班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

土法炼锌导致土壤中铅分布特征和形态变化的研究

对贵州省赫章县土法炼锌区土壤中Pb分布特征和形态变化进行了研究.各炼锌点表层土壤中全铅含量71.8～37 247.4mg·kg^-1,远高于贵州省土壤背景值（29.3 mg·kg^-1）.其分布特征表现为：土壤中Pb含量总趋势随着炼锌时间增加而增加,随着距废渣堆的距离增加而降低.剖面中全铅含量分析表明Pb主要累积在土壤表层,但随着冶炼时间增加深层土壤中Pb累积程度也逐渐加大.以CaCl2和DTPA作为提取剂的简化连续提取法对土壤中Pb形态进行分析,结果显示,土壤中CaCl2和DTPA提取态Pb占全量的比例很低,平均值分别为0.3%和5%,但是其绝对含量高达6.4～1 037mg·kg^-1;并随着Pb在土壤中累积时间的加长,CaCl2和DTPA提取态Pb所占比例呈显著降低的趋势,但其绝对含量逐渐增加.

土法炼锌导致Cd对土壤-农作物系统污染的研究

采用现场取样及室内分析方法，研究了贵州省赫章县的土法炼锌活动导致Cd对当地土壤-农作物系统的污染状况及规律。结果表明，炼锌污染土壤Cd含量高达5．3～144．7mg·k^-1，且Cd在土壤中的累积程度随着冶炼时间的增长而加剧。形态分析结果显示，土壤中的CaCl2和DTPA提取态Cd分别占全量的2．47％～16．80％和3．18％～10．11％，随着Cd在土壤中累积时间的加长，CaCl2和DTPA提取态Cd的百分含量均呈显著下降趋势。土壤污染导致农作物体内Cd的明显蓄积，玉米、土豆和大豆三类当地主要农作物可食部分Cd含量分别为1．8、4．8和2．0mg·kg^-1，分别超过国家粮食卫生标准9、24和10倍。相关分析结果显示，CaCl2提取态Cd与农作物中Cd含量没有相关关系，而DTPA提取态Cd和全量Cd与农作物根和茎叶中Cd含量显著正相关。

简化连续提取法评价污染土壤中Zn、Cd的植物有效性

以0．01mol·L^-1 CaCl2和0．005mol·L^-1 1DTPA作为提取剂，用简化的3步连续提取法对贵州省赫章县土法炼锌污染土壤中Zn、Cd的形态进行了分析．结果显示，污染土壤中Zn、Cd主要以残渣态的形式存在，CaCl2提取态和DTPA提取态Zn、CA平均仅占全量的0．63%、3．91％和lO．94％、10．13％．土壤中不同形态Zn、Cd含量与玉米中Zn、CA含量的相关分析结果显示，CaCl2提取态金属与玉米中金属含量投有显著的相关关系，而DTPA提取态、残渣态以及总量Zn、Cd与玉米根、茎叶中Zn、Cd含量显著正相关．这些结果表明CaCl2提取态Zn、Cd对土壤中该元素的植物有效态可能不具重要贡献，而DTPA提取态金属和金属总量在一定程度上能作为评价土壤中元素植物有效性的标准．

几种萃取剂对土壤中重金属生物有效部分的萃取效果

采用6种萃取剂：pH=7的0.01mol/L CaCl2、pH＝7.3的0.005mol/L DTPA+0.1mol/L TEA(三乙醇胺）＋0.01mol/L CaCl2、0.1mol/L NaNO3、0.43mol/L HOAc、pH=7的0.05mol/L EDTA和pH=4.65的0.5mol/L NH4OAc+0.01mol/L EDTA浸取液，对污染土壤中的重金属Cu、Zn、Cd、Pb的进行了萃取，并比较了萃取剂的萃取能力。实验结果表明，HOAc、EDTA以及NH4OAc－EDTA萃取各种重金属的能力远远大于其它几种萃取剂的萃取能力，是比较理想的萃取剂。

骑田岭A型花岗岩流体包裹体地球化学特征——对芙蓉超大型锡矿成矿流体来源的指示

南岭中段骑田岭A型花岗岩与芙蓉超大型锡矿床具有密切的时间和空间关系。流体包裹体地球化学研究表明,骑田岭A型花岗岩石英斑晶中的流体包裹体类型主要有熔融包裹体、流体-熔融包裹体和流体包裹体。流体-熔融包裹体的显微测温学研究结果显示,骑田岭A花岗岩在岩浆演化过程中可以分异出流体,且岩浆分异出的流体与芙蓉超大型锡矿床流体包裹体所反映的高温和高盐度的CaCl2-NaCl-KCl-H2O流体体系的特征相吻合。综合分析表明,芙蓉超大型锡矿床成矿流体中的高盐度流体应为骑田岭黑云母二长花岗岩结晶过程中分异出的富含Cl等挥发份和成矿物质的高盐度热流体。

滇西北雪鸡坪斑岩铜矿流体包裹体初步研究

雪鸡坪中型斑岩铜矿床位于三江地区义敦岛弧南端的中甸弧，成矿斑岩为石英闪长玢岩和石英二长斑岩，属于印支期产物。含矿岩体蚀变分带明显，由中心向外发育强硅化带→石英绢云母化带→粘土化-石英绢云母化带→青磐岩化带，工业矿体赋存于斑岩体中心强硅化和石英绢云母化带内。矿化类型以网脉状矿化为主，细脉浸染状矿化不发育。本文对主要矿化阶段石英脉中的流体包裹体系统进行了包裹体岩相学、显微测温学和激光拉曼谱学研究，发现与成矿有关的流体包裹体可以分为水溶液包裹体、CO2包裹体和含子矿物包裹体3类，子矿物主要为石盐、方解石、赤铁矿和少量CaCl2水合物及不透明硫化物。其中含子矿物包裹体均一温度为230～420℃，盐度为33．48％～75．40％NaCl equiv．，密度为1．01～1．09g／cm^3。激光拉曼光谱分析表明，包裹体的液相成分主要为H2O，气相成分为H2O和CO2。早期水溶液包裹体和CO2包裹体共生，其均一温度相近，以及纯CO2包裹体的发现，指示成矿流体存在不混溶现象，这种不混溶是由原始岩浆流体“二次沸腾”作用产生的。CO2相分离、温压条件降低和pH值升高是雪鸡坪斑岩铜矿硫化物沉淀的主要原因。晚期低温、低盐度的流体可能来源于大气降水与岩浆流体的混和，对矿化的意义不大。

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。

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。

云南大红山层状铜矿床地球化学及成矿机制研究

云南省大红山铁铜矿床位于康滇地轴南端西缘，介于红河深断裂与绿汁江深断裂所夹持的滇中台坳内，赋存于中元古代大红山群海相火山喷流-沉积岩系中，是我国典型的火山岩型块状硫化物（VHMS）矿床之一。该矿床包括一系列与火山喷发-岩浆侵入活动相关但成因有一定差别的矿床，被统称为“大红山式”铁铜矿床。该矿床经济价值巨大，铁、铜储量均达超大型矿床规模，但其研究程度较低，多停留在矿区地质特征层面上，地球化学研究较为薄弱。本次工作系统地研究了大红山层状铜矿床中各类岩石的岩相学特征，对特征矿物做了电子探针定性和定量分析，挑选火山质岩石中锆石做定年分析，系统分析了岩石的主量元素和微量元素，测定了硫化物的硫和铅同位素，并选取了与富集型硫化物相关的石英脉矿物和碳酸盐矿物分别做流体包裹体和碳、氧同位素研究。论文取得的主要认识如下： 1．红山群曼岗河组火山喷流-沉积年代约为1687±8Ma，即形成于早-中元古代，因此不可能遭受如前人所说的吕梁运动改造作用。在700 ~ 800Ma左右，即晋宁运动期本区遭受了强烈的变质变形以及流体蚀变改造作用。 2．层状铜矿中岩石类型主要为黑云母片岩、白云石钠长石岩和白云石大理岩。黑云母片岩中主要矿物为黑云母、钠长石、铁白云石和石榴子石；白云石钠长石岩中主要矿物为钠长石、铁白云石、石榴子石及少量的黑云母；白云石大理岩中主要矿物为铁白云石，含少量的钠长石和黑云母。岩石原岩恢复表明，三类岩石原岩为火山物质、泥质沉积物和喷流热水沉积混合组成，其中黑云母片岩以泥质为主，包含火山质物质和喷流热水沉积物质；白云石钠长石岩以火山物质和喷流热水为主，含少量的泥质；白云石大理岩以热水喷流沉积为主。 3．本区至少遭受过三期变质作用：区域高温变质作用、流体蚀变改造作用和变形变质作用。区域高温变质作用变质温度最高可达可达660℃，主要集中在600 ~ 630℃之间，形成压力约为4.9 ~ 5.0Kbar。三期变质改造使原岩发生了绿帘-角闪岩相的变质作用，变质过程中，稀土元素（特别是轻稀土元素）和部分高场强元素发生了迁移；流体蚀变改造富集了早期的贫铜矿胚，使之形成工业矿床。 4．硫化物硫同位素研究显示，其δ34S值为-0.6 ~ +10.9‰，主要集中在+5.0 ~ +10.9‰之间。这一组成表明富集型硫化物大体继承了早期硫化物硫源特征，并在改造过程中富集重硫。早期硫化物硫源主要来自岩浆硫和海水无机还原硫。硫化物铅同位素范围为：206Pb/204Pb＝ 18.985 ~ 23.318，均值为21.222；207Pb/204Pb＝15.581 ~ 15.904，均值为15.747；208Pb/204Pb＝39.803 ~ 45.652，均值为42.540。显然，本区硫化物具有极高含量的放射性成因铅，部分放射性成因铅含量稍低的样品与前人所圈定的改造型矿床的硫化物铅同位素范围较为吻合。分析认为，本区硫化物铅同位素代表了两种不同铅源的混合，即早期硫化物的普通铅和围岩中的放射性成因铅。硫铅同位素示踪以及矿相学研究表明，本区早期铜质来源于海底火山喷流-沉积，而晚期富集型铜矿铜质继承了早期铜质，同时也不排除晚期流体中所带来的铜质。 5．流体包裹体研究表明，本区改造型流体中包括三种流体体系：①中-低盐度H2O-NaCl±KCl±FeCl3 ±CaCl2流体，盐度范围为0.53 ~ 24.59 % NaCl equiv.，密度为0.80 ~ 1.16 g/cm3；②高盐度高密度H2O-NaCl±CaCl2流体，盐度为31.2 ~ >59.76% NaCl equiv，密度为1.14 ~ 1.45 g/cm3；③纯液相CO2流体，流体密度为0.77 ~ 1.09 g/cm3。流体包裹体均一温度在100 ~ 456℃之间，主要集中在150 ~ 260℃和260 ~ 456℃两个温度区间。方解石碳、氧同位素范围分别为-5.6 ~ -3.1‰和12.4 ~ 15.5‰。综合分析表明，流体主要来自海底下伏岩浆房的出溶或喷流的高温高盐度流体，部分与海水混合。流体在热液改造过程中活化富集了早期硫化物，经过短距搬运而沉积形成了晚期富集型硫化物。 6．本次研究确定该矿床的成矿机制为：早-中元古代，本区的陆内裂谷作用为火山喷发提供了构造条件，海底火山喷流-沉积形成了早期的贫铜矿胚。元古代末期，本区遭受了强烈的区域变质、变形和流体蚀变改造作用，使原先的贫铜矿胚得到活化富集，形成了工业矿床。

柿竹园钨、锡多金属矿田成矿流体地球化学研究

南岭地区是我国最重要的有色、稀有金属矿产资源产地，尤以钨、锡等金属的大规模爆发式成矿而闻名于世，已发现了一大批大型、超大型稀有和有色金属矿床。近年来的研究发现，这些矿床的形成很可能与华南地区中生代发生的大规模地壳拉张、岩石圈伸展减薄以及壳―幔相互作用的独特地质背景有关。本论文以与千里山花岗岩体密切相关的柿竹园钨锡钼铋铅锌矿田（以下简称柿竹园矿田）为研究对象，运用流体包裹体、稳定同位素和稀有气体同位素地球化学等方法，对其成矿流体的物理化学特征、来源及演化进行了研究，并在此基础上探讨了千里山花岗岩体与柿竹园矿田间的成因联系和矿田的成矿作用机制，获得以下主要研究成果： 1. 利用流体包裹体岩相学、显微测温学以及包裹体成分的激光拉曼分析技术，揭示了矿田中柿竹园钨锡钼铋矿床成矿流体的性质和演化特征。研究表明柿竹园钨锡钼铋矿床成矿流体为中高温、中高盐度H2O-NaCl-CaCl2-CO2-CH4-H2S-F体系。成矿流体的均一温度、盐度、密度和压力变化范围均较大，成矿早期夕卡岩阶段和云英岩阶段的流体具有较高的均一温度（239～477℃）和盐度（0～39.08 wt% NaCl eq.），云英岩网脉夕卡岩阶段和后期石英萤石脉阶段均一温度和盐度逐渐降低（分别为160～450℃，1.23～16.53 wt% NaCl eq.和156～340℃，1.23～4.49 wt% NaCl eq.）。夕卡岩阶段发生了流体沸腾作用。流体密度为0.37～1.12 g/cm3，主要集中在0.7～0.9 g/cm3；压力为10～820 bar，一般小于800 bar。野鸡尾锡铜矿床的成矿流体属于中高温度、中等盐度的H2O-NaCl-CaCl2-CO2-CH4-H2S-F型体系，柴山铅锌矿床属中温中等盐度H2O-NaCl-CaCl2-CO2-F体系，其均一温度和压力变化范围也较大。 2. 通过分析主要矿化类型矿石矿物及脉石矿物的C、H、O、S等稳定同位素特征，揭示了柿竹园矿田成矿流体的来源，并对C、O同位素的组成进行了CO2去气、流体混合和水―岩反应的理论模拟。研究表明矿田成矿流体主要来自千里山花岗岩浆，并有大气降水加入。水―岩反应在成矿过程中起着重要作用。 3. 对矿田不同矿化类型矿石矿物黄铁矿、黄铜矿、毒砂、方铅矿等进行了He、Ar同位素研究，其中3He/4He值为0.059～1.662 Ra（Ra为空气的3He/4He值，1 Ra＝1.39×10-6），40Ar/36Ar值为289.8～1071.8，表明矿田成矿流体具有壳-幔两端员混合的特征。壳源组分为获得了大量地壳放射成因4He，但获得放射成因40Ar*较少的经过地下循环的低温饱和大气水。而幔源组分来自千里山花岗岩浆流体，表明千里山花岗岩并非传统的S型花岗岩。 4. 在总结前人研究成果的基础上，结合本次研究，建立了柿竹园矿田成矿作用模式：中生代华南岩石圈发生拉张、伸展作用，地幔物质上涌，发生壳幔相互作用，形成千里山花岗岩浆。花岗岩浆充分分异演化形成富含挥发分和成矿元素的成矿流体，与泥盆系碳酸盐岩发生反应而沉淀成矿。成矿过程有大气降水的加入，并发生了流体沸腾作用。

THERMODYNMICS AND STRUCTURE OF POLY(ETHYLENE OXIDE) IN MIXTURES OF WATER AND ETHANOL

Poly(ethylene oxide) (PEO) is one of the most researched synthetic polymers due to the complex behavior which arises from the interplay of the hydrophilic and hydrophobic sites on the polymer chain. PEO in ethanol forms an opaque gel-like mixture with a partially crystalline structure. Addition of a small amount of water disrupts the gel: 5 wt % PEO in ethanol becomes a transparent solution with the addition of 4 vol % water. The phase behavior of PEO in mixed solvents have been studied using small-angle neutron scattering (SANS). PEO solutions (5 wt % PEO) which contain 4 vol % - 10 vol % (and higher) water behave as an athermal polymer solution and the phase behavior changes from UCST to LCST rapidly as the fraction of water is increased. 2 wt % PEO in water and 10 wt % PEO in ethanol/ water mixtures are examined to assess the role of hydration. The observed phase behavior is consistent with a hydration layer forming upon the addition of water as the system shifts from UCST to LCST behavior. At the molecular level, two or three water molecules can hydrate one PEO monomer (water molecules form a sheath around the PEO macromolecule) which is consistent with the suppression of crystallization and change in the mentioned phase behavior as observed by SANS. The clustering effect of aqueous PEO solution (M.W of PEO = 90,000 g/mol) is monitored as an excess scattering intensity at low-Q. Clustering intensity at Q = 0.004 Å^-1 is used for evaluating the clustering effect. The clustering intensity is proportional to the inverse temperature and levels off when the temperature is less than 50 ˚C. When the temperature is increased over 50 ˚C, the clustering intensity starts decreasing. The clustering of PEO is monitored in ethanol/ water mixtures. The clustering intensity increases as the fraction of water is increased. Based on the solvation intensity behavior, we confirmed that the ethanol/ water mixtures obey a random solvent mixing rule, whereby solvent mixtures are better at solvating the polymer that any of the two solvents. The solution behavior of PEO in ethanol was investigated in the presence of salt (CaCl2) using SANS. Binding of Ca2+ ions to the PEO oxygens transforms the neutral polymer to a weakly charged polyelectrolyte. We observed that the PEO/ethanol solution is better solvated at higher salt concentration due to the electrostatic repulsion of weakly charged monomers. The association of the Ca2+ ions with the PEO oxygen atoms transforms the neutral polymer to a weakly charged polyelectrolyte and gives rise to repulsive interactions between the PEO/Ca2+ complexes. Addition of salt disrupts the gel, which is consistent with better solvation as the salt concentration is increased. Moreover, SANS shows that the phase behavior of PEO/ethanol changes from UCST to LCST as the salt concentration is increased.

Obtención de cultivos de Azospirillum brasilense Az 39 en sistemas con y sin control automático de PH

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Positive and negative contractile effects of somatostatin-14 on rat ventricular cardiomyocytes.

Somatostatin-14 elicits negative inotropic and chronotropic actions in atrial myocardium. Less is known about the effects of somatostatin-14 in ventricular myocardium. The direct contractile effects of somatostatin-14 were assessed using ventricular cardiomyocytes isolated from the hearts of adult rats. Cells were stimulated at 0.5 Hz with CaCl2 (2 mM) under basal conditions and in the presence of the -adrenoceptor agonist, isoprenaline (1 nM), or the selective inhibitor of the transient outward current (Ito), 4-aminopyridine (500 M). Somatostatin-14 did not alter basal contractile response but it did inhibit (IC50 13 nM) the response to isoprenaline (1 nM). In the presence of 4-aminopyridine (500 M), somatostatin-14 stimulated a positive contractile response (EC50 118 fM) that was attenuated markedly by diltiazem (100 nM). These data indicate that somatostatin-14 exerts dual effects directly in rat ventricular cardiomyocytes: (1) a negative contractile effect, observed in the presence of isoprenaline (1 nM), coupled to activation of Ito; and (2) a previously unreported and very potent positive contractile effect, unmasked by 4-aminopyridine (500 M), coupled to the influx of calcium ions via L-type calcium channels. The greater potency of somatostatin-14 for producing the positive contractile effect indicates that the peptide may exert a predominantly stimulatory influence on the resting contractility of ventricular myocardium in vivo, whereas the negative contractile effect, observed at much higher concentrations, could indicate that localized elevations in the concentration of the peptide may serve as a negative regulatory influence to limit the detrimental effects of excessive stimulation of cardiomyocyte contractility.

Safe fabrication of sharp gold tips for light emission in scanning tunnelling microscopy

Gold is the optimal tip metal for light emission in scanning tunnelling microscopy (LESTM) under ambient conditions. Sharp Au-tips of similar to 10nm radius were produced reliably using a safe, two-step etching method in 20% (w/w) CaCl2 solution. Previous CaCl2-based methods have tended to produce blunter tips, while other etching techniques that do produce sharp Au-tips, do so with the use of toxic or hazardous electrolytes. The tips are characterised using scanning electron microscopy and their efficacy in LESTM is evidenced by high-resolution, simultaneous topographic and photon mapping of Au(1 1 1)- and polycrystalline Au-surfaces. Spectra of the optical emission exhibit only one or two peaks with etched tips in contrast to the more complex spectra typical of cut tips; this feature, together with the highly symmetric geometry of the tips, facilitates a definitive analysis of the light emission process. (c) 2007 Elsevier B. V.. All rights reserved.