Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

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.     

Origin of carbonatite magma during the evolution of ultrapotassic basite magma

Clinopyroxene phenocrysts in fergusite from a diatreme in the Dunkel’dyk potassic alkaline complex in the southeastern Pamirs, Tajikistan, and from carbonate veinlets cutting across this rock contain syngenetic carbonate, silicate, and complex melt inclusions. The homogenization of the silicate and carbonate material of the inclusions with the complete dissolution of daughter crystalline phases and fluid in each of them occur simultaneously at 1150?1180°C. The pressures estimated using fluid inclusions and mineral geobarometers were 0.5–0.7 GPa. The behavior of the inclusions during their heating and their geochemistry are in good agreement with the origin of carbonate melts via liquid immiscibility. Carbonatite magma was segregated at the preservation of volatile components (H₂O, CO₂, F, Cl, and S) in the melt, and this resulted in the crystallization of H₂O-rich minerals and carbonates and testifies that the magma was not intensely degassed during its ascent to the surface. The silicate melts are rich in alkalis (up to 4 wt % Na₂O and 12 wt % K₂O), H₂O, F, Cl, and REE (up to 1000 ppm), LREE, Ba, Th, U, Li, B, and Be. The diagrams of the concentrations of incompatible elements of these rocks typically show deep Nb, Ta, and Ti minima, a fact making them similar to the unusual type of ultrapotassic magmas: lamproites of the Mediterranean type. These magmas are thought to be generated in relation to subduction processes, first of all, the fluid transport of various components from a down-going continental crustal slab into overlying levels of the mantle wedge, from which ultrapotassic magmas are presumably derived.     

Volatile element zonation in Campanian Ignimbrite magmas (Phlegrean Fields, Italy): evidence from the study of glass inclusions and matrix glasses

The distribution of H₂O, F, Cl and S in the Campanian Ignimbrite (CI) magma chamber was investigated through study of primary glass inclusions and matrix glasses from pumices of the Plinian fall deposit. The eruption, fed by trachytic to phono-trachytic magmas, mainly produced a trachytic non-welded to partially welded tuff, underlain by a minor cogenetic fallout deposit. The entire chemical variability of the eruptive products is well represented in the pumices of the Plinian fall deposit, which we divide into a basal Lower Fall Unit (LFU) and an overlying Upper Fall Unit (UFU). Primary glass inclusions were only found in clinopyroxenes associated with the LFU pumice and contain a mean of 1.60ǂ.32 wt% H₂O (analysed by FTIR), 0.11ǂ.08 wt% F, 0.37ǂ.03 wt% Cl and 0.08ǂ.04 wt% SO₃ (EMP analysis); CO₂ concentrations were below the FTIR detection limit (10-20 ppm). The coexisting matrix glasses contain similar amounts of halogens and sulfur but less water (~0.60 wt%). Partially degassed matrix glasses from UFU pumices contain a mean of 0.30ǂ.02 H₂O, 0.28ǂ.10 F, 0.04ǂ.02 SO₃ and 0.80ǂ.04 wt% Cl. To reconstruct the total amount of volatiles dissolved in the most evolved trachytes we have used experimental solubility data and mass balance calculations concerning the amount of crystal fractionation required to produce the most evolved trachyte from the least evolved trachyte; these yield an estimated pre-eruptive magma volatile content (H₂O + Cl + F) of ~5.5 wt% for the most evolved magmas. On the basis of new determinations of Cl solubility limits in hydrous trachytic melts coexisting with an aqueous fluid phase + hydrosaline melt (brine), we suggest that the upper part of the magma chamber which fed the CI eruption was fluid(s) saturated and at a minimum depth of ~2 km. Variations in eruptive style (Plinian fallout, pyroclastic flows) do not appear to be related to significant variations in pre-eruptive volatile contents.     

The genesis of sandstone‐type uranium deposits in the Ordos Basin,NW China: constraints provided by fluid inclusions and stable isotopes

Quartz from sandstone‐type uranium deposits in the east part of the Ordos Basin contains abundant secondary fluid inclusions hosted along sealed fractures or in overgrowths. These inclusions consist mainly of water with NaCl, KCl, CO₂ (135–913 ppm) and trace amounts of CO (0.22–16.8 ppm), CH₄ (0.10–1.38 ppm) and [SO₄]^2? (0.35–111 ppm). Homogenization temperatures of the studied fluid inclusions range from 90 to 210°C, with salinities varying from 0.35 to 12.6 wt‐% (converted to NaCl wt%), implying multiple stages of thermal alteration. Although high U is associated with a high homogenization temperature in one case, overall U mineralization is not correlated with homogenization temperature nor with salinity. The H and O isotopic compositions of fluid inclusions show typical characteristics of formation water, with δ¹⁸O ranging from 9.8 to 12.3‰ and δD from 26.9 to ?48.6‰, indicating that these fluid inclusions are mixtures of magmatic and meteoric waters. The oxygen isotope ratios of carbonates in cement are systematically higher than those of the fluid inclusions. Limited fluid inclusion‐cement pairs show that the oxygen closely approaches equilibrium between water and aragonite at 150°C. Highly varied and overall negative δ¹³C in calcite from cement implies different degrees of biogenetic carbon involvement. Correlations between U in bulk rocks and trace components in fluid inclusions are lacking; however, high U contents are typically coupled with high [SO₄]^2?, implying pre‐enrichment of oxidized materials in the U mineralization layer. All these relationships can be plausibly interpreted to indicate that U (IV), [SO₄]^2? as well as Na, K were washed out from the overlying thick sandstone by oxidizing meteoric water, and then were reduced by reducing agents, such as CH₄ and petroleum, likely from underlying coal and petroleum deposits, and possibly also in situ microbes at low temperatures.     

Evolution of carbon dioxide-bearing saline fluids in the mantle wedge beneath the Northeast Japan arc

Lherzolite xenoliths containing fluid inclusions from the Ichinomegata volcano, located on the rear-arc side of the Northeast Japan arc, may be considered as samples of the uppermost mantle above the melting region in the mantle wedge. Thus, these fluid inclusions provide valuable information on the nature of fluids present in the sub-arc mantle. The inclusions in the Ichinomegata amphibole-bearing spinel–plagioclase lherzolite xenoliths were found to be composed mainly of CO₂–H₂O–Cl–S fluids. At equilibrium temperature of 920 °C, the fluid inclusions preserve pressures of 0.66–0.78 GPa, which correspond to depths of 23–28 km. The molar fraction of H₂O and the salinity of fluid inclusions are 0.18–0.35 and 3.71 ± 0.78 wt% NaCl equivalent, respectively. These fluid inclusions are not believed to be fluids derived directly from the subducting slab, but rather fluids exsolved from sub-arc basaltic magmas that are formed through partial melting of mantle wedge triggered by slab-derived fluids.     

Carbon dioxide in Postojna Cave (Slovenia): spatial distribution,seasonal dynamics and evaluation of plausible sources and sinks

The CO₂ concentration of the air in Postojna Cave (400–7900 ppm) is found to be induced by CO₂ sources (human respiration contributing?~?20,000–58,000 ppm per breath, outgassing of dripwater and water seeping from the vadose zone/epikarst with a pCO₂ values of 5000–29,000 ppm, and underground Pivka River having pCO₂ at 2344–4266 ppm) and CO₂ dilution (inflow of outside air with a CO₂ concentration of?~?400 ppm). Measurements show that sinking Pivka River has the lowest CO₂ concentration among plausible CO₂ sources but still continuously exceeds the surrounding cave air CO₂ concentration. During the winter months, intensive ventilation reduces the cave air CO₂ concentration to outside levels (~?400 ppm), even in the centre of the cave system. CO₂ dilution is less pronounced in summer (CO_2(min)?≈?800 ppm), since the ventilation rate is not as strong as in winter and the outside air that enters the cave through breathing holes and fractures is enriched with soil CO₂. During spring and autumn, the daily alternation of the ventilation regime with a smaller rate of air exchange results in yearly cave air CO₂ peaks of up to?~?2400 ppm. Some dead-end passages can be much less affected by ventilation, resulting in a cave air CO₂ concentration of up to 7900 ppm. The strongest diurnal CO₂ peaks due to human respiration were recorded during the spring holidays (increase of up to 1300 ppm day^?1), compared to considerably smaller summer peaks despite peak visits (increase of?~?600 ppm day^?1).     

Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 1: Principles,procedures, and evaluation of the method

Constraining the pressure of crystallization of magmas is an important but elusive task. In this work, we present a method to derive crystallization pressures for rocks that preserve glass compositions (either glass inclusions or matrix glass) representative of equilibration between melt, quartz, and 1 or 2 feldspars. The method relies on the well-known shift of the quartz–feldspar saturation surface toward higher normative quartz melt compositions with decreasing pressure. The critical realization for development of the method is the fact that melt, quartz and feldspars need to be in equilibrium at the liquidus for the melt composition. The method thus consists of calculating the saturation surfaces for quartz and feldspars using rhyolite-MELTS over a range of pressures, and searching for the pressure at which the expected assemblage (quartz+1 feldspar or quartz+2 feldspars) is found at the liquidus. We evaluate errors resulting from uncertainties in glass composition using a series of Monte Carlo simulations for a quartz-hosted glass inclusion composition from the Bishop Tuff, which reveal errors on the order of 20–45 MPa for the quartz+2 feldspars constraint and on the order of 25–100 MPa for the quartz+1 feldspar constraint; we suggest actual errors are closer to the lower bounds of these ranges. We investigate the effect of fluid saturation in two ways: (1) By applying our procedure over a range of water contents for three glass compositions; we show that the effect of fluid saturation is more important at higher pressures (~300 MPa) than at lower pressures (~100 MPa), but reasonable pressure estimates can be derived irrespective of fluid saturation for geologically relevant H₂O concentrations >3 wt% and (2) by performing the same type of pressure determinations with a preliminary version of rhyolite-MELTS that includes a H₂O–CO₂ mixed fluid phase; we use a range of H₂O and CO₂ concentrations for two compositions characteristic of early-erupted and late-erupted Bishop Tuff glass inclusions and demonstrate that calculated pressures are largely independent of CO₂ concentration (for CO₂ <1,000 ppm), at least for relatively high H₂O contents, as expected in most natural magmas, such that CO₂ concentration can be effectively neglected for application of our method. Finally, we demonstrate that pressures calculated using the rhyolite-MELTS geobarometer compare well with those resulting from H₂O–CO₂ glass inclusion barometry and Al-in-hornblende barometry for an array of natural systems for which data have been compiled from the literature; the agreement is best for quartz-hosted glass inclusions, while matrix glass yields systematically lower rhyolite-MELTS pressures, suggestive of melt evolution during eruptive decompression.     

Sixty thousand years of magmatic volatile history before the caldera-forming eruption of Mount Mazama, Crater Lake, Oregon

The well-documented eruptive history of Mount Mazama, Oregon, provides an excellent opportunity to use pre-eruptive volatile concentrations to study the growth of an explosive silicic magmatic system. Melt inclusions (MI) hosted in pyroxene and plagioclase crystals from eight dacitic–rhyodacitic eruptive deposits (71–7.7?ka) were analyzed to determine variations in volatile-element concentrations and changes in magma storage conditions leading up to and including the climactic eruption of Crater Lake caldera. Temperatures (Fe–Ti oxides) increased through the series of dacites, then decreased, and increased again through the rhyodacites (918–968 to ~950 to 845–895?°C). Oxygen fugacity began at nickel–nickel-oxide buffer (NNO) +0.8 (71?ka), dropped slightly to NNO +0.3, and then climbed to its highest value with the climactic eruption (7.7?ka) at NNO +1.1 log units. In parallel with oxidation state, maximum MI sulfur concentrations were high early in the eruptive sequence (~500?ppm), decreased (to ~200?ppm), and then increased again with the climactic eruption (~500?ppm). Maximum MI sulfur correlates with the Sr content (as a proxy for LREE, Ba, Rb, P₂O₅) of recharge magmas, represented by basaltic andesitic to andesitic enclaves and similar-aged lavas. These results suggest that oxidized Sr-rich recharge magmas dominated early and late in the development of the pre-climactic dacite–rhyodacite system. Dissolved H₂O concentrations in MI do not, however, correlate with these changes in dominant recharge magma, instead recording vapor solubility relations in the developing shallow magma storage and conduit region. Dissolved H₂O concentrations form two populations through time: the first at 3–4.6 wt% (with a few extreme values up to 6.1 wt%) and the second at ≤2.4 wt%. CO₂ concentrations measured in a subset of these inclusions reach up to 240?ppm in early-erupted deposits (71?ka) and are below detection in climactic deposits (7.7?ka). Combined H₂O and CO₂ concentrations and solubility models indicate a dominant storage region at 4–7?km (up to 12?km), with drier inclusions that diffusively re-equilibrated and/or were trapped at shallower depths. Boron and Cl (except in the climactic deposit) largely remained in the melt, suggesting vapor–melt partition coefficients and gas fractions were low. Modeled Li, F, and S vapor–melt partition coefficients are higher than those of B and Cl. The decrease in maximum MI CO₂ concentration following the earliest dacitic eruptions is interpreted to result from a broadening of the shallow storage region to greater than the diameter of subjacent feeders, so that greater proportions of reservoir magma were to the side of CO₂-bearing vapor bubbles ascending vertically from the locus of recharge magma injection, thereby escaping recarbonation by streaming vapor bubbles. The Mazama melt inclusions provide a picture of a growing magma storage region, where chemical variations in melt and magma occur due to changes in the nature and supply rate of magma recharge, the timing of degassing, and the possible degree of equilibration with gases from below.     

The distribution of halogens and carbon in PGE-bearing ultramafics of the Acoje ophiolite block, Zambales, Philippines

Evidence for redistribution of Pt and Pd in the Acoje ultramafic rocks led to an investigation of the role of Cl, Br, F, I and C in Pt and Pd transport in hydrothermal solution. Anomalously high contents of 300–1000 ppm Cl, 3 ppm Br, up to 50 ppm F, 180–380 ppm I and 300–3300 ppm C are characteristic of the Acoje ultramafic rocks. The Cl and Br concentrations are restricted to serpentinized dunites and a positive correlation between Br and Cl indicate their common origin and their introduction during serpentinization. The ratios Br/Cl,F/Cl, and I/Cl correspond to those of sediments that contain seawater which suggests that Cl, Br and I were partly expelled from deep sea sediments during emplacement of the ophiolite. Fluorine could have been derived from mantle material.Carbon occurs in fluid inclusions in olivines as CO₂, CO or CH₄ and/or submicroscopic graphite. The high C content in serpentinized dunites suggests that C, at least in part, is also of serpentinization origin.Chlorine is mainly incorporated into Fe-rich serpentines and Ca-amphiboles. Very low F concentration in hydrous phases is common, except in serpentines from pyroxenes, pargasites and edenites. Brucite is finely dispersed in serpentines derived from olivines, indicating low CO₂-activity during brucite formation and a pH of about 11.The presence of Pt and Pd tellurides, arsenides and bismuthides and the absence of selenides, in spite of elevated Se concentrations in bulk analyses of about 5 ppm, indicates that the stability conditions for selenide formation were not obtained during alteration. The formation of Pt and Pd halogen complexes, requiring highly oxidizing (f_O2 > hematite-magnetite boundary (HM)) and acid environments is not favoured for Pt and Pd transport in Acoje ultramafics. An redistribution caused by the solubility reduction of Pt and Pd by Te, Bi and As and a precipitation of their intermetallic phases is proposed. No correlation between Cl and PGE-bearing rock units was observed, which indicates the minor role of halogens during redistribution of Pt and Pd in the Acoje ophiolite.     

Estimation of the average contents of H2O, Cl, F, and S in the depleted mantle on the basis of the compositions of melt inclusions and quenched glasses of mid-ocean ridge basalts

Using our database of the compositions of melt inclusions and quenched glasses of basaltic magmas from mid-ocean ridges (MORB), the average concentrations and ratios of H₂O, Cl, F, S, K₂O, Ce, and Dy were determined in these magmas. Assuming that the concentration ratios of volatile components to K₂O are constant in the MORB magmas and their sources (depleted mantle, DM), and taking an average K₂O content in the DM of 72 ppm, the following average contents were estimated for the DM: 158 ppm H₂O, 6.6 ppm Cl, and 8.3 ppm F. Using an S/Dy ratio of 212 for MORB melts and a Dy concentration of 0.531 ppm in the DM, the concentration of S in the DM was estimated as 113 ppm. Our value for the average content of Cl is much higher than estimates obtained by other authors. This discrepancy could be due either to the assimilation of crustal (and hydrospheric) Cl by MORB magmas or to the deep mantle recycling of Cl. The latter mechanism is supported by the statistically significant positive correlation of Cl with K₂O, H₂O, and F. Such a correlation is not consistent with the hypothesis of basaltic magma contamination by seawater-derived chloride brines. Similar to other surface processes, the assimilation of crustal material operates within the existing global correlations and disturbs them. Based on the average integrated degree of mantle melting and the average degree of MORB magma differentiation (0.05), the average contents of potassium and volatile components in N-MORB and E-MORB mantle sources were estimated as 39 and 126 ppm K₂O, 103 and 197 ppm H₂O, 4.0 and 10.7 ppm Cl, and 3.9 and 9.1 ppm F, respectively. It is not likely that normal MORB magmas can be derived from depleted mantle that experienced a previous partial melting event (for instance, during the extraction of the primordial continental crust in the Early Precambrian), which was referred to as the ultradepleted mantle. Ordinary (not ultradepleted) MORB magmas can be derived either by the melting of a zone enriched DM (for instance, progressively enriched in incompatible components with depth), which is hardly possible, or by the continuous addition (mixing) of an enriched component to the ultradepleted mantle at the expense of sediments and crustal materials involved in deep recycling.     

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (～50–140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0–25 wt.% NaCl eq.), low fluid δ¹⁸O values (?10 to +2 ‰ V-SMOW), low fluid δ¹³C values (?9 to ?15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO₄/Cl, NO₃/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na–Ca–Cl basinal brines or shield brines, (3) SO₄–NO₃–Cl–(H)CO₃ playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.     

Constraining magma sources using primitive olivine-hosted melt inclusions from Puñalica and Sangay volcanoes (Ecuador)

Constraining arc magma sources at continental arc settings is a delicate task, because chemical signatures from crustal processes obscure the slab and mantle signatures. Here, we present major, trace, and volatile element compositions of olivine-hosted melt inclusions (Fo_82–89) selected from the most primitive lavas (Mg# >?60) from two Ecuadorian volcanoes (Puñalica and Sangay) situated at the southern termination of the Andean Northern Volcanic Zone. Melt inclusions (MI) from Puñalica are nepheline normative and have basaltic-to-basaltic-andesite compositions (45–56 wt% SiO₂) similar to peridotite-derived melts. Sangay MI is also nepheline normative, with high CaO (up to 16 wt% and CaO/Al₂O₃?<?1) and low silica contents (41.9–44.5 wt%) pointing out an amphibole-bearing clinopyroxenite source. Both volcanoes display volatile-rich compositions (up to 6100 ppm Cl, 2200 ppm F, and 6700 ppm S). These MI cannot be related to their host lavas by fractional crystallization, implying that they represent true primitive liquids. The source of Puñalica MI was metasomatized by slab-derived melts that imprints its low Ba/Th, Sr/Th, and high Th/La (average values of 66, 129, and 0.22, respectively). On the contrary, the slab component added to the source of Sangay MI has a higher Ba/Th, Sr/Th, and low Th/La (average values of 261, 517, and 0.11, respectively) which could suggest a relative contribution of aqueous fluids. This dichotomy is related to the presence of the Grijalva Fracture Zone that separates a younger and hotter oceanic crust to the north (below Puñalica) from a colder and older oceanic crust to the south (below Sangay).     

S-rich apatite-hosted glass inclusions in xenoliths from La Palma: constraints on the volatile partitioning in evolved alkaline magmas

The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO₃ (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce₂O₃. Sulfur is incorporated in apatite via several independent exchange reactions involving (P⁵⁺, Ca²⁺) vs. (S⁶⁺, Si⁴⁺, Na⁺, and Ce³⁺). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO₃ (sulfate-saturated systems). The chlorine partition coefficients (D_Cl^{apatite/glass}) range from 0.4 to 1.3 (average D_Cl^{apatite/glass} = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D_F^{apatite/glass} decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to D_F^{apatite/glass} determined experimentally in felsic rock. D_S^{apatite/glass} decreases from 9.1 to 2.9 with increasing SO₃ in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO₃). D_S^{apatite/glass} is only slightly dependent on the melt composition and can be expressed as: SO_{3 apatite} (wt%) = 0.157 * ln SO_{3 glass} (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.     

Volatiles contents, degassing and crystallisation of intermediate magmas at Volcan de Colima, Mexico, inferred from melt inclusions

In volatile-saturated magmas, degassing and crystallisation are interrelated processes which influence the eruption style. Melt inclusions provide critical information on volatile and melt evolution, but this information can be compromised significantly by post-entrapment modification of the inclusions. We assess the reliability and significance of pyroxene-hosted melt inclusion analyses to document the volatile contents (particularly H₂O) and evolution of intermediate arc magmas at Volcán de Colima, Mexico. The melt inclusions have maximal H₂O contents (≤4 wt%) consistent with petrological estimates and the constraint that the magmas crystallised outside the amphibole stability field, demonstrating that pyroxene-hosted melt inclusions can preserve H₂O contents close to their entrapment values even in effusive eruptions with low effusion rates (0.6 m³ s^?1). The absence of noticeable H₂O loss in some of the inclusions requires post-entrapment diffusion coefficients (≤1 × 10^?13 m² s^?1) at least several order of magnitude smaller than experimentally determined H⁺ diffusion coefficient in pyroxenes. The H₂O content distribution is, however, not uniform, and several peaks in the data, interpreted to result from diffusive H₂O reequilibration, are observed around 1 and 0.2 wt%. H₂O diffusive loss is also consistent with the manifest lack of correlations between H₂O and CO₂ or S contents. The absence of textural evidence supporting post-entrapment H₂O loss suggests that diffusion most likely occurred via melt channels prior to sealing of the inclusions, rather than through the host crystals. Good correlation between the melt inclusion sealing and volcano-tectonic seismic swarm depths further indicate that, taken as a whole, the melt inclusion population accurately records the pre-eruptive conditions of the magmatic system. Our data demonstrate that H₂O diffusive loss is a second-order process and that pyroxene-hosted melt inclusions can effectively record the volatile contents and decompression-induced crystallisation paths of vapour-saturated magmas.     

Geochemistry and fluid inclusions study of highly fractionated garnet-bearing granite of Gabal Abu Diab, central Eastern Desert of Egypt

The Neoproterozoic granite of Gabal Abu Diab, central Eastern Desert of Egypt, comprises mainly garnet-bearing granite and alkali feldspar granite intruded into calc-alkaline granodiorite–tonalite and metagabbro–diorite complexes. The garnet-bearing granite is composed mainly of plagioclase, K-feldspar, quartz, garnet and primary muscovite ± biotite. The presence of garnet and primary muscovite of Abu-Diab granite suggests its highly fractionated character. Geochemically, the garnet-bearing granite is highly fractionated as indicated from the high contents of SiO₂ (74.85–77.5%), alkalis (8.27 to 9.2%, Na₂O+K₂O) and the trace elements association: Ga, Zn, Zr, Nb and Y. This granite is depleted in CaO, MgO, P₂O₅, Sr and Ba. The alumina saturation (Shand Index, molar ratio A/CNK) of 1.0 to 1.1 indicates the weak peraluminous nature of this garnet-bearing granite. The geochemical characteristics of the Abu Diab garnet-bearing granite are consistent with either the average I-type or A-type granite and also suggest post-orogenic or anorogenic setting. A fluid inclusions study reveals the presence of three fluid generations trapped into the studied granite. The earlier is a complex CO₂–H₂O fluid trapped in primary fluid inclusions with CO₂ contents >?60 vol.%. These inclusions were probably trapped at minimum temperature >?400°C and minimum pressure >?2 kb. The second is immiscible water–CO₂ fluid trapped in secondary and/or pseudo-secondary inclusions. The trapping conditions were estimated at temperature between 400°C and 170°C and pressure between 900 and 2000 bar. The latest fluid is low-salinity aqueous fluid trapped in secondary two-phase and mono-phase inclusions. The trapping conditions were estimated at temperature between 90°C and 160°C and pressure <?900 bar. The origin of the early fluid generation is magmatic fluid while the second and third fluids are of hydrothermal and meteoric origin, respectively.     

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.     

Chemical composition and crystallization conditions of trachybasalts from the Dzhida field, Southern Baikal volcanic area: Evidence from melt and fluid inclusions

Melt and fluid inclusions have been studied in olivine phenocrysts (Fo 81–79) from trachybasalts of the Southern Baikal volcanic area, Dzhida field. The melt inclusions were homogenized, quenched, and analyzed on an electron and ion microprobe. The study of homogenized glasses of nine inclusions showed that basaltic melts (SiO₂ = 47.1–50.3 wt %, MgO = 5.0–7.7 wt %, CaO = 7.1–11.1 wt %) have high contents of Al₂O₃ (17.1–19.6 wt %), Na₂O (4.1–6.2 wt %), K₂O (2.2–3.3 wt %), and P₂O₅ (0.6–1.1 wt %). The volatile contents are low (in wt %): 0.24–0.31 H₂O, 0.08 F, 0.03 Cl, and 0.02 S. Primary fluid inclusions in olivines from four trachybasalt samples contain high-density CO₂ (0.73–0.87 g/cm³), indicating a CO₂ fluid pressure of 4.3–6.6 kbar at 1200–1300°C and olivine crystallization depths of 16–24 km. Ion microprobe analyses of 20 glasses from melt inclusions for trace elements showed that the magmas of the Baikal rift were enriched in incompatible elements, thus differing from oceanic rift basalts and resembling oceanic island basalts. A comparison of our data on melt and fluid inclusions in olivine from trachybasalts of the Dzhida field with preexisting data on the Eastern Tuva volcanic highland in the Southern Baikal volcanic area showed that they had similar contents of volatiles, major, and trace elements.     

Assessment of hydrogeochemistry and contamination of Varamin deep aquifer,Tehran Province,Iran

The present study investigates the hydrogeochemistry and contamination of Varamin deep aquifer located in the southeast of Tehran province, Iran. The study also evaluates groundwater suitability for irrigation uses. The hydrogeochemical study was conducted by collecting and analyzing 154 groundwater samples seasonally during 2014. Based on evolutionary sequence of Chebotarev, the aquifer is in the stage of SO₄ + HCO₃ in the north half of the plain and it has evolved into SO₄ + Cl in the south half. The unusual increase in TDS and Cl^? toward the western boundaries of the aquifer indicates some anomalies. These anomalies have originated from discharge of untreated wastewater of Tehran city in these areas. The studied aquifer contains four dominant groundwater types including Na–Ca–SO₄ (55%), Na–Ca–HCO₃ (22%), Na–Cl (13%) and Ca–Cl (10%). The spatial distributions of Na–Cl and Ca–Cl water types coincide with observed anomalies. Ionic relationships of SO₄ ^2? versus Cl^? and Na⁺ versus Cl^? confirm that water–rock interaction and anthropogenic contribution are main sources of these ions in the groundwater. The main processes governing the chemistry of the groundwater are the dissolution of calcite, dolomite and gypsum along the flow path, and direct ion exchange. Reverse ion exchange controls the groundwater chemistry in the areas contaminated with untreated wastewater. Based on Na% and SAR, 10.3 and 27% of water samples are unsuitable for irrigation purposes, respectively. Regarding residual sodium carbonate, there is no treat for crop yields. Only 6% of water samples represent magnesium adsorption ratios more than 50% which are harmful and unsuitable for irrigation.     

Small volume andesite magmas and melt–mush interactions at Ruapehu, New Zealand: evidence from melt inclusions

Historical eruptions from Mt. Ruapehu (New Zealand) have been small (<0.001 km³ of juvenile magma) and have often occurred without significant warning. Developing better modelling tools requires an improved understanding of the magma storage and transport system beneath the volcano. Towards that end, we have analysed the volatile content and major element chemistry of groundmass glass and phenocryst-hosted melt inclusions in erupted samples from 1945 to 1996. We find that during this time period, magma has been stored at depths of ~2–9 km, consistent with inferences from geophysical data. Our data also show that Ruapehu magmas are relatively H₂O-poor (<2 wt%) and CO₂-rich (≤1,000 ppm) compared to typical arc andesites. Surprisingly, we find that melt inclusions are often more evolved than their transporting melt (as inferred from groundmass glass compositions). Furthermore, even eruptions that are separated by less than 2 years exhibit distinct major element chemistry, which suggests that each eruption involved magma with a unique ascent history. From these data, we infer that individual melt batches rise through, and interact with, crystal mush zones formed by antecedent magmas. From this perspective, we envision the magmatic system at Ruapehu as frequently recharged by small magma inputs that, in turn, cool and crystallise to varying degrees. Melts that are able to erupt through this network of crystal mush entrain (to a greater or lesser extent) exotic crystals. In the extreme case (such as the 1996 eruption), the resulting scoria contain melt inclusion-bearing crystals that are exotic to the transporting magma. Finally, we suggest that complex interactions between recharge and antecedent magmas are probably common, but that the small volumes and short time scales of recharge at Ruapehu provide a unique window into these processes.