大兴安岭南段中生代火山-侵入杂岩带的双层叠置构造体制兼论滇中武定、易门碳酸质火山岩年代、来源及矿库与找矿研究

These are two parts included in this report. In the first part, the zonation of the complexes in its series, lithofacies, the depth of magma source and chambers is discussed in detailed for the first time based on the new data of petrol-chemistry, isotopes, tectono-magma activity of Mesozoic volcano-plutonic complexes in the southern Great Hinggan Mts. Then, the genetic model of the zonality, double overlapped layer system, is proposed. The main conclusions are presented as follows: The Mesozoic volcanic-plutonic complexes in the southern Great Hinggan were formed by four stages of magma activity on the base of the subduction system formed in late Paleozoic. The Mesozoic magmatic activity began in Meso-Jurassic Epoch, flourished in late Jurassic Epoch, and declined in early Cretaceous Epoch. The complexes consist dominantly of acidic rocks with substantial intermediate rocks and a few mefic ones include the series of calc alkaline, high potassium calc alkaline, shoshonite, and a few alkaline. Most of those rocks are characterized by high potassium. The volcano-plutonic complexes is characterized by zonality, and can be divided mainly into there zones. The west zone, located in northwestern side of gneiss zone in Great Xinggan mountains, are dominated of high potassium basalts and basaltic andesite. The middle zone lies on the southeast side of the Proterozoic gneiss zone, and its southeast margin is along Huangganliang, Wushijiazi, and Baitazi. It composed of dominatly calc-alkaline, high potassium calc-alkaline rocks, deep granite and extrusive rhyolite. The east zone, occurring along Kesheketong Qi-Balinyou Qi-Balinzuo Qi, is dominated of shoshonite. In generally, southeastward from the Proterozoic gneiss zone, the Mesozoic plutons show the zones-mica granitites zone, hornblende-mica granitite zone, mica-hornblende granitite zone; the volcanic rocks also display the zones of calc alkaline-high potassium calc alkaline and shoshonites. In the same space, the late Paleozoic plutons also display the same zonality, which zones are combined of binary granite, granodiorite, quartz diorite and diorite southeast wards from the gneiss. Meso-Jurassic Epoch granite plutons almost distribute in the middle zone on the whole. Whereas late Jurassic Epoch volcanic rocks distribute in the west and east zone. This distribution of the volcano-plutonic complexes reveals that the middle zone was uplifted more intensively then the other zones in Meso-Jurassic and late Jurassic Epoches. Whole rock Rb-Sr isochron ages of the high potassium calc-alkaline volcanic rocks in the west zone, the calc-alkaline and high potassium calc-alkaline granite the middle zone, shoshonite in the east zone are 136Ma, 175Ma and 154Ma, respectively. The alkaline rocks close to the shoshonite zone is 143Ma and 126Ma. The isochron ages are comparable well with the K-Ar ages of the rocks obtained previously by other researchers. The compositions of Sr ans Nd isotopes suggest that the source of Mesozoic volcanic-plutonic complexes in Great Hinggan Mts. is mostly Paleo-Asia oceanic volcanic-sedimentary rocks, which probably was mixed by antiquated gneiss. The tectonic setting for Mesozoic magmatism was subductive continental margin. But this it was not directly formed by present west Pacific subduction. It actully was the re-working of the Paleozoic subduction system( which was formed during the Paleo-Asia ocean shortening) controlled by west Pacific subduction. For this reason, Although Great Hinggan Mts. is far away from west Pacific subduction zone, its volcanic arc still occurred echoing to the volcanic activities of east China, it, but the variation trend of potassium content in volcano-plutonic complexes of Great Hinggan is just reverse to ones of west Pacific. The primitive magmas occurred in the southern Great Hinggan Mts. Include high-potassium calc-alkaline basalt, high potassium calc-alkaline rhyolite, high potassium rhyolite, non-Eu negative anomaly trachy-rhyolite et al. Therefore, all of primitive magmas are either mafic or acid, and most of intermediate rocks occurring in the area are the products of Mesozoic acid magma contaminated by the Paleozoic volcanic- sedimentary rocks. The depth of those primitive magma sources and chambers gradually increase from northwest to southeast. This suggests that Paleozoic subduction still controlled the Mesozoic magmatism. In summary, the lithosphere tectonic system of the southern Great Hinggan Mts. controlling Mesozoic magmatism is a double overlapped layer system developing from Paleozoic subduction system. For this reason, the depth of crust of the southern Great Hinggan Mts. is thicker than that of its two sides, and consequently it causes regional negative gravity abnormity. The second part of this report shows the prolongation of the research work carried on in my doctor's period. Author presents new data about Rb-Sr and Sm-Nd isotopic compositions and ages, geochamical features, genesis mineralogy and ore deposit geology of the volcanic rocks in Kunyang rift. On the base of the substantial work, author presents a prospect of copper bearing magnetite ore deposit. The most important conclusions are as follows: 1. It is proved that all of these carbonatites controlled by a ringing structure system in Wuding-Lufeng basin in the central Yunnan were formed in the Mesoproterozoic period. Two stages could be identified as follows: in the first stage, carbonatitic volcanic rocks, such as lavas(Sm-Nd, 1685Ma), basaltic porphyrite dykes(Sm-Nd, 1645Ma), pyroclastic rocks and volcaniclastic sedimentary rocks, formed in the outer ring; in the second stage, carbonatitic breccias and dykes(Rb-Sr, 1048 Ma) did in the middle ring. The metamorphic age of the carbonatitic lavas (Rb-Sr, 893 Ma) in the outer ring was determined. The magma of carbonatitic volcanic rocks derived mainly form enriched mantle whose basement is depleted mantle that had been metasomated by mantle fluid and contaminated by Archaean lower crust. Carbonatitic spheres were discovered in ore bearing layers in Lishi copper mining in Yimen recently, which formed in calcite carbonatitic magma extrusion. This discovery indicates that the formation of copper ore deposit genesis relates to carbonatitic volcanic activity. The iron and copper ore deposits occurring in carbonatitic volcanic- sedimentary rocks in Kunyang rift results from carbonatitic magmatism. Author calls this kind of ore deposits as subaqueous carbonatitic iron-copper deposit. The magnetic anomaly area in the north of Lishi copper mining in Yimen was a depression more lower than its circumference. Iron and copper ores occurrig on the margin of the magnetic anomaly are volcanic hydrothermal deposit. The magnetic body causing the magnetic anomaly must be magnetite ore. Because the anomaly area is wide, it can be sure that there is a large insidious ore deposit embedding there.

地球化学新方法在隐状矿床找矿预测中的应用研究

With the progress of prospecting, the need for the discovery of blind ore deposits become more and more urgent. To study and find out the method and technology for the discovery of blind and buried ores is now a priority task. New geochemical methods are key technology to discover blind ores. Information of mobile components related to blind ores were extracted using this new methods. These methods were tested and applied based on element' s mobile components migrating and enriched in geophysical-geochemical process. Several kinds of partial extraction techniques have tested based on element' s occurrence in hypergenic zone. Middle-large scale geochemical methods for exploration in forest and swamp have been tested. A serious of methods were tested and applied effetely about evaluation of regional geochemical anomaly, 1:25000 bedrock or soil geochemical methods sampling based on the net in dendritic water system instead of the normal net. 1. Element related with ores can be mobiled to migrate upwards and be absorpted by surface soil. These abnomal components can be concentrated by natural or artificial methods. These trace metalic ions partially exist in dissovlvable ion forms of active state, and partially have been absorbed by Fe-Mn oxide, soil and organic matter in the soil so that a series of reaction such as complex reaction have take place. Employing various partial extraction techniques, metallic ions related with the phase of the blind ores can be extracted, such as the technique of organic complex extraction, Fe-Mn oxide extraction and the extraction technique of metallic ions of various absorption phases. 2.1:200000 regional geochemical evaluation anomaly methods: Advantageous ore-forming areas were selected firstly. Center, concentration, morphological feature, belt of anomaly were choosed then. Geological and geochemical anomalies were combined. And geological and geochemical background information were restrained. Xilekuduke area in Fuyun sheet , Zhaheba area in Qiakuerte sheet, the west-north part in Ertai sheet and Hongshanzui anomaly in Daqiao sheet were selected as target areas, in Alertai, in the north of Xinjiang. in Xilekuduke area, 1:25000 soil geochemical methods sampling based on the net in dendritic water system was carried out. Cu anomaly and copper mineralization were determined in the center area. Au , Cu anomalies and high polarization anomaly were determined in the south part. Prospecting by primary halo and organic complex extraction were used to prognosis blind ore in widely rang outcrop of bedrock. 1:25000 bedrock or soil geochemical methods sampling based on the net in dendritic water system were used in transported overburden outside of mining area. Shallow seismic method and primary halo found a new blind orebody in mining area. A mineralization site was fou and outside of Puziwan gold mine, in the north of Shanxi province. Developing middle-large scale geochemical exploration method is a key technique based 1:200000 regional geochemical exploration. Some conditions were tested as Sampling density , distribution sites of sample, grain size of sample and occurrence of element for exploration. 1:50000 exploration method was advanced to sample clast sediment supplement clast sediment in valley. 1:25000 bedrock or soil geochemical methods sampling based on the net in dendritic water system was applied to sample residual material in A or C horizon. 1:2000 primary or soil halo methods used to check anomalies and determine mineralization. Daliang gold mineralization in the northern Moerdaoga was found appling these methods. Thermomagnetic method was tested in miniqi copper-polymetallic ore. Process methods such as grain size of sample, heated temperature, magnetic separating technique were tested. A suite of Thermomagnetic geochemical method was formed. This method was applied in Xiangshan Cu~Ni deposit which is cover by clast or Gobi in the eastern Xinjiang. Element's content and contrast of anomaly with Thermomagnetic geochemical method were higher than soil anomaly. Susceptibility after samples were heated could be as a assessment conference for anomaly. In some sectors thermo-magnetic Cu, Ni, Ti anomalious were found outside deposits area. There were strong anomal ies response up ore tested by several kind of partial extraction methods include Thermomagnetic, enzyme leach and other partial extractions in Kalatongke Cu-Ni deposit in hungriness area in the northern of Xinjiang. Element's anomalies of meobile were mainly in Fe-Mn oxide and salt. A Copper mineralization site in Xilekuduke anomaly area had been determined. A blind ore was foung by shallow seismic and geochemical method and a mineralization site was found outside this mining area in Puziwan gold deposit in shanxi province. A Gold mineralization site was found by 1:50000 geochemical exploration in Daliang, Inner Mongolia.

REE characteristics of the Fanshan alunite deposit in Zhejiang Province, China

REE geochemistry data from the Fanshan alunite deposit indicated that its ore-forming materials came chiefly from the country rocks, with δCe〉0 for alunite ores. According to the differences in δEu, the alunite ores were divided into three types： weak negative Eu anomaly, weak positive Eu anomaly and remarkable positive Eu anomaly. The phenomena of Ce-enrichment in the ores indicated that the Fanshan alunite deposit was formed in an oxidizing environment. Variations in fO2 are corresponding to those in δEu： Eu anomaly varies from negative to positive with increasing fO2. And two other important factors may impact the occurrence of Eu anomalies： the contents of alkaline feldspar and the protolith structure in the mineralization period.

A preliminary discussion on the bio-metallogenesis of Tl deposits in the low-temperature minerogenetic province of southwestern China

Starting with the research status of bio-metallogenesis of Tl deposits and their geology, this work deals with the geological background of Tl enrichment and mineralization and the mechanism of bio- metal-logenesis of Tl deposits, as exemplified by Tl deposits in the low-temperature minerogenetic province. This research on the bio-metallogenesis of Tl deposits is focused on the correlations between bio-enrichment and Tl, the enrichment of Tl in micro-paleo-animals in rocks and ores, bio-fossil casts in Tl-rich ores, the involvement of bio-sulfur in minerogenesis and the enrichment of bio-genetic organic carbon in Tl ores. Thallium deposits have experienced two ore-forming stages: syngenetic bio- en-richment and epigenetic hydrothermal reworking (or transformation). Owing to the intense epigenetic hydrothermal reworking, almost no bio-residues remain in syngenetically bio-enriched Tl ores, thereby the Tl deposits display the characteristics of hydrothermally reoworked deposits.

湖南芙蓉锡多金属矿床成矿流体地球化学研究

锡的分布和成矿作用通常与花岗岩浆作用具有十分密切的联系。以往研究表明锡矿化与高度分异的S型花岗岩或陆壳改造型花岗岩具有密切的成因联系，但近年来随着大量与A型花岗岩有关的锡矿床的发现，人们开始关注A型花岗岩与锡成矿关系的研究。相对于与S型花岗岩有关的锡矿床来说，与A型花岗岩有关的锡矿床成成矿机理的研究积累少，研究程度相对较低。 湘南地区位于南岭多金属成矿带中部，是我国华南地区重要的有色金属成矿带。近年来在该成矿带上新发现的芙蓉超大型锡多金属矿床为世界瞩目，该矿床的形成与骑田岭花岗岩具有密切的时空关系。近年来研究显示骑田岭花岗岩具有A型花岗岩的特征。本文以芙蓉超大型锡多金属矿床和相关的骑田岭岩体为研究对象，在前人研究的基础上，运用岩石学、矿物学、流体包裹体、微量元素和稳定同位素地球化学等理论和方法，对芙蓉锡矿成矿流体的地球化学特征及其演化机制进行了系统的研究，并在此基础上探讨了骑田岭花岗岩体与芙蓉锡矿间的成因联系和芙蓉锡矿的成因机制。论文取得的主要认识包括以下几个方面： 1. 运用矿物学、岩石化学、微量元素地球化学以及同位素地球化学方法，进一步证实了骑田岭花岗岩体具有A型花岗岩的特征，总体具有偏铝质-弱过铝质、高硅富碱高钾的地球化学特征，早晚两期花岗岩具有同源岩浆演化特征，属于A2型花岗岩。同位素地球化学数据显示花岗岩体具有EMII型富集地幔的特征，形成于华南大陆地壳拉张减薄的构造环境，成岩过程中有地幔物质加入。 2. 通过对矿石矿物组构和成分的岩矿鉴定、扫描电镜和电子探针分析，确定了芙蓉锡多金属矿床原生夕卡岩形成于较氧化的环境，成岩作用主要与早期侵入的角闪石黑云母花岗岩密切相关，锡主要以Sn(IV)进入夕卡岩的造岩矿物晶体内。退蚀变夕卡岩、云英岩和蚀变花岗岩矿化为锡成矿主阶段，三种矿化类型的成矿流体具有相似的地球化学性质，即富Cl、Ti和Sn的特征，而锡石硫化物型矿石形成于成矿晚阶段。 3. 运用流体包裹体地球化学理论和方法以及激光拉曼分析技术，揭示了芙蓉锡矿的成矿流体组成、形成的物理化学条件和演化特征。芙蓉锡多金属矿田成矿流体为CO2-CH4-CaCl2- NaCl-KCl不混溶体系，成矿过程中发生流体不混溶作用。芙蓉锡矿成矿流体盐度为0~50.63 wt%NaCl eq.，密度为0.31~1.12g/cm3，主成矿阶段热液流体的均一温度主要集中在300-450℃，流体压力为179-1800bar，成矿晚阶段锡石硫化物型矿石中均一温度主要集中在150~300℃，流体压力为400-600bar。成矿流体特别是主成矿阶段的流体成矿过程中普遍发生了沸腾现象。从主成矿阶段到成矿晚阶段、矿化期后，热液流体盐度呈降低的趋势，流体成分也从含CO2、CH4的CaCl2-NaCl-KCl-H2O水溶液体系转化为不含CO2的简单NaCl-KCl-H2O水溶液体系。 4. 通过分析主要矿化类型矿石中脉石矿物的稀土元素和稳定同位素特征，揭示了成矿流体来源。研究表明芙蓉矿床成矿期热液脉石矿物的稀土元素地球化学和稳定同位素地球化学显示了与本区花岗岩具明显的相似性，骑田岭黑云母花岗岩形成过程中分异出的岩浆期后热液应是芙蓉矿床成矿流体的主要来源，成矿过程中有少量经过深循环的大气降水加入。 5. 在总结前人研究成果的基础上，综合上述研究，探讨了骑田岭花岗岩体与芙蓉锡矿间的成因联系和芙蓉锡矿的成因机制。本文认为骑田岭岩体中黑云母花岗岩与Sn成矿具有密切的成因联系，芙蓉锡矿田的成矿流体主要来源于黑云母花岗岩岩浆结晶期后分异出的富Cl和Sn的热液流体。芙蓉锡矿成矿流体中锡主要呈Sn(II)与氯离子形成亚锡氯络合物进行迁移，低温的大气降水与高温的岩浆热液流体混合，导致流体体系温度、盐度、压力的降低和富CO2相流体的分离（CO2去气作用），流体的氧逸度升高，使得Sn(II)与氯离子形成亚锡氯络合物解体，Sn(II)被氧化成SnO2并发生沉淀作用。这种流体的混合作用是导致锡石沉淀的最有效的机制。

香花岭锡多金属矿床同位素年代学及地球化学

华南地区中生代地壳拉张、岩石圈伸展减薄与大规模成岩成矿作用的时代分布格局和地球动力学背景一直是国内外关注的重要科学问题。富碱侵入岩及其有关的成矿作用是伸展构造的直接表现之一。近年来的研究发现，南岭中段花山－西山－香花岭－骑田岭NE向的花岗岩带为一中晚侏罗世形成的具有高εNd(t)和低Nd模式年龄的富碱侵入岩带，并伴有大规模的钨锡多金属成矿作用，是研究大规模地壳拉张、岩石圈伸展减薄与该区大规模的钨锡多金属成矿作用的耦合关系及其深部动力学机制的理想对象。本文以香花岭地区花岗岩及其有关的钨锡多金属矿床为研究对象，运用岩石学、元素地球化学、同位素地球化学等方法手段，对香花岭矿区花岗岩的成因和形成构造环境、成矿物质与成矿流体的来源、成矿年代学及成岩成矿的地球动力学背景等方面进行了系统研究，并初步建立了该矿的成矿模式。论文主要获得以下认识： （1）通过对香花岭矿区癞子岭和尖峰岭岩体的主、微量元素及Sr、Nd同位素研究，查明上述两个岩体均具有高硅、富碱及成矿元素，富LILE及Zr、Ga等部分高场强元素(HFSE)，贫Ca、Mg，P，Eu，较高的εNd及较低的Nd模式年龄等特征，具有相同的岩浆源区，属于后造山背景下形成的铝质A型花岗岩（A2型），具有壳、幔混合来源。 （2）利用白云母Ar-Ar同位素定年手段对香花岭锡多金属矿床、香花铺钨多金属矿床及尖峰岭云英岩型锡多金属矿床进行了成矿年代学研究，并首次对该矿的矿石矿物－锡石进行了U-Pb同位素定年。结果表明，香花岭地区钨锡多金属矿床的成矿时限为154-161 Ma，与矿区花岗岩黑云母K-Ar年龄相一致，并与区域主要钨锡矿床的形成时间一致。 （3）微量元素、稀土元素及同位素地球化学的研究表明，香花岭锡多金属矿床与矿区花岗岩具有密切的成因联系，矿区花岗岩不仅为该区成矿作用提供热动力和介质条件，而且为成矿作用提供了主要的物源。此外，矿区内的赋矿地层可能提供了部分成矿物质。早期成矿流体以岩浆水为主，晚期有大量大气降水的加入。 （4）对香花岭锡多金属矿床锡的超常富集机制作了初步探讨，认为该区锡的超常富集可能归功于如下几个因素：首先，富含F等挥发分的花岗岩浆高度分异演化出富含挥发分及成矿元素的超临界流体，成矿流体在流经赋矿地层时萃取了其中的部分成矿元素；其次，伴随着围压的不断降低，成矿流体发生了沸腾及连续的去气作用，导致了成矿流体的高度浓缩，当流体达到饱和或过饱和时，成矿元素沉淀成矿；最后，早期形成的矿床进一步受到后期的叠加改造，从而形成该区高品位的锡矿石。 （5）根据上述研究，香花岭锡多金属矿床与矿区花岗岩具有密切的时间、空间及成因联系，二者应为同一构造背景下形成的产物。结合区域上的研究，香花岭矿区的成岩成矿作用与南岭中段同时代的其他钨锡多金属矿床具有相同的地球动力学背景。这种构造背景可能与该区中－晚侏罗世构造体制转换，地壳拉张－岩石圈伸展减薄背景下，软流圈地幔上涌及发生壳、幔相互作用密切相关。 （6）初步建立了香花岭锡多金属矿床的成因模式：在该区中晚侏罗世大规模地壳拉张、岩石圈伸展减薄背景下，地幔物质上涌到中下地壳，发生壳幔相互作用，形成壳幔混合的花岗岩浆。花岗岩浆经充分分异演化，形成富含挥发分和成矿元素的一种具超临界性质的成矿流体。成矿流体在上升过程中随着围压的不断降低，发生了连续的去气作用，使得成矿流体高度浓缩并沿有利的构造部位成矿，并在后期受到改造、叠加等成矿作用，以至于形成了该区最富的锡矿床。

湖南柿竹园多金属矿尾矿锡综合利用前景分析

柿竹园有色金属矿山是我国已经探明的地质资源储量最大的钨、钼、锡、铋等多金属矿山，其中锡累计探明储量达48万吨。目前柿竹园仅回收钨、铋、钼、铅、锌、萤石矿等，大量锡随着钨、钼、铋等金属的开采作为废料进入尾矿，因此在尾砂库中保留了丰富的锡资源。对柿竹园尾矿中锡进行回收再利用，必须首先对其综合回收利用途径与前景作出科学评价。本文对柿竹园多金属矿床Ⅲ矿带锡的赋存形式、千吨尾矿库尾矿物质组成特征、锡的丰度、赋存形式和分布进行了研究，在此基础上分析柿竹园尾砂锡综合回收利用的前景。

骑田岭A型花岗岩成演过程中流体聚集及其对锡成矿的制约

以往研究表明锡成矿与S型花岗岩具有密切的成因联系。近年来随着大量与A型花岗岩有关的锡矿床的发现，有关锡成矿与A型花岗岩关系的研究成为地学界关注的热点。 芙蓉超大型锡多金属矿床位于我国著名的南岭钨锡多金属成矿带上，锡矿体位于骑田岭A型花岗岩体的内部或者岩体与围岩的内外接触带。成岩成矿年代学研究表明，成岩与成矿为前后相继的地质事件，具有密切的时空关系。本论文以与芙蓉超大型锡多金属矿床有密切时空关系的骑田岭A型花岗岩为研究对象，在详细野外地质调查的基础上，运用岩石学、矿物学、矿物化学、同位素地球化学、流体地球化学等学科的理论和方法，对骑田岭花岗岩的岩石学特征、岩石成因、成岩物理化学条件、岩浆分异的流体特征、挥发性组分特征以及成岩与成矿的关系等方面进行详细的分析，探讨骑田岭花岗岩成岩过程中流体聚集的机制及其对锡成矿的制约，初步揭示A型花岗岩与锡成矿之间的本质联系。本论文主要取得以下成果和认识： （1）通过对与锡矿有关的骑田岭花岗岩体的主量、微量、稀土元素、同位素和花岗岩中黑云母的微量、稀土元素分析研究发现：骑田岭角闪石黑云母花岗岩和黑云母花岗岩为高度分异演化的花岗岩，具有高硅、富铝、富碱、高钾的特征。随着岩体分异演化程度的增加，花岗岩总体向富硅、富碱的方向演化。岩体轻重稀土分异明显，表现为右倾型模式，Eu负异常明显，表现为中等-强烈的负Eu异常。岩体明显富集Rb、Th等大离子亲石元素及Zr、Hf等高场强元素，而亏损Ba、Nb、Sr、P、Ti。骑田岭花岗岩两个阶段岩石有着相似的Sr、Nd同位素特征，揭示其具有相同的物质来源，是同源岩浆演化的产物，为具壳幔混合特征的A2型花岗岩。 （2）对骑田岭花岗岩体矿物学和矿物化学特征、全岩Sn含量分析研究发现：角闪石黑云母花岗岩的结晶温度为774~796℃，氧逸度（logfO2）为-15.30~-15.0。黑云母花岗岩的结晶温度为714~784℃，氧逸度（logfO2）为-17.5~-20.0。随着岩浆的演化，从角闪石黑云母花岗岩到黑云母花岗岩随着结晶温度的降低，氧逸度也随之减小。随着岩浆的演化，岩体中Cl含量不断的减少，而F含量有所增加，Cl趋向分配进入流体相。随着岩浆分异演化程度的增加，岩体成岩温度降低，氧逸度减小，岩体中Sn含量不断的减少，Sn趋向分配进入富Cl流体，表明岩浆演化过程中分异出富Cl、富Sn的流体。 （3）骑田岭花岗岩石英斑晶中的包裹体研究表明：骑田岭角闪石黑云母花岗岩和黑云母花岗岩在岩浆演化过程中经历了两个阶段，即岩浆阶段和岩浆-热液阶段，分别以出现熔融包裹体、流体-熔融包裹体为特征，其中流体-熔融包裹体的出现是岩浆分异流体的直接证据。结合矿物的结构、构造特征，研究发现骑田岭花岗岩浆演化过程分异出流体。骑田岭花岗岩原生流体包裹体地球化学研究表明，岩浆分异出的流体为H2O-CO2-NaCl-KCl-CaCl2不混溶体系，具有盐度高（32.98~52.04Wt%NaCleq.），密度低（0.27~0.95g/cm3），均一温度较高（190~ 494℃）的特征，压力为600~800bar，成岩过程中发生了沸腾现象。 （4）对芙蓉超大型锡矿床和骑田岭花岗岩研究表明，锡矿与花岗岩有着密切的时间、空间和成因联系。矿体产在花岗岩体内部或者岩体与围岩的接触带，成岩与成矿时限一致，随着岩浆分异演化程度的增加，岩体成岩温度降低，氧逸度降低，岩体中的挥发性组分Cl含量减小，而F含量增加，Cl趋向分配进入流体相，这种流体萃取熔体中的成矿元素Sn，并以氯络合物形式迁移。可以认为，随着岩浆的演化，骑田岭花岗岩岩浆结晶期后分异出的热液流体具有富Cl和Sn的特征。芙蓉超大型锡多金属矿床的成矿流体应主要来源于黑云母花岗岩岩浆结晶期后分异出的岩浆热液。

贵州省遵义市大气降水中有机和无机地球化学特征研究

正确认识降水中的化学组分是评价酸雨和大气环境质量的重要途径，降水中低分子有机酸的研究是认识C、H、O等元素生物地球化学循环和酸雨成因的重要内容。贵州省遵义市作为我国酸雨高发地区，是降水化学组成尤其是低分子有机酸地球化学循环研究的典型区域。我们在遵义市进行了为期一年(2006年5月~2007年4月)的降水采集(共76个样品)，对pH值、电导率和主要的阴离子(包括有机和无机)、阳离子进行了测定，并进行了分析和讨论。 (1) pH和电导率的雨量加权平均值分别为4.11(范围：2.30~ 6.04)和62.10 μs•cm-1 (范围：6.60 ~ 1630.00 μs•cm-1)，酸雨频率高达93.2%，pH存在着显著的季节变化，其中冬季pH值最低，表明遵义市酸雨污染较为严重，冬季为最。 (2) 遵义市监测期间离子浓度的大小顺序为SO42-> Ca2+> H+> NH4+> NO3-> Cl-> F->HCOO-> Mg2+> K+> CH3COO-> Na+> (COO)22-> PO43-> NO2-，其中SO42-、Ca2+、H+、NH4+、NO3-是最主要离子，浓度分别为148.15 μmol•L-1、81.89 μmol•L-1、77.74 μmol•L-1、43.80 μmol•L-1和31.50μmol•L-1，它们分别占离子总量的31.97%、17.67%、16.78%、9.45%和6.54%；遵义市大气降水中主要的致酸物质是SO42-和NO3-，主要的缓冲物质是Ca2+和NH4+，大气污染类型属硫酸钙型。相对酸度和中和因子结果表明降水中仅有77%的降水酸度被碱性物质(以Ca2+和NH4+为主)中和；因子分析中H+、NO3-、nss-SO42-(非海源性硫酸根)、NH4+归为一组，再次表明SO42-和NO3-对降水酸度的重要贡献。富集系数和源的贡献分析表明，SO42-和NO3-主要来自人为活动的贡献，SO42-来源主要包括工业、民用的燃煤燃烧释放的SO2，NO3-主要是遵义市电厂和其它工厂向大气中排放的NOx的化学转化而成。Ca2+主要来自于遵义市的土壤及水泥厂等的排放；Mg2+主要来自陆源输入，部分来自海水的贡献。氮肥生产、大面积农田化肥的使用以及生物排放源很可能是该地区降水中NH4+的主要污染源。值得注意的是，作为海盐性离子的Cl-，在遵义市降水中重要的部分还是人为活动，主要是遵义工厂(如碱厂和钛厂)向大气中排放的HCl和Cl2转化而成。无机离子浓度的季节变化表明，对于遵义市，需要逐步改变能源结构尤其是冬季工业、居民燃煤的使用，才能有效地改善遵义市当前的环境污染。 (3) 遵义市降水中含量较高的常见有机酸是[HCOO-]T、[CH3COO-]T和[(COO)22-]T，它们的雨量加权平均值各为9.29 μmol•L -1、6.47 μmol•L-1和5.06 μmol•L-1；遵义市区降水中有机酸总浓度为22.28 μmol•L-1，占阴离子总量的9.39 %；遵义市降水中四季的有机酸浓度由高到低分别为：春季>冬季>秋季>夏季。以上结果表明，遵义市的有机酸是降水中的重要组成部分，其浓度存在明显的季节性变化。在一次降雨事件中，有机酸的浓度一般随降雨时间的延长而降低，但在降雨中后期有时会出现上升的现象，表明有机酸主要来自云下淋滤作用，少数情况下来自大气远距离的传输。 (4) 相关性分析发现甲酸和乙酸具有强烈的正相关(r= 0.86)，表明甲酸和乙酸具有共同的来源。有机酸与降水中的主要无机离子NO3-、nss-SO42-、K+、Na+、Ca2+等存在着中度相关，表明有机酸的来源与人为活动有着重要的关系。应用气液平衡的原理，提出了降水中甲酸、乙酸比值(F/A)aq的有机酸来源判定方法。发现遵义降水中的有机酸春季和冬季主要来自人类活动的释放，其中春季主要来自遵义市南郊的工业污染，由南方水汽(占春季总量的54%)将其污染物传输至遵义市中心城区，冬季主要是大量燃煤的燃烧释放；夏季和秋季则主要来自植物的释放，其中秋季中的部分有机酸也受到华中和华东地区(其气团占秋季总量的45%)的远距离影响。而遵义市区的山间盆地地形、高湿度、高静风率和低风速、以尘埃为主的大气污染物和有机酸的短生命周期(几小时~几天)为有机酸来源于当地创造了有利条件。 (5) 根据热力学平衡计算新方法，发现遵义市pH≤5的降水中甲酸和乙酸对自由酸度的贡献分别为14.79% (范围：0.42~91.14%)、3.66% (范围：0.02~31.55%)。对比显示，遵义市的有机酸贡献量低于边远地区，主要由于遵义市降水的低pH值和高无机酸度所致。在春、夏、秋、冬季节，降水中的有机酸对自由酸度的平均贡献值分别为31.95%、26.16%、8.02%、11.17%，表明有机酸酸度有着明显的季节性差异，春季有机酸的高贡献量主要受降水中的有机酸高含量、低水温和高pH值的共同作用，夏季受高pH值的影响，而秋季和冬季的低贡献量主要受降水的低pH值所控制。 (6) 在遵义市的沉降通量中，无机离子的湿沉降通量占所有离子湿沉降总量的94%，并存在明显的季节性变化。SO42-、Ca2+、H+、NH4+、NO3-为最主要的贡献者，分别为90.1、49.8、47.3、26.0和19.2 mmol•m-2•yr-1。对比显示，SO42-、Ca2+、H+的沉降量均属于我国的高值区，而NO3-的沉降量属于我国中值区，NH4+的沉降量属我国低值水平。营养元素总无机氮TIN(TIN= NH4+ -N+ NO3- -N+ NO2- -N)的湿沉降总量为45.7 mmol•m-2•yr-1，其中NH4+和NO3-分别占TIN的57.0%和41.9%，遵义地区高TIN值当地氮肥的施用量和工业NOx的释放量密不可分；营养元素P的沉降量为1.97 mmol•m-2•yr-1，由于P的来源较少，促使P的湿沉降通量较低。有机酸占湿沉降总量的6%，其四季的湿沉降量顺序由高到低依次为：春>秋>冬>夏，这是有机离子的浓度和四季的降雨量共同作用的结果。根据气液平衡理论可知，挥发性有机酸(HCOO-、CH3COO-和CH3CH2COO-)的干沉降量占总沉降量的47.2%，表明遵义市有机酸沉降方式包括干湿沉降两种。因此在研究遵义市的污染物尤其是有机酸类对生态系统和城市建设的影响时，有必要同时收集气样和水样。

锡在流体和花岗质熔体间分配行为的实验研究

锡矿床是与花岗岩在时间、空间、成因上有着密切联系的典型矿种之一。与锡矿有关的花岗岩多具有过铝、富钾、硅含量高的特征。传统观点认为与锡矿有关的花岗岩主要是S型花岗岩，可是近年在国内外相继发现了许多具有重要经济价值的锡矿床与富碱侵入岩有着密切成因联系。与富碱侵入岩有关的锡成矿作用日益受到地质学家的重视，锡矿床与富碱侵入岩的关系已成为研究热点之一，相关的研究工作虽然取得了很大的进展，但是富碱侵入岩体能否分异出富锡成矿流体还存在争议。研究表明，与岩浆岩有关的成矿与岩浆演化过程中成矿元素在流体-熔体相间的分配行为有着密切的关系。成矿元素在流体-熔体相间的分配行为除受到温度、压力及氧逸度等物理化学条件的制约外，还受到岩浆熔体成份及岩浆分异出来的流体化学组成的影响。以往有关锡在流体-熔体相间分配行为的实验研究主要侧重于改变流体相来观测锡的分配系数，且多为单一的含氯或含氟岩浆体系，这制约了对岩浆演化过程中元素在流体-熔体相间分配行为的深入认识。本文通过改变流体相、熔体相的化学组成，开展了一系列锡在流体和花岗质熔体相间分配行为的实验研究。综合分析了锡在晶体-熔体-流体间的分配行为，并结合地质实际探讨与富碱侵入岩有关的锡成矿的物理化学条件和成矿机理。研究成果对深入认识与花岗岩有关锡矿的成矿机理、丰富和完善与花岗岩有关的锡成矿理论、为进一步探索与花岗岩有关的锡成矿规律提供重要的实验依据。此外，实验对进一步推动实验地球化学学科发展具有重要意义。 实验在中国科学院地球化学研究所矿床地球化学国家重点实验室的成矿实验室完成，主要实验设备为快速内冷（RQV）高压釜。实验的温度为850℃，压力100MPa、氧逸度接近NNO。实验首先采用人工合成硅酸盐凝胶的方法制成具有不同化学组成的花岗质熔体，使用分析纯化学试剂配制不同成分和不同浓度的溶液，分别作为实验初始固液相。主要开展了三方面的实验研究：1．熔体相组成不变，以改变流体相组成来观察锡的分配行为。这组实验固相初始物为过碱质富钾的硅酸盐，初始液相分别为NaCl、KCl、HCl、HF、去离子水溶液；2．流体相组成不变，改变熔体化学组成观察锡分配行为。初始液相选用低浓度的0.1mol/L HCl溶液，熔体相为具不同化学组成的凝胶（其中一组改变熔体碱质含量和铝饱和指数ASI、另一组改变熔体钠钾摩尔比值）；3．氟氯共存含水的花岗质岩浆体系中氟氯含量相对变化时锡分配行为。实验通过改变熔体相中氟含量和液相盐酸溶液的浓度来观察锡在含氟硅酸盐熔体和不同浓度盐酸溶液间的分配行为。氟主要以(NaF+KF)混合物的形式加入初始固相中。实验研究结果表明： 1．流体相络阴离子种类及含量对锡在流体-熔体相间的分配行为有着明显的影响。当流体相中络阴离子Cl－、F－含量增大时，有利于增大锡在流体-熔体相间的分配系数；尤其当流体为富氯的酸性流体时，锡在流体-熔体相间的分配系数随液相中HCl浓度的增大而增大并存在关系式logD Sn=2.0247×log[HCl]＋0.6717（[HCl]的单位为mol/L），锡在流体相中主要以二价锡氯配合物的形式迁移，锡倾向于分配进入富氯的酸性流体中。此外，富氯酸性流体与共存的熔体反应后，熔体中的碱质含量降低，铝饱和指数增大。 2．熔体化学组成对锡在熔体相/流体相的分配行为有着明显的影响。D Sn随着熔体中碱质含量增大而减小：D Sn=－0.0489×MAlk＋0.4516, R2=0.98（MAlk为熔体中Na2O+K2O摩尔含量），表明富碱质熔体有利于锡在熔体相中富集，从而可能为锡矿形成提供矿质来源。D Sn随熔体ASI值的增大而增大：D Sn=0.1886×ASI－0.1256, R2=0.99，即过铝质熔体相对有利于锡分配进入流体相中。过铝质熔体中碱质总量及其它组分相对不变的前提下，熔体钠钾摩尔比值越高D Sn越小：D Sn=－0.0314×RNa/K＋0.0483, R2=0.82（RNa/K为Na/K摩尔比值），富钠的熔体有利于锡分配进入熔体相，而富钾的熔体却相对有利于锡分配进入流体相中。 3．在氟氯共存花岗质岩浆体系中：①熔体相中氟含量对氯在流体-熔体相间的分配有着明显影响，熔体中氟含量降低有利于氯分配进入流体相。②熔体中氟含量大于约1 wt%后，D Sn小于0.1且变化不大，当液相富含HCl且熔体中氟含量从约1 wt%降低后，D Sn 迅速增大，即熔体中氟含量小于约1 wt%后锡倾向于分配进入富氯的酸性流体中。而富氟（F含量大于约1 wt%）的熔体有利于萃取锡并使锡在熔体相中富集。③熔体铝饱和指数ASI值越大，相应锡的分配系数越大；流体相中HCl浓度增大时，锡分配系数随之增大；当熔体为过铝质的花岗质熔体、流体富含HCl时有利于锡分配进入流体相。 分析总结与花岗岩有关的锡成矿特征和锡在不同晶体相和熔体相间的分配行为得出：壳源铝质、富碱、富挥发份、贫钙铁镁的岩浆在结晶分异演化过程中相对有利于锡在残余熔流体相中富集。因此，具有这些特征的岩浆结晶分异演化产生的晚期岩浆可富含锡，能为后期锡矿床的形成提供矿质来源。这种富锡富挥发份的岩浆在上侵过程中，当温度压力降低、岩浆水饱和度增大、硅含量增大、熔体相氟含量降低时，可分异出含氯富锡的成矿流体。 根据上述结论，分析了与湖南芙蓉锡矿床有着密切成因联系的骑田岭花岗岩的岩石化学特征、成岩成矿物理化学条件，得出芙蓉锡矿床成矿流体可由骑田岭晚期岩浆分异产生。 最后得出如下认识：1)当花岗质岩浆体系水不饱和、流体相络阴离子浓度低的情况下，锡倾向于分配进入熔体相中；2)水饱和富含挥发份的过铝、富钾的岩浆体系有利于锡分配进入流体相；3) 铝质、富钾、富挥发份的富碱侵入岩岩浆演化过程中可在有利的物理化学条件下分异出富锡的流体相，与芙蓉超大型锡矿床有成因联系的骑田岭富碱侵入岩体成岩过程中可分异出富锡的成矿流体。

滇东南都龙锡锌多金属矿床矿物学及年代学

都龙锡锌多金属矿床位于云南省马关县都龙镇，是我国最大的锡石硫化物矿床之一。在野外地质和岩矿鉴定基础上,本文对该矿床的绿泥石、鲕状黄铁矿、磁黄铁矿异构交生体、铁闪锌矿的“黄铜矿疾病”等矿物和特殊组构，开展了比较系统的电子探针、拉曼光谱和X光衍射等微束分析，结合对该矿床的黑云母Ar-Ar年代学、锡石TIMS法U-Pb年代学研究，基本明确了矿床各个成矿期次的具体成矿特点，丰富和完善了该矿床的成矿模式。论文取得的主要认识有： （1）绿泥石与锡矿化同为燕山期岩浆热液作用的产物。绿泥石的形成温度（231~304oC）和环境（还原环境）表明，岩浆热液叠加成矿环境为中、低温的还原环境。 （2）鲕状黄铁矿为热水沉积期的特征矿物，是Fe、Zn、S等成矿元素的主要物源。 （3）磁黄铁矿主要在区域变质晚期，由黄铁矿（主要为鲕状黄铁矿）变质脱硫而成。辣子寨矿段单斜磁黄铁矿的出现，说明燕山期岩浆热液叠加成矿温度在该矿段以中低温为主。 （4）铁闪锌矿的“黄铜矿疾病”主要是黄铜矿交代铁闪锌矿的结果，其中的Fe主要来自变质期形成的铁闪锌矿和磁黄铁矿，而Cu主要来自岩浆热液。 （5）自然铋、自然银、锡石、黄铜矿、方铅矿等矿物广泛共生，且交代、穿切其他矿物，表明岩浆热液期的成矿元素组合主要为Bi+Ag+Sn+Cu+Pb。在该矿床首次发现的自然铋和自然银，指示岩浆热液期为低硫、中低温的还原环境。 （6）利用远红外（IR-Laser）阶段加热技术，获得黑云母的低温段和高温段坪年龄，分别为179.0± 5 .0Ma和195.7± 6.6Ma。在黑云母组构显微分析的基础上，认为179.0± 5 .0Ma大致代表了变质成矿作用的年龄。 （7）都龙锡锌多金属矿床属于多成因复成矿床，其形成主要经历了热水沉积、变质改造和岩浆热液叠加三个过程。热水沉积成矿作用形成的鲕状黄铁矿，可能是后期成矿作用中Fe、Zn、S等成矿元素的主要物源。变质改造成矿作用与印支期晚期区域变形-变质作用有关，形成了大量铁闪锌矿、磁黄铁矿，可能对应于造山后伸展事件。岩浆热液叠加成矿作用与燕山晚期老君山花岗岩有关，发生大规模的锡、铜、银、铅、铋矿化。 另外，本次研究在该矿床中首次发现了自然铋、自然银等自然元素，其矿床成因意义有待进一步研究。

Electrode catalysts behavior during direct ethanol fuel cell life-time test

In the present paper, a 60 h life-time test of a direct ethanol fuel cell (DEFC) at a current density of 20 mA cm(-2) (the beginning 38 h) and 40 mA cm(-2) (the last 22 h) was carried out. After the life-time test, the MEA could not achieve the former performance. X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX) were employed to characterize the anode and cathode catalyst before and after the life-time test. The XRD and TEM results showed that the particle size of the anode catalyst increased from 2.3 to 3.3 nm and the cathode from 3.0 to 4.6 nm. The EDX results of PtSn/C anode catalysts before and after the life-time test indicated that the content of the oxygen and tin, especially the content of the platinum, decreased prominently after the life-time test. The results suggest that the agglomeration of electrocatalysts, the destruction of the anode catalyst together with the fuel/water crossover from anode to cathode concurrently contribute to the performance degradation of the DEFC. (C) 2005 Elsevier B.V. All rights reserved.

Size-controllable synthesis of monodispersed SnO2 nanoparticles and application in electrocatalysts

Size-controllable tin oxide nanoparticles are prepared by heating ethylene glycol solutions containing SnCl2 at atmospheric pressure. The particles were characterized by means of transmission electron microscopic (TEM), X-ray diffraction (XRD) studies. TEM micrographs show that the obtained material are spherical nanoparticles, the size and size distribution of which depends on the initial experimental conditions of pH value, reaction time, water concentration, and tin precursor concentration. The XRD pattern result shows that the obtained powder is SnO2 with tetragonal crystalline structure. On the basis of UV/vis and FTIR characterization, the formation mechanism of SnO2 nanoparticles is deduced. Moreover, the SnO2 nanoparticles were employed to synthesize carbon-supported PtSnO2 catalyst, and it exhibits surprisingly high promoting catalytic activity for ethanol electrooxidation.

Structure and chemical composition of supported Pt-Sn electrocatalysts for ethanol oxidation

Carbon supported PtSn alloy and PtSnOx particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0-3.0 nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnOx nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnOx clearly shows that the change of the spacing of Pt (111) plane is neglectable, meanwhile, SnO2 nanoparticles, characterized with the nominal 0.264 nm spacing of SnO2 (10 1) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (111) plane extends to 0.234 nm from the original 0.226 nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnOx catalyst. PtSnOx catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnOx catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites. (C) 2005 Elsevier Ltd. All rights reserved.