo species in benzyl alcohol conversion

Supported catalysts containing 15 wt.% of molybdenum have been prepared by the incipient wetness impregnation method. CaO, MgO, Al2O3, Zr(OH)4 and Al(OH)3 have been used as supports for the preparation of supported Mo catalysts. Characterisation of all the materials prepared has been carried out through BET surface area measurement, X-ray diffractometry and FT-IR spectroscopy. Catalytic activity measurements have been carried out with reference to structure-sensitive benzyl alcohol conversion in the liquid phase. The percentage conversion of benzyl alcohol to benzaldehyde and toluene varied over a large range depending on the support used for the preparation of catalysts, indicating the importance of the support on catalytic activity of Mo catalysts. Al(OH)3 has been found to be the best support for molybdenum among all the supports used. Support–metal interaction (SMI) has been found to play an important role in determining the catalytic activity of supported catalysts.

用硼泥制备大尺寸氧化镁单晶及其性能研究

介绍用废渣硼泥制取高纯氧化镁粉末来制备大尺寸氧化镁单晶的生长方法。实验结果表明各项性能指标优良。而且 ,MgO原料的纯度及SiO2 和CaO材料的配比与晶体生长技术是我们获得优质晶体的关键因素。同时探讨了晶体的加工和应用前景

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.

泥河湾盆地大长梁剖面岩石磁学和环境磁学研究

The fluvio-lacustrine sequence in the Nihewan Basin is an important archive of late Pliocene-Pleistocene climate and environment changes in temperate northern China, which provides excellent sources of early human settlements in high latitude East Asia. The recent years have witnessed a considerable progress in the paleomagnetic dating of its stratigraphy, which has notably increased our understanding of a series of important issues such as the early human occupation in the Old World, the infilling history of the Nihewan Basin, and the chronological sequence of the Nihewan faunas. Up to now, the long-term paleoenvironmental changes directly retrieved from this basin, which might influence the evolution and expansion of early humans in the Nihewan Basin, are still poorly constrained, although several paleoclimatic records have been retrieved from this area. In this study, a combined mineral-magnetic and geochemical investigation was carried out on the fluvio-lacustrine sequence from the Dachangliang section at the eastern margin of the basin in order to reveal its rock magnetic and environmental magnetic characteristics and its implications for early human evolution in East Asia. The major findings and conclusions are listed as the following: First, there is an increased cooling coupled with an intensified aridification recorded in the fluvio-lacustrine sequence of the Dachangliang section. The cooling is related to an up-section decrease in propensity to chemical weathering as inferred from an increase in low-field susceptibility after cycling to 700 °C. Close to 700 °C, reacting chlorite is providing the iron source for newly formed very fine-grained ferrimagnetic minerals which enhances the susceptibility signal. The reactivity of chlorite after annealing at temperatures above 600 °C is documented with X-ray diffraction. Second, degrees of chemical weathering in the Nihewan Basin are further estimated by clay mineralogy (i.e. chlorite and illite contents and chlorite/illite ratio) and a series of major element proxies (i.e. Na2O/Al2O3 versus K2O/Al2O3 diagram, Al2O3-(CaO + Na2O)-K2O ternary diagram (A-CN-K), chemical index of alteration (CIA), (CaO + Na2O + MgO)/TiO2, (CaO + Na2O + MgO + K2O)/(TiO2 + Al2O3), CaO/Al2O3 and CaO/TiO2). The up-section decrease in propensity to chemical weathering suggested by the aforementioned rock mangetic measurement is further confirmed by these geochemical analyses. Combining the chemical weathering records from the Nihewan Basin, Chinese Loess Plateau, South China Sea and eastern China, we find that the consecutive decreasing trend in chemical weathering intensity during the late Cenozoic is ubiquitous across China. This pattern may result from a long-term decreasing East Asian summer monsoon and increasing East Asian winter monsoon, and thus a consecutive increasing of aridification and cooling in Asia during the Quaternary. Furthermore, the chemical weathering intensity increased from South China to North China during the Quaternary, in line with the decreasing East Asian summer monsoon and increasing East Asian winter monsoon and thus the gradually intensified aridification and cooling from South China to North China. Third, a combined mineral-magnetic and geochemical investigation provides evidences that the large-amplitude alterations of concentration of magnetic minerals mainly result from preservation/dissolution cycles of detrital magnetic minerals in alternately oxic and anoxic depositional environments. The preservation/dissolution model implies that the high-magnetic and low-magnetic cycles of this sedimentary sequence represent glacial and interglacial climate cycles, respectively. This contribute significnatly to our understanding of the link between climate and magnetic properties. Finally, the paleoclimatic implications of these rock magnetic and geochemical characteristics significantly increase our understanding of the general setting of early humans in high northern latitude in East Asia. We propose that the cold and dry climate may have contributed significantly to the expansion and adaptation of early humans, rather than bringing hardship, as is often thought. The relationship between magnetic properties and climate possibly provides valuable information on the climatic context of the Paleolithic sites in the basin, especially whether the occupation occurred during an interglacial or glacial period.

滇东南八布蛇绿岩地球化学特征及构造背景

八布蛇绿岩出露在北西向文山-麻栗坡和富宁走滑断裂之间的断块内，主要由蛇纹岩、辉长岩、玄武岩三个单元组成，彼此间均以断裂相接。地球化学研究表明，蛇纹岩SiO2、Al2O3、TiO2、MgO含量变化较大，依据主、微量元素组成可以分为两类，第一类球粒陨石标准化稀土元素分配模式整体较为平坦，推测原岩为镁铁质堆晶岩；另一类呈U型配分，推断原岩是方辉橄榄岩。玄武岩属拉斑系列，主量元素具有富MgO、TiO2，低Al2O3、K2O、P2O5，并且Na2O〉K2O等特征，类似于MORB型玄武岩；REE配分模式也显示出N-MORB型玄武岩的特征；同时，微量元素普遍具有LILE、Th富集，Nb、Ta、Zr、Hf等元素具明显亏损特征，又暗示源区曾遭受不同程度的俯冲带流体交代作用。综合分析认为，八布蛇绿岩形成于弧后盆地环境，其形成可能是古太平洋从SE至NW向华南大陆俯冲的产物。

高温高压下花岗闪长质熔体结晶作用的实验研究

岩浆的分离结晶作用是岩浆演化的重要过程，与许多火成岩石的形成密切相关。自二十世纪50年代以来，采用实验手段研究岩浆的形成、演化一直受到地质学家的高度重视。 本文在0.5-2.0GPa、650-750℃和一定水含量条件下，以东准噶尔花岗闪长岩为初始物，进行了花岗闪长质岩浆结晶作用的实验研究。其结果可为东准噶尔地区A型花岗岩的成因提供一定的实验依据。通过对实验产物详细的岩相学观察和电子探针分析，获得以下主要认识： （1）熔体的含水量对矿物开始结晶的温度和晶出矿物的形状、颗粒大小有重要影响。相同时间内熔体含水量高时结晶出的矿物自形程度更好、粒度增大；随着熔体含水量的增加，斜长石的液相线温度降低；保持熔体含水量不变的情况下，随着压力的增加斜长石从熔体中结晶的温度降低。 （2）在压力为0.5GPa、熔体水饱和的条件下，花岗闪长质熔体中斜长石在675℃时开始结晶。结晶的斜长石与原岩的斜长石相比，其成分相对富钠长石而贫钙长石。在温度和熔体水含量一定的条件下，从花岗闪长质熔体中晶出的斜长石随着压力的增加，其钙长石组分增加。 （3）实验产物中的角闪石属于钙角闪石类，具体以普通角闪石为主。与初始花岗闪长岩的角闪石相比，实验产物的角闪石SiO2含量低，Fe3+很少。结晶形成的黑云母为铁叶云母，在2.0GPa压力时没有黑云母晶出而出现多硅白云母。 （4）花岗闪长质熔体发生矿物结晶后的残余熔体的成分受温度、压力和含水量的变化而变化。残余熔体中SiO2含量随着矿物从熔体中结晶程度的增加而升高。与无斜长石结晶的情况相比，有斜长石结晶时残余熔体的SiO2含量要高。在Na2O+K2O-CaO、FeO/(FeO+MgO)分别与SiO2的协变图中，残余熔体成分均落入A型花岗岩区，反映了它们与A型花岗岩在主量元素组成上的近似。因此，本文的实验证明，东准噶尔地区的A型花岗岩浆可以通过花岗闪长质岩浆发生角闪石、黑云母、斜长石的分离结晶作用形成。

地幔柱与岩浆成矿-峨嵋山大火成岩省地震波速层物相解释及典型PGE矿床成岩成矿机制研究

地幔柱概念在19世纪60至70年代就被提出，但是由于板块构造理论在解释地球上岩浆活动的分布规律时取得了空前的成功，在当时这一理论是被排斥的。板块边界概念可以解释地球上绝大部分的岩浆产出，但在解释板内岩浆的成因时往往显得力不从心，尽管这些岩浆的体积只占地球岩浆总量的2％。地幔柱理论模型发展到现在得到不同学科的支持。地质学、地球化学、地球物理学、古生物学、比较行星学、实验岩石学等等都提供了直接或间接的证据，证明地幔柱几乎存在整个地：质历史时期。当前地幔柱理论中在地球化学领域有两大研究热点：高钦低钦玄武岩的起源以及地幔柱中是否存在循环俯冲洋壳物质。完全解决这些问题才可能深入系统地建立地慢柱成矿作用模型。现在已经建立了一些矿床类型与地慢柱作用的联系：如现在认为赋存在金伯利岩中的金刚石矿床的形成与地慢柱作用密不可分，一些岩浆硫化物矿床和岩浆氧化物矿床很显然是地慢柱岩浆作用形成的，如西伯利亚火成岩省的Noril'sk-Talnakh铜镍铂族元素矿床以及KeweenawaJI大陆裂谷体系的Dultlth杂岩体的Cu-Ni矿床。另外还有赋存在大型基性一超基性层状岩体中的PGE、Ni和cu矿床，如Great Dyke和布什维尔德杂岩体。一些超大型热液矿床也与地慢柱有可能的联系（Pirajno，2000）：如270oMa形成的超大型Kidd Creek火山成因块状硫化物矿床（Bleeker et al.，1 999；Wynan et al.，1999）和南澳大利亚1600Ma形成的超大型olymPicD翻矿床。本文的研究工作包含两方面内容：通过热力学计算峨眉山玄武岩在深部的结晶分异，对峨眉山大火成岩省的岩浆量分布和岩浆氧化物矿床（华Ti磁铁矿矿床）的分布以及下地壳高波速层的物相进行理论解释；对峨眉山大火成岩省金宝山PGE典型矿床进行成岩成矿的地球化学研究，预测整个大火成岩省的岩浆硫化物矿床产出位置。大多数峨眉山玄武岩的 MgO＜7％，Ni为4-232ppm，它们是原始岩浆结晶分异后的产物。峨眉山玄武岩省下地壳和上地幔之间存在厚度为：8-25km1，P彼速为7.1-7.8km／s的附加层（高地震波速层）。滇西地区出露的洲套第三纪富碱斑岩，地球化学和同位素研究表明斑岩的岩浆源是来自“壳一慢混合层”，源区的形成时代为220-25Ma，与峨眉山玄武岩的形成时代一致。所以有理由认为该附加层是由峨眉山玄武岩在此结晶分异形成的。与地慢柱有关的洋岛Hawaii、Marquesas Islands；海底高原Oniong Java、大陆火山岩省ColumbiaRiver Plateaus地震彼研究都表明在上地慢顶部有一高速附加层，Farnetani etal.（1996）的研歼表明高速附加层是由来自地幔柱的岩浆在此结晶分异形成的。玄武岩是一种混合的部分熔融产物，是不同成分的地幔橄榄岩在不同的压力下熔出的。这种降压熔融高温高压实验是做不到的。熔出的熔体成分是温度、压力及橄榄岩成分（源区）的函数，形成的岩浆是一个多压熔融的集合体。热力学计算能够较为精确地计算出生成的岩浆成分和约束岩浆产生的过程。岩浆的结晶分异也是同样的情形，尤其是分离结晶过程，实验岩石学是很精确难模拟其过程的。热力学计算使用的MELTS程序，MELTS适用范围很广，适用于模拟岩石熔融生成岩浆和岩浆的冷却结晶。现今峨眉山大火成岩省的地壳厚度为40恤，这被认为是后期褶皱加厚的缘故。根据峨眉山玄武岩中辉石斑晶成分和玄武岩本身成分计算出分异结晶的压力为6kb，那么当时的地壳厚度约为20km：选择氧逸度为QFM，这一氧逸度范围认为是大多数大陆溢流玄武岩结晶分异时的氧化还原环境。热力学计算结果通过峨眉山玄武岩成分进行约束和验证。Al2O3、NaZO＋K 20、CaO与MgO计算的演化趋势线与实际观察的演化符合较好，橄榄石和斜方辉石的结晶使得CaO随着MgO的降低而增高；当单斜辉石成为液相线矿物时，cao也随着Mgo的降低而降低了。单斜辉石在岩浆演化到MgO＝10．3％时成为液相线矿物。整个计算过程中斜长石未成为液相线矿物，这与大多数玄武岩不具有Eu异常是一致的，并月＿Al2O3随着MgO的减小单调增加也说明了这点。不过大多数峨眉山玄武岩常含有斜长石斑晶，这是低压下结晶分异的结果。由于斜长石密度小，所有很难与高铁玄武岩分离。整个计算的难点也是创新点是波速计算。通过分离的堆晶矿物组合中各种矿物的成分和质量分数计算的附加层波速比观察值高，不过堆积岩体常常会有残留岩浆存在矿物晶粒间，这样会降低岩石的压缩波速。大型基性一超基性岩体常常会残留有或者捕获5-30％的岩浆。假定两个高波速附加层分别捕获7叭，和巧％的残留岩浆，计算的结果就大体等于观察值。热力学和质量平衡计算研究表明：高地震波速层为橄榄辉石岩一辉石岩的巨型侵入岩体；峨眉山中岩区的岩浆量最大也符合含V-Ti磁铁矿矿床只产在中岩区，如太和、白马、攀枝花、红格等岩体；西岩区的岩浆量最小表明几乎没有可能在西岩区形成有规模的V-Ti磁铁矿矿床，实际观察仅仅只见到数量少而小的岩体；东岩区下地壳厚达20灿1的高波速层暗示东岩区上地壳的侵入岩体积也应该具有相当规模，应该是V－Ti磁铁矿矿床成矿区。目前在东岩区很少发现与峨眉山玄武岩有关的岩浆矿床的主要原因是：东岩区的剥蚀深度不够，没有可观的侵入岩体出露，而中岩区侵入岩都侵入在元古代地层中。按照质量平衡的计算方法，最保守的估算整个峨眉地慢柱岩浆事件产生的岩浆量为8.9*106km3，上地壳峨眉山玄武岩和侵入岩体积为3.9*106km3。如果按照初始覆盖面积5x106km2计算（与西伯利亚暗色岩初始覆盖面积相当），喷发高峰期为2Ma，计算的喷发速率为3.9km3／year。这并不亚于西伯利亚暗色岩的喷发速率4km3／year。这对于研究峨眉山大火成岩浆事件与二叠·三叠交界或end-QuadaluPian生物灭绝之间的可能联系具有重要意义。本文另一方面的研究工作是：首先系统地介绍了岩浆硫化物矿床的基本原理，然后通过金宝山PGE矿床实例研究，提出金宝山岩体成岩模式，并且对整个峨眉山大火成岩省的岩浆硫化物矿床产出位置进行理论预测。详细地球化学研究表明金宝山镁铁一超镁铁岩是峨眉山大火成岩省古老火山岩浆房的残留物。岩体主要由底部超镁铁岩和上部镁铁岩组成，两种岩石的质量大致相同。根据超镁铁岩的矿物组合计算的成岩时的氧逸度较高，热力学方法计算的成岩压力为2kb左右。超镁铁岩的包嵌结构和铁铁岩的微晶一细晶结构说明超镁铁岩为镁铁岩结晶的矿物堆积形成的。镁铁一超镁铁岩的蚀变程度不同以及Sc、Sr、Eu等元素在两类岩石中的不同特征指示了整个成岩过程。金宝山岩体的原始岩浆 MgO=8％说明高镁玄武岩并不是形成PGE矿床的必要条件。金宝山的成岩模式是：在火山喷发前，岩浆侵位时橄榄石和少量铬尖晶石先结晶，沉淀在岩浆房底部；随后结晶的是斜方辉石和斜长石，斜方辉石也沉淀在岩浆房底部，斜长石由于密度较小集中中岩浆房上部，岩浆房的中部是：少量的斜长石小斑晶。由于斜方辉石和斜长石的结晶，这样岩浆中的Sc、Sr和Eu就会亏损，也是岩浆房底部堆积岩的原始捕获岩浆。火山喷发后，由于压力的突然降低，岩浆房底部的堆晶会发生再熔融，几乎消耗掉所有的斜方辉石，橄榄石也呈熔蚀状浑圆形态，重新熔融的斜方辉石导致超镁铁岩中残留岩浆比原始捕获岩浆更加富Sc，这种岩浆由于富MgO和在快速冷却的环境下同时结晶，最终形成光性方位一致的单刹辉石。喷发后岩浆房空间的剩余导致围岩-灰岩进入，造成岩浆房中剩余岩浆强烈的碳酸盐化。峨眉山玄武岩Cr-Mg#的相关关系定义一条正常玄武岩演化线。大多数这些玄武岩的Ni也保持了这种演化关系，其中低钦玄武岩和过渡型高钦玄武岩Ni-Mg＃相关关系远离了正常演化线，这些玄武岩的Cu-Mg#相关关系也有类似的情形。峨眉山低钦和过渡类型高钦玄武岩Ni和 Cu的非正常亏损，表明它们在地表下经历了硫饱和事件。金宝山岩浆硫化物矿床成岩模型的建立，为在整个大火成岩省寻找岩浆硫化物矿床提供了一种新认识。低钦和过渡型高钦玄武岩的古老火山口下部是岩浆硫化物矿床的所在地。

氟、氯对热液钨、铜成矿的制约-以江西德兴铜矿、大吉山钨矿为例

矿化剂在热液矿床成矿过程中的重要作用一直为人们所关注，矿化剂地球化学行为直接影响成矿元素的富集成矿，不同的矿化剂元素可能对金属成矿具有一定的专属性。本文以著名的江西德兴铜厂超大型斑岩铜矿床和大吉山钨矿床作为研究对象，研究F、Cl与W、Cu成矿的关系。主要的认识如下：（1）F在花岗质岩浆中，可以降低岩浆的粘度、密度、固液相线温度、改变熔体结构，而Cl对熔体结构没有多大的影响。F在流体一花岗质熔体相间，绝大多数配分系数小于1.0，趋向于熔体相中配分，DF随体系中F浓度的升高而增加。Cl在流体一花岗质熔体相间的配分系数均大于1.0，且Dc1 随体系中Cl浓度的升高而增大·Cl强烈地趋向富集于流体相中。（2）Cu在流体一花岗质熔体作用过程中，铜总趋向于流体相中分布（DCu都大于1）。特别是在富Cl流体中Cu浓度较高，说明在富含Cl的热液流体能够从共存的熔体中活化迁移出大量的 Cu，S的加入DCu有降低的趋势。钨趋向于熔体相中富集，其配分系数大多小于1.0。（3）德兴铜厂花岗闪长斑岩属钙碱性系列岩石属I型花岗岩类，具有埃达克岩的特征。岩浆来源于深部，在结晶演化过程中发生了围岩物质的混染，这种高铜含量围岩的混染使成矿物质在岩浆中得到富集，有利于铜的活化、迁移。在铜厂岩体不同的蚀变带中，SiO2、K2O、Cu、Mo等从新鲜斑岩甚至弱蚀变带中带出，而在强蚀变带强烈富集，Cl同样有在强蚀变岩石中富集的趋势；而Na2O、Fe从斑岩体中带出，进入流体相中，流体中大量Fe的存在，有利于铜的沉淀、富集成矿。（4）德兴铜厂斑岩体微量元素和稀土元素地球化学特征表明，该岩体发生了流体一熔体作用，分异出来的流体是一种相对富氯的流体，同时成矿流体的流向是从岩体中心向接触带方向流动。（5）大吉山花岗岩具有高SiO2、A/CNK值，显示过铝质特点。黑云母花岗岩是壳源花岗岩但又受到慢源岩浆或慢源流体的影响。随着花岗岩的演化（从I→II→III）SiO2、K2O＋Na2O逐渐增加，ΣFe、Al2O3、CaO、F含量降低，为成矿提供了大量的矿化剂（F）和沉淀剂（Fe、Ca）。Eu负异常从I至III阶段花岗岩逐渐加强，表明该岩浆经历了高度的分异演化。（6）大吉山花岗岩类稀土元素具有“四重效应”配分的特点以及微量元素对玲Rb、Y/Ho、Zr/Hf以及Nb／Ta发生明显分异，暗示在花岗岩岩浆的演化过程中，经历了充分的流体一熔体作用，同时分异出大量富含F、W等矿化剂元素和成矿元素的热液流体，致使钨矿的形成。大吉山石英脉型钨矿的成矿年龄大约在155 Ma。（7）通过对成矿流体和花岗质岩石黑云母、白云母中卤素相对逸度的研究（log(H2O/fHCl）fluid、log（fHF/fHCl）fluid）发现，铜厂斑岩型铜矿床的成矿体系是相对富氯体系，而大吉山石英脉型钨矿床成矿体系相对富氟，同时氟可能主要迁移W、Sn、Nb、Ta等金属元素。（8）结合斑岩型铜矿床成矿流体特征，铜主要以C1的络合物形式存在和迁移，迁移形式主要是CuCl0、CuCl2等。石英脉型钨矿床中，钨主要以钨酸、钨酸盐及其离解形式存在和迁移，如WO42-、HWO4-、NaHWO4、Naw伍．等；在高度富氟的成矿流体中，钨的氟氧络合物（如WO3F-，WO2F42-等）对钨迁移也具有重要的作用。因此，不同矿化剂类型具有一定的成矿专属性，热液铜矿床主要与Cl、S有 关，而热液钨矿床大多与F有关。

Diopside-fluorapatite-wollastonite based bioactive glasses and glass-ceramics

Bioactive glasses and glass–ceramics are a class of biomaterials which elicit special response on their surface when in contact with biological fluids, leading to strong bonding to living tissue. This particular trait along with good sintering ability and high mechanical strength make them ideal materials for scaffold fabrication. The work presented in this thesis is directed towards understanding the composition-structure-property relationships in potentially bioactive glasses designed in CaOMgOP2O5SiO2F system, in some cases with added Na2O. The main emphasis has been on unearthing the influence of glass composition on molecular structure, sintering ability and bioactivity of phosphosilicate glasses. The parent glass compositions have been designed in the primary crystallization field of the pseudo-ternary system of diopside (CaO•MgO•2SiO2) – fluorapatite (9CaO•3P2O5•CaF2) – wollastonite (CaO•SiO2), followed by studying the impact of compositional variations on the structure-property relationships and sintering ability of these glasses. All the glasses investigated in this work have been synthesized via melt-quenching route and have been characterized for their molecular structure, sintering ability, chemical degradation and bioactivity using wide array of experimental tools and techniques. It has been shown that in all investigated glass compositions the silicate network was mainly dominated by Q2 units while phosphate in all the glasses was found to be coordinated in orthophosphate environment. The glass compositions designed in alkali-free region of diopside – fluorapatite system demonstrated excellent sintering ability and good bioactivity in order to qualify them as potential materials for scaffold fabrication while alkali-rich bioactive glasses not only hinder the densification during sintering but also induce cytotoxicity in vitro, thus, are not ideal candidates for in vitro tissue engineering. One of our bioglass compositions with low sodium content has been tested successfully both in vivo and in preliminary clinical trials. But this work needs to be continued and deepened. The dispersing of fine glass particles in aqueous media or in other suitable solvents, and the study of the most important factors that affect the rheology of the suspensions are essential steps to enable the manufacture of porous structures with tailor-made hierarchical pores by advanced processing techniques such as Robocasting.

Understanding the Crystallization Mechanism of a Wollastonite Base Glass Using Isoconversional, IKP Methods and Master Plots

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Pb-210 and composition data of near-surface sediments and interstitial waters evidencing anthropogenic inputs in Amazon River mouth, Macapa, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Pb-210-derived chronology in sediment cores evidencing the anthropogenic occupation history at Corumbata River basin, Brazil

Activity profiles of excess Pb-210 combined with chemical data determined in two sediment cores from Corumbatai River basin, São Paulo State, Brazil, provided new insights into the reconstruction of historical inputs of anthropogenic constituents, contributing to improving management strategies of the hydrological resources in the basin since most of the municipalities extensively utilize the waters of Corumbatai River and tributaries for drinking purposes, among other uses. Excellent significant relationships between loss on ignition (LOI) and organic matter were found for sediments of both analyzed profiles. Silica was found to be inversely related to organic matter at both analyzed profiles: its decrease accompanied an increase in the specific surface of the sediments. This relationship was confirmed by a great number of inverse significant correlations among silica and oxides Na2O, K2O, CaO, MgO, Al2O3, P2O5, Fe2O3, MnO, and TiO2. It was possible to identify the role of organic matter on adsorption of several oxides/elements in the core sediments profiles. Apparent sediment mass accumulation rates corresponding to 224 and 802 mg cm(-2) year(-1) were obtained, and are compatible with field evidence, indicating a higher value associated with sand mining activities interfering with the natural/normal sedimentation process, due to modifications of the channel drainage.

Chemistry of Biotites and Whole Rocks from the Rapakivi Itu Complex (Late Precambrian), State of São Paulo, SE Brazil

Chemical analyses for biotites and their host rocks from the Cabreúva (three facies) and Salto (five facies) intrusions from the multiple-centered rapakivi Itu Complex, State of São Paulo, Brazil, are presented and compared. The Cabreúva intrusion comprises different kinds of mainly even-grained biotite and hornblende-bearing syenogranites, monzogranites and quartz syenites and the Salto intrusion several types of mainly porphyritic biotite syenogranites, some of them hornblende-bearing. The biotites from the Salto intrusion (S-micas) show a more restricted composition than those from the Cabreúva intrusion (C-micas). This reflects the chemical variability of the two bodies which is smaller in the Salto intrusion and larger in the Cabreúva pluton. In the AlIV x Fet/(Fet+Mg) diagram the S- and C-micas show similar AlIV contents, around 2.2-2.3, but C-micas have higher Fet/(Fet+Mg) ratios (0.7-0.9) compared to those of S-micas (0.5-0.6). In the Mg:(Al+Fe+3+Ti):(Fe+2+Mn) diagram the S-micas are defined as Fe+2-biotites and the C-micas occupy the area between the Fe+2-biotites and the siderophyllite/lepidomelane fields, slightly overlapping the latter. In the Al2O3 × FeOt, MgO × FeOt, Al2O3 x MgO and Alt x Mg diagrams, the S-micas always lie on the calc-alkaline/alkaline boundary (or in the subalkaline field) whereas the C-micas systematically plot in the alkaline field, reflecting the higher alkalis content of the Cabreúva intrusion. In the Fet/(Fet+Mg) x SiO2 diagram, the S-micas lie on a smooth line whereas the C-micas from the different facies are separated by distinct chemical gaps reflecting the major or minor chemical overlapping of the facies from the Salto and Cabreúva intrusions.

Petrogenesis of dunite, wehrlite and websterite xenoliths from Kimberley, South Africa: Origin as mantle peridotites of cumulates

Dunite, wehrlite and websterite xenoliths occur amongst a large abundance of mantle xenoliths in kimberlites of the Kimberley cluster in South Africa. Up to know they have mostly been neglected. On the basis of texture, major and trace elements, oxygen isotopes as well as Re-Os isotope characteristics, they can be subdivided into two groups. A coarse-grained mantle peridotite group, comprising dunite, wehrlite and websterite xenoliths, that are similar to fertile peridotites and represent upper mantle assemblages that are differently influenced by mantle metasomatism. And a cumulate group, containing fine-grained Fe-rich dunite xenoliths that represent cumulates of flood basalt magmatism related to ~183 Ma Karoo and ~2.7 Ga Ventersdorp events in southern Africa. Dunite, wehrlite and websterite xenoliths have preserved a complex history of melt depletion and metasomatic re-enrichment events, which gives information about the different re-enrichment stages of the subcratonic lithospheric mantle and the spatial differences within the Kaapvaal craton upper mantle. Websterite xenoliths comprise orthopyroxene (40-85 Vol. %), clinopyroxene (5-42 Vol. %), garnet (4-10 Vol. %) and subordinately olivine, while dunite and wehrlite xenoliths contain predominantly olivine (65-100 Vol %) and subordinately orthopyroxene, clinopyroxene and garnet. High melt depletion and a dunitic to harzburgitic protolith composition are reflected by high forsterite (Fo90-92) and high olivine NiO contents (2800-5000 ppm) and high orthopyroxene Mg# (Mg/(Mg+Fe)) of 0.91-0.93. Re-depletion ages of predominantly 2.9 Ga reflect a minimum age of melt depletion. Melt depletion ceased in conjunction with collision of the Kimberley block with the Witwatersrand block ~2.9 Ga ago. Subduction related re-fertilisation of the previously depleted mantle xenoliths is documented by i) amoeboid textured orthopyroxene, clinopyroxene and garnet, which crystallized in schlieren along olivine grain boundaries, ii) high whole-rock SiO2, Al2O3, CaO, TiO2, FeO contents, iii) low oxygen isotope ratios in clinopyroxene and garnet of 4.8-5.4 ‰ and 4.7-5.3 ‰, respectively and iv) trace element compositions of wehrlitic clinopyroxene and garnet in equilibrium with high-pressure partial melts of eclogite. Trace element disequilibrium of orthopyroxene with clinopyroxene and garnet indicates a separate origin for orthopyroxene, on one side as primary mantle orthopyroxene in dunite and wehrlite xenoliths and on the other side as reaction product with Si-rich melts produced by partial melting of eclogite. This reaction triggered replacement of olivine by orthopyroxene in the surrounding mantle and produced the typical Si-rich composition of Kaapvaal mantle peridotites. Partial melting of eclogite at higher temperatures produced a second metasomatic melt with lower SiO2, but higher Al2O3, CaO, FeO, Ti, Zr, Hf and a low oxygen isotope ratio. This melt triggered clinopyroxene and locally garnet and rutile crystallization in percolation veins, replacing olivine and orthopyroxene in the Kaapvaal upper mantle. Additionally, websterite xenoliths have experienced late stage cryptic metasomatism by the host kimberlite melt, changing the trace element composition of clinopyroxene, orthopyroxene and garnet to different extent. Hence websterite and most fertile lherzolite xenoliths have experienced three metasomatic events: i) reaction with high-Si melt, ii) percolation of subduction related silica melt with lower SiO2 content and iii) cryptic metasomatism by kimberlite. In contrast, dunite and wehrlite xenoliths have only experienced the second metasomatic event. They represent mantle lithologies further away from metasomatising agents. The Fe-rich dunites comprise olivine neoblasts with subordinate olivine porphyroclasts and parallel-orientated needles of ilmenite, which may enclose spinel. The lower forsterite and NiO contents of olivine in Fe-rich dunites compared to mantle peridotite xenoliths (Fo87-89 vs. Fo93-95 and 1300-2800ppm vs. 2200-3900 ppm, respectively), rules out a restitic origin. Cr-rich spinels are remnants of the original cumulate mineralogy that survived a late stage metasomatic overprint related to the production of the host kimberlite, producing ilmenite and phlogopite in some samples. Olivine porphyroclasts and neoblasts have different trace element compositions, the latter having high Ti, V, Cr and Ni and low Zn, Zr and Nb contents, indicating contrasting origins for neoblasts and porphyroclasts. The dunites have high 187Os/188Os ratios (0.11-0.15) indicating young (Phanerozoic) model ages for most samples, whereas three samples show isotopic mixtures between Phanerozoic neoblasts and ancient porphyroclastic material. Most Fe-rich dunite xenoliths can be interpreted as cumulates of fractional crystallization of Karoo magmatism, whereas the porphyroclasts are interpreted to be remnants from the much earlier Archaean Ventersdorp magmatism.

Development of glass-ceramics from combination of industrial wastes together with boron mining waste

The utilization of borate mineral wastes with glass-ceramic technology was first time studied and primarily not investigated combinations of wastes were incorporated into the research. These wastes consist of; soda lime silica glass, meat bone and meal ash and fly ash. In order to investigate possible and relevant application areas in ceramics, kaolin clay, an essential raw material for ceramic industry was also employed in some studied compositions. As a result, three different glass-ceramic articles obtained by using powder sintering method via individual sintering processes. Light weight micro porous glass-ceramic from borate mining waste, meat bone and meal ash and kaolin clay was developed. In some compositions in related study, soda lime silica glass waste was used as an additive providing lightweight structure with a density below 0.45 g/cm3 and a crushing strength of 1.8±0.1 MPa. In another study within the research, compositions respecting the B2O3–P2O5–SiO2 glass-ceramic ternary system were prepared from; borate wastes, meat bone and meal ash and soda lime silica glass waste and sintered up to 950ºC. Low porous, highly crystallized glass-ceramic structures with density ranging between 1.8 ± 0,7 to 2.0 ± 0,3 g/cm3 and tensile strength ranging between 8,0 ± 2 to 15,0 ± 0,5 MPa were achieved. Lastly, diopside - wollastonite (SiO2-Al2O3-CaO )glass-ceramics from borate wastes, fly ash and soda lime silica glass waste were successfully obtained with controlled rapid sintering between 950 and 1050ºC. The wollastonite and diopside crystal sizes were improved by adopting varied combinations of formulations and heating rates. The properties of the obtained materials show; the articles with a uniform pore structure could be useful for thermal and acoustic insulations and can be embedded in lightweight concrete where low porous glass-ceramics can be employed as building blocks or additive in cement and ceramic industries.