Primary fluid inclusions in galena crystals. II. Chemical composition of the liquid and gas phase

The chemical composition of primary individual inclusions in large galena crystals from the Madan ore district, Bulgaria (see Pt. I), is studied in this paper. The liquid phase was analysed for Na, K, Ca, Fe, Mn, Mg, NH _inf4 ^sup+ , Pb, Cu, Zn, Al, Cl^–, F^–, SO ₄ ^2– , HCO ₃ ^– , and HS^– (+S^2–): pH was also determined. The following analytical methods were used: atomic-absorption spectrophotometry, emission spectral analysis, spectrophotometry, nephelometry, microcrystalloscopic and drop reactions. The gas phase was mass-spectrometrically analysed after opening the vacuoles in vacuum. It was found to consist of water vapour and CO₂ only. It was also found that the solutions are chloride-sodium-potassium with a total salinity of 4–4.5%. They do not contain measurable amounts of sulphur components. The CO₂/H₂O ratios vary strongly between the various vacuoles, which is explained by the crystallization in boiling solutions. The problems of the hermeticity of inclusions, the partial pressure of CO₂, the temperature of crystallization, and of the possible role of boiling in the ore-forming process are discussed.     

辽宁高家堡子大型银矿床流体包裹体特征及矿床成因

高家堡子银矿床为辽东地区近年来发现的一大型独立银矿床,它赋存于早元古代辽河群大石桥组大理岩地层之中,受层间破碎带构造控制。矿区发育含银-铅-锌碎裂大理岩型及硅化石英脉型两种主要类型矿石。流体包裹体研究表明,前者石英中主要发育气液两相、含CO2三相、CO2及单液相四种类型的原生流体包裹体,成矿流体属H2O-CO2-NaCl体系类型,与造山型矿床成矿流体相似;后者石英中主要发育气液两相及单液相包裹体,成矿流体属H2O-NaCl体系类型,其低温低盐度特点及氢、氧同位素数据表明成矿流体主要来自大气降水。综合分析表明,本区银的大规模富集成矿作用是印支期以来以大气降水来源为主的热液活动的产物。     

Mobility and H2O loss from fluid inclusions in natural quartz crystals

Petrographic observations on quartz crystals from the Mole Granite (Australia) and other localities shed new light on the mechanisms of post-entrapment modification of fluid inclusions. These modifications include migration away from pseudosecondary trails, changes in fluid salinity and density, shape distortion and the formation of “sweat-haloes” around strongly deformed inclusions. Increases in fluid salinity, which usually are associated with inclusion migration, indicate water-losses of up to 50%. However, LA-ICP-MS-analysis of unmobilized and mobilized inclusions of the same trail reveals basically unchanged ratios of major – and trace element cations, with the exception of Li, which seems to be incorporated into the crystal lattice during migration. Despite the fact that all these modifications are closely related to deformation processes, they occur not only in mechanically deformed quartz, but also in free-standing crystals. In the latter samples, stress has been generated internally as a result of brazil-twinned growth and compositional zonation. These observations and their interpretation leads to a list of practical criteria that should help in differentiating between reliable and suspect fluid inclusions in other samples. Received: 17 November 1998 / Accepted: 16 April 1999     

流体不混溶性和流体包裹体

大多数流体包裹体是捕获于均匀体系,但有一部分包裹体捕获自非均匀体系(不混溶体系)。在自然界存在着许多不混溶的过程,这包括基性岩浆和酸性岩浆之间,岩浆与热液,岩浆与CO2,盐水溶液与CO2等。液体的不混溶性对于成矿作用十分重要,这方面有3个典型的例子,第一个是金矿的成矿作用与NaCl-H2O-CO2体系流体的不混溶有着重大的关系;第二个例子是斑岩铜矿;第三个例子是伟晶岩,发现在伟晶岩演化和成矿作用中存在着岩浆和热液的不混溶作用。实际上不混溶的大部分证据是从流体包裹体的研究中获得的。现在的问题是如何来确定哪些包裹体是从不混溶过程中捕获的。这种捕获于不混溶过程中的流体包裹体怎么来确定他的Th和成分。这种捕获于不混溶过程中的流体包裹体怎么与"卡脖子""拉伸作用"中捕获的包裹体和捕获自均匀体系的流体包裹体相区分。     

Metamorphic reactions between fluid inclusions and mineral hosts. I. Progress of the reaction calcite+quartz=wollastonite+CO2 in natural wollastonite-hosted fluid inclusions

 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO₂. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)_Cleq=64–73 wt%; X _{CO 2}≤0.02]; (2) low density vapour-rich CO₂-bearing inclusions [Th(L-V)≈500±100° C; X _{CO 2}=0.22–0.44; X _NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm⁻³. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H₂O-CO₂-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO₂=Cc+Qz of the host with the CO₂-proportion of the fluid during retrogression. All of the CO₂ was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H₂O-CO₂-NaCl, along with f _{CO 2}-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995     

Synthetic fluid inclusions - VII. Re-equilibration of fluid inclusions in quartz during laboratory-simulated metamorphic burial and uplift

ABSTRACT P-T conditions inferred from fluid inclusions in metamorphic rocks often disagree with the values predicted from mineral equilibria calculations. These observations suggest that inclusions formed during early stages of regional metamorphism continue to re-equilibrate during burial and subsequent uplift in response to differential pressure. P-T conditions accompanying burial and uplift were experimentally simulated by initially forming pure H₂O inclusions in quartz at elevated temperatures and pressures, and then re-equilibrating the inclusions in the presence of a 20 wt% NaCl solution such that final confining pressures ranged from 5 kbar above to 4 kbar below the initial internal pressure of the inclusions at the temperature of re-equilibration. In all samples re-equilibrated at confining pressures below the internal pressure, some inclusions were formed that had compositions of 20 wt% NaCl and densities in accord with the final P-T conditions. Additionally, some inclusions were observed to contain fluids of intermediate salinities (between 0 and 20 wt% NaCl). Densities of these inclusions were also consistent with formation at the re-equilibration P-T conditions. The remainder of the fluid inclusions observed in these samples contained pure H₂O and their homogenization temperatures corresponded to densities intermediate between the initial and final P-T conditions. In short-term experiments (7 days) where the initial internal overpressure exceeded 1 kbar, no inclusions were found that contained the original density and none were found to have totally re-equilibrated. Instead, most H₂O inclusions re-equilibrated until their internal pressures were between ∼750 and 1500 bars above the confining pressure, regardless of the initial pressure differential. In a long-term experiment (52 days), inclusions re-equilibrated at a lower confining pressure than the initial internal pressure displayed homogenization temperatures corresponding to a range in final internal pressures between 0 kbar (i.e. total re-equilibration) and 1.2 kbar above the confining pressure. In experiments where the confining pressure during re-equilibration exceeded the initial internal pressure, densities of pure H₂O inclusions increased to values intermediate between the initial and final P-T conditions. Additionally, these inclusions were generally surrounded by a three-dimensional halo of smaller inclusions, also of intermediate density, resulting in a texture similar to that previously ascribed to decrepitation from internal overpressure. In extreme cases where confining pressures were 4–5 kbar above the initial pressure, the parent inclusion almost completely closed leaving only the three-dimensional array of small (5 μm) inclusions, the outline of which may be several times the volume of the original inclusion. Groups of such inclusions closely resemble textures commonly observed in medium- to high-grade metamorphic rocks. Inclusions containing 10 and 42 wt% NaCl solutions trapped at 600 °c and 3 kbar were re-equilibrated at 600 °c and 1 kbar for 5 days in dry argon to evaluate the importance of H₂O diffusion as a mechanism of lowering the inclusion bulk density. Salinities of re-equilibrated inclusions obtained from freezing point depressions and halite dissolution temperatures indicate that original compositions were preserved. Density changes similar to those previously described were noted in these experiments, in inclusions showing no visible microfractures. Therefore, density variations observed in inclusions in this study, re-equilibrated under rapid deformation conditions, are considered to result from a change in the inclusion volume, without significant loss of contents by diffusion or leakage.     

江西银山多金属矿床高盐度包裹体及其成因意义

流体包裹体岩相学和显微测温学研究表明,银山矿床石英斑岩和金金属矿床中都发现须含石盐的高盐度流体包裹体,表明至少在成矿作用的早期成矿流体为高盐度流体,高盐度流体不是由热水溶液的不混溶作用或沸腾作用形成的,而是直接从饱和水的结晶岩浆熔体中出溶的,银山矿床的成矿流体与斑岩铜矿的成矿流体具有相似性,证实矿床深部可能有隐伏斑岩铜矿。     

Characteristics and Applications of Fluid Inclusions in the Eogene System of the Biyang Depression—I.A Fluid Inclusion Study

Presented in this paper are the rypes,salinities,homogenization temperatures and organic components of fluid inclusions formed at the four stages of diagenetic authigenesis in the Eogene of the Biyang Depression.The results of cooling experiments on fluid inclusions were used to determine the fluid system and composition of saline aqueous solution in each of the stages .The homogenization temperatures of saline aqueous solution inclusions and hydrocarbon organic inclu-sions have been corrected by two approaches ,and the trapping temperatures and pressures of fluid inclusions at each of the stages have been obtained.This strdy has shed light on the physicochemistry and evolution of diagenetic fluids.The diagentic fluid system is a system which was transformed from a chloride-bearing to a carbonate-bearing system along with the diagenic evolu-tion.The decrease of diagenetic temperature at Stage III of diagenetic authigenesis suggests that the depression would have experiences uplifting at that time.The fluorescent characteristics of fluid inclusions indicate the varieties of organic components in fluid inclusions both in time and in space.     

Synthetic fluid inclusions. XV. TEM investigation of plastic flow associated with reequilibration of fluid inclusions in natural quartz

The nature and abundance of dislocations in quartz surrounding fluid inclusions were studied to obtain a better understanding of processes associated with fluid inclusion reequilibration. Synthetic fluid inclusions containing 10 wt% NaCl aqueous solution were formed in three samples at 700 °C and 5 kbar. One of the samples was quenched along an isochore to serve as a reference sample. The other two samples were quenched along a P-T path that generated internal pressures in excess of the confining pressure. The two samples were held at the final reequilibration P-T conditions of 625 °C and 2 kbar for 30 and 180 days, respectively. Following the experiments, microstructures associated with fluid inclusions were examined with the TEM. Quartz in healed fractures in the reference sample that was quenched isochorically shows a moderate dislocation activity. Quartz adjacent to reequilibrated fluid inclusions in the other two samples, however, showed a marked increase in dislocation activity compared to the un-reequilibrated sample. Deformation of the inclusion walls occurred anisotropically by expansion of mobile dislocations in their slip systems. Dislocation expansion was controlled by glide in the rhombohedral planes {1 0 1 1} that was restricted to narrow zones (≤3 μm) in the immediate vicinity of the fluid inclusion walls outside of the healed fracture plane. These plastic zones were observed after both short term (30 days) and long term (180 days) experiments and are attributed to hydrolytic weakening of quartz around fluid inclusions owing to diffusion of water into the quartz matrix during the experiment. The close spatial association of submicroscopic water bubbles with dislocations, and the rarity of water bubbles in the reference sample, show clearly that in both the 30 and 180 day experiments reequilibration involves water loss from the fluid inclusions. Our results indicate that synthetic fluid inclusions in this study recover (chemically and volumetrically), even at relatively fast experimental loading rates, such that internal stresses never reach the point of brittle failure. The driving force for fluid inclusion deformation involves two related mechanisms: plastic deformation of hydrolytically weakened wet quartz in the healed fracture, and water leakage associated with preexisting and strain-induced dislocations. Received: 5 May 1998 / Accepted: 10 February 2000     

CCSD HP-UHP变质岩中石英脉和东海水晶流体包裹体惰性气体同位素组成及其成因指示意义

中国大陆科学钻探（CCSD）岩心中存在大量石英脉和长英质脉体，关于其成因目前存在板块折返过程中的减压和流体释放以及后期流体穿插等不同成因观点。本文利用高真空气相质谱系统分析了CCSD石英脉和东海水晶流体包裹体中惰性气体同位素组成，其He-Ar、Xe和Ne同位素体系均清楚显示它们主要由地壳变质流体和大气饱和水组成，而基本不含深源地幔流体。在CCSD900～1500m深度的石英脉流体包裹体出现^40Ar／^36Ar和δ^18O同步下降，且与前人对CCSD中HP-UHP岩石的矿物原位δ^18O测定结果变化趋势相似，说明该段原岩在板块俯冲前曾与大气降水发生较为充分的水／岩反应，石英脉继承了围岩的同位素组成特征。流体包裹体惰性气体同位素组成显示CCSD中石英脉和东海水晶可能具有相似的成因，它们均主要形成于HP-UHP岩石在板块折返到地壳中的压力降低和流体释放过程。CCSD HP-UHP岩石及其石英脉中基本不合地幔流体的原因在于本区印支期快速的俯冲和折返过程，被俯冲地壳物质无法与地幔进行充分的同位素交换。此外，退变质作用及其伴生的地壳流体也进一步减弱了HP-UHP岩石中的地幔流体信息。     

On the origin of CO2-rich fluid inclusions in migmatites

Abstract Nearly pure CO₂ fluid inclusions are abundant in migmatites although H₂O-rich fluids are predicted from the phase equilibria. Processes which may play a role in this observation include (1) the effects of decompression on melt, (2) generation of a CO₂-bearing volatile phase by the reaction graphite + quartz + biotite + plagioclase = melt + orthopyroxene + CO₂-rich vapour, (3) selective leakage of H₂O from CO₂+ H₂O inclusions when the pressure in the inclusion exceeds the confining pressure during decompression, and (4) enrichment of grain-boundary vapour in CO₂ by subsolidus retrograde hydration reactions.     

Physicochemical parameters of the origin of hydrothermal mineral deposits: Evidence from fluid inclusions. IV. Copper and molybdenum deposits

Physicochemical parameters of the origin of Cu and Mo deposits are reviewed based on an original database that currently includes information from more than 21000 publications on fluid and melt inclusions hosted in various minerals. The deposits are classified into three types: (i) Cu–Mo (usually porphyry), (ii) Cu (usually without Mo but often with base metals), and (iii) Mo (without Cu but often with Be and W). For these deposits, the temperature and pressure of their origin and the density, salinity, and gas composition of the fluids are discussed. The average composition of the dominant volatile components of natural fluids is reported for Cu and Mo deposits and is compared with the composition of volatiles in fluids at Au, Sn, W, Pb, and Zn deposits. Data on individual inclusions are used to evaluate the Cu and Mo concentrations in the magmatic silicate melts and mineral-forming fluids.     

Radiogenic isotopes in fluid inclusions

Radiogenic isotopes studied in fluid inclusions are still a limited field, with great potential for expansion as analytical techniques improve. The main limitation for Sr, Ar and He isotope work is the very small number of radiogenic atoms produced in a typical fluid inclusion. The requirements to analysts are correspondingly high. Examples show that isotopic tracing on fluid inclusion fluids can be a decisive tool in solving geological problems.     

Primary melt and fluid inclusions in regenerated crystals and phenocrysts of olivine from kimberlites of the Udachnaya-East Pipe,Yakutia: The problem of the kimberlite melt

The primary melt and fluid inclusions in regenerated zonal crystals of olivine and homogeneous phenocrysts of olivine from kimberlites of the Udachnaya-East pipe, were first studied by means of microthermometry, optic and scanning electron microscopy, electron and ion microprobe analysis (SIMS), inductively coupled plasma mass-spectrometry (ICP MSC), and Raman spectroscopy. It was established that olivine crystals were regenerated from silicate–carbonate melts at a temperature of ~1100°C.

     

地幔矿物中CO2流体包裹体的微量元素特征

本文在镜下观测基础上，挑选富含CO2包裹体的地幔橄榄岩的橄榄石、斜方辉石和单斜辉石样品，运用热爆法提取和ICP—MS技术，直接测定了单矿物中CO2流体包裹体的稀土和微量元素含量。在同样条件下，采用四极质谱法测定了CO2等气相成分，并以CO2含量为参考值，得出流体中的微量元素相对含量。热爆样品的显微镜观测表明，靠近颗粒表面的较大的CO2包裹体在1000℃爆裂时均已破裂，所测定的REE和其他微量元素主要来自CO2包裹体。CO2流体／球粒陨石标准化的REE数据表明，地幔CO2流体相对于地幔岩或地幔矿物而言，富集稀土元素，特别是轻稀土元素，LREE／HREE为1．53～11．96，REE分馏程度较大，(La／Yb)N一般大于1。CO2流体／上地幔岩石标准化值研究表明，除Co、Ni外，铁族元素在地幔流体中趋于贫化；Cu、Mo、W、Bi、Ag等热液矿床的重金属成矿元素在地幔CO2流体中富集。     

Short-chain carboxylates in fluid inclusions in minerals

The carboxylate (formate, acetate, propionate and oxalate) and common inorganic anions (F⁻, Cl⁻ and SO²⁻₄) compositions for aqueous fluid inclusion leachates from 17 mineral samples collected from various deposits have been determined using ion chromatography in conjunction with microthermometric measurements on the fluid inclusions of their host minerals. The minerals, quartz, fluorite, barite, beryl and a few `ore' minerals (wolframite, pyrite and galena), came from hydrothermal vein-type deposits in felsic igneous rocks or Archean metamorphic rocks. The results indicate that short-chain carboxylates are common components in hydrothermal fluids and can be present in considerable amounts. Formic acid (as formate) is the dominant species over other carboxylic acids. The present study raises new questions about the origin and geochemical significance of carboxylates in hydrothermal ore-forming processes.     

Synthetic fluid inclusions - VI. Quantitative evaluation of the decrepitation behaviour of fluid inclusions in quartz at one atmosphere confining pressure

ABSTRACT The decrepitation behaviour of fluid inclusions in quartz at one atmosphere confining pressure has been evaluated using pure H₂O synthetic inclusions formed by healing fractures in natural quartz. Three different modes of non-elastic deformation, referred to as stretching, leakage or partial decrepitation, and total decrepitation have been observed. The internal pressure required to initiate non-elastic deformation is inversely related to inclusion size according to the equation: internal pressure (kbar) = 4.26 D^-0.423 where D is the inclusion diameter in microns. Regularly shaped inclusions require a higher internal pressure to initiate non-elastic deformation than do irregularly shaped inclusions of similar size. Heating inclusions through the α/β quartz inversion results in mechanical instability in the quartz crystal and leads to mass decrepitation of inclusions owing to structural mismatches generated by pressure gradients in the quartz around each inclusion. Long-term heating experiments (∼2 years) suggest that the internal pressure required to initiate non-elastic deformation does not decrease significantly with time and indicates that short-lived thermal fluctuations in natural systems should not alter the inclusion density and homogenization temperature. Inclusions that do exhibit decreased density (higher homogenization temperature) are, however, always accompanied by a change in shape from irregular to that of a negative crystal. Observations of this study are consistent with elasticity theory related to fracture generation and propagation around inclusions in minerals. These results indicate that an inclusion will not be influenced by a neighbouring inclusion, or other defect in the host phase, as long as the distance between the two is >2–4 diameters of the larger of the two inclusions.