Computer simulation studies of Crystallization under confinement conditions

Crystallization under confinement conditions is a very important process in geochemistry and geophysics. Computer simulations of fluids in nanometer scale pore spaces can provide a unique microscopic insight into the structure, dynamics and forces arising from the crystallization process. We discuss in this paper molecular dynamics computer simulations of crystallization in pores of nanometer dimensions. The crystallization pressure due to the freezing of a model of Argon in a nanopore is computed using molecular dynamics simulations. We also investigate the influence of pore geometry in determining the dynamics of confined fluids, as well as mass separation in binary mixtures. It turns out that the pore geometry reveals itself as an important variable, leading to 1) new mechanisms for fast diffusion in confined spaces, and 2) accumulation of solute in specific regions inside the pore.     

Kübler Index and K-Ar Ages of Illite in the Yinshan Polymetallic Deposit, Jiangxi Province, South China: Analyses and Implications

Abstract. The Yinshan polymetallic deposit is a hydrothermal vein-type deposit closely related to Late Jurassic felsic-inter-mediate volcanic-subvolcanic activity in Jiangxi Province, South China. Illite is a major alteration mineral observed in the deposit. Our study shows that the Kübler index of the illite has a close relation to ore-forming fluids of different stages of hydrothermal alteration and mineralization. The early Pb-Zn-Ag mineralization dated at 130–136 Ma is characterized by relatively low water/rock ratios and diffusive fluid movement within phyllite, whereas the later Cu-Au-S mineralization at 122 -125 Ma was accompanied by higher water/rock ratios and localized fluid flow through fractures and channels. Illite formed in the early Pb-Zn-Ag mineralization stage contains swelling layers while the illite formed in the later Cu-Au-S mineralization stage has no swelling layers but was associated with intensive chloritization. The last stage of mineralization (at 104 Ma) was minor and did not produce significant amounts of illite.     

川中地区茅口组两期流体叠合控制下的白云石化模式

岩相学特征、地化分析揭示:川中地区下二叠统茅口组白云岩存在三种白云石:①平直晶面细晶白云石(δ13C_PDB=3.06‰,δ18O_PDB=-6.81‰;Fe:1×10-6,Mn:未检出,Sr:150×10-6);②非平直晶面粗晶鞍状白云石(δ13C_PDB=3.22‰,δ18O_PDB=-7.82‰;Fe:149×10-6,Mn:185×10-6,Sr:85×10-6);③非平直晶面细晶白云石(δ13C_PDB=3.49‰,δ18O_PDB=-9.45‰;Th=123℃,S=133~139‰NaCl;Fe:58×10-6,Mn:59×10-6,Sr:76×10-6)。研究结果表明存在两期白云石化流体:①早期压实作用形成的埋藏白云石化流体(T=37.4℃;S=29.8‰NaCl);②晚期受构造控制的热液白云石化流体(Th=114.8℃;S=153~226‰NaCl)。明确了三种白云石的成因:平直晶面细晶白云石是由早期埋藏流体交代泥晶基质形成的;非平直晶面细晶白云石是平直晶面细晶白云石在受到热液流体改造后所形成的;而非平直晶面粗晶鞍状白云石则是由热液流体直接沉淀出的。基于研究结果建立了相应的白云化模式。     

The nature and distribution of fluids during amphibolite facies metamorphism, Naxos (Greece)

On the basis of fluid inclusion evidence, pervasive influx of deep-seated CO₂-rich fluids has been invoked to account for mid- to upper amphibolite facies (M2_B) metamorphism on the island of Naxos (Cyclades, Greece). In this paper, mineral devolatilization and melt equilibria are used to constrain the composition of both syn- and post-peak-M2_B fluids in the deepest exposed levels of the metamorphic complex. The results indicate that peak-M2_B fluids were spatially and compositionally heterogeneous throughout the high-grade core of the complex, whereas post-peak-M2_B fluids were generally water-rich. The observed heterogeneities in syn-M2_B fluid composition are inconsistent with pervasive CO₂-flushing models invoked by previous workers on the basis of fluid inclusion evidence. It is likely that few CO₂-rich fluid inclusions on Naxos preserve fluids trapped under peak metamorphic conditions. It is suggested that many of these inclusions have behaved as chemically open systems during the intense deformation that accompanied the uplift of the metamorphic complex. A similar process may explain the occurrence of some CO₂-rich fluid inclusions in granulite facies rocks.     

爆裂法作为快速测定流体包裹体中二氧化碳（和其它气体）含量的手段及其在勘探中的使用：以中国山东和河北省金矿为例

The acoustic decrepitation method heats a small monomineralic sample and counts pressure impulses as the inclusions burst when they develop high internal pressures. For aqueous fluids, the decrepitation temperature is correlated with the homogenisation temperature, but gas rich fluids give a distinct and characteristic low temperature decrepitation peak which can be used to recognize gas rich fluid inclusions. This information is useful in exploration for Au deposits, which are frequently associated with CO2 rich and sometimes CH4 rich fluids. This distinctive decrepitation occurs because the CO2 rich inclusion fluids expand according to the gas law and develop internal pressures high enough to burst the host mineral grain at temperatures well below their homogenisation temperatures. In contrast, aqueous fluids condense to a liquid and vapour phase during post-entrapment cooling. Upon subsequent heating their internal pressures do not increase significantly until after homogenisation to a single phase occurs and hence they do not decrepitate ＂prematurely＂ as gas rich inclusions do. This behaviour is usually regarded as an annoyance in conventional microthermometric homogenisation studies, but can readily be used as an exploration aid to find mineralisation deposited from such gas rich fluids. Decrepitation results on samples from Cowra Ck, NSW, Australia, which have also been microthermometrically measured for CO2 content, show that amounts of less than 5 mole % CO2 are easily distinguished by decrepitation and amounts as low as 1 mole % CO2 may be determinable. Examples of the use of acoustic decrepitation in the study of 6 gold mines in the Shandong and Hebei provinces of China are discussed.     

Experimental diffusion of hydrogen into synthetic fluid inclusions in quartz

Abstract Quartz-hosted, synthetic CO₂-H₂O fluid inclusions behave as open systems with respect to diffusional transfer of hydrogen during laboratory-simulated metamorphic re-equilibration at 650, 750 and 825°C and 1.5 kbar total pressure with f_O2 defined by the C-CH₄ buffer. Microthermometry and Raman spectroscopy show that the initial CO₂-H₂O inclusions become CO₂-CH₄-H₂-H_2O
inclusions after diffusive influx of hydrogen from the reducing confining medium. Measurable changes are observed in inclusion compositions after only 15 days of re-equilibration, implying significant hydrogen mobility at still lower temperatures over geological time spans. Results of synthetic inclusion re-equilibrium experiments have profound implications for the interpretation of natural fluid-inclusion data; failure to account for potential hydrogen migration in inclusions from high-temperature geological environments may lead to erroneous estimates of P-T, and/or the compositions of metamorphic fluids.     

Experimental and petrological constraints on local-scale interaction of biotite-amphibole gneiss with H2O-CO2-（K, Na）Cl fluids at middle-crustal conditions： Example from the Limpopo Complex, South Africa

Reaction textures and fluid inclusions in the～2.0 Ga pyroxene-bearing dehydration zones within the Sand River biotite-hornblende orthogneisses（Central Zone of the Limpopo Complex） suggest that the formation of these zones is a result of close interplay between dehydration process along ductile shear zones triggered by H₂O-CO₂-salt fluids at 750—800℃and 5.5—6.2 kbar.partial melting,and later exsolution of residual brine and H₂O-CO₂ fluids during melt crystallization at 650—700℃.These processes caused local variations of water and alkali activity in the fluids,resulting in various mineral assemblages within the dehydration zone.The petrological observations are substantiated by experiments on the interaction of the Sand River gneiss with the H₂O-CO-2-（K,Na）Cl fluids at 750 and 800℃and 5.5 kbar.It follows that the interaction of biotite-amphibole gneiss with H₂O-CO₂-（K.Na）Cl fluids is accompanied by partial melting at 750—800℃.Orthopyroxene-bearing assemblages are characteristic for temperature 800℃and are stable in equilibrium with fluids with low salt concentrations,while salt-rich fluids produce clinopyroxene-bearing assemblages.These observations arc in good agreement with the petrological data on the dehydration zones within the Sand River orthoeneisses.     

保山镇康地块矽卡岩型铅锌矿床成因初探

保山镇康地块是"三江"南段重要的铅锌多金属成矿区之一,地质构造复杂,铅锌成矿地质条件优越,其中核桃坪与芦子园是近年发现的两个大型铅锌矿床,矿床受近NE向断裂、背斜轴部和地层控制明显,上寒武统核桃坪组与沙河床组大理岩化灰岩为主要赋矿地层,近矿围岩矽卡岩化强烈,流体包裹体,Pb、S、H、O同位素和微量元素等地球化学对比研究表明:核桃坪和芦子园铅锌矿床均经历了中温、高温两个矿化阶段;核桃坪铅锌矿床矿石铅同位素较芦子园铅锌矿床有较高的比值和较大的变化范围,均以高μ值为特征,属于放射性成因铅,暗示其成矿物质以壳源铅为主;硫化物硫同位素均多为较低正值并呈塔式分布,具有岩浆硫特征,两者均无生物硫酸盐热化学还原作用的参与,其中硫同位素分馏已达平衡;与硫化物共生的石英δDH2O(-109‰~-91‰)和δ18OH2O(-4.3‰~2.3‰)同位素研究表明核桃坪矿床成矿流体主要来自深部岩浆水,并遭受后期大气降水或地层水的混合;核桃坪矿床与芦子园矿床的微量元素具有岩浆热液型矿床特征,不同于VMS型、MVT型铅锌矿床。因此,笔者认为两个矿床应属于与深部隐伏岩体有关的中-高温矽卡岩型铅锌矿床,矿区深部隐伏岩体的侵入产生岩浆热液并携带Pb、Zn等成矿物质与地层水或大气降水混合,在背斜轴部与NE向断裂的交汇处形成该类型矿床。     

地壳流体与地幔流体间的关系

通过铀、金矿床及地幔岩捕虏体研究，初步得出以下认识：（１）在热液作用中岩浆分异热液是不存在的；（２）碱交代作用是整个地幔交代作用和地壳交代作用的基本运作机制，现已构成有几十条具体规律的理论系统；碱交代岩是地幔流体转变为热液的化石记录；（３）拆离断层构造体系是地幔流体上升到地壳后的活动通道；（４）磷（Ｐ）是地幔流体的特征性示踪成分；（５）大洋缺氧事件、生物种属灭绝、厄尔尼诺等有共同的地幔流体致因；（６）天然气－油－盐－金属成矿是统一的热液成矿作用。软流体是今后区域成矿预测的重要新依据。软流体的顶部发育有次级、再次级的局部上凸部，这是矿带、矿田群的重要成矿控制因素和找矿新标志。     

黔西北富锗银铅锌矿集区成矿流体运移方向及其制约因素

黔西北矿集区作为川滇黔富锗铅锌多金属成矿区的重要组成部分,成矿条件优越,找矿潜力巨大。已有研究表明,该区铅锌矿床成矿时代为印支晚期,但对成矿流体运移方向的研究相对薄弱,这也直接影响到区内资源勘查部署。在综合剖析该矿集区典型矿床的矿体特征、成矿温度、同位素组成和成矿年龄等资料的基础上,本文划分成矿流体类型,系统总结铅锌成矿作用过程中与成矿流体运移相关的“行迹”标志,研判成矿流体在区域尺度的运移方向,进一步讨论流体运移的制约因素。研究表明,在黔西北富锗银铅锌矿集区,构造为成矿流体运移提供了主要的驱动力和通道,成矿构造的优势方位决定成矿流体的主体运移方向。成矿温度、同位素组成和成矿构造等方面的区域性变化特征均指示成矿流体在平面上主体从南东至北西方向运移;除印支期陆块碰撞作用导致古特提斯洋闭合的因素外,雪峰山陆内变形构造作用也可能为成矿流体运移提供了动力,进而控制了流体的运移方向。该研究不仅对黔西北矿集区的“战略性”铅锌找矿部署具有现实意义,而且为热液矿床成矿流体运移方向研究提供了路径。