X-ray imaging of uranium in individual fluid inclusions

The spatial distribution of major (K, Ca, Mn, Fe) and trace elements (Ti, Cr, Cu, As, Br, Rb, Sr, Zr, Pb, Th, U) were determined in individual fluid inclusions from quartz veins of the Streltsov uranium deposit, Russia, using synchrotron radiation X-ray fluorescence (SXRF). The analyses were performed on the beamline ID-22 Micro-FID (Fluorescence, Imaging, Diffraction) of the European Synchrotron Research Facility (ESRF, Grenoble, France). Fluorescence X-ray maps of single fluid inclusions show a relatively homogeneous distribution of most elements throughout the inclusion, whereas Fe and, to a lesser extent, Sr display highly localized count rates. This observation argues for the presence of minute, optically invisible, compounds that are precipitated inside the inclusion. Simple model calculations indicate that relatively diluted solutions (10–100 ppm U) trapped at geologically relevant temperatures (e.g. 250 °C) would precipitate submicron sized particles. These particles would be highly reactive to the photon flux but not necessarily visible under the microscope. These results indicate that third-generation synchrotron light source can be a powerful technique to study the physical processes undergone by the fluid. When combined with chemical data, this technique can help to clarify fluid transport properties in natural systems.     

Quantitative trace element analysis of single fluid inclusions by proton-induced X-ray emission (PIXE): application to fluid inclusions in hydrothermal quartz

Single fluid inclusion analogues with known elemental composition and regular shape were analyzed for trace element contents by particle-induced X-ray emission (PIXE)—a nondestructive method for the analysis of single fluid inclusions—to evaluate the accuracy and detection limits of this type of analysis. Elements with concentrations of 10 to 1000 ppm were measured with average estimated relative error of ±7%. For natural fluid inclusions with 30 μm radius and 20 μm depth in quartz, the total analytical errors were estimated to be ±40% relative for Ca, ±16% for Fe, ±13% for Zn, ±12% for Sr, and ±11% for Br and Rb, by considering uncertainties in microscopic measurements of inclusion depths. Detection limits of 4 to 46 ppm for elements of mass numbers 25-50 were achieved for analyses of a spherical fluid inclusion with 30 μm radius and 20 μm depth in quartz, at an integrated charge of 1.0 μC. The trace element compositions of single fluid inclusions in a hydrothermal quartz crystal were also determined. The elemental concentrations in the inclusions varied widely: 0.2-9 wt.% for Ca and Fe, 300-8000 ppm for Mn and Zn, 40-3000 ppm for Cu, 100-4000 ppm for Br, Rb, Sr, and Pb, and less than 100 ppm for Ge. Elemental concentrations of secondary fluid inclusions on the same trail varied over an order of magnitude, even though all these inclusions were formed from the same fluid. Elemental concentrations in inclusions on the same trail are positively correlated with each other, except for Cu and Rb. Ratios of almost all elements in the inclusions on the trail were essentially unchanged; thus, the elemental ratios can provide original information on trace element compositions of a hydrothermal fluid.     

Mixed messages in iron oxide–copper–gold systems of the Cloncurry district,Australia: insights from PIXE analysis of halogens and copper in fluid inclusions

Proterozoic rocks of the Cloncurry district in NW Queensland, Australia, are host to giant (tens to hundreds of square kilometers) hydrothermal systems that include (1) barren regional sodic–calcic alteration, (2) granite-hosted hydrothermal complexes with magmatic–hydrothermal transition features, and (3) iron oxide–copper–gold (IOCG) deposits. Fluid inclusion microthermometry and proton-induced X-ray emission (PIXE) show that IOCG deposits and the granite-hosted hydrothermal complexes contain abundant high temperature, ultrasaline, complex multisolid (type 1) inclusions that are less common in the regional sodic–calcic alteration. The latter is characterized by lower salinity three-phase halite-bearing (type 2) and two-phase (type 3) aqueous inclusions. Copper contents of the type 1 inclusions (>300 ppm) is higher than in type 2 and 3 inclusions (<300 ppm), and the highest copper concentrations (>1,000 ppm) are found both in the granite-hosted systems and in inclusions with Br/Cl ratios that are consistent with a magmatic source. The Br/Cl ratios of the inclusions with lower Cu contents are consistent with an evaporite-related origin. Wide ranges in salinity and homogenization temperatures for fluid inclusions in IOCG deposits and evidence for multiple fluid sources, as suggested by halogen ratios, indicate fluid mixing as an important process in IOCG genesis. The data support both leaching of Cu by voluminous nonmagmatic fluids from crustal rocks, as well as the direct exsolution of Cu-rich fluids from magmas. However, larger IOCG deposits may form from magmatic-derived fluids based on their higher Cu content.     

Preliminary Study on the Chemical Mapping of Individual Fluid Inclusion by Synchrotron X-ray Fluorescence Microprobe

Abstract: Synchrotron X-ray fluorescence analyses on individual hypersaline fluid inclusions were tested to using synchrotron source at Tsukuba (KEK), Japan. The XRF instrumentation at KEK meets the purpose of fluid inclusion analysis, nondestructive, multi–element, ppm detection limits, with micro spatial resolution. In practice, however, the quantitative chemical analysis of fluid inclusion requires further considerable data accumulation. Semi-quantitative distribution of elements (mass number > 25) in single fluid inclusion was obtained.     

飞行时间二次离子质谱(TOF-SIMS)在矿物包裹体研究中的应用

矿物包裹体的化学成分研究在地质学、矿床学和油气勘探等方面具有重要意义。目前对包裹体化学成分分析的主要分析方法有激光烧蚀电感耦合等离子体质谱(LA-ICP-MS)、电子探针(EPMA)、显微激光拉曼光谱(LRS)、傅里叶变换红外光谱(FTIR)、质子诱发X射线光谱分析(PIXE)、同步辐射X射线荧光光谱(SXRF)和(传统的)二次离子质谱分析(SIMS)等。本文在对上述方法的分析特点进行简单介绍的基础上,重点阐述了对于矿床学样品表征具有广泛应用潜力的飞行时间二次离子质谱(TOF-SIMS)的原理、特点和技术优势,总结了国内外学者应用TOF-SIMS对矿物包裹体化学成分分析的研究进展与存在问题,并做了相关领域的展望。     

单个流体包裹体LA-ICP-MS分析及应用进展

独立封存的单个流体包裹体,能够准确地反演被捕获时期的流体信息.激光剥蚀电感耦合等离子体质谱仪（LA-ICP-MS）是单个流体包裹体微区分析的重要手段,展现了原位、实时、高空间分辨率、高灵敏度、高精密度、低检出限、多元素同时检测的优点.单个流体包裹体组成信息的LA-ICP-MS测定技术,在单个流体包裹体选取、激光剥蚀采样方式、气溶胶传输与电离、质谱瞬时信号采集效率、定量校准与内标元素准确测定等方面逐步突破,且该技术应用于成矿元素来源及分配、成矿流体来源及特征、建立成矿模式等方面的研究广泛.因此提高单个流体包裹体分析成功率、降低小体积流体包裹体元素检出限、测定矿石矿物流体包裹体成分等成为该分析技术亟待解决的问题.      

Composition and origin of fluids associated with lode gold deposits in a Mesoarchean greenstone belt (Warrawoona Syncline, Pilbara Craton, Western Australia) using synchrotron radiation X-ray fluorescence

Microthermometry and Raman spectroscopy techniques are routinely use to constrain ore-fluids δ¹⁸O and molar proportions of anhydrous gas species (CO₂, CH₄, N₂). However, these methods remain imprecise concerning the ore-fluids composition and source. Synchrotron radiation X-ray fluorescence allows access to major and trace element concentrations (Cl, Br and K, Ca, Fe, Cu, Zn, As, Rb, Sr) of single fluid inclusion. In this paper, we present the results of the combination of these routine and newly developed techniques in order to document the fluids composition and source associated with a Mesoarchaean lode gold deposit (Warrawoona Syncline, Western Australia). Fluid inclusion analyses show that quartz veins preserved records of three fluid inclusion populations. Early fluids inclusions, related to quartz veins precipitation, are characterized by a moderate to high Br/Cl ratio relative to modern seawater, CO₂ ± CH₄ ± N₂, low to moderate salinities and significant base metal (Fe, Cu, Zn) and metalloid (As) concentrations. Late fluid inclusions trapped in secondary aqueous fluid inclusions are divided into two populations with distinct compositions. The first population consists of moderately saline aqueous brines, with a Br/Cl ratio close to modern seawater and a low concentration of base metals and metalloids. The second population is a fluid of low to moderate salinity, with a low Br/Cl ratio relative to modern seawater and significant enrichment in Fe, Zn, Sr and Rb. These three fluid inclusion populations point to three contrasting sources: (1) a carbonic fluid of mixed metamorphic and magmatic origin associated with the gold-bearing quartz precipitation; (2) a secondary aqueous fluid with seawater affinity; and (3) a surface-derived secondary aqueous fluid modified through interaction with felsic lithologies, before being flushed into the syncline. Primary carbonic fluids present similar characteristics than those ascribed to Mesoarchaean lode gold deposits. This suggests similar mineralization processes for mid- and Mesoarchaean lode gold deposits despite contrasting fluid–rock interaction histories. However, in regard to the protracted history documented in the Warrawoona Syncline, we question the robustness of the epigenetic crustal continuum model, as ore-fluid characteristics equally support an epigenetic or a polyphased mineralization process.     

Halogen contents of eclogite facies fluid inclusions and minerals: Caledonides,western Norway

Primary multiphase brine fluid inclusions in omphacite and garnet from low‐ to medium‐temperature eclogites have been analysed for Cl, Br, I, F, Li and SO₄. Halogen contents and ratios provide information about trapped lower crustal fluids, even though the major element (Na, K, Ca) contents of inclusion fluids have been modified by fluid–mineral interactions and (step‐) daughter‐crystal formation after trapping. Halogens in the inclusion fluids were analysed with crush–leach techniques. Cl/Br and Cl/I mass ratios of eclogite fluids are in the range 31–395 and 5000–33 000, respectively. Most fluids have a Cl/Br ratio lower than modern seawater and a Cl/I ratio one order of magnitude lower than modern seawater. Fluids with the lowest Cl/Br and highest Cl/I ratios come from an eclogite that formed by hydration of granulite facies rocks, and may indicate that Br and I are fractionated into hydrous minerals. Reconstructions indicate that the inclusion fluids originally contained 500–4000 ppm Br, 1–14 ppm I and 33–438 ppm Li. Electron microprobe analyses of eclogite facies amphibole, biotite, phengite and apatite indicate that F and Cl fractionate most strongly between phengite (F/Cl mass ratio of 1469 ± 1048) and fluid (F/Cl mass ratio of 0.008), and the least between amphibole and fluid. The chemical evolution of Cl and Br in pore fluids during hydration reactions is in many ways analogous to Cl and Br in seawater during evaporation: the Cl/Br ratio remains constant until the a_H2O value is sufficiently lowered for Cl to be removed from solution by incorporation into hydrous minerals.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

Microthermometrical and chemical studies of fluid inclusions in minerals from Alpine veins from the penninic rocks of the central and western Tauern Window (Austria/Italy)

The fluid inclusions in samples of quartz, apatite, epidote, diopside, beryl and phenakite from Alpine veins in gneisses, amphibolites and mica schists from the western Tauern Window were analysed by microthermometrical, chemical and neutron activation methods. The inclusions of the eclogites contain a high density CO₂ phase without optically detectable H₂. In the Greiner Schieferserie the fluid inclusions show high CO₂/H₂O ratios and low salt contents. In the Zentralgneis area inclusions with low CO₂/H₂O ratios and high salt contents are typical. In the calcareous mica schists of the lower Schieferhülle, in the eastern part of the investigated area, generally no CO₂ could be detected in the inclusions. These inclusions contain aqueous solutions showing a low salt content. The only CO₂ bearing inclusions observed here were in the graphite-rich rocks of the so-called Habachzungen and in the eclogites from south of the Großvenediger. Trapping pressures estimated from the fluid inclusions are up to 7.5 kbar in the eclogites, but in general the pressures are between 2 and 4 kbar. These pressure data are in good agreement with the pressure data of mineral equilibria. The chemically analysed elements in the fluid inclusions are Na, K, Cs, Mg, Ca, Mn, As, Cl and Br. From the K/Na ratios temperatures between 435 and 490°C can be deduced. The very low Cl/Br ratios (<110) suggest that the dissolved elements came from the country rocks. The alkali/chlorine ratios (～1) indicate that the positive loadings of the cations are balanced by Cl.     

Major and trace-element composition and pressure–temperature evolution of rock-buffered fluids in low-grade accretionary-wedge metasediments, Central Alps

The chemical composition of fluid inclusions in quartz crystals from Alpine fissure veins was determined by combination of microthermometry, Raman spectroscopy, and LA-ICPMS analysis. The veins are hosted in carbonate-bearing, organic-rich, low-grade metamorphic metapelites of the Bündnerschiefer of the eastern Central Alps (Switzerland). This strongly deformed tectonic unit is interpreted as a partly subducted accretionary wedge, on the basis of widespread carpholite assemblages that were later overprinted by lower greenschist facies metamorphism. Veins and their host rocks from two locations were studied to compare several indicators for the conditions during metamorphism, including illite crystallinity, graphite thermometry, stability of mineral assemblages, chlorite thermometry, fluid inclusion solute thermometry, and fluid inclusion isochores. Fluid inclusions are aqueous two-phase with 3.7–4.0 wt% equivalent NaCl at Thusis and 1.6–1.7 wt% at Schiers. Reproducible concentrations of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, B, Al, Mn, Cu, Zn, Pb, As, Sb, Cl, Br, and S could be determined for 97 fluid inclusion assemblages. Fluid and mineral geothermometry consistently indicate temperatures of 320 ± 20 °C for the host rocks at Thusis and of 250 ± 30 °C at Schiers. Combining fluid inclusion isochores with independent geothermometers results in pressure estimates of 2.8–3.8 kbar for Thusis, and of 3.3–3.4 kbar for Schiers. Pressure–temperature estimates are confirmed by pseudosection modeling. Fluid compositions and petrological modeling consistently demonstrate that chemical fluid-rock equilibrium was attained during vein formation, indicating that the fluids originated locally by metamorphic dehydration during near-isothermal decompression in a rock-buffered system.     

流体包裹体成分分析研究

笔者在日本研修期间学习和了解了先进的流体包裹体成分分的方法,其中包括分析群体包裹体液相成分的ＩＣＰ－ＭＳ和ＰＩＸＥ分析方法;分析单个包裹体液相成分的ＬＡ－ＩＣＰ－ＭＳ方法,ＬＲＭ,ＦＴ－ＩＲ单个包裹体气相成分分析方法等。这些方法极大地提高了包裹体成分分析的水平,促进了包裹体研究的发展,本文简要介绍这几种流体包裹体成分分析方法和其它包裹体研究方法及笔者的一些研究成果,以供国内同行借鉴和共同探讨。     

Metamorphic fluid origins in the Osborne Fe oxide–Cu–Au deposit,Australia: evidence from noble gases and halogens

The Osborne iron oxide–copper–gold (IOCG) deposit is hosted by amphibolite facies metasedimentary rocks and associated with pegmatite sheets formed by anatexis during peak metamorphism. Eleven samples of ore-related hydrothermal quartz and two pegmatitic quartz–feldspar samples contain similarly complex fluid inclusion assemblages that include variably saline (<12–65 wt% salts) aqueous and liquid carbon dioxide varieties that are typical of IOCG mineralisation. The diverse fluid inclusion types present in each of these different samples have been investigated by neutron-activated noble gas analysis using a combination of semi-selective thermal and mechanical decrepitation techniques. Ore-related quartz contains aqueous and carbonic fluid inclusions that have similar ⁴⁰Ar/³⁶Ar values of between 300 and 2,200. The highest-salinity fluid inclusions (47–65 wt% salts) have calculated ³⁶Ar concentrations of approximately 1–5 ppb, which are more variable than air-saturated water (ASW = 1.3–2.7 ppb). These fluid inclusions have extremely variable Br/Cl values of between 3.8 × 10⁻³ and 0.3 × 10⁻³, and I/Cl values of between 27 × 10⁻⁶ and 2.4 × 10⁻⁶ (all ratios are molar). Fluid inclusions in the two pegmatite samples have similar ⁴⁰Ar/³⁶Ar values of ≤1,700 and an overlapping range of Br/Cl and I/Cl values. High-salinity fluid inclusions in the pegmatite samples have 2.5–21 ppb ³⁶Ar, that overlap the range determined for ore-related samples in only one case. The fluid inclusions in both sample groups have ⁸⁴Kr/³⁶Ar and ¹²⁹Xe/³⁶Ar ratios that are mainly in the range of air and air-saturated water and are similar to mid-crustal rocks and fluids from other settings. The uniformly low ⁴⁰Ar/³⁶Ar values (<2,200) and extremely variable Br/Cl and I/Cl values do not favour a singular or dominant fluid origin from basement- or mantle-derived magmatic fluids related to A-type magmatism. Instead, the data are compatible with the involvement of metamorphic fluids that have interacted with anatectic melts to variable extents. The ‘metamorphic’ fluids probably represent a mixture of (1) inherited sedimentary pore fluids and (2) locally derived metamorphic volatilisation products. The lowest Br/Cl and I/Cl values and the ultra-high salinities are most easily explained by the dissolution of evaporites. The data demonstrate that externally derived magmatic fluids are not a ubiquitous component of IOCG ore-forming systems, but are compatible with models in which IOCG mineralisation is localised at sites of mixing between fluids of different origin. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorised users.     

SILLS软件在单个萤石流体包裹体LA-ICP-MS微量元素分析数据处理中的应用

近年来激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)应用于单个流体包裹体成分定量分析已成为研究流体包裹体的最佳手段之一。该实验过程和数据处理比较复杂,目前国内外采用的数据分析软件为一款基于MATLAB的SILLS软件,该软件主要是对矿物(锆石)、流体包裹体以及熔体包裹体LA-ICP-MS分析结果进行处理。本文以萤石流体包裹体LA-ICP-MS分析为例,阐述了样品制备与流体包裹体的优选方法,对流体包裹体片厚度以及单个流体包裹体的选取要求作了详细描述,对仪器参数设置、内外标样选取和剥蚀方法等进行了说明。基于SILLS软件采用尖峰消除的方法对待处理数据进行校正,对不同种类型的波峰进行峰宽的选取。在元素比值校正和等效盐度计算过程中,由于被测样品是萤石,Ca元素具有较高的背景值,选择以Na作为流体包裹体的内标元素,以Ca作为寄主矿物的内标元素对寄主矿物浓度进行计算,同时提出以电价平衡代替质量平衡进行等效盐度计算。以上方案提高了LA-ICP-MS分析单个萤石流体包裹体的准确性,有助于解释成矿流体来源和矿床成因等问题。     

流体包裹体及石英LA-ICP-MS分析方法的建立及其在矿床学中的应用

流体包裹体LA-ICP-MS(激光剥蚀-电感耦合等离子体质谱仪)分析具有高精度、低检测限、多元素同时微区原位检测的特点,因此在精细刻画成矿过程、深入揭示成矿机理方面具有传统方法无可比拟的优势。通过人工合成石英Na Cl-H2O-Rb-Cs和Na Cl-KCl-Ca Cl2-H2O-Rb-Cs流体包裹体,使用NIST610为外标、显微测温Na Cl等效盐度(电价平衡方法)为内标,建立了流体包裹体L A-ICP-MS分析方法。分析结果的相对误差在±16%以内,绝大部分在±10%以内,相对标准偏差(RSD)小于7%。同时结合国际上推荐的石英标样,使用NIST610为外标、无内标法,建立了石英微量元素LA-ICP-MS分析方法。分析结果表明,石英中主要元素Li、Al和Ti的相对误差在±10%以内,相对标准偏差小于5%。利用建立的方法对鲁西早白垩世王家庄Cu-Mo矿开展了应用研究,结果显示该矿富气相包裹体更富Cu,而含子矿物包裹体富Mo,暗示Cu和Mo可能具有不同的搬运机制,Cu更倾向于气相,Mo则倾向于进入液相,结合流体沸腾现象的存在,这可能是导致该矿上铜下钼分带沉淀的重要因素。此外,从早期岩浆成因石英到成矿期热液石英以及成矿期后石英,微量元素具有明显的Ti降低而Al升高的趋势,暗示成矿元素Cu、Mo的沉淀可能同时还受到温度和流体酸碱度变化的控制。     

满洲里-新巴尔虎右旗斑岩系列矿床石英流体包裹体液相组分的PIXE分析和地质应用

ＰＩＸＥ（质子感应Ｘ射线分析）方法是目前国际上新的流体包裹体成分分析方法。在前人工作的基础上,尝试用ＰＩＸＥ方法分析了满洲里－新巴尔虎右旗斑岩系列多金属矿床石英流体包裹体的液相多元素化学组分,其结果反映了地质矿化规律。该方法对于多金属矿床石英流体包裹体成分研究非常有用。结合其他包裹体研究,提出甲乌拉与直干布拉根矿床流体组分和成矿物理化学条件均不同,初步认为不存在同一矿化中心;还提出了查干布拉根矿床西矿段深部可能存在乌奴格吐山式斑岩型Ｃｕ矿床,应引起注意。     

应用显微激光拉曼光谱分析单个流体包裹体同位素

单个流体包裹体同位素是研究特定成岩成矿（藏）阶段古流体成因和来源最有效的方法之一,在矿床、油气、地质流体和大地构造演化动力学等多个领域具有十分重要的用途。但是,目前还没有成熟的分析单个流体包裹体同位素的方法。文中在对目前国内外流体包裹体分析技术总结分析基础上,认为激光拉曼光谱是一项可以分析单个流体包裹体同位素的最有效方法,国外在该领域已经开展了许多创新性的研究工作,并取得了一些重要进展。对激光拉曼光谱分析单个流体包裹体同位素的原理和可行性进行了分析论证,提出通过对已知比值的同位素标准物质拉曼光谱测试和研究,在确定稳定同位素分子的拉曼参数和实验条件等基础上,可以建立起单个流体包裹体稳定同位素激光拉曼测试方法,从而改变目前只能依靠分析群体包裹体同位素来示踪古流体成因和来源的局限性和不确定性。     

Determination par activation neutronique des rapports Cl/Br des inclusions fluides de divers gypses. Correlation avec les donnees de la microcryoscopie et interpretations genetiques

Gypsum contains liquid inclusions which fill mainly primary cavities. Analysis of inclusions may give some information about the mineral formation process. In places, diagenetic solutions have filled secondary cavities along cleavage planes or replaced initial liquid inclusions in primary cavities; the presence of such secondary inclusions must, therefore, be taken into consideration. This study presents our results on the Cl/Br ratio of liquid inclusions in gypsum. The Cl/Br ratio is practically constant in present sea water, and has been measured in many different types of waters. The Br content of halite has also been extensively studied to trace the compositional changes of a salt-depositing brine. In gypsum Br is present only in microscopic fluid inclusions. For this reason we used the neutron-activation method. We adopted the technique in order to prevent any contamination and obtain directly Cl/Br ratio within 10% accuracy. In order to ascertain that liquid inclusions reside mainly in primary cavities of gypsum, we selected our samples only after microscopic observation. Fifty-eight samples from different types of gypsum were analysed. The salinities of the inclusions, obtained through the data on freezing, and the Cl/Br ratio, obtained through activation-analysis, give us clues as to the nature of the fluids depositing the gypsum. Recent gypsum deposits from French salt-pans of Mediterranean and Atlantic coasts were sampled. The latter has apparently been diagenetically altered by meteoric water; the salinity of many inclusions having been changed while the Cl/Br ratio (315 and 350) in both remains close to the value of present sea water (#300). Liquid inclusions of Recent crystals from New Caledonia, deposited in mangrove swamps are enriched in Br (Cl/Br = 150 and 200). The enrichment might be related to the presence of abundant organic materials. Inclusions in crystals from Sebkha el Melah (Tunisia) also show high Br content (Cl/Br = 194). In this case, the brine was highly concentrated and was saturated with NaCl. The Upper Miocene gypsum from Sicily was studied to test the various models for the genesis of this important evaporite formation of the Mediterranean. Freezing data show some decrease of salinities, probably by groundwater diagenesis, but the Br content is high. The Cl/Br ratio is 175, and this value is similar to that of Sebkha el Melah. Samples from three thick Eocene and Oligocene sequences near Paris and in the South of France were studied. Freezing data and Cl/Br ratio of their inclusions indicate that those gypsum deposits have crystallized in marine environments receiving considerable influx of river-waters.     

Magmatic Fluid Inclusions from the Zaldivar Deposit, Northern Chile: The Role of Early Metal-bearing Fluids in a Porphyry Copper System

Abstract. The occurrence of a distinct type of multi-solid, highly-saline fluid inclusions, hosted in igneous quartz phe-nocrysts from the Llamo porphyry, in the Zaldivar porphyry copper deposit of northern Chile is documented. Total homoge-nization of the multi-solid type inclusions occurs at magmatic temperatures (over 750C), well above the typical temperatures of hydro thermal fluids (less than 600C) usually recorded in porphyry copper systems. The analysis of this type of fluid inclusions, using a combination of non-destructive microthermometry, Raman and PIXE techniques and the identification of daughter minerals by SEM method, indicates that the trapped fluid was a dense, complex chloride brine in which Cl, Na, K, Fe, Cu, and Mn are dominant. The high chlorine and metal contents indicate that the metals were separated from the crystallizing magma as homogeneous aqueous chloride-rich solutions that represent the primary magmatic fluids exsolved at high temperatures and depth during the crystallization of the parental intrusive.
The multi-solid type inclusion illustrates the mechanism by which ore components are sequestered from the crystallizing parental magma and concentrated in the exsolved magmatic aqueous fluids. These fluids are significant with respect to the origin of porphyry copper deposits, as they are responsible for the first enrichment of metals and represent the precursors of metal-bearing hydrothermal fluids in a porphyry copper system.     

Part I. Decrepitation and degassing behaviour of quartz up to 1560 °C: Analysis of noble gases and halogens in complex fluid inclusion assemblages

Stepped heating and crushing experiments have been used to investigate the noble gas and halogen degassing behaviour of quartz in detail. Samples with diverse character were selected from the Eloise and Osborne, Iron Oxide Copper Gold (IOCG) ore deposits, and the Railway Fault, 13 km south of the Mt Isa Mine, in the Proterozoic Mt Isa Inlier of northeast Australia. Quartz has been shown to have a bimodal degassing profile. The first degassing mode at temperatures of <700 °C is caused by thermally induced mechanical decrepitation of fluid inclusions. Changes in the Br/Cl, I/Cl, Ar/Cl and ⁴⁰Ar/³⁶Ar composition of gas released at different temperatures up to 700 °C can be related to the decrepitation of different types of fluid inclusion observed by microthermometry. These variations with temperature permit deconvolution of the complex fluid inclusion assemblages associated with the IOCG samples; the ultra high salinity, multi solid (MS) and liquid-vapour-daughter (LVD) fluid inclusions, with a predominantly primary origin, decrepitate at higher temperatures than lower salinity liquid-vapour (LV) and monophase (M) fluid inclusions that have a predominantly secondary origin. Three of the IOCG samples have primary MS and LVD fluid inclusions characterized by molar Br/Cl values of between 0.25 × 10⁻³ and 0.66 × 10⁻³, I/Cl between 0.37 × 10⁻⁶ and 5.0 × 10⁻⁶, ⁴⁰Ar/³⁶Ar values of <1000 and low ³⁶Ar concentrations of 0.7-1.0 × 10⁻⁶ cm³ cm⁻³H₂O. These low values are most easily explained by the involvement of halite dissolution water in IOCG genesis. One of the IOCG samples has Br/Cl of 1.3-2.0 × 10⁻³ and I/Cl of 10 × 10⁻⁶, similar to juvenile magmatic fluids in Phanerozoic Porphyry Copper Deposits. This sample also has a higher ³⁶Ar concentration of 3.5 × 10⁻⁶ cm³ cm⁻³H₂O and a slightly elevated ⁴⁰Ar/³⁶Ar of 2236. Step heating reveals limited and non-systematic variation within the more homogenous population of LV fluid inclusions from the Railway Fault. The samples have mean values of 8.1 × 10⁻³ for Br/Cl; 9.4-12 × 10⁻⁶ for I/Cl; <2000 for ⁴⁰Ar/³⁶Ar; and 4.7-4.8 × 10⁻⁶ cm³ cm⁻³H₂O for ³⁶Ar concentration. The Br/Cl values are similar to those previously reported for basinal brines present in silicic alteration at the Mt Isa Mine and the additional data can be explained by interaction of such a bittern brine with fine grained sedimentary rocks in the sub-surface. The second mode of quartz degassing occurs between 1200 and 1450 °C and releases a greater volume of gas than the first degassing mode. Several lines of evidence, including microscope observations, indicate that the gas released at high temperature is also from the fluid inclusion reservoir. However, its release may be triggered by a metastable phase transition of quartz (∼1200 °C) and caution is required in interpretation of the fluid compositions obtained at these temperatures. The data provide an improved understanding of fluid inclusion decrepitation behaviour that is different to that obtained in lower temperatures experiments designed by other workers to investigate H-isotope fractionation.