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International audience; We report new carbon dioxide (CO2) abundance and isotope data for 71 geothermal gases and fluids from both high-temperature (HT > 150 °C at 1 km depth) and low-temperature (LT < 150 °C at 1 km depth) geothermal systems located within neovolcanic zones and older segments of the Icelandic crust, respectively. These data are supplemented by CO2 data obtained by stepped heating of 47 subglacial basaltic glasses collected from the neovolcanic zones. The sample suite has been characterized previously for He–Ne (geothermal) and He–Ne–Ar (basalt) systematics (Füri et al., 2010), allowing elemental ratios to be calculated for individual samples. Geothermal fluids are characterized by a wide range in carbon isotope ratios (δ13C), from −18.8‰ to +4.6‰ (vs. VPDB), and CO2/3He values that span eight orders of magnitude, from 1 × 104 to 2 × 1012. Extreme geothermal values suggest that original source compositions have been extensively modified by hydrothermal processes such as degassing and/or calcite precipitation. Basaltic glasses are also characterized by a wide range in δ13C values, from −27.2‰ to −3.6‰, whereas CO2/3He values span a narrower range, from 1 × 108 to 1 × 1012. The combination of both low δ13C values and low CO2 contents in basalts indicates that magmas are extensively and variably degassed. Using an equilibrium degassing model, we estimate that pre-eruptive basaltic melts beneath Iceland contain ∼531 ± 64 ppm CO2 with δ13C values of −2.5 ± 1.1‰, in good agreement with estimates from olivine-hosted melt inclusions (Metrich et al., 1991) and depleted MORB mantle (DMM) CO2 source estimates (Marty, 2012). In addition, pre-eruptive CO2 compositions are estimated for individual segments of the Icelandic axial rift zones, and show a marked decrease from north to south (Northern Rift Zone = 550 ± 66 ppm; Eastern Rift Zone = 371 ± 45 ppm; Western Rift Zone = 206 ± 24 ppm). Notably, these results are model dependent, and selection of a lower δ13C fractionation factor will result in lower source estimates and larger uncertainties associated with the initial δ13C estimate. Degassing can adequately explain low CO2 contents in basalts; however, degassing alone is unlikely to generate the entire spectrum of observed δ13C variations, and we suggest that melt–crust interaction, involving a low δ13C component, may also contribute to observed signatures. Using representative samples, the CO2 flux from Iceland is estimated using three independent methods: (1) combining measured CO2/3He values (in gases and basalts) with 3He flux estimates (Hilton et al., 1990), (2) merging basaltic emplacement rates of Iceland with pre-eruptive magma source estimates of ∼531 ± 64 ppm CO2, and (3) combining fluid CO2 contents with estimated regional fluid discharge rates. These methods yield CO2 flux estimates from of 0.2–23 × 1010 mol a−1, which represent ∼0.1–10% of the estimated global ridge flux (2.2 × 1012 mol a−1; Marty and Tolstikhin, 1998).

We report combined He-Ne-Ar isotope data of mantle-derived xenoliths and/or lavas from all segments of the East Africa Rift System (EARS). Plume-like helium isotope (3He/4He) ratios (i.e., greater than the depleted MORB mantle (DMM) range of 8 ± 1RA) are restricted to the Ethiopia Rift and Rungwe, the southernmost volcanic province of the Western Rift. In contrast, neon isotope trends reveal the presence of an ubiquitous solar (plume-like) Ne component throughout the EARS, with (21Ne/22Ne)EX values (where (21Ne/22Ne)EX is the air-corrected 21Ne/22Ne ratio extrapolated to Ne-B) as low as 0.034, close to that of solar Ne-B (0.031). Coupling (21Ne/22Ne)EX with 4He/3He ratios indicates that all samples can be explained by admixture between a single mantle plume source, common to the entire rift, and either a DMM or subcontinental lithospheric mantle source. Additionally, we show that the entire sample suite is characterized by low 3He/22NeS ratios (mostly

Change history: In this Article, the original affiliation 2 was not applicable and has been removed. In addition, in the Acknowledgements there was a statement missing and an error in a name. These errors have been corrected online.

We present the chemical and isotope (HeCN) characterization of active fumaroles and hydrothermal gases and waters from the summits and flanks of 19 volcanic centers along the western Sunda arc, Indonesia. Samples were collected over two field expeditions (1991 and 2010) and cover 13 volcanic centers in Sumatra, 5 in Java and one in Bali. In addition, we present data from three geothermal sites in Sumatra associated with active fault systems in-between volcanic centers (IBVC). The overall aim is to resolve volatiles associated with the sub-arc mantle (subducting slab and mantle wedge) from inputs derived from the over-riding arc crust. The western Sunda arc is a prime locality to assess controls on volatile provenance at subduction zones due to changes in composition and thickness of over-riding crust and variations in sediment input rates along the strike of the arc. The dry gas chemistry of the majority of volcanic samples is dominated by CO2 with inert gas variations (HeArN2) typical of subduction zone gases. However, there is a strong crustal control on the HeCO2 isotope and relative abundance systematics on a number of volcanic centers: this effect is most clearly observed at flank localities and in water phase samples. Filtering the entire database for modifications due to air contamination, degassing-induced fractionation (C-isotopes and CO2/3He ratios) and crustal contamination associated with volatile transport within shallow-level hydrothermal systems allows recognition of the magmatic volatile signature of individual volcanoes along the arc. Helium isotopes at all but two volcanic centers (Talang and Dempo on Sumatra) range from 5.3 RA to 8.1 RA (RA = air 3He/4He) pointing to the mantle wedge as the principal source of He but with a small input of crustal (radiogenic) He at some localities. Samples from Java and Bali span an even more limited range (6.6 to 7.9 RA) implying a relatively smaller input of crustal He. Carbon isotope and CO2/3He ratios vary from − 1.4‰ to − 6.4‰ and 4.38 to 150 (× 109), respectively, with higher and more variable values to the north of Sumatra. This latitudinal effect is not apparent in air-corrected N-isotope values (δ15NC = − 3.91 to + 5.92‰) or various elemental ratios such as N2/Ar and N2/He. The three IBVC sites, all located in Sumatra, have significantly lower 3He/4He ratios (

In Table 1 of the above published paper, N2/40Ar* ratios (column 13) are incorrect. A corrected table and updated figures (Figs. 6–8) are shown below. The correct N2/40Ar* values vary between 178 and 2.6 X 10^4, with a mean of 4.1 ± 2.1 (X10^3). Although this range in N2/40Ar* ratios is somewhat smaller compared to what was reported, it still displays considerably more heterogeneity compared to the DMM database. The new mean value is also significantly higher than the DMM mean (138 ± 65), as discussed. Therefore, the findings in the paper concerning heterogeneous and elevated N2/40Ar* ratios in Icelandic subglacial basalts still stand.

Large volcanic eruptions on Earth commonly occur with a collapse of the roof of a crustal magma reservoir, forming a caldera. Only a few such collapses occur per century, and the lack of detailed observations has obscured insight into the mechanical interplay between collapse and eruption.We usemultiparameter geophysical and geochemical data to show that the 110-square kilometer and 65-meter-deep collapse of Bárdarbunga caldera in 2014–2015 was initiated through withdrawal of magma, and lateral migration through a 48-kilometers-long dike, from a 12-kilometers deep reservoir. Interaction between the pressure exerted by the subsiding reservoir roof and the physical properties of the subsurface flow path explain the gradual, near exponential decline of both collapse rate and the intensity of the 180-day- long eruption., Civil Protection Department of the National Commissioner of the Icelandic Police. European Community’s Seventh Framework Programme grant no. 308377 (Project FUTUREVOLC). EU Seventh Framework Marie Curie project NEMOH no. 289976 CO2Volc ERC grant no. 279802, the Research Fund of the University of Iceland, the Irish Research Council, the Helmholtz Alliance on Remote Sensing and Earth System Dynamics (EDA), Bayerisches Geoinstitut through their DFG core facility for high pressure research, and UNAM/CIC Intercambio Académico.

The Indonesian island of Sumatra, located in one of the most active zones of the Pacific Ring of Fire, is characterized by a chain of subduction-zone volcanoes which extend the entire length of the island. As a group of volcanic geochemists, we embarked upon a five-week sampling expedition to these exotic, remote, and in part explosive volcanoes (SAGE 2010; Sumatran Arc Geochemical Expedition). We set out to collect rock and gas samples from 17 volcanic centres from the Sumatran segment of the Sunda arc system, with the aim of obtaining a regionally significant sample set that will allow quantification of the respective roles of mantle versus crustal sources to magma genesis along the strike of the arc. Here we document our geological journey through Sumatra's unpredictable terrain, including the many challenges faced when working on active volcanoes in pristine tropical climes.

We present new He–Ne data for geothermal fluids and He–Ne–Ar data for basalts from throughout the Icelandic neovolcanic zones and older parts of the Icelandic crust. Geothermal fluids, subglacial glasses, and mafic phenocrysts are characterized by a wide range in helium isotope ratios ( 3 He/ 4 He) encompassing typical MORB-like ratios through values as high as 36.8 RA (where RA = air 3 He/ 4 He). Although neon in geothermal fluids is dominated by an atmospheric component, samples from the northwest peninsula show a small excess of nucleogenic 21 Ne, likely produced in-situ and released to circulating fluids. In contrast, geothermal fluids from the neovolcanic zones show evidence of a contribution of mantle-derived neon, as indicated by 20 Ne enrichments up to 3% compared to air. The neon isotope composition of subglacial glasses reveals that mantle neon is derived from both depleted MORB-mantle and a primordial, ‘solar’ mantle component. However, binary mixing between these two endmembers can account for the He–Ne isotope characteristics of the basalts only if the 3 He/ 22 Ne ratio of the primordial mantle endmember is lower than in the MORB component. Indeed, the helium to neon elemental ratios ( 4 He/ 21 Ne* and 3 He/ 22 Nes where 21 Ne* = nucleogenic 21 Ne and 22 Nes = ‘solar’-derived 22 Ne) of the majority of Icelandic subglacial glasses are lower than theoretical values for Earth’s mantle, as observed previously for other OIB samples. Helium may be depleted relative to neon in high- 3 He/ 4 He ratio parental melts due to either more compatible behavior during low-degree partial melting or more extensive diffusive loss relative to the heavier noble gases. However, Icelandic glasses show higher 4 He/ 40 Ar* ( 40 Ar* = radiogenic Ar) values for a given 4 He/ 21 Ne* value compared to the majority of other OIB samples: this observation is consistent with extensive open-system equilibrium degassing, likely promoted by lower confining pressures during subglacial eruptions of Icelandic lavas. Taken together, the He–Ne–Ar systematics of Icelandic subglacial glasses are imprinted with the overlapping effects of helium depletion in the high- 3 He/ 4 He ratio parental melt, binary mixing of two distinct mantle components, degassing fractionation and interaction with atmospheric noble gases. However, it is still possible to discern differences in the noble gas characteristics of the Icelandic mantle source beneath the neovolcanic zones, with MORB-like He–Ne isotope features prevalent in the Northern Rift Zone and a sharp transition to more primitive ‘solar-like’ characteristics in central and southern Iceland.

The Thjorsa lava in South Iceland is an early Holocene fissure lava within the Bardarbunga volcanic system—the most productive segment of the Eastern Rift Zone during the Quaternary and Holocene. The lava has a volume of 25 km 3 and is one of notably plagioclase-porphyritic early Holocene lava flows in Iceland. The possible genetic relationship between the large plagioclase phenocrysts and the host lava is investigated by analyzing carefully separated groundmass/plagioclase pairs. The groundmass was analyzed for major and trace elements and isotopic ratios of Sr, Nd and Pb. The large plagioclases were analyzed by microprobe and 87 Sr/ 86 Sr by mass spectrometry. The groundmass (host magma) of the host lava has a restricted range of elemental and isotopic composition. Both the groundmass and the separated plagioclases show a significant range of 87 Sr/ 86 Sr—but interestingly with only minor overlap between the two groups. Both are, however, within the range of values observed for the lavas of the Bardarbunga volcanic system. This lack of overlap suggests that the plagioclase and the host lava are genetically unrelated and derived from two distinct mantle sources. The suggested source for the large plagioclases is deep layered crustal gabbros formed in earlier intrusive events. The plagioclases are accompanied by minor amounts of Fo-rich olivine and occasional disintegrating Cr-diopside. There is a clear compositional gap between the An-rich (> An 80) plagioclases and the small groundmass plagioclase that appear to be in equilibrium with the groundmass composition. The parental magma of the anorthositic gabbro must have been relatively primitive, crystallizing additional olivine and Cr-diopside and with 87 Sr/ 86 Sr at the low end of the range observed in the Bardarbunga rift segment. During ascent of the host magma the gabbros were infiltrated and broken up by this more evolved host magma. With lowered pressures during ascent and lava effusion the Cr-diopside comes unstable with up to 5% being assimilated into the host magma mildly affecting isotopic ratios and those elements with clinopyroxene affinity. The two components—the host magma and the plagioclases are therefore genetically unrelated and with only minor mixing effect on the host magma. The results of the present study show that whole-rock chemical analyses of such rocks must be treated with caution as they may not represent actual magmatic liquids. At the beginning of the Holocene there was a large isostatic rebound in Iceland following the rapid ice melting. This was accompanied by a major pulse of basaltic eruptions and many of these eruptions, especially around Central Iceland, carry abundant large plagioclases. This is clearly not the only cause as there are a number of very plagioclase-porphyritic lavas in the Tertiary formations but may have facilitated plagioclase incorporation.

We investigate the helium (He-3/He-4) and carbon (delta C-13) isotope compositions and relative abundance ratios (CO2/He-3) of gas samples together with the stable isotope compositions of dissolved carbon and sulfur and the oxygen and hydrogen isotopic compositions of the associated water phase from a number of geothermal fields located around Lake Van in eastern Anatolia, Turkey. The mantle-derived helium component, which is likely transferred to the crust beneath eastern Turkey by recent magmatism, is found to constitute up to 96% (e.g. Nemrut Caldera) of the total He content in fluids. As regards the spatial distribution of He, samples collected from areas of Pliocene-Quaternary volcanics are characterized by a wide and generally higher range of R/R-A ratios (0.93 to 7.76 R-A) compared to those of non-volcanic regions ((1.85 to 1.0 R-A). CO2/He-3 ratios vary over a wide range (2.4 x 10(5)-3.8 x 10(13)) but are mostly higher than that of the nominal upper mantle (similar to 2 x 10(9)). Oxygen-hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and indicate a local meteoric origin. Sulfate in waters is most probably derived from dissolution of marine carbonates and terrestrial evaporite units. Temperatures calculated by SO4-H2O isotope geothermometry lie between 40 and 199 degrees C, and are in poor agreement with reservoir temperatures estimated from silica geothermometers. Discordant temperatures may be due to either the relatively slow rate of isotopic equilibrium between water and sulfate or mixing of geothermal water with sulfate-bearing shallow waters which may modify the delta O-18 value. The delta C-13 (CO2) values of gas samples are consistently lower than those of their water counterparts, consistent with loss of CO2 from waters by degassing. Mixing between mantle and various crustal C-sources appears to be the main control on the C-isotope composition. The principal origin of CO2 in all samples is crustal lithologies, mainly limestone (similar to 85 to 98% of the total carbon inventory): thus, the crustal carbon flux is at least 10 times that from the mantle. There is a broad correlation between high He-3/He-4 values and thinner crust in the western part of the Lake Van region, where several historically-active volcanoes are located. This observation indicates that localized volcanic and magmatic activity exerts the primary control on the balance between mantle and crustally-derived volatiles in the region. (C) 2012 Elsevier B.V. All rights reserved. We investigate the helium (3He/4He) and carbon (δ13C) isotope compositions and relative abundance ratios (CO2/3He) of gas samples together with the stable isotope compositions of dissolved carbon and sulfur and the oxygen and hydrogen isotopic compositions of the associated water phase from a number of geothermal fields located around Lake Van in eastern Anatolia, Turkey. The mantle-derived helium component, which is likely transferred to the crust beneath eastern Turkey by recent magmatism, is found to constitute up to 96% (e.g. Nemrut Caldera) of the total He content in fluids. As regards the spatial distribution of He, samples collected from areas of Pliocene–Quaternary volcanics are characterized by a wide and generally higher range of R/RAratios (0.93 to 7.76 RA) compared to those of non-volcanic regions (0.85 to 1.0 RA). CO2/3He ratios vary over a wide range (2.4×105–3.8×1013) but are mostly higher than that of the nominal upper mantle (~2×109). Oxygen–hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and indicate a local meteoric origin. Sulfate in waters is most probably derived from dissolution of marine carbonates and terrestrial evaporite units. Temperatures calculated by SO4–H2O isotope geothermometry lie between 40 and 199°C, and are in poor agreement with reservoir temperatures estimated from silica geothermometers. Discordant temperatures may be due to either the relatively slow rate of isotopic equilibrium between water and sulfate or mixing of geothermal water with sulfate-bearing shallow waters which may modify the δ18O value. The δ13C (CO2) values of gas samples are consistently lower than those of their water counterparts, consistent with loss of CO2from waters by degassing. Mixing between mantle and various crustal C-sources appears to be the main control on the C-isotope composition. The principal origin of CO2in all samples is crustal lithologies, mainly limestone (~85 to 98% of the total carbon inventory): thus, the crustal carbon flux is at least 10 times that from the mantle. There is a broad correlation between high3He/4He values and thinner crust in the western part of the Lake Van region, where several historically-active volcanoes are located. This observation indicates that localized volcanic and magmatic activity exerts the primary control on the balance between mantle and crustally-derived volatiles in the region.

[1] We describe a new system for the simultaneous static triple-collection of nitrogen isotopes at the

[1] We report helium isotope ratios (3He/4He) of lavas and tephra of the Rungwe Volcanic Province (RVP) in southern Tanzania. Values as high as 15RA (RA = air 3He/4He) far exceed typical upper mantle values, and are the first observation of plume-like ratios south of the Turkana Depression which separates the topographic highs of the Ethiopia and Kenya domes. The African Superplume - a tilted low-velocity seismic anomaly extending to the core-mantle boundary beneath southern Africa – is the likely source of these high 3He/4He ratios. High 3He/4He ratios at RVP together with similarly-high values along the Main Ethiopian Rift and in Afar provide compelling evidence that the African Superplume is a feature that extends through the 670-km seismic discontinuity and provides dynamic support – either as a single plume or via multiple upwellings – for the two main topographic features of the East Africa Rift System as well as heat and mass to drive continuing rift-related magmatism.

Clinopyroxene–liquid geothermobarometry is a widely used tool for estimating the conditions under which mafic magmas are stored before they erupt. However, redox variability, sector zoning and disequilibrium crystallization present major challenges to the robust estimation of magma storage conditions. Moreover, most recent studies seeking to address these challenges have focused on clinopyroxenes from alkalic systems and are thus of limited use for understanding clinopyroxenes from the tholeiitic systems that dominate global magma budgets. Here we combine observations on natural clinopyroxenes from the 2014–2015 Holuhraun lava in Iceland with observations on experimental clinopyroxenes synthesized during high-pressure, high-temperature experiments on the same lava in order to investigate clinopyroxene–liquid equilibria in tholeiitic systems and optimize of geothermobarometric strategies. Natural clinopyroxenes from the 2014–2015 Holuhraun lava are sector zoned, with {1-11} hourglass sectors being enriched in the enstatite–ferrosillite component at the expense of all other components with respect to {hk0} prism sectors. In contrast with observations on clinopyroxenes from alkalic systems, sector zoning in clinopyroxenes from the 2014–2015 Holuhraun lava is characterized by differences in Ca and Na contents as well as in Ti and Al contents. The products of crystallization experiments performed at 100–600 MPa and 1140–1220 °C on a powdered starting glass at two sets of melt H2O content–oxygen fugacity conditions (∼0·1 wt % H2O and close to the graphite-oxygen redox buffer, and 0·5–1·0 wt % H2O and approximately one and half log units above the quartz–fayalite–magnetite redox buffer) demonstrate that clinopyroxene crystals from nominally equilibrium experiments can preserve strongly disequilibrium compositions. The compositional systematics of experimental clinopyroxenes are consistent with the presence of sector zoning. Furthermore, the magnitude of compositional variability increases with decreasing melt H2O content and increasing deviations of experimental temperatures below clinopyroxene liquidus temperatures (i.e. degrees of undercooling sensu lato), indicating that kinetic processes play a key role in controlling clinopyroxene compositions, even under notionally equilibrium conditions. Few published analyses of experimental clinopyroxene crystals may thus represent truly equilibrium compositions. Stoichiometric calculations on natural and experimental clinopyroxenes show that Fe3+ is a major constituent of clinopyroxenes from tholeiitic magmas under naturally relevant oxygen fugacity conditions. They also show that Fe3+ is most likely incorporated as Ca- and Al- bearing Ca–Fe-Tschermak’s component rather than Na-bearing aegirine component at oxygen fugacities up to one and a half log units above the quartz–fayalite–magnetite buffer. Elevated oxygen fugacities are thus less likely to compromise clinopyroxene–liquid geothermobarometry than previously thought. Guided by our experimental results, we combined published descriptions of clinopyroxene–liquid equilibria with geothermobarometric equations to develop an internally consistent and widely applicable method for performing geothermobarometry on tholeiitic magmas that does not require equilibrium zones to be selected a priori. Applying this method to natural clinopyroxene crystals from the 2014–2015 Holuhraun lava that formed under low but variable degrees of undercooling (perhaps 25 °C or less) returns values in excellent agreement with those from independent methods (232 ± 86 MPa, 1161 ± 11 °C). Robust estimates of magma storage conditions can thus be obtained by performing clinopyroxene–liquid geothermobarometry on tholeiitic magmas when disequilibrium is suitably accounted for.