Quantitative analysis of melt and fluid inclusions by LA-ICP-MS: Practical aspects and selected results

Quantitative analysis of melt and fluid inclusions by LA-ICP-MS: Practical aspects and selected resultsAudétatA.,GüntherD.,andHeinrichC.A.1998.Formation of a m agm atic- hydrothermal ore deposit:Insights withL A-ICP-MS analysis of fluid inclusions.Science,279:2091～2094 AudétatA .,GüntherD.,andHeinrichC.A.2000 a.Causes for large- scale m etal zonation around mineralized plutons:FluidinclusionL A-ICP-MS evidence from theMoleGranite,Australia.EconomicGeology,(in press) …     

川西甲基卡花岗伟晶岩型锂矿床中熔体、流体包裹体固相物质研究

川西甲基卡二云母花岗岩和伟晶岩内发育大量原生熔体包裹体和富晶体流体包裹体。为了查明甲基卡成矿熔体、流体性质与演化特征,运用激光拉曼光谱和扫描电镜鉴定了甲基卡花岗伟晶岩型锂矿床中二云母花岗岩及伟晶岩脉不同结构带内的原生熔体、流体包裹体的固相物质。分析结果表明,甲基卡二云母花岗岩石英内熔体包裹体的矿物组合为磷灰石+白云母、白云母+钠长石、白云母+石墨;伟晶岩绿柱石内富晶体流体包裹体的矿物组合主要为刚玉、富铝铁硅酸盐+刚玉+锂辉石、锂辉石+石英+锂绿泥石;伟晶岩锂辉石内富晶体流体包裹体的矿物组合主要为磷灰石、锡石、磁铁矿、石英+钠长石+锂绿泥石、萤石、富钙镁硅酸盐+富铁铝硅酸盐+富铁硅酸盐+石英;花岗岩浆熔体与伟晶岩浆熔体(流体)具有一定的差异,成矿熔体、流体成分总体呈现出碱质元素(Na、Si、Al)、挥发分(F、P、CO_2)含量增高及基性元素(Fe、Mg、Ca)降低的特征;包裹体中子矿物与主矿物的化学成分具有一定的差别,揭示出伟晶岩熔体(流体)存在局部岩浆分异作用,具不混溶性及非均匀性。因此认为,伟晶岩熔浆(流体)为岩浆分异与岩浆不混溶共同作用的产物,挥发分含量的增高(F、P、CO_2)使伟晶岩能够与稀有金属组成各类络合物或化合物,这对于稀有金属成矿起到了至关重要的作用。     

LA-ICPMS analyses of silicate melt inclusions in co-precipitated minerals: Quantification, data analysis and mineral/melt partitioning

We present a new approach to determine the composition of silicate melt inclusions (SMI) using LA-ICPMS. In this study, we take advantage of the occurrence of SMI in co-precipitated mineral phases to quantify their composition without depending on additional sources of information. Quantitative SMI analyses are obtained by assuming that the ratio of selected elements in SMI trapped in different phases are identical. In addition Fe/Mg exchange equilibrium between olivine and melt was successfully used to quantify LA-ICPMS analyses of SMI in olivine. Results show that compositions of SMI from the different host minerals are identical within their uncertainty. Thus (1) the quantification approach is valid; (2) analyses are not affected by the composition of the host phase; (3) the derived melt compositions are representative of the original melt, excluding significant syn- or postentrapment modification such as boundary layer effects or diffusive reequilibration with the host mineral. With this data we established a large dataset of mineral/melt partition coefficients for the investigated mineral phases in hydrous calc-alkaline basaltic-andesitic melts. The clinopyroxene/melt and plagioclase/melt partition coefficients are consistent with the lattice strain model of Blundy and Wood [Blundy, J., Wood B., 1994. Prediction of crystal-melt partition-coefficients from elastic-moduli. Nature372, 452-454].     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.     

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.     

Petrogenetic analysis of fluid and melt inclusions in minerals from mantle xenoliths from the Bele pipe basanites (North Minusa depression)

Results of study of different types of inclusions in minerals from mantle xenoliths from the Bele pipe basanites are presented. Two groups of inclusions were recognized in the host minerals according to their genesis. The first group includes single, apparently primary, fluid inclusions. They were discovered only in orthopyroxenes and consist of CO₂ (95 mol.%) and N₂ (5 mol.%). These inclusions had partly leaked. The densities of two least leaked inclusions from different xenoliths are 1.05 and 1.14 g/cm³, and their trapping pressures are estimated at >8.5 and 12 kbar, respectively. The second group includes syngenetic secondary fluid, melt, and crystalline inclusions. In composition the secondary fluid inclusions differ from the primary ones in higher concentrations of N₂ (up to 7 mol.%). Their maximum density is 0.57 g/cm³, which corresponds to 2.4–2.6 kbar and 1100–1200 °C (homogenization temperature of secondary melt inclusions). Comparison of data on melt inclusions in xenolith minerals and host-basanite phenocrysts shows that the secondary inclusions in the xenoliths are, most likely, the result of infiltration and partial reaction of basanitic melt with the xenoliths. On the ascent, the basanitic melt vigorously reacted with mantle xenoliths, which led to the appearance of secondary inclusions in nodule minerals at shallow depths and interstitial mineral assemblages in the xenoliths.     

The geochemistry of volatile species in melt inclusions and sulfide minerals from Izu-Oshima volcano, Japan

Olivine-hosted melt inclusions in the O95 pyroclastic layer of Izu-Oshima volcano, Japan are basaltic to basaltic-andesitic in composition. The negative correlation between SiO₂ and H₂O in melt inclusions and reverse compositional zoning observed in olivine and other mineral phenocrysts is inferred to arise from mixing between a highly evolved and a less evolved magma. The latter is characterized by the highest S (0.15 wt.%) and H₂O (3.4 wt.%) concentrations among those described in reports of previous studies. The S⁶⁺/S_total ratios in melt inclusions were 0.64?–?0.73, suggesting a relatively high oxidation state (NNO + 0.87 at 1150°C). The presence of pyrrhotites, which are found only in titanomagnetite microlites, suggests that sulfide saturation occurred during microlite growth under at a sulfur fugacity (log fS₂) value of around + 0.5 for T = 1060°C. The groundmass glass compositions are more evolved (andesitic composition) than any melt inclusions containing high amounts of Cl (0.13 wt.%) but negligible H₂O (0.20 wt.%) and S (< 70 ppm), suggesting that Cl was retained in the magma, in contrast to S and H₂O, which degassed strongly during magma effusion.     

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.     

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.     

Platinum-group minerals in fluid inclusions from the Marathon deposit,Coldwell Complex,Canada

Summary Platinum-group minerals (PGM) project into fluid inclusions that occur in chalcopyrite and cubanite from the Marathon deposit, Two Duck Lake gabbro, Coldwell Complex, Ontario. Semi-quantitative analyses of the micron-sized PGM were made by SEM-EDS; they reveal Ag-bearing intermetallic compounds of Pd₃Sn-Pd₃Pb-Pd₃Te (i.e., atokitezvyagintsevite-keithconnite) and telargpalite (Pd₂AgTe) on broken, irregular surfaces of the Cu-Fe-S minerals. Halite daughter minerals, and quenched brine occur in and around some opened fluid inclusions. These data confirm the hypothesis based on petrography and mineral compositions that saline fluids remobilized PGE, Cu, and other elements and precipitated them well after crystallization of sulfide and silicate magmas in the Marathon deposit.

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Platin-Gruppenminerale in Flüssigkeitseinschlüssen aus der Marathon Lagerstdtte, Coldwall Komplex, Kanada

Zusammenfassung Platin-Gruppenminerale (PGM) ragen in Flüzssigkeiteinschliisse, die im Kupferkies und Cubanit der Marathon Lagerstätte, Two Duke Lake Gabbro, Coldwell Komplex, Ontario, vorkommen, hinein. Semiqantitative Analysen der mikrongroßen PGM wurden mit einem SEM-EDS durchgeführt. Sie ergaben Ag-führende, intermetallische Verbindungen von Pd₃Sn-Pd₃Pb-Pd₃Te (Atokit-Zvyagintsevit-Keithconnit) und Telargpalit (Pd₂AgTe) auf zerbrochenen, irregulären Oberflächen der Cu-Fe-SMinerale. Steinsalz-Tochterkristalle und abgeschreckte Salzlösungen treten innerhalb und in der unmittelbaren Umgebung geöffneter Flüssigkeitseinschlüsse auf. Diese Daten bestätigen die Hypothese, basierend auf der Petrographie und der Mineralzusammensetzung, daß saline Fluida PGE, Cu und andere Elemente remobilisieren können, und daß d iese nach der Kristallisation der Sulfide und des Silikatmagmas in der Marathon Lagerstätte zur Ablagerung gekommen sind.

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With 3 Figures     

山东昌乐玄武岩内刚玉巨晶中流体和熔融包裹体测温及激光拉曼密度分析

通过详细的测温并辅以新发展的激光拉曼分析流体包裹体密度技术,对山东昌乐玄武岩内刚玉巨晶中的流体和熔融包裹体进行了测试,鉴定出:刚玉中多类流体包裹体为富CO2包裹体,也含少量其他挥发分,密度低于0.55g/cm3(多数<0.3 g/cm3)或位于0.65～0.75 g/cm3范围,前者指示包裹体遭受泄漏;另外一类流体包裹体为富CO2盐水包裹体,也含少量其他挥发分,密度0.64～0.78 g/cm3.各类熔融包裹体中,一类在1 100～1 300℃均一,另3类在1 040～1 280℃均一,但熔融包裹体中也有许多无法均一,是由于其内固体物质粘滞性高同时升温时间有限或富CO2相、富熔体相不均一捕获所致.以熔融包裹体最低均一温度(1 000～1 100℃)代表刚玉内包裹体的捕获温度,用"等容线法"限定包裹体捕获压力为350～640 MPa,经静岩压力换算深度为12～23 km,即中-下地壳深度.大量富CO2包裹体在测温过程中无法观察到相变行为,是鉴定昌乐刚玉的重要标志,而富CO2及含CO2盐水包裹体与熔融包裹体密切伴生及熔融包裹体不均一捕获的特点,反映捕获温压条件下深部流体和熔体存在不混溶现象,也表明昌乐刚玉形成于中一下地壳CO2过饱和的高温熔体环境.     

云南腾冲新期火山岩矿物及其熔体包裹体研究

腾冲火山群位于我国云南省西部和缅甸的交界处,由黑空山、大空山、小空山、打鹰山、马鞍山等一系列火山组成,是我国著名的第四纪火山群,从喷发活动时间上可分为老期火山和新期火山.前人研究证实,打鹰山、马鞍山和黑空山为新期火山,它们在全新世都有过喷发活动.这些新期火山岩的主要斑晶矿物为辉石、橄榄石和长石,主要的斑晶矿物中都含有熔体包裹体,它们形态多样,分布不规则,且部分显示后期有变化.探针分析表明,新期火山岩矿物中熔体包裹体成分的变化范围大于其基质玻璃成分的变化范围,它们的化学成分分布范围涵盖了玄武粗安岩、粗面安山岩、粗面岩和流纹岩等岩石类型,与腾冲火山区晚更新世以来火山岩的成分分布范围基本一致.根据对新期火山岩斑晶和微晶矿物中熔体包裹体及基质玻璃成分的测试研究,其中挥发分Cl的含量在包裹体和基质中变化不大,但F、SO3在熔体包裹体中的含量高于基质,总体上腾冲新期火山喷发时岩浆的脱气率较低,喷发时并未向空中喷出大量气体,推测对当时的气候环境影响不大,但未来喷发的灾害效应不容忽视.     

Evolution of parental magmas of Miocene shield basalts of Gran Canaria (Canary Islands): constraints from crystal,melt and fluid inclusions in minerals

 Picritic units of the Miocene shield volcanics on Gran Canaria, Canary Islands, contain olivine and clinopyroxene phenocrysts with abundant primary melt, crystal and fluid inclusions. Composition and crystallization conditions of primary magmas in equilibrium with olivine Fo_90-92 were inferred from high-temperature microthermometric quench experiments, low-temperature microthermometry of fluid inclusions and simulation of the reverse path of olivine fractional crystallization based on major element composition of melt inclusions. Primary magmas parental for the Miocene shield basalts range from transitional to alkaline picrites (14.7–19.3 wt% MgO, 43.2–45.7 wt% SiO₂). Crystallization of these primary magmas is believed to have occurred over the temperature range 1490–1150° C at pressures ≈5 kbar producing olivine of Fo_80.6-90.2, high-Ti chrome spinel [Mg/ (Mg+Fe²⁺)=0.32–0.56, Cr/(Cr+Al)=0.50–0.78, 2.52–8.58 wt% TiO₂], and clinopyroxene [Mg/(Mg+Fe)=0.79–0.88, Wo_44.1-45.3, En_43.9-48.0, Fs_6.8-11.0] which appeared on the liquidus together with olivine≈Fo₈₆. Redox conditions evolved from intermediate between the QFM and WM buffers to late-stage conditions of NNO+1 to NNO+2. The primary magmas crystallized in the presence of an essentially pure CO₂ fluid. The primary magmas originated at pressures >30 kbar and temperatures of 1500–1600° C, assuming equilibrium with mantle peridotite. This implies melting of the mantle source at a depth of ≈100 km within the garnet stability field followed by migration of melts into magma reservoirs located at the boundary between the upper mantle and lower crust. The temperatures and pressures of primary magma generation suggest that the Canarian plume originated in the lower mantle at depth ≈900 km that supports the plume concept of origin of the Canary Islands. Received: 23 October 1995/Accepted: 21 February 1996     

西华山钨矿床共生透明矿物与不透明矿物中流体包裹体的对比研究

西华山钨矿床是一个产于燕山期花岗岩中的大脉型钨矿床。笔者利用红外显微镜、冷热台及其他相关设备对矿床中的透明矿物(石英、绿柱石和萤石)与不透明矿物(黑钨矿、黄铁矿)中的流体包裹体进行了对比研究。结果显示,共生透明矿物与不透明矿物之间,在包裹体均一温度等特征上既可基本相同又可出现很大差异。一般来说,黑钨矿能有效地保存原生流体包裹体(t_h=300～420℃;晶洞中为220～290℃),仅有少量次生包裹体(t_h=160～280℃),而与之共生的石英中原生包裹体则几乎被破坏殆尽,现在所见到的包裹体绝大多数是次生的或是在较晚结晶时捕获的(t_h=130～270℃)。只有未经后期应力作用和流体改造的晶洞水晶及与其共生的黑钨矿,二者获得的结果才相同或相似。绿柱石中通常有大量的次生包裹体和原生包裹体。黑钨矿与绿柱石中硅酸盐熔融包裹体的出现,表明西华山钨矿床的成矿作用始于岩浆-热液过渡阶段,其初始成矿流体是一种岩浆-热液过渡性流体,尔后才演变成单一的热水溶液。笔者认为,在进行金属矿床流体包裹体研究时,应强调共生透明矿物与不透明矿物的对比研究,在进行对比研究时,详尽的基础地质研究和包裹体岩相学观察必不可少;当单独利用透明矿物包裹体资料对金属矿床进行地质解释时,需慎之又慎。     

Hg and As Minerals in Fluid Inclusions from the Williams Mine,Hemlo,and Their Genetic Implications

The Hemlo mineralization is enigmatic compared to general Archean lode gold deposits based on the fact that is characterized by an exotic mineralogy containing elements such as As,Hg,Sb,Ba,V and Mo.The genetic concepts range from syngenetc to epigenetic types of mineralization.This reconnaissance study was designed to examine the relationshp of Hg-As minerals with respect of fluid inclusions in the Williams mine(formerly known as the Page Williams mine)covering the A and C ore zones.     

Episodic fluid migration in the Fennoscandian Shield recorded by stable isotopes, rare earth elements and fluid inclusions in fracture minerals at Forsmark, Sweden

Drilling through the Palaeoproterozoic bedrock at Forsmark, central Sweden, during the site investigation for a potential geological repository of highly radioactive nuclear waste has provided high quality drill-core material from the upper 1 km of the Fennoscandian Shield. Analyses of stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr), rare earth elements and fluid inclusions in fracture filling calcite and pyrite from these drill cores have resulted in the discrimination of several episodes of fracture mineralisations. These events represent migration of fluids during a wide range of conditions, ranging from high-temperature hydrothermal to present-day groundwater circulation. Four major events have been distinguished: 1) Precipitation of epidote, chlorite and quartz under hydrothermal conditions (T > 150–200 °C) during the Proterozoic, sometime between 1.8 and 1.1 Ga. 2) Hydrothermal circulation at temperatures close to 200 °C with precipitation of adularia, albite, prehnite, laumontite, calcite and chlorite. Most of these minerals precipitated during a tectonothermal event between 1.1 and 1.0 Ga, possibly in response to far-field effects of the Sveconorwegian orogeny. 3) Precipitation of mainly quartz, calcite, pyrite and asphaltite occurred during the Palaeozoic, at temperatures between 60 and 190 °C (mainly at < 100 °C). Mixing of a fluid emanating from an organic rich overlying sedimentary cover and a deep basinal fluid from the crystalline bedrock is suggested to have caused this precipitation, possibly as a far-field response to the Caledonian orogeny and/or the development of the Caledonian foreland basin. 4) The youngest generation of fracture minerals is associated with formation of clay minerals and calcite with minor occurrences of pyrite and goethite. These minerals have probably precipitated episodically during a long time period (possibly from the Late Palaeozoic to the present) from various fluids at low temperature conditions (< 50 °C). Few calcites in equilibrium with the present groundwater suggest that the ongoing precipitation of calcite is very limited.     

Pressure estimated from syngenetic melt and fluid inclusions: Probable reasons for discrepancies

Doklady Earth Sciences -