东天山后碰撞镁铁-超镁铁岩镍铜硫化物矿床PGE地球化学示踪与富集规律研究

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

东天山镁铁-超镁铁岩铜镍硫化物矿床通道式成矿机制与岩体含矿性评价研究

A mafic-ultramafic complex belt well developed in Eastern Tianshan, Xinjiang, NW China, which contains a series of Cu-Ni sulfide deposits. This area is the important production basis for Cu-Ni deposits, including Tulargen deposit, Hulu deposit, Huangshan-Huangshandong deposit, Hulu deposit, Xiangshan deposit, Tianyu deposit, Chuanzhu deposit. In China, especially Eastern Tianshan, it is prevalent that large Cu-Ni deposits occurred in small intrusions, typically including Jinchuan, Kalatongke, et al., so the ore-forming mechanism and evaluation rule for those small intrusions are very meaningful and of universal significance. On the basis of the research to typical Cu-Ni deposits, ore-forming conditions and processes are summarized through which to evaluate the ore-bearing potential for barren intrusions and unexplored mafic-ultramafic intrusions. By the contrast, metallogenic rule and mechanism of ore genesis are concluded, and evaluation system is preliminarily set up on the basis of these conclusions. Quantitatively simulation for the composition of olivine is introduced for the first time in China to discuss the interaction between magma and sulfide, and a new method to calculate the Mg-Fe composition of primitive magma is developed. Interaction between magma and sulfide liquid is used to get the Ni content in sulfide liquid. Sulfur isotopic characteristics in sulfide minerals in country rocks and ores are used to judge crustal sulfur introduction, which is applied for the first time in China. Re-Os isotopic characteristics are related to the ore-forming process, to interpret the process of enrichment of chalcophile elements. On the basis of the evaluation system, Mati, Chuanzhu, Luodong, Xiadong, those intrusions are evaluated to their ore-bearing potential. According to the studies to typical Cu-Ni deposits, conduit-type ore-forming model is set up, and the characteristics of the model are concluded systematically. The evaluation system and conduit-type ore-forming model can be helpful to the evaluation of mafic-ultramafic intrusions in this and similar mafic-ultramafic intrusion belts. The studied typical deposits and mafic-ultramafic intrusion include Tulargen deposit, Hulu deposit, Huangshandong deposit, Chuanzhu deposit, Mati intrusion，Luodong intrusion, Xiadong intrusion, and others. Through studies, there are similar characteristics for Tulargen and Hulu deposits in magma origin, composition of primitive magma（MgO=12.5%, FeO=12% and MgO=11%, FeO=10.5% respectively）, magma evolution, mechanism of sulfide segregation and conduit-type ore-forming process. By Re-Os isotopic system, the ore forming date of Tulargen deposit is 265.6±9.2Ma, which is consistent to regional metallogenic event, but little younger. The Mg-Fe composition of primitive magma of Baishiquan, Huangshandong area, Kalatongke is lower than that of Tulargen and Hulu deposit, showing common basalt composition. The Mg# value（Mg#=(Mg/Mg+Fe）increases gradually from Kalatongke to Baishiquan to Huangshan-Huangshandong East. Baishiquan intrusions show relatively higher crustal contamination by evidence of trace element, which indicates the lower magma original source, from depleted mantle to crust. One break is the discovery of komatiitic intrusion, Xiadong intrusion, which shows characteristics of highly magnesium (Max Fo=96). The primitive magma is calculated of MgO=28%，FeO=9%, belonging to komatiitic magma. Tectonic evolution of Eastern Tianshan is discussed. By the statistics of ore-forming data of porphyry copper deposits, magmatic sulfide Cu-Ni deposits, orogenic hydrothermal gold deposits, we believe that those deposits are the successive products of oceanic subduction, are and back-arc basin collision and post-orogenic extention. And Cu-Ni sulfide deposits and orogenic gold deposits occurred in the stage of post-orogenic extention. According to the conclusions, the conduit-type ore-forming mechanism of magmatic sulfide deposit is set up, and its characteristics and conditions are concluded as well. The conduit-type ore-forming system includes magma generation, sulfide segregation, enrichment of chalcophile elements, interaction of sulfide and magma, sulfide collection in limited space in magma conduit and bottom of the chamber, which make a whole ore-forming system.The ore-forming process of Cu-Ni sulfide deposits is concluded as three steps: 1. mantle derived magma rises upward to the middle-upper crust; 2. magma suffers crustal contamination of different degrees and assimilates crustal sulfur, which leads to sulfur saturation and sulfide segregation. Sulfide liquid interacts with magma and concentrates chalcophile elements; 3. enriched sulfide located in the conduit(Tulargen) or bottom of the chamber (Hulu). Depleted magma rises upward continuously to form barren complexes. For the practical cases, Tulargen deposit represents the feeding conduit, and Hulu deposit represents the bottom of the staging magma chamber. So the deeper of west of Tulargen and southwest of Hulu are the favorite locate for ore location. The evaluation for ore potential can be summarized as follows: (1) Olivine can be served as indicator for magma evolution and events of sulfide segregation; (2) Sulfur isotopic characteristics is an efficient method to judge sulfur origin for magmatic sulfide deposit; (3) Re-Os content of the ores can indicate interaction between sulfide and silicate magma and crustal contamination; (4) PGE mineralization is effected by degree of partial melting of mantle; (5) Cu/Zr is efficient parameter to judge sulfide segregation; (6) The effects of multiple magma fractionation and emplacement are important, for inverse order shows the destruction to previous solid lithofacies and orebodies. Mati, Chuanzhu, Xiadong, Luodong, mafic-ultramafic intrusions are evaluated using evaluation system above. Remarkable Ni depletion is found in olivine of Mati, and southwest of the intrusion can be hopeful location for ore location. Chuanzhu intrusion has remarkable evidence of sulfide segregation, but the intrusion represents the narrow feeder conduit, so the wide part of the conduit maybe the favorite location for sulfide to deposit. The ore potential of Luodong and Xiadong is not good. Both the intrusions show no Ni depletion in olivine, and there is no sulfide in country rocks, so no crustal sulfur is added into the magmatic system. For Sidingheishan, a very large intrusion, the phenomenon of sulfide segregation is found, but there are no favorite places for sulfide to deposit. So the Cu-Ni ore potential maybe not good, but PGE mineralization should be evaluated further.

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.

青海德尔尼铜钴锌矿床地质构造背景与成因

The Derni large Cu-Co-Zn sulfide deposit is occurred in the Derni melange belt, which is located in the eastern section of the A'nyemaqen ophiolite melange belt. The Derni deposit is hosted in the mantle peridotites and is very special in the world. Because the studying area is of very bad natural environment and very low geological research, the geotectonic setting and genesis of the deposit have long been debated. This paper studied these two questions and answered them. The research is of great significance to reveal impotant information of deep geology, crust-mantle interaction and geotectonic evolution, to enrich theories in the study of mineral deposit and provide scientific basic data for exploration and exploit of this kind of deposit. Based on the series of new achievements and new cognitions, to start with the geologic setting of the Derni deposit, through detailed field, tectonics, petrology, geochemistry, isotopic geochronology, microfossil, and study of mineral deposit, belongs to a melange belt, including mantle peridotites slice with ore, Late Precambrian sandstone and slate slice, metamorphic rock slice. 2. Petrological and geochemical characteristics indicate that the Derni mantle peridotite is not ophiolite mantle peridotite, but is occurred under the continental crust. 3. The U-Pb isotopic age of single-grain zircon form the accumulative rock suggests that the Derni mantle peridotite were formed in 747±10Ma, and underwent a great period of metamorphic process in 441.5±2.5Ma. 4. Microfossil assemblage from the carbonaceous slate belongs to Late Precambrian. Through petrography and petrochemistry, sandstone and slate were formed in the continental margin. 5. Sideronitic texture, which is first discovered in this study, reveals the characteristics of magmatic liquation. 6. Fluid inclusion explosion temperature of pyrite is in the range of -6.15～+6.64‰, and Pb isotope is consistent with mantle peridotite, which suggest ore-forming materials are from the mantle. To sum up, the upper mantle was melting partially, when it was metasomated by the mantle fluids with abundant Cu, Co, Zn, S, Au and LREE etc. The pockets of magma became enlarged by mantle tenacity shearing, and the pockets of magma occurred magmatic differentiation in the stable field, then the magma and ore pulp together with mantle refractory remnant dirpired and crystallized in the shallow part of the crust.

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.

东天山地区金矿床成矿流体地球化学及其成矿机制

The mechanism of gold ore formation in the eastern Tianshan Mountains, Xinjiang Uygur Autonomous Region, that has been dealt with from various aspects, remains unclear. On the basis of investigations of regional geology, ore deposit geology, and microscopic observations of ores and related rocks of the Jinwozi, the 210, and the Mazhuangshan gold ore deposits, this thesis made a systematic research on the microthermometry of gangue quartz-hosted fluid inclusions, gas, liquid ion and rare earth element compositions and hydrogen, oxygen isotope compositions of sulfide- and quartz-hosted fluid inclusions, and sulfur and lead isotope compositions of sulfide ore minerals from the major ores in the three deposits. On the basis of the above synthetic studies, sources of ore-forming fluids and metals, and mechanism of gold ore formation in the region were discussed. Gas compositions of pyrite- and sphalerite-hosted fluid inclusions were first analyzed in this thesis. Compared with gangue quartz-hosted fluid inclusions, the sulfide-hosted ones are richer in gaseous species CO2, CO, and CH4 etc. Both gas and liquid CO2 are commonly observed in fluid inclusions, whereas halite daughter minerals rarely occur. Ore-forming fluids for the three gold ore deposits are characteristically of medium to low temperatures, medium to low salinities, are rich in CO2 and Na+, K+, Cl" ions. Gas covariation diagrams exhibit linear trends that are interpreted as reflecting mixing between the magamtic fluid and meteoric-derived groundwater. Regarding rare earth element compositions, the Jinwozi and the 210 deposits show moderate to strong LREE/HREE fractionations with negative Eu anomalies. However, the Mazhuangshan deposit shows little LREE/HREE fractionation with positive Eu anomalies. Hydrogen and oxygen isotope compositions of pyrite-hosted fluid inclusions that were first analyzed in this thesis indicate the presence of magmatic water. Hydrogen and oxygen isotope compositions of pyrite- and quartz-hosted fluid inclusions suggest mixing between magmatic water and meteoric-derived groundwater. Sulfur and lead isotope compositions of sulfide ore minerals indicate multi-sources for the metallogenetic materials that range from the crust to the mantle. On the basis of the above synthetic studies, genesis of the gold ore deposits in the eastern Tianshan Mountains was approached. From the Middle-Late Hercynian to Early Indosinian, geodynamic regime of the region was changing from the collisional compression to the post-collisional extension. During the period, magmas were derived from the crust and the mantle and carried metallogenetic materials. Magma intrusion in the upper crust released the magmatic fluids, and drove circulation of groundwater. Mixing of magmatic fluid with groundwater, and extraction of metallogenetic materials from the country rocks are the mechanism for the gold ore formation in the eastern Tianshan Mountains.

河北寿王坟铜矿成矿定年及同位素地球化学特征

Samples from carbonate wall-rocks, skarn, ore of skarn type, later calcite vein, and ore of porphyry type in Shouwangfen copper deposit district were collected. Systematic study was carried out on carbon, oxygen, rubidium, strontium and sulfur isotope compositions of carbonates and sulfides in these samples. The first Isochron dating by the Rb-Sr isotopes in chalcopyrite of ore sub-sample was done as well. The following conclusions were obtained. The age (113.6±4.3Ma), obtained by Rb-Sr isotope isochron dating of chalcopyrite and pyrite from sub-sample of skarn ores, probably represents the true mineralization age of skarn ores. That demonstrates the genetic relationship between granodiorite in Shouwangfen complex and skarn copper ores. On the other hand, the Rb-Sr isochron age (73±15Ma) of chalcopyrite from porphyry ores is a little incredible because of bad synthesizing evaluation. But combined with other age data of igneous rocks, it implies the possibility of hydrothermal mineralization in connection with magma activity during the fourth period of Yanshanian in Hebei Province, even in the whole northern edge of Huabei continental block. Together from structure analysis of sulfide sub-samples, from pretreating preccedure of Rb-Sr isotope isochron and its' valuating, we found out that Rb-Sr isotope isochron of sulfide sub-samples is influenced by the crystal structure of sulfides. That is, sulfide ores with very big crystals are not suitable for sub-sample isochron. Carbon, oxygen, sulfur and strontium compositions, of different minerals in these two kinds of ores, imply that the ore-forming hydrothermal fluids were probably derived from magma deep under the crust. The calcite ~(87)Sr/~(86)Sr ratios from the porphyry are consistent to the initial 87Sr/86Sr ratio of the Rb-Sr isochron of chalcopyrite and pyrite in the skarn ore, indicating that these two kinds of ores have the same source characteristic, although the porphyry deposit was formed probably 40 million years later than the skarn one according to our dating results. Skarn and skarn ores are usually considered as interaction product between carbonate wall-rocks and magmatic fluids, but the carbon of the sedimentary carbonate seems not involved in the skarn ores. Considering the connection of magmatic processes and hydrothermal ore formation in the Shouwangfen district, particularly, the spatial distribution of skarn-type and porphyry-type ores, it is possible that the Shouwangfen ore district corresponds to a hydrothermal ore-forming system, which was promoted by high-intruding magmatic rocks. Systematic stable isotopic research can help to reveal the upper part of this hydrothermal ore-forming system, which mainly related to heated and circulating meteoric water, and the lower part principally related to ascending magmatic fluids. Both skarn and porphyry ore-bodies are formed by up-intruding magmatic fluids (even more deep mantle-derived fluids).

甘肃金川II号岩体岩浆演化及铜镍硫化物成矿过程探讨

金川矿床是超大型岩浆 Ni-Cu-PGE 硫化物矿床，它赋存有世界第三的镍储量（5.45×106 t，Ni 的平均品位为 1.2%）。该矿床位于华北板块西侧阿拉善地块西南边缘龙首山隆起中。本论文以金川矿区的 II 号岩体为研究对象，在系统整理前人工作的基础上，通过深入细致的野外地质考察和系统采样，选取有代表性的样品，进行详细的显微镜鉴定，并运用元素地球化学等手段，对 II 号岩体的源区特征、岩浆演化过程及其赋存的⑴、⑵号矿体的成矿机制等主要矿床学问题进行了系统成因研究，并尝试提出了二次硫化物熔离成矿模式。本论文主要取得以下几点结论性成果： 1）岩浆起源：起源于上地幔尖晶石－石榴石二辉橄榄岩过渡地带的下部。通过上地幔源岩的柱状部分熔融模式（≥25%）或三角部分熔融模式（10～15%），形成富PGE的S不饱和原始岩浆。 2）地壳同化混染：地壳物质的同化混染主要是由早期下地壳物质的同化混染和晚期上地壳物质的同化混染组成的多阶段同化混染，并且其成分为富钙质围岩。 3）结晶分异演化：金川II号岩体作为橄榄石堆积相，其橄榄石的结晶主要发生在上地壳深部岩浆房，而橄榄石与熔浆的反应及辉石和斜长石的结晶则主要发生在浅部岩浆房，既现今岩体所在位置。 4）S 的饱和机制：岩浆通道内下地壳物质的同化混染，导致岩浆硫饱和，并于岩浆通道中发生了第一次硫化物熔离；上地壳深部岩浆房中地壳物质的同化混染和橄榄石的分离结晶，促使硫饱和的母岩浆发生了第二次硫化物熔离。 5）深部岩浆房的演化：上地壳深部岩浆房中橄榄石分离结晶与硫化物熔离之后，在重力分异作用下，形成了自上而下的硅酸盐岩浆、橄榄石“晶粥”、含硫化物熔体的橄榄石“晶粥”以及矿浆的四层分层格局。同时，底部部分硫化物熔体发生了Pt合金（Pt-Fe）的脱离。 6）侵入期次：上地壳深部岩浆房中，母岩浆分异演化早期，其顶部含有尚未完全成长橄榄石颗粒的“晶粥”在构造应力挤压下首先上侵、成岩形成金川II号岩体顶部、呈“上悬体”的中细粒含辉橄榄岩；分层格局形成之后，橄榄石“晶 VI 粥”、含硫化物熔体的橄榄石“晶粥”以及矿浆依次上侵成岩、成矿，分别形成金川 II 号岩体上部的二辉橄榄岩相、⑴、⑵号矿体的主体以及⑵号矿体底部的块状矿石。

地幔副矿物和硫化物的热（PVT）状态方程研究

矿物PVT状态方程是研究矿物在一定温压条件下的晶胞体积与温度、压力之间的关系，依据这个基本关系，可以了解矿物在高温高压下的密度、弹性、热膨胀等性质。矿物PVT状态方程的研究可以了解矿物在地球深部存在的结构状态，为进一步的理论计算提供基础的数据，其结果也可以与天然和人工地震的地震波反演的结果对比，对地球深部的地质作用过程、物质结构状态和组成进行限制。然而，目前矿物PVT状态方程的研究主要集中在氧化物矿物和上地幔主要矿物（橄榄石和辉石）及其高压相（瓦兹利石、林伍德石、方镁铁矿、Majorite、Mg-Perovskite、Ca-Perovskite）的研究上，对石榴石、尖晶石等地幔常见副矿物和硫化物矿物的PVT状态方程的研究很少。 作者在参与搭建并完善金刚石压腔外加温系统的基础上，利用北京同步辐射X射线衍射实验技术结合金刚石压腔外加温技术对天然铁铝榴石、锰铝榴石、铬尖晶石进行了PVT状态方程的研究，同时对闪锌矿、辰砂、方铅矿、辉钼矿、辉锑矿等硫化物矿物进行了相变及状态方程的研究。结合前人研究成果，讨论了类质同象置换对镁铝－铁铝系列石榴石、锰铝－铁铝系列石榴石、尖晶石和硫化物矿物相变及状态方程的影响。获得了以下研究结果： 1）镁铝－铁铝系列石榴石和锰铝－铁铝系列石榴石的体弹模量都随着铁铝榴石组分的增加而增大。其主要原因是在二价阳离子位置上Fe2+取代了Mg2+、Mn2+。在镁铝－铁铝榴石系列中Mg2+的共价键半径（1.36Å）要大于Fe2+的共价键半径（1.17Å），而Mg2+－O键长（2.270Å）与铁铝榴石中的Fe2+－O（2.299Å）键长基本相当。在锰铝－铁铝榴石系列中， 尽管Mn2+的共价键半径（1.17Å）与铁铝榴石中的Fe2+共价键半径（1.17Å）相等，但是Mn2+－O键长（2.326Å）大于Fe2+－O键长（2.299Å）。较小的键长和共价键半径将会增强离子间的结合力，从而具有较强的抗压缩能力，因此随铁铝榴石组分的增加，镁铝－铁铝榴石系列和锰铝－铁铝榴石系列具有较大的体弹模量。 2）首次获得了铬尖晶石（(Mg0.6766Fe0.2808Na0.0073Ti0.0014)0.9661(Cr1.4874Al0.5367)2.0241O4）的体弹模量的温度导数。结合前人关于其他组分尖晶石的实验结果发现，尖晶石中在四面体位置上发生Fe2+－Mg2+置换对体弹模量的影响要大于在八面体位置上发生Cr3+－Al3+置换对体弹模量的影响。而造成铬尖晶石的体弹模量值比其他组分尖晶石的体弹模量值大的主要原因也是四面体位置上的Fe2+－Mg2+的类质置换。 3）依据获得的尖晶石和石榴石的状态方程计算了不同地幔岩模型（橄榄岩和榴辉岩模型）的密度值在上地幔温压条件下的变化情况。结果表明，在尖晶石二辉橄榄岩模型中尖晶石含量的改变（2％－10％）会引起较大的密度变化（2.2％）；在石榴石二辉橄榄岩（石榴石含量14％－20％）和榴辉岩（石榴石含量37％－45％）模型中石榴石含量的变化几乎未引起其密度值的变化，但石榴石是这两种地幔岩模型中的重要组成矿物。 4）首次获得了辰砂的Cinnabar相、方铅矿的B33相、辉钼矿、辉锑矿体弹模量的温度导数和热膨胀系数。讨论了闪锌矿、辰砂、方铅矿的相变情况。 5）总结了锌的、汞的、铅的硫族化合物发生结构相变的规律。认为造成锌的、汞的、铅的硫族化合物的相变压力随阴离子原子序数的增加（S→Se→Te）而逐渐减小的原因是：元素周期表中相对较大原子序数的原子具有更多的核内电子，引起价电子及导带电子的有效位能相对变弱，引起电离能降低，因此在相对较低的压力下就容易发生结构相变。 6）分析了ZnS中Fe2+替代Zn2+、Sb2S3－Bi2S3、MoS2－WS2以及同族相同结构不同组分的简单硫化物矿物的阴、阳离子对体弹模量值的影响。认为简单硫化物矿物的体弹模量值取决于阴、阳离子的离子半径、电负性以及键长。

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Adsorption and interaction of H2S/SO2 on TiO2

Adsorption and interaction of H2S/SO2 on titania as well as on alumina for comparison has been studied by temperature programmed desorption (TPD), infrared (IR) spectroscopy and temperature programmed electronic conductivity (TPEC) techniques. It was found that the adsorption of both H2S acid SO2 on TiO2 is much greater than on Al2O3. The electronic conductivity of TiO2 measured by TPEC varies significantly as adsorption and desorption takes place on TiO2, showing a strong interaction between TiO2 and adsorbates. At temperature above 200 degrees C, H2S or SO2 adsorbed on TiO2 can be converted into S, H2O and SO2 or SO3. While on the hydrogen treated TiO2, H2S is decomposed into S and H-2, SO2 into S. The active sites on TiO2 surface cannot be so strongly adsorbed by SO2 that it is much more resistant to the sulfation reaction. Unlike TiO2, Al2O3 only provides surface adsorption sites, which can be readily sulfated. The data obtained support one's understanding why TiO2 exhibits a better catalytic performance than that of Al2O3 as a Claus reaction catalyst. (C) 1999 Elsevier Science B.V. All rights reserved.

XPS and XRD studies of fresh and sulfided Mo2N

Mo surface species of molybdenum nitride and their changes under sulfiding conditions were investigated by XRD and XPS. Mo2N was synthesized by temperature-programmed reaction of MoO3, with NH3. The decomposition of the Mo3d spectra gave a Mo3d doubler which corresponded to Modelta+ (2 less than or equal to delta < 4), Mo4+ and Mo5+ Or Mo6+ species. The BE of the Mo species of passivated Mo2N shifted to higher energy level compared with the freshly prepared Mo2N due to the oxidation of Mo nitride during passivation. When Mo2N was contacted for 4 h with a 15% H2S-H-2 mixture at 400 degrees C, the XRD spectra did not reveal any new phase, which indicates a high stability of Mo2N against sulfidation, but XPS data showed the presence of sulfur, including S-0 and S2- species, and a decrease of the N/Mo atomic ratio revealed some changes in surface composition. More than one monolayer of Mo2N was transformed to sulfide. It is probable that the oxygen incorporated during passivation reacted with sulfur and formed a thin layer of molybdenum sulfide on the Mo2N surface. (C) 1998 Elsevier Science B.V. All rights reserved.

Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney Nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C Is peak has disappeared, leaving nickel sulfide on the surface.

Determinação de cádmio e chumbo em brinquedos para crianças com idade inferior a 3 anos

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Synthetic and mechanistic aspects of the reactions of α-diazosulfoxides

The research described in this thesis focuses, principally, on synthesis of stable α-diazosulfoxides and investigation of their reactivity under various reaction conditions (transition-metal catalysed, photochemical, thermal and microwave) with a particular emphasis on the reactive intermediates and mechanistic aspects of the reaction pathways involved. In agreement with previous studies carried out on these compounds, the key reaction pathway of α-diazosulfoxides was found to be hetero-Wolff rearrangement to give α-oxosulfine intermediates. However, a competing reaction pathway involving oxygen migration from sulfur to oxygen was also observed. Critically, isomerisation of α-oxosulfine stereoisomers was observed directly by 1H NMR spectroscopy in this work and this observation accounts for the stereochemical outcomes of the various cycloaddition reactions, whether carried out with in situ trapping or with preformed solutions of sulfines. Furthermore, matrix isolation experiments have shown that electrocyclisation of α-oxosulfines to oxathiiranes takes place and this verifies the proposed mechanisms for enol and disulfide formation. The introductory chapter includes a brief literature review of the synthesis and reactivity of α-diazosulfoxides prior to the commencement of research in this field by the Maguire group. The Wolff rearrangement is also discussed and the characteristic reactions of a number of reactive intermediates (sulfines, sulfenes and oxathiiranes) are outlined. The use of microwave-assisted organic synthesis is also examined, specifically, in the context of α-diazocarbonyl compounds as substrates. The second chapter describes the synthesis of stable monocyclic and bicyclic lactone derivatives of α-diazosulfoxides from sulfide precursors according to established experimental procedures. Approaches to precursors of ketone and sulfimide derivatives of α-diazosulfoxides are also described. The third chapter examines the reactivity of α-diazosulfoxides under thermal, microwave, rhodium(II)-catalysed and photochemical conditions. Comparison of the results obtained under thermal and microwave conditions indicates that there was no evidence for any effect, other than thermal, induced by microwave irradiation. The results of catalyst studies involving several rhodium(II) carboxylate and rhodium(II) carboxamidate catalysts are outlined. Under photochemical conditions, sulfur extrusion is a significant reaction pathway while under thermal or transition metal catalysed conditions, oxygen extrusion is observed. One of the most important observations in this work was the direct spectroscopic observation (by 1H NMR) of interconversion of the E and Z-oxosulfines. Trapping of the α-oxosulfine intermediates as cycloadducts by reaction with 2,3-dimethyl-1,3-butadiene proved useful both synthetically and mechanistically. As the stereochemistry of the α-oxosulfine is retained in the cycloadducts, this provided an ideal method for characterisation of this key feature. In the case of one α-oxosulfine, a novel [2+2] cycloaddition was observed. Preliminary experiments to investigate the reactivity of an α-diazosulfone under rhodium(II) catalysis and microwave irradiation are also described. The fourth chapter describes matrix isolation experiments which were carried out in Rühr Universität, Bochum in collaboration with Prof. Wolfram Sander. These experiments provide direct spectroscopic evidence of an α-oxosulfine intermediate formed by hetero-Wolff rearrangement of an α-diazosulfoxide and subsequent cyclisation of the sulfine to an oxathiirane was also observed. Furthermore, it was possible to identify which stereoisomer of the α-oxosulfine was present in the matrix. A preliminary laser flash photolysis experiment is also discussed. The experimental details, including all spectral and analytical data, are reported at the end of each chapter. The structural interpretation of 1H NMR spectra of the cycloadducts, described in Chapter 3, is discussed in Appendix I.