Melt Inclusion Entrapment Research Articles

Multiple hydrothermal events at martian surface revealed by H and Cl isotope systematics of melt inclusions and hydrous minerals from chassignite NWA 2737

The chassignites and nakhlites could have co-magmatic origin but display distinct hydrogen and chlorine isotopic compositions, indicating that they may have experienced distinct hydrothermal activities on Mars. However, the details are not yet fully understood. Here, we performed H and Cl isotopic investigations on hydrous minerals (kaersutite and apatite) and glass-bearing melt inclusions from chassignite NWA 2737 to unravel the details of the hydrothermal events experienced by chassignites on Mars. Our results demonstrate that at least two hydrothermal events on Mars have been recorded in NWA 2737. A D- and 37Cl-rich martian crustal/underground fluid was added to the parent magma of NWA 2737 prior to the entrapment of melt inclusions and later interaction of the parent rock with a D-poor fluid, probably deriving from magma degassing. The notable high-δD values (up to 6239‰) of kaersutite in NWA 2737 are comparable with those recorded in younger shergottites, suggesting that the martian exchangeable water reservoir has retained a nearly constant δD value over the past 1.3 Ga.

Diffusive equilibration of H2O and oxygen fugacity in natural olivine-hosted melt inclusions

Arc basalts are oxidized relative to mid-ocean ridge basalts; however, the mechanism through which arc basalts gain this elevated oxidative state is debated. This observation has been extended to include Fe3+/∑Fe measurements from olivine-hosted melt inclusions enclosed in relatively Fo-rich olivines (i.e., which have presumably trapped relatively unevolved liquid compositions as melt inclusions). Experimental data suggest, however, that Fe3+/∑Fe recorded by melt inclusions can diffusively equilibrate with the host magma on short timescales, perhaps as rapidly as timescales relevant for H+ diffusive equilibration. Here, we present major, minor, and trace element concentrations, H2O concentrations, and Fe3+/∑Fe of naturally glassy olivine-hosted melt inclusions from the Basalt of Round Valley Butte, a cinder cone in the Lassen Region of northern California. These melt inclusions record H2O loss through diffusion of H+ and can be used to constrain the extent of Fe3+/∑Fe equilibration in a suite of natural melt inclusions. The H2O concentrations of Basalt of Round Valley Butte melt inclusions decrease with decreasing melt inclusion radius, consistent with diffusive H+ loss. The Fe3+/∑Fe do not correlate with H2O or inclusion diameter, suggesting that Fe3+/∑Fe equilibration does not occur on the same timescale as H+ diffusion. Calculated oxygen fugacities (ƒO2) from the partitioning of vanadium between olivine and melt are ∼1 log unit higher than those calculated from Fe3+/∑Fe. One explanation for these combined observations is that Fe3+/∑Fe of the Basalt of Round Valley Butte melt inclusions diffusively equilibrated with a host magma at low pressure on shorter timescales than H+ diffusion. This scenario requires that the host magma decreased in ƒO2 after the time of melt inclusion entrapment to explain the offset between ƒO2 constraints from Fe3+/∑Fe of the melt inclusions and the partitioning of vanadium between olivine and melt. One volcanological process known to result in a decrease in ƒO2 of magmas stored at shallow pressure is the degassing of S, CO2, and H2O. We show that reasonable estimates for the extent of degassing of Basalt of Round Valley Butte magma, coupled with diffusive equilibration of both H+ and Fe3+/∑Fe, can reconcile Fe- and V-proxies for ƒO2. Additionally, we have compared estimates of ƒO2 from vanadium abundances of melt inclusions and their olivine hosts with recently reported measurements of Fe3+/∑Fe of the melt inclusions for several Mariana arc volcanoes and conclude that this process – small decreases in host magma ƒO2 driven by degassing and rapid equilibration of the Fe3+/∑Fe of olivine-hosted melt inclusions with this host magma - may be a widespread phenomenon.

Experimental determination of H 2 O and CO 2 solubilities of mafic alkaline magmas from Canary Islands

We present new H 2 O and CO 2 solubility data in mafic to intermediate alkaline magmas from Fasnia and Garachico volcanoes, Tenerife. H 2 O-and CO 2-saturated experiments were conducted at ∼50-400 MPa, 1200°C, and f O 2 from 2 log units below the NiNiO solid buffer to 3.2 log units above it. Although existing solubility models for alkali-rich mafic magmas broadly describe H 2 O and CO 2 behaviour, associated errors are worthy of consideration since they usually exceed 15-20%. For this reason, we have determined the specific solubility laws of basanitic and phonotephritic melts from the Canary Islands. Results show similar H 2 O solubilities for both compositions, whereas the basanite can dissolve an average of ∼45% more CO 2 than the phonotephrite. By combining these data, we have established a simple empirical model that allows us to calculate melt inclusion entrapment pressures accurately and, therefore, better understand the inner workings of volcanic oceanic islands. Application to El Hierro 2011-2012 and young (<20 ka) basanites from this location shows that previous barometric estimates were, on average, overestimated by 15-28%. Our results suggest that magmas rising from depth experienced a first but short episode of equilibration at 8-10 km, whereas the bulk of the crystallization occurred during the subsequent dyke injection, ascent, and degassing at P ⇐ 200 MPa (6-1.5 km).

Reconstructing Magma Storage Depths for the 2018 Kı̄lauean Eruption From Melt Inclusion CO2 Contents: The Importance of Vapor Bubbles

AbstractThe 2018 lower East Rift Zone (LERZ) eruption and the accompanying collapse of the summit caldera marked the most destructive episode of activity at Kı̄lauea Volcano in the last 200 years. The eruption was extremely well‐monitored, with extensive real‐time lava sampling as well as continuous geodetic data capturing the caldera collapse. This multiparameter data set provides an exceptional opportunity to determine the reservoir geometry and magma transport paths supplying Kı̄lauea’s LERZ. The forsterite contents of olivine crystals, together with the degree of major element disequilibrium with carrier melts, indicates that two distinct crystal populations were erupted from Fissure 8 (termed high‐ and low‐Fo). Melt inclusion entrapment pressures reveal that low‐Fo olivines (close to equilibrium with their carrier melts) crystallized within the Halema’uma’u reservoir (∼2‐km depth), while many high‐Fo olivines (&gt;Fo81.5; far from equilibrium with their carrier melts) crystallized within the South Caldera reservoir (∼3–5‐km depth). Melt inclusions in high‐Fo olivines experienced extensive post‐entrapment crystallization following their incorporation into cooler, more evolved melts. This favored the growth of a CO2‐rich vapor bubble, containing up to 99% of the total melt inclusion CO2 budget (median = 93%). If this CO2‐rich bubble is not accounted for, entrapment depths are significantly underestimated. Conversely, reconstructions using equation of state methods rather than direct measurements of vapor bubbles overestimate entrapment depths. Overall, we show that direct measurements of melts and vapor bubbles by secondary‐ion mass spectrometry and Raman spectroscopy, combined with a suitable H2O‐CO2 solubility model, is a powerful tool to identify the magma storage reservoirs supplying volcanic eruptions.

EOCENE MAGMA PLUMBING SYSTEM BENEATH CORTEZ HILLS CARLIN-TYPE GOLD DEPOSIT, NEVADA: IS THERE A DEEP-SEATED PLUTON?

Abstract The magmatic-hydrothermal conceptual model for Carlin-type gold deposit genesis calls upon deep-seated Eocene plutons as the primary source of gold-bearing fluids. However, geophysical surveys, geologic mapping, drilling, geochronology, isotopic tracers, and fluid inclusion chemistry have returned ambiguous evidence for the existence of such plutons. The high-grade Cortez Hills gold deposit in northern Nevada hosts shallow, Eocene syn- and postmineralization intrusions, offering an ideal site to investigate the existence of a deep-seated pluton beneath the district. Here, major and trace element analyses of quartz-hosted melt inclusions from four Eocene rhyolite dikes cropping out within the Cortez Hills pit and results from independent thermobarometers provide a window into the subsurface Eocene magmatic plumbing system to test the existence of a deep-seated source pluton. Dissolved volatile contents, melt inclusion entrapment pressures, and thermodynamic phase equilibria indicate that dike magmas were sourced from ~4- to ≥9-km depth from a polybaric magma reservoir residing as a physically and geochemically interconnected crystal mush with extractable or eruptible magma pockets. Magmas ascended adiabatically (nearly isothermally), exsolving fluids, evolving modestly by fractional crystallization, while trapping quartz-hosted melt inclusions steadily from depth to subvolcanic levels where they were emplaced. These data represent the first unequivocal evidence for a deep-seated magma reservoir from which fluid-saturated magma emanated and released magmatic fluids beneath the Cortez district during gold mineralization. However, further investigation into the specific metallogenic potential and metal budget of parental magmas and the partitioning of gold between silicate melt and aqueous fluids will be necessary to provide evidence that exsolved magmatic fluids may have been gold bearing.

Chlorine and felsic magma evolution: Modeling the behavior of an under-appreciated volatile component

Research on magmatic Cl has proven useful for understanding melt evolution, degassing, and other igneous processes. Magmatic Cl behavior varies strongly with its solubility in melt, and Cl solubility and its partitioning between melts and fluids vary with the Cl content of the system, melt composition, pressure, and the abundance of oxidized magmatic sulfur. Given these relationships and given that they differ from other magmatic volatiles, Cl can provide unique insights on magma evolution. We present a new method of interpreting melt Cl concentrations that are normalized to their calculated Cl solubilities, and the most accurate results apply to solubilities computed at 200 MPa due to insufficient experimental data for other pressures. We apply the new method to compositional data for more than 3500 dacitic to rhyolitic melt inclusions and matrix glasses, representing 64 felsic igneous systems, to demonstrate how the behavior of Cl during magmatic, magmatic-hydrothermal, and degassing processes can be more accurately interpreted.Variations in Cl for most of the 64 systems agree with modeled Cl behavior indicative of melt evolution dominated by fractional crystallization of fluid(s)-saturated melts, and the majority of these systems were apparently saturated in fluid(s) well before melt inclusion entrapment. Comparison of Cl solubility-normalized Cl concentrations of these glasses with modeled results identifies magmas saturated in hydrosaline liquid ± vapor at pressures as high as 600 MPa. Modeling of pressure reductions from 600 down to 20 MPa distinguishes other magmas that exsolved hydrosaline liquid as magmas ascend to shallower depths. This new approach also supports computation of Cl concentrations of magmatic fluids at 200 MPa, for each of the >3500 glasses, and shows how the Cl contents of fluids vary with the (fluid/melt) mass ratio. For example, Cl contents of magmatic fluids range from 0.3 to nearly 70 wt.% at fluid/melt mass ratios of 2 × 10−3, and from 0.3 to a maximum of only 11 wt.% Cl for fluid/melt mass ratios of 4.2 × 10−2.Compositional trends in the glass data show either increasing Cl contents of residual melt, essentially no change of Cl in melt, or decreasing Cl contents of aliquots of residual melt with progressive melt evolution. This method identifies melts that have assimilated magmatic or externally sourced hydrosaline liquids. Plots of (measured Cl in melt/modeled solubility of Cl in melt; Cl[Me/Mo]) versus the Larsen melt differentiation index show minimal dispersion for the least-evolved dacitic melts and increasing dispersion with melt evolution to rhyolitic compositions. Increased dispersion may be a consequence and indication of equilibrium or non-equilibrium degassing and/or assimilation of hydrosaline liquid.

Understanding melt evolution and eruption dynamics of the 1666 C.E. eruption of Cinder Cone, Lassen Volcanic National Park, California: Insights from olivine-hosted melt inclusions

Cinder Cone is the youngest scoria cone volcano in the continental United States. Erupted in 1666 C.E. within what is now Lassen Volcanic National Park, Cinder Cone is an un-vegetated scoria cone with well-preserved lava flows and tephra deposits that display complex geochemical variability. In this study, we utilize the volatile (H2O, CO2, Cl), major, and trace element chemistry of olivine-hosted melt inclusions from the tephra deposit of Cinder Cone to better understand the sub-surface evolution of magmas that erupt to produce scoria cones. High-Fo olivine phenocrysts from all erupted units contain melt inclusions that are more primitive in composition than the erupted material. The evolved compositions of the lava and bulk tephra and the abundance of quartz xenocrysts within the deposits suggest the basaltic parental magmas were rapidly contaminated by granitic material in the middle to upper crust, after melt inclusion entrapment. Distinct compositional variability between early and late erupted units suggests two different mantle-derived basaltic magmas were tapped and erupted sequentially as two distinct eruptive phases. The CO2 concentrations in the melt inclusions, after correction for the presence of vapor bubbles, suggest minimum entrapment depths of ~9.5–20km and show no resolvable differences between early and late erupted units at the time of olivine crystallization. Diffusion modeling of Ni and Fo gradients in olivine rims indicates that olivine residence times in an evolving magma were on the order of weeks to years, similar to those calculated for longer-lived scoria cone eruptions, such as Jorullo, in Mexico. Additionally, geochemical evidence suggests that the evolution of parental magmas was likely driven by the partial melting, disaggregation, and assimilation of granitic material in the upper crust. Our combined results provide new insight into the complexities of short-lived monogenetic eruptions.

The significance of plagioclase textures in mid-ocean ridge basalt (Gakkel Ridge, Arctic Ocean)

Textures and compositions of minerals can be used to infer the physiochemical conditions present within magmatic systems. Given that plagioclase is an abundant phase in many magmatic systems, understanding the link between texture and process is vital. Here, we present a database of textural and compositional data for > 1800 plagioclase crystals in mid-ocean ridge basalt from the Gakkel Ridge (Arctic Ocean) to investigate the physiochemical conditions and processes that govern the formation of plagioclase textures and compositions. The Gakkel basalts have high modal crystal contents (up to 50%). The crystal cargo is complex, with both individual plagioclase and glomerocrysts showing large variations in crystal habit, zoning and resorption. The most common types of zoning are reverse and patchy; we attribute patchy zoning to infilling following either skeletal growth or resorption. Resorption is abundant, with multiple resorption events commonly present in a single crystal, and results from both magmatic recharge and decompression. Periods of strong undercooling, distinct to quench crystallisation, are indicated by matured skeletal crystals and thin normally zoned melt inclusion-rich bands following resorption. Individual samples often contain diverse textural and compositional plagioclase groups. Furthermore, most plagioclase is not in equilibrium with its host melt. Finally, the porous open structures of some glomerocrysts suggest that they represent pieces of entrained disaggregated mush. We interpret this to indicate that the crystal cargo is not generally phenocrystic in origin. Instead, plagioclase crystals that formed in different parts of a mush-dominated plumbing system were entrained into ascending melts. The textures of individual crystals are a function of their respective histories of (under)cooling, magma mixing and decompression. The morphologies of melt inclusion trapped in the plagioclase crystals are associated with specific host crystal textures, suggesting a link between plagioclase crystallisation processes and melt inclusion entrapment. The database of plagioclase presented herein may serve as a template for the interpretation of plagioclase textures in magmatic systems elsewhere.

Petrology and geochemistry of the 2014–2015 Holuhraun eruption, central Iceland: compositional and mineralogical characteristics, temporal variability and magma storage

The 2014–2015 Holuhraun fissure eruption provided a rare opportunity to study in detail the magmatic processes and magma plumbing system dynamics during a 6-month-long, moderate- to large-volume basaltic fissure eruption. In this contribution, we present a comprehensive dataset, including major and trace elements of whole-rock and glassy tephra samples, mineral chemistry, and radiogenic and oxygen isotope analyses from an extensive set of samples (n = 62) that were collected systematically in several field campaigns throughout the entire eruptive period. We also present the first detailed chemical and isotopic characterization of magmatic sulfides from Iceland. In conjunction with a unique set of geophysical data, our approach provides a detailed temporal and spatial resolution of magmatic processes before and during this eruption. The 2014–2015 Holuhraun magma is compositionally indistinguishable from recent basalts erupted from the Barðarbunga volcanic system, consistent with seismic observations for magma ascent close to the Barðarbunga central volcano, followed by dyke propagation to the Holuhraun eruption site. Whole-rock elemental and isotopic compositions are remarkably constant throughout the eruption. Moreover, the inferred depth of the magma reservoir tapped during the eruption is consistently 8 ± 5 km, in agreement with geodetic observations and melt inclusion entrapment pressures, but inconsistent with vertically extensive multi-tiered magma storage prior to eruption. The near constancy in the chemical and isotopic composition of the lava is consistent with the efficient homogenization of mantle-derived compositional variability. In contrast, occurrence of different mineral populations, including sulfide globules, which display significant compositional variability, requires a more complex earlier magmatic history. This may include sampling of heterogeneous mantle melts that mixed, crystallized and finally homogenized at mid- to lower-crustal conditions.

Weekly to monthly time scale of melt inclusion entrapment prior to eruption recorded by phosphorus distribution in olivine from mid-ocean ridges

Melt inclusions (MIs) hosted in euhedral olivine have been pro - posed to represent droplets of primary melt, protected from processes occurring near Earth’s surface during eruption. The complex zoning of phosphorus (P) in some olivines and the presence of a P-depleted zone around MIs indicate a complex history for the host-MI system. We analyzed P in olivine and MIs from two mid-oceanic ridge basalt (MORB) samples from the Mid-Atlantic Ridge (MAR) by electron probe microanalyzer, secondary ion mass spectrometry (SIMS), and NanoSIMS. Phosphorus dendrites in olivine suggest an initial fast olivine growth followed by a stage of slower growth. Dissolution tex- tures around some MIs were identified and were probably caused by adiabatic decompression melting. Based on diffusion modeling of P in olivine, we infer that olivine beneath the MAR remains in the system (1) for days to weeks after crystallization of P-rich lamellae, and (2) for a few hours after recrystallization of dissolved olivine. Dissolution and reprecipitation of olivine containing boundary layers suggests that most MIs might be affected by late post-entrapment processes.

Direct Observation of Boro-Aluminosilicate Melt Compositions: Insights From Raman Spectroscopy of Melt Inclusions In Pegmatitic Tourmaline of the Gatumba-Gitarama Area (Rwanda)

Abstract This study presents Raman spectroscopic analyses of melt inclusions in tourmaline from tourmaline-quartz-(muscovite) assemblages of common pegmatites of the Gatumba-Gitarama area (Rwanda). The melt inclusions show a main mineralogy composed of muscovite, α-quartz, moganite, dickite, and minor feldspars which demonstrate, in combination with the observation of dawsonite, nahcolite, jeremejevite, and childrenite daughter minerals, a CO 2 -, H 2 O-, B 2 O 3 -, and P 3 O 4 -enriched peraluminous boro-aluminosilicate composition for the trapped melt. The variable amount of acidic interstitial fluids inside the melt inclusions resulted mainly from heterogeneous trapping of omnipresent, exsolved aqueous fluids during melt inclusion entrapment. Aliquots of this exsolved alkali-rich aqueous fluid phase are preserved in the numerous coexisting fluid inclusions in tourmaline. The observed mineralogy and composition of the melt inclusions deviates strongly from a bulk single-phase melt crystallization model for pegmatite formation. Based on reported experimental, theoretical, and natural constraints, an alternative hypothesis can offer an explanation for the formation of the anomalous but omnipresent residual melts trapped in tourmaline: i.e ., the immiscibility of a hydrous fluid and a boro-aluminosilicate melt from the residual bulk aluminosilicate melt. The chemically anomalous composition of the immiscible boro-aluminosilicate melt trapped inside the melt inclusions can explain the mineralogical transition from a granitic mineral mode towards a schorl-quartz-(muscovite) assemblage within the common mineralogical zonation of the pegmatite dike.

Investigating the subsurface connection beneath Cerro Negro volcano and the El Hoyo Complex, Nicaragua

Cerro Negro, the youngest volcano along the Central American Volcanic Belt (CAVB), is a polygenetic cinder cone with relatively frequent basaltic eruptions. The neighbouring El Hoyo complex, of which Las Pilas is the dominant edifice, is a much larger and older complex with milder and less frequent eruptions. Previous studies have suggested a deep link beneath these two closely spaced volcanoes (McKnight, 1995; MacQueen, 2013). Melt inclusions were collected from various tephra samples in order to determine whether a connection exists and to delineate the features of this link. Major, volatile, and trace elemental compositions reveal a distinct geochemical continuum with Cerro Negro defining the primitive endmember and El Hoyo representing the evolved endmember. Magmatic conditions at the time of melt inclusion entrapment were estimated with major and volatile contents: 2.4kbar and 1170°C for Cerro Negro melts and 1.3kbar and 1130°C for El Hoyo melts with an overall oxygen fugacity at the NNO buffer. Trace element contents are distinct and suggest Cerro Negro magmas fractionally crystallise while El Hoyo magmas are a mix between primitive Cerro Negro melts and residual and evolved El Hoyo magma. Modelling of end member compositions with alphaMELTS confirms the unique nature of El Hoyo magmas as resulting from incremental mixing between Cerro Negro and residual evolved magma at 4km depth. Combining all available literature data, this study presents a model of the interconnected subsurface plumbing system. This model considers the modern day analogue of the Lemptégy cinder cones in Massif Central, France and incorporates structurally controlled dykes. The main implications of this study are the classification of Cerro Negro as the newest conduit within the El Hoyo Complex as well as the potential re-activation of the El Hoyo edifice.

The composition of nanogranitoids in migmatites overlying the Ronda peridotites (Betic Cordillera, S Spain): the anatectic history of a polymetamorphic basement

The study of the composition of primary melts during anatexis of high-pressure granulitic migmatites is relevant to understand the generation and differentiation of continental crust. Peritectic minerals in migmatites can trap droplets of melt that forms via incongruent melting reactions during crustal anatexis. These melt inclusions commonly crystallize and form nanogranitoids upon slow cooling of the anatectic terrane. To obtain the primary compositions of crustal melts recorded in these nanogranitoids, including volatile concentrations and information on fluid regimes, they must be remelted and rehomogenized before analysis. A new occurrence of nanogranitoids was recently reported in garnets of mylonitic metapelitic gneisses (former high pressure granulitic migmatites) at the bottom of the prograde metamorphic sequence of Jubrique, located on top of the Ronda peridotite slab (Betic Cordillera, S Spain). Nanogranitoids within separated chips of cores and rims of large garnets from these migmatites were remelted at 15 kbar and 850, 825 or 800 °C and dry (without added H2O), during 24 h, using a piston cylinder apparatus. Although all experiments show glass (former melt) within melt inclusions, the extent of rehomogenization depends on the experimental temperature. Experiments at 850–825 °C show abundant disequilibrium microstructures, whereas those at 800 °C show a relatively high proportion of rehomogenized nanogranitoids, indicating that anatexis and entrapment of melt inclusions in these rocks likely occurred at pressures ≤1.5 GPa and temperatures close to 800 °C. Electron microprobe and NanoSIMS analyses show that experimental glasses are leucogranitoid and peraluminous, though define two distinct compositional groups. Type I melt inclusions correspond to K-rich, Ca- and H2O-poor leucogranitic melts, whereas type II melt inclusions represent K-poor, Ca- and H2O-rich granodioritic to tonalitic melts. Type I and II melt inclusions are found in most cases at the cores and rims of large garnets porphyroclasts, respectively. We tentatively interpret these two distinct melt compositions as suggesting that these former migmatites underwent two melting events under contrasting fluid regimes, possibly during two different orogenic periods. This study demonstrates the strong potential of melt inclusions studies in migmatites and granulites in order to unravel their anatectic history, particularly in strongly deformed rocks where most of the classical anatectic microstructures and macrostructures have been erased during deformation.

The evolution and storage of primitive melts in the Eastern Volcanic Zone of Iceland: the 10 ka Grímsvötn tephra series (i.e. the Saksunarvatn ash)

Major, trace and volatile elements were measured in a suite of primitive macrocrysts and melt inclusions from the thickest layer of the 10 ka Grímsvötn tephra series (i.e. Saksunarvatn ash) at Lake Hvítárvatn in central Iceland. In the absence of primitive tholeiitic eruptions (MgO > 7 wt%) within the Eastern Volcanic Zone (EVZ) of Iceland, these crystal and inclusion compositions provide an important insight into magmatic processes in this volcanically productive region. Matrix glass compositions show strong similarities with glass compositions from the AD 1783–1784 Laki eruption, confirming the affinity of the tephra series with the Grímsvötn volcanic system. Macrocrysts can be divided into a primitive assemblage of zoned macrocryst cores (An78–An92, Mg#cpx = 82–87, Fo79.5–Fo87) and an evolved assemblage consisting of unzoned macrocrysts and the rims of zoned macrocrysts (An60–An68, Mg#cpx = 71–78, Fo70–Fo76). Although the evolved assemblage is close to being in equilibrium with the matrix glass, trace element disequilibrium between primitive and evolved assemblages indicates that they were derived from different distributions of mantle melt compositions. Juxtaposition of disequilibrium assemblages probably occurred during disaggregation of incompatible trace element-depleted mushes (mean La/Ybmelt = 2.1) into aphyric and incompatible trace element-enriched liquids (La/Ybmelt = 3.6) shortly before the growth of the evolved macrocryst assemblage. Post-entrapment modification of plagioclase-hosted melt inclusions has been minimal and high-Mg# inclusions record differentiation and mixing of compositionally variable mantle melts that are amongst the most primitive liquids known from the EVZ. Coupled high-field strength element (HFSE) depletion and incompatible trace element enrichment in a subset of primitive plagioclase-hosted melt inclusions can be accounted for by inclusion formation following plagioclase dissolution driven by interaction with plagioclase-undersaturated melts. Thermobarometric calculations indicate that final crystal–melt equilibration within the evolved assemblage occurred at ~1140 °C and 0.0–1.5 kbar. Considering the large volume of the erupted tephra and textural evidence for rapid crystallisation of the evolved assemblage, 0.0–1.5 kbar is considered unlikely to represent a pressure of long-term magma accumulation and storage. Multiple thermometers indicate that the primitive assemblage crystallised at high temperatures of 1240–1300 °C. Different barometers, however, return markedly different crystallisation depth estimates. Raw clinopyroxene–melt pressures of 5.5–7.5 kbar conflict with apparent melt inclusion entrapment pressures of 1.4 kbar. After applying a correction derived from published experimental data, clinopyroxene–melt equilibria return mid-crustal pressures of 4 ± 1.5 kbar, which are consistent with pressures estimated from the major element content of primitive melt inclusions. Long-term storage of primitive magmas in the mid-crust implies that low CO2 concentrations measured in primitive plagioclase-hosted inclusions (262–800 ppm) result from post-entrapment CO2 loss during transport through the shallow crust. In order to reconstruct basaltic plumbing system geometries from petrological data with greater confidence, mineral–melt equilibrium models require refinement at pressures of magma storage in Iceland. Further basalt phase equilibria experiments are thus needed within the crucial 1–7 kbar range.

Genesis of mugearites and benmoreites of Nemrut Volcano, eastern Turkey: Magma mixing and fractional crystallization of trachybasaltic melt

Presents detailed mineralogical and phase characteristics of trachybasalt, mugearite, trachydacite, and comendite samples from Nemrut Volcano in eastern Turkey, estimates of mineral formation conditions, and analyses of glasses from melt inclusions in olivine and rock matrix. Based on the analysis of the mineralogy and geochemistry of the rocks and mass balance calculations, the most feasible models of mugearitic and benmoreitic magma formation were proposed. The crystallization conditions of olivine, feldspar, and Fe-Ti oxides (titanomagnetite and ilmenite) were determined. Titanomagnetite and ilmenite were formed under the following conditions: 960-922°C, \(\Delta \log _{f_{O_2 } } \) NNO from −1.54 to −0.73 in the mugearite, 940-890°C, \(\Delta \log _{f_{O_2 } } \) NNO from −1.46 to −0.79 in the benmoreite, 870-845°C and \(\Delta \log _{f_{O_2 } } \) NNO from −2.11 to −1.82 in the trachydacite, and 705-667°C, \(\Delta \log _{f_{O_2 } } \) NNO from −2.48 to −2.18 in the comendite. Feldspars crystallized at 1150-950°C in the trachybasalt, 920-800°C in the benmoreite, and 760-720°C in the comendite. The temperature of melt inclusion entrapment in olivine (Fo75-40) from the trachybasalt, mugearite, benmoreite, and trachydacite was estimated as 1270-860°C. Except for the trachybasalt, partly resorbed phenocrysts and/or xenocrysts were observed in all the samples, which indicates their formation under nonequilibrium conditions. Mass balance calculations for rock compositions (FC, AFC, and FCA models) and mineralogical observations suggest that the magmas or melts of mugearitic and benmoreitic compositions could be produced by the fractional crystallization of trachybasaltic melt (mass fraction of melt F = 0.63–0.79), which assimilated a small amount of crustal material, as well as by the mixing of trachybasaltic (F = 0.16–0.45) and trachydacitic (F = 0.45–0.58) magmas in the presence of excess olivine, plagioclase, magnetite, and apatite (totaling 10–24 wt %). Pre-caldera comendites are enriched in Fe (4–5 wt % FeOtot) and trace elements compared with post-caldera comendites (2–3 wt % FeOtot). The analysis of the geochemical data and mass balance calculations indicated that the post-caldera benmoreitic magma could not be produced by the fractionation of trachybasaltic melt. This magma and corresponding post-caldera benmoreites have anomalously low Ba (46–54 ppm) and Sr (203–269 ppm) contents, which could not be obtained in the models of fractional crystallization of trachybasaltic melt accompanied by crustal assimilation. The compositions of post-caldera benmoreites and hybrid rocks of trachydacitic composition showing evidence for magma mixing (presence of xenocrysts from benmoreitic and comenditic magmas and compositionally variable glasses) were best reproduced by mixing trachybasaltic (F = 0.7-0.5) and low-Fe comenditic (F = 0.3–0.5) melts. Magma chambers with low-Fe comenditic melts appeared during the post-caldera stage owing to the fractional crystallization of pre-caldera trachytic and trachyte-comenditic magmas. Perhaps, the repeated eruptions of low-Fe comendites in the caldera and “rift” zone of Nemrut Volcano were related to the injection of benmoreitic magma into these chambers.

Quantification of the CO2 budget and H2O–CO2 systematics in subduction-zone magmas through the experimental hydration of melt inclusions in olivine at high H2O pressure

Reliable evaluation of CO2 contents in parental arc magmas, which can be preserved in melt inclusions in phenocrysts, is required to verify the proposed efficiency of CO2 recycling at convergent margins. Quantification of bulk CO2 concentration in melt inclusions requires their complete homogenization. Using samples from lavas from the Bulochka vent of Klyuchevskoy Volcano (Kamchatka), we applied a novel experimental approach to homogenize and re-equilibrate naturally dehydrated (<1 wt.% H2O) melt inclusions from high-Fo (85–91 mol.%) olivine. The experiments were performed at temperatures of 1150–1400 °C, pressures of up to 500 MPa, under dry to H2O-saturated conditions and with oxygen fugacity ranging from CCO to QFM+3.3. No homogenization was achieved at dry conditions. Complete dissolution of fluid bubbles (homogenization) in the melt inclusions was achieved at H2O pressures of 500 MPa and temperature of 1150 °C, when water content in the melt inclusions reached 4–5 wt.% H2O. The CO2 content in the homogenized inclusions is 3800±140 ppm and CO2/Nb = 3000 ± 420, which are the highest values reported so far for the typical middle-K primitive arc melts and fall within the range of values inferred from the magmatic flux and volcanic gas data for primary arc magma compositions. About 83% of the CO2 in Klyuchevskoy magmas is likely to be derived from the subducting slab and can be attributed to flux melting with a fluid having a CO2/H2O ratio of ∼0.06. The H2O and CO2 contents in the melt inclusions after hydrous experiments were found to correlate positively with each other and negatively with the volume of fluid bubble, reflecting increasing internal pressure in melt inclusions with increasing melt hydration. Therefore, similar trends observed in some natural sets of melt inclusions can be attributed to a partial dehydration of melts after entrapment, operating simultaneously with or following post-entrapment crystallization. Our study implies that the process of post-entrapment dehydration can be completely reversed under high pressure experimental conditions. If temperature, redox conditions and pressure of melt inclusion entrapment can be independently estimated, then our novel experimental approach (homogenization at high H2O pressure) can be used to reconstruct the initial CO2 content and also the entire composition of melt inclusions in olivine, including their initial H2O content, from any type of volcanic rock. With this approach volatiles in ancient lavas can also be determined, expanding our knowledge of volatile recycling further back in Earth history.

Pre-Eruptive Conditions of the Hideaway Park Topaz Rhyolite: Insights into Metal Source and Evolution of Magma Parental to the Henderson Porphyry Molybdenum Deposit, Colorado

The Hideaway Park tuff is the only preserved extrusive volcanic unit related to the Red Mountain intrusive complex, which produced the world-class Henderson porphyry Mo deposit. Located within the Colorado Mineral Belt, USA, Henderson is the second largest Climax-type Mo deposit in the world, and is therefore an excellent location to investigate magmatic processes leading to Climax-type Mo mineralization. We combine an extensive dataset of major element, volatile, and trace element abundances in quartz-hosted melt inclusions and pumice matrix glass with major element geochemistry from phenocrysts to reconstruct the pre-eruptive conditions and the source and evolution of metals within the magma. Melt inclusions are slightly peraluminous topaz rhyolitic in composition and are volatile-charged (� 6w t % H2O, � 600 ppm CO2, � 0� 3–1� 0w t % F, � 2300–3500 ppm Cl) and metal-rich (� 7–24 ppm Mo, � 4–14 ppm W, � 21–52 ppm Pb, � 28–2700 ppm Zn, <0� 1–29 ppm Cu, � 0� 3–1� 8 ppm Bi, � 40–760 ppb Ag, � 690–1400 ppm Mn). Melt inclusion and pumice matrix glass chemistry reveal that the Hideaway Park magma evolved by large degrees of fractional crystallization (� 60–70%) during quartz crystallization and melt inclusion entrapment at pressures of � 300 MPa (� 8 km depth), with little to no crystallization upon shallow ascent and eruption. Filter pressing, crystal settling, magma recharge and mixing of less evolved rhyolite melt, and volatile exsolution were important processes during magma evolution; the low estimated viscosities (� 10 5 –10 10 Pa s) of these H2O- and F-rich melts probably enhanced these processes. A noteworthy discrepancy between the metal contents in the pumice matrix glass and in the melt inclusions suggests that after quartz crystallization ceased upon shallow magma ascent and eruption, the Hideaway Park magma exsolved an aqueous fluid into which Mo, Bi, Ag, Zn, Mn, Cs, and Y strongly partitioned. Given that the Henderson deposit contains anomalous abundances of not only Mo, but also W, Pb, Zn, Cu, Bi, Ag, and Mn, we suggest that these metals were sourced from similar fluids exsolved from unerupted portions of the same magmatic system. Trace element ratios imply that Mo was sourced deep, from either the lower crust or metasomatized mantle. The origin of sulfur remains unresolved; however, given the extremely low S solubility of rhyolite melts in the shallow crust we favor the possibility that another source of S might supplement or account for that present in the ore deposit, probably the comagmatic, mantle-derived lamprophyres that occur in minor quantities with the voluminous topaz rhyolites in the area. To account for the 437 Mt of MoS2 (� 1� 0 � 10 6 t Mo) present in the Henderson ore deposit, a volume of � 45 km 3 of Hideaway Park rhyolite magma would have been necessary to supply the Mo (a cylindrical pluton measuring

Constraints from melt inclusions on depths of magma residence at intermediate magma supply along the Galápagos Spreading Center

Shallow, seismically imaged melt lenses are a ubiquitous feature of mid-ocean ridges with high magma supply; melt lenses deepen and become less continuous along axis as the rate of magma supply decreases. Despite compelling petrologic evidence for evolution of magma within the crust prior to eruption at lower magma supply, melt lenses are rarely detected along ridge segments with rates of magma supply less than 0.3×106 m3/yr/km, and the depths of sub-axial magma reservoirs are therefore poorly known. We use ion microprobe measurements of H2O and CO2 concentrations of olivine-hosted melt inclusions to calculate vapor saturation pressures that constrain crystallization depths at two locations along the Galápagos Spreading Center (94.2°W and 95°W). These sites were chosen to examine crystallization pressures in the presence (94.2°W) and absence (95°W) of a seismically imaged melt lens. At 95°W, where magma supply is too low to sustain a seismically resolvable melt lens, samples were selected from each of the three most recent eruptive units, allowing us to document temporal variations in vapor saturation pressures and the depth of magma residence at this location. Clusters in melt inclusion entrapment depths for these eruptions range from 3.0 to 3.4 km below the seafloor, indicating that magmas at 95°W resided at a narrow range of mid-crustal depths prior to eruption, generally consistent with the global trend of increasing melt lens depth with decreasing rate of magma supply. A discrepancy between seismic data and the peak in melt inclusion entrapment depths at 94.2°W may reflect temporal variability of magmatic systems at this location. This study demonstrates the potential for using measurements of the concentrations of H2O and CO2 in olivine-hosted melt inclusions to determine the depths of crustal magmatic systems that feed mid-ocean ridge eruptions, even in locations where seismic studies have not detected melt lenses.

Melt mixing causes negative correlation of trace element enrichment and CO2 content prior to an Icelandic eruption

Major elements, trace elements and volatiles were measured in 110 olivine-hosted melt inclusions from the subglacial Skuggafjöll eruption in the Eastern Volcanic Zone of Iceland. Variations in melt inclusion trace element concentrations can be accounted for by incomplete mixing of diverse mantle parental melts accompanied by variable extents of fractional crystallisation. Binary mixing between an incompatible trace element-enriched and depleted melts provides a good fit to observed variations in trace element ratios such as Ce/Y. Surprisingly, the CO2 contents of melt inclusions correlate negatively with their degree of trace element enrichment. Depleted, low-Ce/Y inclusions with ∼1200 ppm CO2 have high CO2/Nb contents (∼400), suggesting that melts experienced little or no CO2 exsolution before inclusion entrapment. Enriched, high-Ce/Y inclusions contain ∼300 ppm CO2, have low CO2/Nb (contents 50–100) and melts are likely to have exsolved much of their original CO2 contents prior to inclusion entrapment. The negative correlation between CO2 content and trace element enrichment may arise either from the more efficient exsolution of CO2 from enriched melts, or from the intrusion of CO2-supersaturated depleted melts into enriched melts that had already exsolved much of their original CO2 contents. Some inclusions have lower CO2 contents than predicted from binary mixing models, which suggests that at least some CO2 exsolution occurred concurrently with mixing. Enriched inclusions record entrapment pressures of ∼0.5 kbar. These pressures probably correspond to the depth of mixing. Higher pressures recorded in depleted inclusions may have resulted from the development of CO2 supersaturation during ascent from storage at ≥1.5 kbar. The presence of CO2 supersaturation in melt inclusions has the potential to constrain timescales of melt inclusion entrapment.

The Behavior of Metals (Pb, Zn, As, Mo, Cu) During Crystallization and Degassing of Rhyolites from the Okataina Volcanic Center, Taupo Volcanic Zone, New Zealand

The Taupo Volcanic Zone (TVZ), New Zealand is a region of voluminous and frequent rhyolitic volcanism and widespread geothermal activity. Additionally, the hydrothermal systems of the TVZ contain relatively high concentrations of base and precious metals. Here we present an extensive dataset of major element, volatile, and trace element (including Pb, Zn, As, Mo, Cu) abundances in melt inclusions, pumice glasses and minerals from eight eruptions within the Okataina Volcanic Center (OVC) of the TVZ to investigate the behavior of metals during melt evolution. The high-SiO2 rhyolites of the OVC contain high concentrations of volatiles (≤6 wt % H2O, ≤0·25 wt % Cl) and underwent significant degassing prior to and during eruption. The OVC melts contain moderate concentrations of metals (11–24 ppm Pb, 20–50 ppm Zn, 2–7 ppm As, <2·5 ppm Mo, <∼5 ppm Cu). Ferromagnesian minerals (amphibole, biotite and orthopyroxene) in the OVC pumice have high concentrations of Zn (≤1500 ppm), and plagioclase and biotite contain moderate amounts of Pb (≤11 ppm). The melt inclusion and pumice glass trace element data reveal complex histories of magma mixing and mingling prior to eruption; however, discrete melt batches are easily identified based on trace element geochemistry. Variations in incompatible trace elements within these melt batches suggest that the OVC rhyolites underwent at least ∼20–25% fractional crystallization during quartz crystallization and melt inclusion entrapment (at pressures of ∼100–200 MPa) and little to no crystallization (≤5%) during ascent and eruption. Comparison of melt inclusion metal and incompatible element (e.g. U) concentrations reveals that melt Pb, Mo and As increase, whereas melt Zn decreases, during fractional crystallization at depth (∼100–200 MPa). These observations can be explained by minor partitioning of the metals Pb, Mo and As into the fractionating minerals and stronger partitioning of Zn into the ferromagnesian phases, supported by calculated metal D values and analyzed metal concentrations in OVC minerals. Interestingly, throughout both deep, vapor-saturated crystallization and during extensive degassing during magma ascent and eruption (as recorded by pumice glasses), the metals analyzed here do not appear to partition appreciably into the vapor. We propose that the lack of volatility of the metals analyzed in this study can be attributed to a combination of several factors. First, vapor–melt partitioning requires the presence of ligands—commonly Cl, S and OH—with which the metals may complex. Given the low Cl/H2O ratios in the OVC melts and the extensive degassing of H2O compared with Cl, it seems likely that the rhyolites would have exsolved H2O-rich vapor with insufficient Cl to transport metals (in particular Pb and Zn) into the vapor phase, either at depth or during magma ascent. Second, the overall small volumes of vapor present during crystallization at pressures of 100–200 MPa would have impeded significant vapor–melt partitioning of the metals. Finally, the estimated very rapid ascent of the OVC melts from depths of 4–8 km suggests that there was insufficient time at low pressure for diffusion of metals out of the melt. These results imply that there may be an indirect connection between the rhyolites and the metals of the hydrothermal systems of the TVZ. As the metals, and other species such as Cl, remain in the rhyolitic magmas upon eruption, they are available in the large volumes of rhyolite emplaced in the upper crust of the TVZ for leaching by heated meteoric waters.