Volume 4, Issue 2 - ECROFI XXI Guest Editors: Ronald J. Bakker, email: bakker@unileoben.ac.at Miriam Baumgartner, email:Miriam.Baumgartner@unileoben.ac.at Resource Mineralogy, Department of Applied Geosciences and Geophysics, University of Leoben, Peter Tunner-Str. 5, A-8700 Leoben, Austria

Melt inclusions (MI) trapped in igneous phenocrysts provide one of the best tools available for characterizing magmatic processes. Some MI experience post-entrapment modifications, including crystallization of material on the walls, formation of a vapor bubble containing volatiles originally dissolved in the melt, or partial to complete crystallization of the melt. In these cases, laboratory heating may be necessary to return the MI to its original homogeneous melt state, followed by rapid quenching of the melt to produce a homogeneous glass phase, before microanalyses can be undertaken. Here we describe a series of heating experiments that have been performed on crystallized MI hosted in olivine, clinopyroxene and quartz phenocrysts, using the Linkam TS1400XY microscope heating stage. During the experiments, we have recorded the melting behaviors of the MI up to a maximum temperature of 1360°C. In most of the experiments, the MI were homogenized completely (without crystals or bubbles) and remained homogeneous during quenching to room temperature. The resulting single phase MI contained a homogeneous glass phase. These tests demonstrate the applicability of the Linkam TS1400XY microscope heating stage to homogenize and quench MI to produce homogeneous glasses that can be analyzed with various techniques such as Electron Microprobe (EMP), Secondary Ion Mass Spectrometry (SIMS), Laser ablation Inductively Coupled Plasma Mass Spectrometry (LA ICP-MS), Raman spectroscopy, FTIR spectroscopy, etc. During heating experiments, the optical quality varied greatly between samples and was a function of not only the temperature of observation, but also on the amount of matrix glass attached to the phenocryst, the presence of other MI in the sample which are connected to the outside of the crystal, and the existence of mineral inclusions in the host.

Two crushing cells have been described for the release of volatiles from fluid inclusions in minerals in vacuum, static gas, and gas-flow applications. To minimize the adsorption of released volatiles on the freshly created mineral surfaces, both devices employed heated crushing. In the MTSN (Museo Tridentine di Scienze Naturali) crusher, samples were disintegrated by a piston driven by an induction coil. For efficient crushing, the electromagnet operated in dynamic impulse mode. In the LFU (Leopold-Franzens-Universität) crusher, the sample was disintegrated through the combined action of compression (manually operated hydraulic ram) and attrition. Crushers are able to be used in off-line and on-line modes, in gas chromatographic and mass spectrometric analyses.

Phase assemblages and temperatures of phase changes provide important information about the bulk properties of fluid inclusions, and are typically obtained by microthermometry. Inclusions are synthesized in natural quartz containing an aqueous fluid with a composition in the ternary systems of H2O-NaCl2-CaCl2, H2O-NaCl-MgCl2, and H2O-CaCl2-MgCl2. This study reveals that these fluid inclusions may behave highly unpredictably at low temperatures due to the formation of metastable phase assemblages. Eutectic temperatures cannot be detected in most of the fluid inclusions containing these ternary systems. Nucleation of a variety of solid ice and salt-hydrate phases in single fluid inclusions is often partly inhibited. Raman spectroscopy at low temperatures provides an important tool for interpreting and understanding microthermometric experiments, and visualizing stable and metastable phase assemblages. Final dissolution temperatures of ice, salt-hydrates, and salt must be treated with care, as they can only be interpreted by purely empirical or thermodynamic models at stable conditions.

The bulk salinity cannot be directly obtained from the dissolution temperatures of halite in highly saline fluid inclusions that contain solid, liquid, and vapour at room temperature. At least two of the following independent parameters must be determined to estimate the bulk composition and density of these inclusions: 1. dissolution temperature of halite in the presence of vapour; 2. total homogenization temperature of liquid and vapour; and 3. volume fraction of the vapour phase. A new V m-x diagram for phase stabilities in the H2O-NaCl system has been constructed to obtain these bulk fluid properties from inclusions that homogenize liquid and vapour phase at higher temperatures than dissolution of halite.

This study reports a complex fluid and thermal history using petrography, electron microprobe, isotopic analysis and fluid inclusions in replacement minerals within gypsum pseudomorphs in Tithonian-Berriasian lacustrine deposits in Northern Spain. Limestones and dolostones, formed in the alkaline lakes, contain lenticularly shaped gypsum pseudomorphs, considered to form in an evaporative lake. The gypsum was replaced by quartz and non-ferroan calcite (Ca-2), which partially replaces the quartz. Quartz contains solid inclusions of a preexisting non-ferroan calcite (Ca-1), anhydrite and celestine. High homogenization temperatures (T h) values and inconsistent thermometric behaviour within secondary fluid inclusion assemblages in quartz (147–351°C) and calcite (108–352°C) indicate high temperatures after precipitation and entrapment of lower temperature FIAs. Th are in the same range as other reequilibrated fluid inclusions from quartz veins in the same area that are related to Cretaceous hydrothermalism. Gypsum was replaced by anhydrite, likely during early burial. Later, anhydrite was partially replaced by Ca-1 associated with intermediate burial temperatures. Afterward, both anhydrite and Ca-1 were partially replaced by quartz and this by Ca-2. All were affected during higher temperature hydrothermalism and a CO2-H2O fluid. Progressive heating and hydrothermal pulses, involving a CO2-H2O fluid, produce the reequilibration of the FIAs, which was followed by uplift and cooling.

The Jurassic pillow basalt blocks in the Szarvaskő Unit in the SW-Bükk Mountains are incorporated into an accretionary mélange of Cretaceous age which had been displaced from the Dinarides to NE-Hungary during the Alpine-Carpathian collision. The pillow basalt series is a part of an incomplete remnant of an ophiolite-like sequence from which ultramafic units and sheeted dikes are almost completely absent. At the studied Egerbakta quarry, closely packed pillow, pillow fragmented hyaloclastite breccia and peperitic facies of submarine basaltic volcanism were recognized. Peperitic facies was formed by local admixture of unconsolidated siliciclastic sediment into the basaltic lava. Basaltic pillows contains short and thin prehnite-chlorite-carbonate-quartz veins formed during the interaction of seawater with the cooling lava, as well as cross-cutting datolite-prehnite-quartzchlorite-albite bearing veins. Calcite in the short cooling cracks crystallised from upheated seawater at around 160°C temperature and 0.5–0.6 kbar pressure (water depth of about 5–6 km). Datolite precipitations in veins can be classified into at least three different textural-morphological types but all of them contain methane bearing primary fluid inclusion assemblages, with variable methane/water ratios, suggesting an inhomogeneous entrapment from a heterogeneous aqueous-carbonic fluid. End member primary fluid inclusions contain aqueous liquid with methane rich vapour phase and apparently methane only inclusions characterized by liquid phase on room temperature. A combination of results from fluid inclusion microthermometry, Raman spectroscopy (used not only for phase identification but also for determination of salinities) and temperatures calculated from chlorite compositions, show that the precipitation of datolite had taken place from low salinity (0.2–2 NaCl equiv. mass%) aqueous-methane fluids under increasing temperature and pressure (from 160 to 210°C, and from 0.6 to 1.1 kbar) conditions. The elevated pressures and temperatures in comparison to the submarine hydrothermal processes suggest that the datolite bearing mineral parageneses had been formed during the progression of Alpine very low grade metamorphic processes.

Results of a numerical modeling study of quartz dissolution and precipitation in a sub-seafloor hydrothermal system have been used to predict where in the system quartz could be deposited and potentially trap fluid inclusions. The spatial distribution of zones of quartz dissolution and precipitation is complex, owing to the fact that quartz solubility depends on many inter-related factors, including temperature, fluid salinity and fluid immiscibility, and is further complicated by the fact that quartz exhibits both prograde and retrograde solubility behavior, depending on the fluid temperature and salinity. Using the PVTX properties of H2O-NaCl, the petrographic and microthermometric properties of fluid inclusions trapped at various locations within the hydrothermal system have been predicted. Vapor-rich inclusions are trapped as a result of the retrograde temperature-dependence of quartz solubility as the convecting fluid is heated in the vicinity of the magmatic heat source. Coexisting liquid-rich and vapor-rich inclusions are also trapped in this region when quartz precipitates as a result of fluid immiscibility that lowers the overall bulk quartz solubility in the system. Fluid inclusions trapped in the shallow subsurface near the seafloor vents and in the underlying stockwork are liquid-rich with homogenization temperatures of 200–400°C and salinities close to that of seawater. Volcanogenic massive sulfide (VMS) deposits represent the uplifted and partially eroded remnants of fossil submarine hydrothermal systems, and the relationship between fluid-inclusion properties and location within the hydrothermal system described here can be used in exploration for VMS deposits to infer the direction towards potential massive sulfide ore.

The Emmaville-Torrington emeralds were first discovered in 1890 in quartz veins hosted within a Permian metasedimentary sequence, consisting of meta-siltstones, slates and quartzites intruded by pegmatite and aplite veins from the Moule Granite. The emerald deposit genesis is consistent with a typical granite-related emerald vein system. Emeralds from these veins display colour zonation alternating between emerald and clear beryl. Two fluid inclusion types are identified: three-phase (brine+vapour+halite) and two-phase (vapour+liquid) fluid inclusions. Fluid inclusion studies indicate the emeralds were precipitated from saline fluids ranging from approximately 33 mass percent NaCl equivalent. Formational pressures and temperatures of 350 to 400 °C and approximately 150 to 250 bars were derived from fluid inclusion and petrographic studies that also indicate emerald and beryl precipitation respectively from the liquid and vapour portions of a two-phase (boiling) system. The distinct colour zonations observed in the emerald from these deposits is the first recorded emerald locality which shows evidence of colour variation as a function of boiling. The primary three-phase and primary two-phase FITs are consistent with alternating chromium-rich ‘striped’ colour banding. Alternating emerald zones with colourless beryl are due to chromium and vanadium partitioning in the liquid portion of the boiling system. The chemical variations observed at Emmaville-Torrington are similar to other colour zoned emeralds from other localities worldwide likely precipitated from a boiling system as well.

Successful exploration for mineral deposits requires tools that the explorationist can use to distinguish between targets with high potential for mineralization and those with lower economic potential. In this study, we describe a technique based on gangue mineral textures and fluid inclusion characteristics that has been applied to identify an area of high potential for gold-silver mineralization in the epithermal Ag-Au deposits at Guanajuato, Mexico. The Guanajuato mining district in Mexico is one of the largest silver producing districts in the world with continuous mining activity for nearly 500 years. Previous work conducted on the Veta Madre vein system that is located in the central part of this district identified favorable areas for further exploration in the deepest levels that have been developed and explored. The resulting exploration program discovered one of the richest gold-silver veins ever found in the district. This newly discovered vein that runs parallel to the Veta Madre was named the Santa Margarita vein. Selected mineralized samples from this vein contain up to 249 g/t of Au and up to 2,280 g/t Ag. Fluid inclusions in these samples show homogenization temperatures that range from 184 to 300°C and salinities ranging from 0 to 5 wt.% NaCl. Barren samples show the same range in homogenization temperature, but salinities range only up to 3 wt.% NaCl. Evidence of boiling was observed in most of the samples based on fluid inclusions and/or quartz and calcite textures. Liquid-rich inclusions with trapped illite are closely associated with high silver grades. The presence of assemblages of vapor-rich-only fluid inclusions, indicative of intense boiling or “flashing”, shows the best correlation with high gold grades.

Inductively coupled plasma-mass spectrometry (ICP-MS) has been used to determine rare earth element concentrations in aqueous solutions extracted from fluid inclusions. Quartz has been sampled from ores of three major types of polygenic gold hydrothermal systems of North-Eastern Russia: (1) gold-quartz-sulphide (Au-Q, Nezhdaninsk); (2) gold-antimony (Au-Sb, Sarylakh) and (3) intrusion-related gold-bismuth-siderite-polysulphide (Au-Bi-Sid, Arkachan) large deposits located in terrigenous rocks of the Verkhoyansk fold belt. The total concentration of REE in the fluid inclusions is not high (up to 52 ppm). The contribution of LREE dominates in REE balance (ΣLREE/ΣHREE=7.4–112.1). The chondrite-normalized REE patterns of inclusion fluids for the Au-Q and Au-Bi-Sid deposits are characterized by LREE enrichment with a positive or negative Eu anomaly. REE patterns for the regenerated quartz from Au-Sb deposits are characterized by pronounced differentiation between light and heavy lanthanides in fluid inclusions. Significant total REE concentration decreasing (on 1–2 order) from early to late stages of Nezhdaninsk and Arkachan deposits is revealed. The positive correlations of total REE concentrations with Rb, Cs, Li and B contents in fluid inclusions are shown. The REE distribution in fluid inclusions can be used as indicators of the contribution of magmatic fluid in the hydrothermal system.

Nodules (coarse-grain “plutonic” rocks) were collected from the ca. 20 ka Pomici di Base (PB)-Sarno eruption of Mt. Somma-Vesuvius, Italy. The nodules are classified as monzonite-monzogabbro based on their modal composition. The nodules have porphyrogranular texture, and consist of An-rich plagioclase, K-feldspar, clinopyroxene (ferroan-diopside), mica (phlogopite-biotite) ± olivine and amphibole. Aggregates of irregular intergrowths of mostly alkali feldspar and plagioclase, along with mica, Fe-Ti-oxides and clinopyroxene, in the nodules are interpreted as crystallized melt pockets. Crystallized silicate melt inclusions (MI) are common in the nodules, especially in clinopyroxenes. Two types of MI have been identified. Type I consists of mica, Fe-Ti-oxides and/or dark green spinel, clinopyroxene, feldspar and a vapor bubble. Volatiles (CO2, H2O) could not be detected in the vapor bubbles by Raman spectroscopy. Type II inclusions are generally lighter in color and contain subhedral feldspar and/or glass and several opaque phases, most of which are confirmed to be oxide minerals by SEM analysis. Some of the opaque-appearing phases that are below the surface may be tiny vapor bubbles. The two types of MI have different chemical compositions. Type I MI are classified as phono-tephrite — tephri-phonolite — basaltic trachy-andesite, while Type II MI have basaltic composition. The petrography and MI geochemistry led us to conclude that the nodules represent samples of the crystal mush zone in the active plumbing system of Mt. Somma-Vesuvius that were entrained into the upwelling magma during the PB-Sarno eruption.

The Aeolian Islands are an arcuate chain of submarine seamounts and volcanic islands, lying just north of Sicily in southern Italy. The second largest of the islands, Salina, exhibits a wide range of compositional variation in its erupted products, from basaltic lavas to rhyolitic pumice. The Monte dei Porri eruptions occurred between 60 ka and 30 ka, following a period of approximately 60,000 years of repose. The bulk rock composition of the Monte dei Porri products range from basaltic-andesite scoria to andesitic pumice in the Grey Porri Tuff (GPT), with the Monte dei Porri lavas having basaltic-andesite compositions. The typical mineral assemblage of the GPT is calcic plagioclase, clinopyroxene (augite), olivine (Fo72−84) and orthopyroxene (enstatite) ± amphibole and Ti-Fe oxides. The lava units show a similar mineral assemblage, but contain lower Fo olivines (Fo57−78). The lava units also contain numerous glomerocrysts, including an unusual variety that contains quartz, K-feldspar and mica. Melt inclusions (MI) are ubiquitous in all mineral phases from all units of the Monte dei Porri eruptions; however, only data from olivine-hosted MI in the GPT are reported here. Compositions of MI in the GPT are typically basaltic (average SiO2 of 49.8 wt %) in the pumices and basaltic-andesite (average SiO2 of 55.6 wt %) in the scoriae and show a bimodal distribution in most compositional discrimination plots. The compositions of most of the MI in the scoriae overlap with bulk rock compositions of the lavas. Petrological and geochemical evidence suggest that mixing of one or more magmas and/or crustal assimilation played a role in the evolution of the Monte dei Porri magmatic system, especially the GPT. Analyses of the more evolved mineral phases are required to better constrain the evolution of the magma.