Hauri, Erik

San Cristóbal volcano in northwest Nicaragua is one of the most active basaltic–andesitic stratovolcanoes of the Central American Volcanic Arc (CAVA). Here we provide novel constraints on the volcano's magmatic plumbing system, by presenting the first direct measurements of major volatile contents in mafic-to-intermediate glass inclusions from Holocene and historic-present volcanic activity. Olivine-hosted (forsterite [Fo] b80; Fob80) glass inclusions from Holocene tephra layers contain moderate amounts of H2O (0.1–3.3 wt%) and S and Cl up to 2500 μg/g, and define the mafic (basaltic) endmember component. Historic-present scoriae and tephra layers exhibit more-evolved olivines (Fo69–72) that contain distinctly lower volatile contents (0.1–2.2 wt% H2O, 760–1675 μg/g S, and 1021–1970 μg/g Cl), and represent a more-evolved basaltic–andesitic magma. All glass inclusions are relatively poor in CO2, with contents reaching 527 μg/g (as measured by nanoscale secondary ion mass spectrometry), suggesting pre- to postentrapment CO2 loss to a magmatic vapor. We use results of Raman spectroscopy obtained in a population of small (b50 μm) inclusions with CO2-bearing shrinkage bubbles (3–12 μm) to correct for postentrapment CO2 loss to bubbles, and to estimate the original minimumCO2 content in San Cristóbal parental melts at ~1889 μg/g, which is consistent with the less-CO2-degassed melt inclusions (MI) (N1500 μg/g) found in Nicaragua at Cerro Negro, Nejapa, and Granada. Models of H2O and CO2 solubilities constrain the degassing pathway of magmas up to 425 MPa (~16 km depth), which includes a deep CO2 degassing step (only partially preserved in the MI record), followed by coupled degassing of H2O and S plus crystal fractionation at magma volatile saturation pressures from ∼195 to b10 MPa. The variation in volatile contents from San Cristóbal MI is interpreted to reflect (1) Holocene eruptive cycles characterized by the rapid emplacement of basaltic magma batches, saturated in volatiles, at depths of 3.8–7.4 km, and (2) the ascent of more-differentiated and cogenetic volatile-poor basaltic andesites during historic-present eruptions, having longer residence times in the shallowest (b3.4 km) and hence coolest regions of the magmatic plumbing system. We also report the first measurements of the compositions of noble-gas isotopes (He, Ne, and Ar) in fluid inclusions in olivine and pyroxene crystals. While the measured 40Ar/36Ar ratios (300–304) and 4He/20Ne ratios (9–373) indicate some degree of air contamination, the 3He/4He ratios (7.01–7.20 Ra) support a common mantle source for Holocene basalts and historic-present basaltic andesites. The magmatic source is interpreted as generated by a primitive MORB-like mantle, that is influenced to variable extents by distinct slab fluid components for basalts (Ba/La ~ 76 and U/Th ~ 0.8) and basaltic andesites (Ba/La ~ 86 and U/Th ~ 1.0) in addition to effects of magma differentiation. These values for the geochemical markers are particularly high, and their correlation with strong plume CO2/S ratios from San Cristóbal is highly consistent with volatile recycling at the CAVA subduction zone, where sediment involvement in mantle fluids influences the typical relatively C-rich signature of volcanic gases in Nicaragua.

Due to its very low solubility in silicate melts, CO2 concentrations in melt inclusions (MIs) within crystals are commonly orders of magnitude less than the total concentration in the multiphase magma, strongly limiting the possibility to constrain CO2 abundance based on the dissolved quantities. Here we develop a statistical method to process MI data, which allows analytical uncertainties to be taken into account together with the peculiar features of the local saturation surface. The method developed leads to retrieve total H2O and CO2 concentrations in magma as well as the gas phase abundance at the time of magma crystallization. Application to a set of 29 high-resolution secondary ion mass spectrometry (SIMS) MI data from a single specimen of the 1842–1844 eruption of Kilauea, Hawaii, reveals the existence of heterogeneous total CO2 abundance, and of at least 2–6 wt % total CO2 in some magma batches, two orders of magnitude higher than the dissolved amounts and 30–50 times more abundant than the corresponding total H2O content. Heterogeneous total volatile concentrations are interpreted as due to a combination of degassing and gas flushing in magma subject to convective motion at shallow depth where P < 100 MPa. In such a view, the magma rising to shallow depth in the volcanic system carries initially a total volatile content ≤1 wt %, corresponding to the determined low total CO2 population, and consistent with previous global estimates. The high CO2 populations correspond to progressive CO2 enrichment due to degassing at low P and flushing from a deep CO2-rich gas. A total CO2 content >1 wt % is likely to characterize the >30 km deep magma, not represented in the analyzed inclusions, from which a CO2-rich gas phase exsolves and decouples from the liquid.

New analytical results for the composition of shrinkage bubbles (0·9–7·0 vol. %) in olivine-hosted (Fo <80%) primary melt inclusions (MIs) have been incorporated into a novel geochemical model for San Cristóbal volcano, Nicaragua. The vapour, liquid, and mineral components found inside shrinkage bubbles may represent relics of early C–O–H–S fluids exsolved from a magmatic-hydrothermal system. This conclusion is supported by high-resolution Raman microspectroscopy revealing: (1) gaseous CO2 (d = 0·17–0·31 g/cm3 in 31 samples) coexisting with liquid H2O (in seven samples) at ambient temperature (<22°C) inside the shrinkage bubbles of naturally quenched inclusions; (2) several mineral phases (i.e. Fe, Cu-sulfides, Ca-sulfates and Mg-carbonates) formed along the bubble–glass interface, as confirmed by electron backscattered/energy-dispersive spectroscopy. The presence of liquid water was revealed by applying a novel subtraction method to fitted Raman spectra that isolated an isosbestic liquid-water band at 3460 ± 60/cm-1 (mean ± SD). In MIs, the major oxide composition of glasses containing shrinkage bubbles were analysed by electron microprobe, whereas glass volatile contents were measured with nanoscale secondary-ion mass spectroscopy. According to the water content of the glass inclusions (≤ 3·3 wt %) and the presence of liquid water at the bubble–glass interface, only small amounts of water (0·3 wt %) appear to have migrated inside the bubbles. From pre-eruptive (up to 1200°C) to post-eruptive temperatures, aqueous fluids represent the principal agents for chemical reactions inside MI bubbles involving dissolved ionic species (e.g. SO42-, CO32-, and Cl-) and major and/or trace elements from the inclusion glass (e.g. Mg, Fe, Cu, Si, Al, Na, and K). After the initiation of nucleation (1009–1141°C), the volume of shrinkage bubbles expands and the surrounding glass contracts (at <530°C). The Fe–Mg–Cu-rich (vapour) shrinkage-bubble paragenetic mineral sequence formed during different cooling stages: (A) high-temperature sulfide precipitation at 500–700°C; (B) low-temperature magnesite precipitation at hydrothermal conditions <350°C; and finally (C) low-to-ambient temperature precipitation of carbonates and sulfates in liquid water at <150°C. Our findings indicate that the C–O–H–S fluids in shrinkage bubbles can represent an ideal preserved/closed magmatic-hydrothermal system evolving after the exsolution of magmatic fluids during cooling.

Telica volcano, in north-west Nicaragua, is a young stratovolcano of intermediate magma composition producing frequent Vulcanian to phreatic explosive eruptions. The Telica stratigraphic record also includes examples of (pre)historic sub-Plinian activity. To refine our knowledge of this very active volcano, weanalyzedmajor element composition and volatile content of melt inclusions fromsomestratigraphically significant Telica tephra deposits. These include: (1) the Scoria Telica Superior (STS) deposit (2000 to 200 years Before Present; Volcanic Explosive Index, VEI, of 2–3) and (2) pyroclasts from the post-1970s eruptive cycle (1982; 2011). Based on measurements with nanoscale secondary ion mass spectrometry, olivine-hosted (forsterite [Fo] N 80) glass inclusions fall into 2 distinct clusters: a group of H2O-rich (1.8–5.2 wt%) inclusions, similar to those of nearby Cerro Negro volcano, and a second group of CO2-rich (360–1700 μg/g CO2) inclusions (Nejapa, Granada). Model calculations show that CO2 dominates the equilibrium magmatic vapor phase in the majority of the primitive inclusions (XCO2 N 0.62–0.95). CO2, sulfur (generally b2000 μg/g) and H2O are lost to the vapor phase during deep decompression (P N 400 MPa) and early crystallization of magmas. Chlorine exhibits a wide concentration range (400–2300 μg/g) in primitive olivine-entrapped melts (likely suggesting variable source heterogeneity) and is typically enriched in the most differentiated melts (1000–3000 μg/g). Primitive, volatile-rich olivine-hosted melt inclusions (entrapment pressures, 5–15 km depth) are exclusively found in the largest-scale Telica eruptions (exemplified by STS in our study). These eruptions are thus tentatively explained as due to injection of deep CO2-rich mafic magma into the shallow crustal plumbing system. More recent (post-1970), milder (VEI 1–2) eruptions, instead, do only exhibit evidence for low-pressure (P b 50–60 MPa), volatile-poor (H2O b 0.3–1.7 wt%; CO2 b 23–308 μg/g) magmatic conditions. These are manifested as andesitic magmas, recording multiple magma mixing events, in pyroxene inclusions.Wepropose that post-1970s eruptions are possibly related to the high viscosity of resident magma in shallow plumbing system (b2.4 km), due to crystallization and degassing

We use volatiles in melt inclusions and nominally anhydrous phenocrysts, with volcanic gas flux and composition, and textural analysis of mafic inclusions to estimate the mass of exsolved vapour prior to eruption at Soufrière Hills Volcano (SHV). Pre-eruptive andesite coexists with exsolved vapour comprising 1.6–2.4 wt% of the bulk magma. The water content of orthopyroxenes indicates a zone of magma storage at pressures of approximately 200–300 MPa, whereas melt inclusions have equilibrated at shallower pressures. Inclusions containing >3 wt% H2O are enriched in CO2, suggesting flushing with CO2-rich gases. Intruding mafic magma contains >8 wt% H2O at 200–300 MPa. Rapid quenching is accompanied by crystallization and vesiculation. Upon entrainment into the andesite, mafic inclusions may undergo disaggregation, where expansion of volatiles in the interior overcomes the strength of the crystal frameworks, thereby recharging the vapour content of the andesite. Exsolved vapour may amount to 4.3–8.2 vol% at 300 MPa, with implications for eruption longevity and volume; we estimate the magma reservoir volume to be 60–200 km3. Exsolved vapour may account for the small volume change at depth during eruptions from geodetic models, and has implications for magma flow: exsolution is likely to be in equilibrium during rapid magma ascent, with little nucleation of new bubbles.