High-temperature Fluid Inclusions Research Articles

Emerald from the Habachtal: new observations

The emerald mineralization in the Habachtal (Austria) is geologically and tectonically complex, and previous investigators have identified fluid inclusion evidence for a hydrothermal/metamorphic origin for the emeralds. In this paper we report the discovery of emeralds with a distinctly different inclusion population including melt inclusions, which demonstrates that at least some and probably most of the emerald mineralization in the Habachtal occurred from an extremely fluid-rich pegmatite-like aluminosilicate melt under supercritical conditions, at high temperatures and moderate pressures (~700 °C, 5 kbar). This conclusion is based on the presence of very highly-ordered graphite, and extremely water-rich melt inclusions in emerald. The Lorentz distribution of MgCO3 against the water concentration is a very robust proof for the supercritical state. We suggest that the purely metamorphic model, based on the extrapolation of fluid inclusion data to the regional metamorphic conditions (550 °C and 5 kbar) by some previous investigators are inconsistent with our finding of high-temperature indications (well-ordered graphite, high-temperature fluid inclusions and melt inclusions). This apparent conflict suggests a more complex situation and requires a re-investigation of the emerald genesis in the Habachtal deposit.

The Metal Content of Magmatic-Hydrothermal Fluids and Its Relationship to Mineralization Potential

Abstract A fundamental question in the study of magmatic-hydrothermal ore deposits is whether the mineralization potential of intrusions was already predetermined by the metal content of the exsolving fluids. The present study aims at addressing this question by reviewing the large number of microanalytical data (mostly laser-ablation ICP-MS data) obtained on fluid inclusions from this type of ore deposits over the last 20 years. Published data sets were screened for analyses of high-temperature fluid inclusions that are representative of premineralization fluids. A set of criteria was developed to distinguish such fluids from later, lower temperature fluids. In order to compensate differences in absolute metal concentrations caused by fluid immiscibility, all element concentrations were normalized to Na. A numerical model was developed to explore at which stage different metals are most efficiently extracted from a cooling pluton. The results suggest that the timing of most efficient metal extraction varies from metal to metal and strongly depends on pressure, the fluid/melt partition coefficient and the bulk mineral-melt partition coefficient. As a consequence, fluid compositions were chosen over the entire range of Cs/Na ratios recorded from a given pluton, as this ratio gives an indication of the fractionation degree of the silicate melts from which a fluid exsolved. In order to avoid bias toward occurrences from which a large amount of data are available, maximum four intermediate-density (ID)-type fluid inclusion assemblages plus four brines assemblages were chosen from each occurrence. Using the above-mentioned criteria, 169 fluid compositions from 12 Cu (Mo, Au) mineralized intrusions, 10 Sn/W mineralized intrusions, two Mo mineralized intrusions, and one U-Th-REE mineralized intrusion were finally chosen and plotted in graphs of X/Na versus Cs/Na. The results reveal that Sn- and Cu-mineralizing fluids contained more Sn and Cu, respectively, than the fluids analyzed from barren and Mo or U-Th REE mineralized intrusions. Positive correlations between fluid metal content and mineralization potential may exist also for W and REEs, whereas for Mo no such trend is evident. Therefore, at least for certain metals, the metal content of high-temperature fluid inclusions can be used as an indicator of the type and extent of mineralization. However, elevated metal concentrations are present also in some fluids from barren intrusions, which implies that the mineralization potential additionally depends on other factors such as the size of the intrusion and the development of structures that promote focused fluid flow.

A renewed look at calcite cement in marine-deltaic sandstones: the Brent Reservoir, Heather Field, northern North Sea, UK

Abstract Wireline and seismic acoustic impedance imaging show that the marine part of the clastic Brent Group reservoir in the Heather Field, northern North Sea, contains much calcite cement in the flank parts of the structure. The non-marine Ness Formation and crest parts of the structure contain negligible calcite cement. This localized calcite cement has led to relatively poor reservoir performance since first oil in 1978, although a new suite of wells has boosted production with plans to keep the field active until 2030. Understanding the origin and distribution of calcite cement would help the development of more realistic reservoir models and boost production rates through optimum well location. We have thus used a suite of techniques, including standard point counting, SEM-EDS mineralogy, BSE microscopy, fluid inclusion thermometry and stable isotope analysis, to develop new and improved models of calcite distribution. Calcite seems to have attributes of both early and late diagenetic cement. A 30–40% intergranular volume in calcite cemented beds seems to support pre-compactional growth but high-temperature fluid inclusions and the presence of primary oil inclusions suggest late growth. Much calcite may have developed early but it seems to have recrystallized, and possibly undergone redistribution, at close to maximum burial or had a late growth event. Calcite cement probably originated as marine-derived micrite, bioclasts or early marine cement but adopted the isotopic characteristics of high-temperature growth as it recrystallized. Quartz grains have corroded outlines in calcite-cemented areas with one sample, with 79% calcite cement, displaying signs of nearly total replacement of quartz grains by calcite. The flank localization of calcite cement remains to be explained, although it could be due to primary depositional factors, early diagenetic loss of calcite from crestal regions or late diagenetic loss of calcite from crestal regions. Controversially, the growth of calcite seems to be associated with quartz dissolution, although the geochemical and petrophysical cause of this remains obscure. Diagenetic loss of quartz from sandstones cannot easily be explained by conventional modelling approaches and yet seems to be an important phenomenon in Heather sandstones.

Mineralized breccia clasts: a window into hidden porphyry-type mineralization underlying the epithermal polymetallic deposit of Cerro de Pasco (Peru)

Cerro de Pasco (Peru) is known for its large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) mineralization emplaced at shallow level, a few hundred meters below the paleo-surface, at the border of a large diatreme–dome complex. Porphyry-style veins crosscutting hornfels and magmatic rock clasts are found in the diatreme breccia and in quartz–monzonite porphyry dikes. Such mineralized veins in clasts allow investigation of high-temperature porphyry-style mineralization developed in the deep portions of magmatic–hydrothermal systems. Quartz in porphyry-style veins contains silicate melt inclusions as well as fluid and solid mineral inclusions. Two types of high-temperature (> 600 °C) quartz–molybdenite–(chalcopyrite)–(pyrite) veins are found in the clasts. Early, thin (1–2 mm), and sinuous HT1 veins are crosscut by slightly thicker (up to 2 cm) and more regular HT2 veins. The HT1 vein quartz hosts CO2- and sulfur-rich high-density vapor inclusions. Two subtypes of the HT1 veins have been defined, based on the nature of mineral inclusions hosted in quartz: (i) HT1bt veins with inclusions of K-feldspar, biotite, rutile, and minor titanite and (ii) HT1px veins with inclusions of actinolite, augite, titanite, apatite, and minor rutile. Using an emplacement depth of the veins of between 2 and 3 km (500 to 800 bar), derived from the diatreme breccia architecture and the supposed erosion preceding the diatreme formation, multiple mineral thermobarometers are applied. The data indicate that HT1 veins were formed at temperatures > 700 °C. HT2 veins host assemblages of polyphase brine inclusions, generally coexisting with low-density vapor-rich inclusions, trapped at temperatures around 600 °C. Rhyolitic silicate melt inclusions found in both HT1 and HT2 veins represent melt droplets transported by the ascending hydrothermal fluids. LA-ICP-MS analyses reveal a chemical evolution coherent with the crystallization of an evolved rhyolitic melt. Quartz from both HT1 and HT2 veins also contains secondary, low-temperature (~ 300 °C) brine and aqueous fluid inclusions that record the cooling of the system. Both vein types are locally crosscut and/or reopened by a pre-diatreme polymetallic event consisting of pyrite, sphalerite with “chalcopyrite disease,” galena, chalcopyrite, tetrahedrite–tennantite, and minor quartz. LA-ICP-MS analyses of mineral and high-temperature fluid inclusions hosted in HT1 and HT2 veins and in situ secondary-ion mass spectrometry oxygen isotope analyses of vein quartz indicate a magmatic signature for the mineralizing fluids with no major meteoric water input and allow reconstruction of the source and chemical evolution of fluids that formed these porphyry-style veins as snapshots of the early and deep mineralizations at Cerro de Pasco. This detailed study of the porphyry-type mineralization hosted in clasts offers a unique opportunity to reconstruct the late magmatic and early hydrothermal evolutions of porphyry mineralization underlying the world-class Cerro de Pasco epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) deposit.

Geochemistry, fluid inclusion and stable isotope constraints (C and O) of the Sivrikaya Fe-skarn mineralization (Rize, NE Turkey)

The Sivrikaya Fe-skarn mineralization is hosted by dolomitic limestone layers of Late Cretaceous volcano-sedimentary unit, comprised of andesite, basalt and their pyroclastites, including, sandstone, shale and dolomitic limestone layers. Intrusion of the Late Cretaceous–Eocene İkizdere Granitoid in the volcano–sedimentary unit resulted in skarn mineralization along the granitoid–dolomitic limestone contact. The ore is associated with exoskarns, and mineralization is characterized by early anhydrous garnet and pyroxene with late hydrous minerals, such as epidote, tremolite, actinolite and chlorite. The ore minerals are mainly magnetite and hematite, with minor amounts of pyrite and chalcopyrite. The composition of garnet and pyroxene in the exoskarn is Adr79.45−99.03Grs0−17.9Prs0.97−2.65 and Di69.1−77.1Hd22.2−29.8Jhn0.6−1.4, respectively, and abundances of magnetite in the ore suggest that the Fe-skarn mineralization formed under relatively oxidized conditions.Homogenization temperatures (Th) of all fluid inclusions and calculated salinity content are in the range of 166 °C–462 °C and 0.35–14.3 wt% NaCl equ., respectively. Well-defined positive correlation between Th and salinity values indicates that meteoric water was involved in the hydrothermal solutions. Eutectic temperatures (Te) between −40.8 °C and −53.6 °C correspond to the presence of CaCl2 in the early stage of fluid inclusions. On the other hand, the Te temperatures of later-stage fluid inclusions, in the range of −38 °C and −21.2 °C, correspond to the presence of MgCl2, FeCl2, KCl and NaCl type salt combinations. None of the fluid inclusions were found to contain separated gas phases in microscopy observations. However, a limited amount of dissolved CH4 was identified in the early stage, high temperature fluid inclusions using Raman spectroscopic studies.Δ18O values in both dolomitic limestone (10.8–12.5‰) and skarn calcite (7.6–9.8‰) were highly depleted compared to the typical δ18O values of marine limestones. Decreases in δ18O values are accepted as an indication of dilution by meteoric water because retrograde brecciation of garnet, magnetite and breccia filling epidote and quartz in volcanic host rocks are an indication of increasing permeability, allowing infiltration of meteoric water. Highly depleted δ13C isotopes (up to −6.5‰) of dolomitic limestone, indicate that organic matter in carbonates had an effect on the decreasing isotopic ratios. The presence of CH4 and CH2 in fluid inclusions can be explained by the thermal degradation of these organic materials.

Metasomatized asthenospheric mantle contributing to the generation of Cu-Mo deposits within an intracontinental setting: A case study of the ∼128 Ma Wangjiazhuang Cu-Mo deposit, eastern North China Craton

Cu-Mo deposits are commonly associated with calc-alkaline porphyries and derived from subduction-modified lithosphere in magmatic arcs. Here we report the Wangjiazhuang Cu-Mo deposit, which is peculiarly associated with an alkaline quartz monzonite that originated from a metasomatized asthenospheric mantle within an intracontinental setting in the eastern North China Craton (NCC). The deposit was formed at ca. 128.3±0.7Ma (2σ), basically coincident with the emplacement of the host quartz monzonite (128.8±1.0Ma, 2σ). Pegmatitic vein-type and stockwork-/disseminated-type mineralizations were identified in the deposit, of which the former is shallowly situated and characterized by coarse and well-crystallized Cu- and Mo-bearing sulfides+quartz+biotite+K-feldspar assemblages, whereas the latter is deeply situated and characterized by stockworks or Cu- and Mo-bearing sulfides disseminated in the altered quartz monzonite. Separation between Cu-rich and Mo-rich ore bodies at shallow depth was also observed. The Cu-Mo mineralization is typically associated with potassic-silicic alteration. High-temperature fluid inclusions with halite/sylvite daughter minerals (having homogenization temperatures of 287–466°C and salinities of 33.8–55.3wt% NaCl equivalent) suggest a magmatic origin of the ore-forming fluids. Differentiation of the fluids into vapor-rich and liquid-rich phases occurred during the magmatic-hydrothermal processes, as indicated by the coexistence of vapor-rich, liquid-rich and daughter mineral-rich fluid inclusions with similar homogenization temperatures. LA-ICP-MS analysis of the fluid inclusions shows that Cu is highly partitioned into the vapor-rich fluid inclusions, whereas Mo is mainly concentrated in the daughter mineral-rich fluid inclusions. This implies that phase differentiation of the ore-forming fluids was likely responsible for the separation of Cu-rich and Mo-rich ore bodies. The presence of hematite in the fluid inclusions also suggests high oxidation state of the ore-forming fluids. Based on the variations of δ34S in sulfides and Al contents in quartz, continuous reduction of the oxidized ore-forming fluids, coupled with pH change of the fluids during water-rock interaction, led to the deposition of the ore-forming metals.The host quartz monzonite shows adakitic geochemical signatures. Fractional crystallization of low-Mg amphiboles contributed to the adakitic signatures. According to the mixing modeling using Sr-Nd isotopes, the quartz monzonite was mainly derived from asthenospheric mantle-derived magma mixed by ∼15–20% lower crust components at the base of the lower crust. Zircon saturation thermometry and Ti-in-quartz thermobarometer suggest that the rock was emplaced at the temperature of ∼746°C and the depth of ∼4km. High water (H2O≥4wt%) and metal (Cu is up to 840ppm and Mo is up to 11.9ppm) contents as well as high oxidation state (fO2>fayalite-magnetite-quartz oxygen buffer) are featured in the quartz monzonite, indicating that the asthenospheric mantle source had been hydrated and oxidized by the water released from the stagnant Paleo-Pacific slab in the transition zone (410–610km). Such modification by the deep stagnant oceanic slab beneath the eastern NCC thus not only triggered the remarkable thinning of the Archean lithospheric keel (loss of >120km), but also promoted the asthenospheric mantle to become the favorable magma and metal source for the Cu-Mo deposits in the study region.

Trace element diffusion and incorporation in quartz during heating experiments

Heating of quartz crystals in order to study melt and high-temperature fluid inclusions is a common practice to constrain major physical and chemical parameters of magmatic and hydrothermal processes. Diffusion and modification of trace element content in quartz and its hosted melt inclusions have been investigated through step-heating experiments of both matrix-free quartz crystals and quartz crystals associated with sulfides and other minerals using a Linkam TS1500 stage. Magmatic and hydrothermal quartz were successively analyzed after each heating step for Cu, Al, and Ti using electron probe micro-analyzer. After the last heating step, quartz crystals and their hosted melt inclusions were analyzed by laser ablation inductively coupled plasma mass spectrometry and compared to unheated samples. Heated samples reveal modification of Cu, Li, Na, and B contents in quartz and modification of Cu, Li, Ag, and K concentrations in melt inclusions. Our results show that different mechanisms of Cu, Li, and Na incorporation occur in magmatic and hydrothermal quartz. Heated magmatic quartz records only small, up to a few ppm, enrichment in Cu and Na, mostly substituting for Li. By contrast, heated hydrothermal quartz shows enrichment up to several hundreds of ppm in Cu, Li, and Na, which substitute for originally present H. This study reveals that the composition of both quartz and its hosted melt inclusions may be significantly modified upon heating experiments, leading to erroneous quantification of elemental concentrations. In addition, each quartz crystal also becomes significantly enriched in Cu in the sub-surface layer during heating. We propose that sub-surface Cu enrichment is a direct indication of Cu diffusion in quartz externally sourced from both the surrounding sulfides as well as the copper pins belonging to the heating device. Our study shows that the chemical compositions of both heated quartz and its hosted inclusions must be interpreted with great caution to avoid misleading geological interpretations.

The Stillwater Complex, Montana – Overview and the significance of volatiles

AbstractThe geology of the 2.7 Ga Stillwater Complex in South-Central Montana is reviewed with a focus on the role of volatiles in locally modifying both the crystallization sequence of the evolving parent magma and the initially precipitated solid assemblages to favour olivine ± chromite. A secondary origin for these two minerals is particularly probable for the olivine-bearing rocks of the Banded series and, at a minimum, also increasing their modal abundance in the Peridotite zone of the Ultramafic series. Direct evidence for volatiles includes the presence of high-temperature fluid inclusions in pegmatoids and hydrous melt inclusions (now crystallized) in chromite and olivine from both the Ultramafic and the Banded series rocks. Indirect evidence includes the boninitic character of the parent magma, the presence of volatile-bearing minerals including high-temperature carbonates, rock textures, and Cl / F variations in apatite. Mechanisms which favour the formation of olivine (± chromite) over pyroxene include volatile phase boundary shifts induced by added H2O, incongruent melting of pyroxene by hydration of a partly-molten mush, and the near- to sub-solidus replacement of pyroxene by olivine and chromite by silica-undersaturated fluids. These mechanisms cast doubt that magmas with different liquid lines of descent were involved in the crystallization of the Stillwater Complex. A dry Stillwater magma would have been mineralogically and modally much less varied and lacking in high-grade platinum-group element and chromium deposits.

The La Unión Au ± Cu prospect, Camagüey District, Cuba: fluid inclusion and stable isotope evidence for ore-forming processes

The Camaguey district, Cuba, is known for its epithermal precious metal deposits in a Cretaceous volcanic arc setting. Recently, the La Union prospect was discovered in the southern part of the district, containing gold and minor copper mineralization interpreted as porphyry type. Mineralization is hosted in a 73.0 ± 1.5 Ma calc–alkaline I-type oxidized porphyry quartz diorite intrusive within volcanic and volcaniclastic rocks of the early Cretaceous Guaimaro Formation. The porphyry is affected by propylitic alteration and crosscut by a network of quartz and carbonate veinlets and veins. Chlorite, epidote, sericite, quartz, and pyrite are the main minerals in the early veins which are cut by late carbonate and zeolite veins. Late barite pseudomorphously replaces pyrite. Gold is associated with pyrite as disseminations in the altered quartz diorite and in the veins, occurring as inclusions or filling fractures in pyrite with 4 g/t Au in bulk samples, and up to 900 ppm Au in in pyrite. Fluid inclusion and oxygen isotope data are consistent with a H2O–NaCl–(KCl) mineralizing fluid, derived from the quartz diorite magma, and trapped at least at 425°C and 1.2 kbar. This primary fluid unmixed into two fluid phases, a hypersaline aqueous fluid and a low-salinity vapor-rich fluid. Boiling during cooling may have played an important role in metal precipitation. Pyrite δ34S values for the La Union prospect range between 0.71‰ and 1.31‰, consistent with a homogeneous magmatic sulfur source. The fluids in equilibrium with the mineralized rocks have estimated δ18O values from 8‰ to 11.8‰, calculated for a temperature range of 480–505°C. The tectonic environment of the La Union prospect, its high gold and low copper contents, the physical–chemical characteristics of the mineralizing fluids and the isotopic signature of the alteration minerals and fluids indicate that the La Union gold mineralization is similar to the porphyry gold type, even though the ore-related epidote–chlorite alteration can be classified as propylitic and not the classic potassic and/or phyllic alteration. The low copper contents in the prospect could be due to a mineralizing fluid previously saturated in copper, which is indicated by trapped chalcopyrite crystals in high-temperature fluid inclusions. The low-temperature paragenesis, represented by carbonate, zeolite and barite, indicates epithermal overprint. The study shows the potential for other gold porphyry-type deposits in the Cretaceous volcanoplutonic arc of Cuba.

Geology, mineralogy and stable isotope geochemistry of the Kabwe carbonate-hosted Pb–Zn deposit, Central Zambia

The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu. Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ 34S CDT permil (‰) values of − 17.75 ± 0.28 (1 σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ 34S for sphalerite and of − 11.91 ± 0.71‰ δ 34S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur. Carbon and oxygen isotope ratios of the host dolomite have mean δ 13C PDB and δ 18O SMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO 2 content introduced during silicification of the host dolomite. The depletion in 18O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and 18O-rich hydrothermal solution. Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl. Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.

LA-ICP-MS micro-analysis of fluid inclusions in quartz using a commercial Merchantek 266 nm Nd:YAG laser: a pilot study

The results of this pilot study show that using a commercial Merchantek 266 nm Nd:YAG laser system, laser ablation -inductively coupled plasma - mass spectrometric analysis of fluid inclusions in quartz is possible. Fifteen elements (Li, Na, K, Mg, Fe, As, Rb, Sr, Sn, Ba, Mo, U, W, Mn, and Pb) were determined for aqueous fluid inclusions from the Zinnwald Sn deposit (Ore Mountains, Germany). The concentrations of the measured major and trace elements are in good agreement with literature data for the same location. A first evaluation of the data shows that the high temperature inclusions (Th: 400 - 370 °C) contain high Fe and Na concentrations as well as Sn contents typical of tin-bearing fluids. A decrease in salinity from the high temperature fluid inclusions to low temperature secondary inclusions probably reflects a dilution trend of the magmatic fluid by external fluids.

Laser ablation-ICP-AES for the determination of metals in fluid inclusions: An application to the study of magmatic ore fluids

The laser ablation-ICP-AES (L-ICP-AES) technique is an effective method for the multielement analysis of individual fluid inclusions. Recent tests on synthetic fluid inclusions and improvements in data processing suggest that the method is valid for the analysis of a range of alkali-, alkali-earth, and transition metals in single, large inclusions (> 30 μm) of moderate to high salinity (>20 wt% NaCl equiv.). The system, involving a small, perspex ablation chamber, a 1 J ruby laser focussed through an optical microscope, and a conventional ICP-AES instrument is discussed and applied to natural fluid inclusions in quartz from two contrasting types of magmatic-hydrothermal mineralization. Samples were selected from the San Pedro Cu-Au porphyry system, New Mexico, USA, and the Sn-W-Cu-mineralized Dartmoor granite of southwest England. Variable salinity, high temperature fluid inclusions in hydrothermal quartz from both environments display similarly high concentrations and ratios of Na, K, Ca, and Fe. The ore metals Cu, Zn, and Mn (but not Sn, Mo, W) were detected in inclusions from both environments. The estimated combined concentrations of up to 3 wt% show that these three elements are major components of these fluids. A method has been devised to estimate the confidence intervals of the measured concentration ratios. The confidence intervals obtained show that the analytical uncertainty for an inclusion is much less than the natural geochemical variation between inclusions so that geologically useful information can be obtained. A trend of increasing salinity with decreasing Na and K and increasing Ca and Fe contents is observed in inclusions from San Pedro, consistent with the continuous evolution of a magmatic aqueous phase exsolved from a low pressure melt during crystallization. In contrast, the combined compositional and microthermometric data for samples from Lee Moor, Dartmoor, suggest that a magmatic aqueous phase evolved from Fe-K-rich to Na-Ca-rich compositions during cooling and was periodically diluted by meteoric fluids.