High fluxes of deep volatiles from ocean island volcanoes: Insights from El Hierro, Canary Islands

Basaltic volcanism contributes significant fluxes of volatiles (CO2, H2O, S, F, Cl) to the Earth’s surface environment. Quantifying volatile fluxes requires initial melt volatile concentrations to be determined, which can be accessed through crystal-hosted melt inclusions. However, melt inclusions in volatile-rich mafic alkaline basalts, such as those erupted at ocean islands, often trap partially degassed melts, meaning that magmatic volatile fluxes from these tectonic settings are often significantly underestimated. We have measured major, trace element and volatile concentrations in melt inclusions from a series of young (<20 ka) basanites from El Hierro, Canary Islands. Our melt inclusions show some of the highest CO2 (up to 3600 ppm) and S (up to 4290 ppm) concentrations measured in ocean island basalts to date, in agreement with data from the recent 2011-2012 eruption. Volatile enrichment is observed in melt inclusions with crystallisation-controlled major element compositions and highly variable trace element ratios such as La/Yb. We use volatile-trace element ratios to calculate original magmatic CO2 contents up to 4.2 wt%, which indicates at least 65% of the original CO2 was degassed prior to melt inclusion trapping. The trace element contents and ratios of El Hierro magmas are best reproduced by 1-8% partial melting of a garnet lherzolite mantle source. Our projected CO2 (200-680 ppm) and S (265-450 ppm) concentrations for the source are consistent with upper estimates for primitive mantle. However, El Hierro magmas have elevated F/Nd and F/Cl in comparison with melts from a primitive mantle, indicating that the mantle must also contain a component enriched in F and other volatiles, most probably recycled oceanic lithosphere. Our modelled original magmatic CO2 contents indicates that, per mass unit, volatile fluxes from El Hierro magmas are up to two orders of magnitude greater than from typical mid-ocean ridge basalts and 1.5 to 7 times greater than from recent Icelandic eruptions, indicating large variability in the primary volatile content of magmas formed in di fferent geodynamic settings, or even within di fferent ocean islands. Our results highlight the importance of characterising mantle heterogeneity in order to accurately constrain both short- and long-term magmatic volatile emissions and fluxes from ocean island volcanoes.NERC studentship NE/L002469/1 NERC grant 526 IMF600/101

The role of water and compression in the genesis of alkaline basalts: Inferences from the Carpathian-Pannonian region

We present a new model for the formation of Plio-Pleistocene alkaline basalts in the central part of the Carpathian-Pannonian region (CPR). Based on the structural hydroxyl content of clinopyroxene megacrysts, the ‘water’ content of their host basalts is 2.0–2.5 wt.%, typical for island arc basalts. Likewise, the source region of the host basalts is ‘water’ rich (290–660 ppm), akin to the source of ocean island basalts. This high ‘water’ content could be the result of several subduction events from the Mesozoic onwards (e.g. Penninic, Vardar and Magura oceans), which have transported significant amounts of water back to the upper mantle, or hydrous plumes originating from the subduction graveyard beneath the Pannonian Basin. The asthenosphere with such a relatively high ‘water’ content beneath the CPR may have been above the ‘pargasite dehydration’ (90 km) solidi. This means that neither decompressional melting nor the presence of voluminous pyroxenite and eclogite lithologies are required to explain partial melting. While basaltic partial melts have been present in the asthenosphere for a long time, they were not extracted during the syn-rift phase, but were only emplaced at the onset of the subsequent tectonic inversion stage at ~8–5 Ma. We propose that the extraction has been facilitated by evolving vertical foliation in the asthenosphere as a response to the compression between the Adriatic indenter and the stable European platform. The vertical foliation and the prevailing compression effectively squeezed the partial basaltic melts from the asthenosphere. The overlying lithosphere may have been affected by buckling in response to compression, which was probably accompanied by formation of deep faults and deformation zones. These zones formed conduits towards the surface for melts squeezed out of the asthenosphere. This implies that basaltic partial melts could be present in the asthenosphere in cases where the bulk ‘water’ content is relatively high (>~200 ppm) at temperatures exceeding ~1000–1100 °C. These melts could be extracted even under a compressional tectonic regime, where the combination of vertical foliation in the asthenosphere and deep fractures and deformation zones in the folded lithosphere provides pathways towards the surface. This model is also valid for deep seated transpressional or transtensional fault zones in the lithosphere

Data for: High fluxes of deep volatiles from ocean island volcanoes: Insights from El Hierro, Canary Islands

The excel spreasheat attached here contains all new geochemical data presented in this work, including trace and volatile element measurements done by SIMS and major and minor element measurements carried out using EPMA. SIMS data is only normalised to SiO2 contents measured by EPMA, with no additional processing done. Uncorrected glass compositions are also provided as a .csv file. PEC and Fe-loss corrected melt inclusion are also proveded as a .csv file. Raw raman data (intensities as function of wavenumber) are also added as .csv. All literature data used for modelling crystallisation paths and trace element melting models are proveded in the excel spreadsheet

Data for: High fluxes of deep volatiles from ocean island volcanoes: Insights from El Hierro, Canary Islands

The excel spreasheat attached here contains all new geochemical data presented in this work, including trace and volatile element measurements done by SIMS and major and minor element measurements carried out using EPMA. SIMS data is only normalised to SiO2 contents measured by EPMA, with no additional processing done. Uncorrected glass compositions are also provided as a .csv file. PEC and Fe-loss corrected melt inclusion are also proveded as a .csv file. Raw raman data (intensities as function of wavenumber) are also added as .csv. All literature data used for modelling crystallisation paths and trace element melting models are proveded in the excel spreadsheet.THIS DATASET IS ARCHIVED AT DANS/EASY, BUT NOT ACCESSIBLE HERE. TO VIEW A LIST OF FILES AND ACCESS THE FILES IN THIS DATASET CLICK ON THE DOI-LINK ABOV

Data for: Instrumental mass fractionation during sulfur isotope analysis by secondary ion mass spectrometry in natural and synthetic glasses

Supplementary spreadsheets containing the sulfur isotope data collected from glasses by SIMS (spreadsheet1), a comparison between sulfur contents of the glasses measured by SIMS and EPMA (spreadsheet2), and the starting composition of the experimental glasses used in the study (spreadsheet3). Tables presented in the manuscript are also provided as an excel spreadsheet for easy access

Sulfur from the subducted slab dominates the sulfur budget of the mantle wedge under volcanic arcs

Sulfur is of a crucial importance in the Earth system influencing biological, climate, ore-forming, and redox processes. Subduction zones play a key role in the global sulfur cycle. Arc magmas have higher sulfur contents and are more oxidised than mid-ocean ridge basalts (MORBs) due to either an oxidised mantle source or magma differentiation. Melt oxidation state and sulfur content may interrelate, as sulfur is a potential oxidising agent during slab-mantle interaction. Here, we use melt inclusions (MIs) to determine the sulfur isotopic composition (δ 34S) of primary arc magmas from three volcanic centres along the Central American Volcanic Arc (CAVA): Fuego (Guatemala), Cerro Negro (Nicaragua), and Turrialba (Costa Rica). These three locations sample much of the global arc magma trace element variability: Ba/La ratios range from 22 (Turrialba) to 118 (Cerro Negro). Melt δ 34S values are between -0.5h and +4.9h. Sulfur contents and δ 34S values of homogenised and naturally quenched MIs overlap, indicating post-entrapment processes do not affect sulfur contents and sulfur isotope ratios in the studied MIs. Degassing causes limited sulfur isotope fractionation; calculated gas-melt isotope fractionation factors are between 0.998-1.001. Our model calculations predict that most volcanic gases along the CAVA have δ 34S between -1h and +6h, becoming enriched in 34S as degassing progresses. We estimate initial melt δ 34S values for Fuego, Cerro Negro, and Turrialba to be +0.7±1.4h, +2.2±1.0h, and +1.6±0.8h (two standard errors), respectively. All these values are elevated compared to MORBs (-0.9h). Addition of oxidised slab material enriched in 34S to the mantle wedge can explain elevated arc primary melt δ 34S and the oxidising conditions observed in arc magmas globally. Based on mass balance, a slab component with δ 34S between +2h to +5h is present in the mantle wedge under the CAVA, elevating local arc mantle S contents to 360±30 ppm at Fuego, 462±11 ppm at Cerro Negro. Modelling suggests that 40-70% of sulfur in the mantle wedge originates from a slab-derived component. Slab subduction is expected to have major control on the evolution of Earth’s sulfur cycle and mantle oxidation state over its geological history

Instrumental mass fractionation during sulfur isotope analysis by secondary ion mass spectrometry in natural and synthetic glasses

Sulfur isotope ratios are among the most commonly studied isotope systems in geochemistry. While sulfur isotope ratio analyses of materials such as bulk rock samples, gases, and sulfide grains are routinely carried out, in-situ analyses of silicate glasses such as those formed in magmatic systems are relatively scarce in the literature. Despite a number of attempts in recent years to analyse sulfur isotope ratios in volcanic and experimental glasses by secondary ion mass spectrometry (SIMS), the effects of instrumental mass fractionation (IMF) during analysis remain poorly understood. In this study we use more than 600 sulfur isotope analyses of nine different glasses to characterise the matrix effects that arise during sulfur isotope analysis of glasses by SIMS. Samples were characterised for major element composition, sulfur content, and sulfur isotope ratios by independent methods. Our glasses contain between 500 and 3400 ppm sulfur and cover a wide compositional range, including low-silica basanite, rhyolite, and phonolite, allowing us to investigate composition-dependent IMF. We use SIMS in multi-collection mode with a Faraday cup/electron multiplier detector configuration to achieve uncertainty of 0.3‰ to 2‰ (2σ) on measured δ34S. At high sulfur content, the analytical error of our SIMS analyses is similar to that of bulk analytical methods, such as gas-source isotope ratio mass spectrometry. We find IMF causes an offset of −12‰ to +1‰ between bulk sulfur isotope ratios and those measured by SIMS. Instrumental mass fractionation correlates non-linearly with glass sulfur contents and with a multivariate regression model combining glass Al, Na, and K contents. Both ln(S) and Al-Na-K models are capable of predicting IMF with good accuracy: 84% (ln(S)) and 87% (Al-Na-K) of our analyses can be reproduced within 2σ combined analytical uncertainty after a correction for composition-dependent IMF is applied. The process driving IMF is challenging to identify. The non-linear correlation between glass S content and IMF in our dataset resembles previously documented correlation between glass H2O abundance and IMF during D/H ratio analyses by SIMS, and could be attributed to changes in 32S− and 34S− ion yields with changing S content and glass composition. However, a clear correlation between S ion yields and S content cannot be identified in our dataset. We speculate that accumulation of alkalis at the SIMS crater floor may be the principal driving force of composition-dependent IMF. Nonetheless, other currently unknown factors could also influence IMF observed during S isotope ratio analyses of glasses by SIMS. Our results demonstrate that the use of multiple, well-characterised standards with a wide compositional range is required to calibrate SIMS instruments prior to sulfur isotope analyses of unknown silicate glasses. Matrix effects related to glass Al-Na-K contents are of particular importance for felsic systems, where alkali and aluminium contents can vary considerably more than in mafic magmas

The role of water and compression in the genesis of alkaline basalts: Inferences from the Carpathian-Pannonian region

We present a new model for the formation of Plio-Pleistocene alkaline basalts in the central part of the Carpathian-Pannonian region (CPR). Based on the structural hydroxyl content of clinopyroxene megacrysts, the ‘water’ content of their host basalts is 2.0–2.5 wt.%, typical for island arc basalts. Likewise, the source region of the host basalts is ‘water’ rich (290–660 ppm), akin to the source of ocean island basalts. This high ‘water’ content could be the result of several subduction events from the Mesozoic onwards (e.g. Penninic, Vardar and Magura oceans), which have transported significant amounts of water back to the upper mantle, or hydrous plumes originating from the subduction graveyard beneath the Pannonian Basin. The asthenosphere with such a relatively high ‘water’ content beneath the CPR may have been above the ‘pargasite dehydration’ (90 km) solidi. This means that neither decompressional melting nor the presence of voluminous pyroxenite and eclogite lithologies are required to explain partial melting. While basaltic partial melts have been present in the asthenosphere for a long time, they were not extracted during the syn-rift phase, but were only emplaced at the onset of the subsequent tectonic inversion stage at ~8–5 Ma. We propose that the extraction has been facilitated by evolving vertical foliation in the asthenosphere as a response to the compression between the Adriatic indenter and the stable European platform. The vertical foliation and the prevailing compression effectively squeezed the partial basaltic melts from the asthenosphere. The overlying lithosphere may have been affected by buckling in response to compression, which was probably accompanied by formation of deep faults and deformation zones. These zones formed conduits towards the surface for melts squeezed out of the asthenosphere. This implies that basaltic partial melts could be present in the asthenosphere in cases where the bulk ‘water’ content is relatively high (>~200 ppm) at temperatures exceeding ~1000–1100 °C. These melts could be extracted even under a compressional tectonic regime, where the combination of vertical foliation in the asthenosphere and deep fractures and deformation zones in the folded lithosphere provides pathways towards the surface. This model is also valid for deep seated transpressional or transtensional fault zones in the lithosphere