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We measured the N concentrations and isotopic compositions of 44 samples of terrestrial potassic and micro- and meso-porous minerals and a small number of whole-rocks to determine the extent to which N is incorporated and stored during weathering and low-temperature hydrothermal alteration in Mars surface/near-surface environments. The selection of these minerals and other materials was partly guided by the study of altered volcanic glass from Antarctica and Iceland, in which the incorporation of N as NH

Indium (In) behaves as a moderately volatile metal during nebular and planetary processes, and its volatility depends strongly on oxygen fugacity. The In isotopic composition of the bulk silicate Earth (BSE) could provide a critical constraint on the nature of Earth's building blocks and mechanisms that lead to its volatile depletion. However, accurately and precisely determining the isotopic composition of In of the silicate Earth is challenging due to its low abundance in igneous rocks and the presence of significant isobaric interferences on its isotopes (e.g., 113Cd+ on 113In+ and 115Sn+ on 115In+). Here, we present a purification procedure for In from rock matrices and report the first dataset of In isotopic compositions of 30 terrestrial igneous rocks, one biotite geostandard, and one carbonaceous chondrite (Allende) measured on a Nu Sapphire collision-cell equipped multi-collector inductively-coupled-plasma mass-spectrometer (CC-MC-ICP-MS) with an external reproducibility of 0.11‰ (2SD). At this level of precision, we find no statistically significant difference in the In isotopic compositions of mid-ocean-ridge basalts (MORB), oceanic island basalts (OIB), and continental flood basalts (CFB). Furthermore, Canary Islands, Iceland and Afar lavas display no analytically resolvable In isotopic variations from basalts to rhyolites. Therefore, In isotope fractionation during igneous processes is smaller than our analytical uncertainty and the In isotopic compositions of basalts are likely to be representative samples of their mantle sources. The twenty-one terrestrial basalts from diverse geological settings have an average δ115In of 0.35 ± 0.07 ‰ (2SD). This value represents the current best estimate of the In isotopic composition of the mantle as well as of the bulk silicate Earth, assuming limited In isotope fractionation during mantle partial melting, and due to the small contribution of the continental crust to the In budget (

Mantle-derived noble gases in volcanic gases are powerful tracers of terrestrial volatile evolution, as they contain mixtures of both primordial (from Earth’s accretion) and secondary (e.g., radiogenic) isotope signals that characterize the composition of deep Earth. However, volcanic gases emitted through subaerial hydrothermal systems also contain contributions from shallow reservoirs (groundwater, crust, atmosphere). Deconvolving deep and shallow source signals is critical for robust interpretations of mantle-derived signals. Here, we use a novel dynamic mass spectrometry technique to measure argon, krypton, and xenon isotopes in volcanic gas with ultrahigh precision. Data from Iceland, Germany, United States (Yellowstone, Salton Sea), Costa Rica, and Chile show that subsurface isotope fractionation within hydrothermal systems is a globally pervasive and previously unrecognized process causing substantial nonradiogenic Ar-Kr-Xe isotope variations. Quantitatively accounting for this process is vital for accurately interpreting mantle-derived volatile (e.g., noble gas and nitrogen) signals, with profound implications for our understanding of terrestrial volatile evolution.

Microbial communities in terrestrial geothermal systems often contain chemolithoautotrophs with well-characterized distributions and metabolic capabilities. However, the extent to which organic matter produced by these chemolithoautotrophs supports heterotrophs remains largely unknown. Here we compared the abundance and activity of peptidases and carbohydrate active enzymes (CAZymes) that are predicted to be extracellular identified in metagenomic assemblies from 63 springs in the Central American and the Andean convergent margin (Argentinian backarc of the Central Volcanic Zone), as well as the plume-influenced spreading center in Iceland. All assemblies contain two orders of magnitude more peptidases than CAZymes, suggesting that the microorganisms more often use proteins for their carbon and/or nitrogen acquisition instead of complex sugars. The CAZy families in highest abundance are GH23 and CBM50, and the most abundant peptidase families are M23 and C26, all four of which degrade peptidoglycan found in bacterial cells. This implies that the heterotrophic community relies on autochthonous dead cell biomass, rather than allochthonous plant matter, for organic material. Enzymes involved in the degradation of cyanobacterial- and algal-derived compounds are in lower abundance at every site, with volcanic sites having more enzymes degrading cyanobacterial compounds and non-volcanic sites having more enzymes degrading algal compounds. Activity assays showed that many of these enzyme classes are active in these samples. High temperature sites (> 80°C) had similar extracellular carbon-degrading enzymes regardless of their province, suggesting a less well-developed population of secondary consumers at these sites, possibly connected with the limited extent of the subsurface biosphere in these high temperature sites. We conclude that in < 80°C springs, chemolithoautotrophic production supports heterotrophs capable of degrading a wide range of organic compounds that do not vary by geological province, even though the taxonomic and respiratory repertoire of chemolithoautotrophs and heterotrophs differ greatly across these regions.

The Icelandic mantle contains a range of lithologies associated with the depleted upper mantle, a mantle plume, and recycled oceanic lithosphere but the precise nature of depleted and enriched components in the mantle and their relative contributions to melt production remain poorly constrained. In this study, we collect new olivine- and plagioclase-hosted melt inclusion data and compile this with existing literature data to investigate the relative contributions from different mantle lithologies to basaltic magmas erupted in Icelandic flank zones and neovolcanic zones by modelling the melting of a heterogeneous mantle and subsequent mixing of derived melts. We find that observed melt inclusion compositions from off-axis flank zones are best explained as homogenized mixtures of pyroxenite- and lherzolite-derived melts produced at depths around 80-93 km, by which point lherzolite has only experienced a low degree of melting whereas the pyroxenite lithology has melted extensively. These melts represent the onset of channelization in the mantle and are transported rapidly to the surface without input from shallower melts. Melt compositions from the on-axis neovolcanic zones and off-axis Öræfajökull, are produced by mixing this deep melt component with higher degree lherzolite melts produced at shallower depths, between 57-93 km. Proportions of shallow lherzolite-derived melts and deep homogenized melt vary, but the lowest contribution from the deep homogenized melt is seen in the Northern Volcanic Zone. Ourresults support a model whereby deep melts mix until melt channelization starts in the mantle, after which binary mixing between the homogenized deep melt and shallower fractional melts occurs.

The episodic growth of high-elevation orogenic plateaux is controlled by a series of geodynamic processes. However, determining the underlying mechanisms that drive plateau growth dynamics over geological history and constraining the depths at which growth originates, remains challenging. Here we present He-CO2-N2 systematics of hydrothermal fluids that reveal the existence of a lithospheric-scale fault system in the southeastern Tibetan Plateau, whereby multi-stage plateau growth occurred in the geological past and continues to the present. He isotopes provide unambiguous evidence for the involvement of mantle-scale dynamics in lateral expansion and localized surface uplift of the Tibetan Plateau. The excellent correlation between 3He/4He values and strain rates, along the strike of Indian indentation into Asia, suggests non-uniform distribution of stresses between the plateau boundary and interior, which modulate southeastward growth of the Tibetan Plateau within the context of India-Asia convergence. Our results demonstrate that deeply-sourced volatile geochemistry can be used to constrain deep dynamic processes involved in orogenic plateau growth., Deeply-sourced volatiles are releasing from orogenic plateau regions, providing windows to plateau growth dynamics occurring at variable depths. Here the authors show that mantle-derived volatiles reveal the involvement of mantle dynamics in southeastward growth of the Tibetan Plateau.

The timescales of magmatic processes within a volcanic system may be variable over a volcano’s geological history. Crystals reflect environmental perturbations under which they grew, and compositional gradients quenched inside crystals on eruption can be exploited to extract timescales of magmatic processes. Here, we use multi-element diffusion chronometry in olivine macrocrysts to recover their residence time in a melt that ultimately erupted at the surface. The macrocrysts were mobilized by the carrier melt from mushy layers in the magma reservoir, and diffusion timescales likely reflect the time interval between mush disaggregation, ascent, and eruption. To unravel the evolution of mush disaggregation timescales with time, we target early-Holocene, middle-Holocene, and historical magmatic units erupted in the Bárðarbunga-Veiðivötn volcanic system in Iceland’s Eastern Volcanic Zone. Macrocryst contents vary between samples; early-Holocene samples are highly phyric (10–45 vol% macrocrysts) and contain gabbroic nodules, whereas middle-Holocene (5–15 vol%) and historical units (5–10 vol%) tend to be generally less phyric. Early-Holocene olivine macrocrysts have core compositions in the range Fo84–87, while middle-Holocene and historical samples record a wider range in core compositions from Fo80 to Fo86.5. Olivine rims are in chemical equilibrium with their carrier liquid and are slightly more evolved in early-Holocene units (Fo76–81) compared to middle-Holocene (Fo78–80) and historical (Fo81–83) units. Diffusion chronometry reveals that the timescale between mush dis-aggregation and eruption has changed over time, with timescales getting shorter approaching recent times. Early-Holocene olivine macrocrysts dominantly record Fe-Mg diffusion timescales between 200–400 days, while middle-Holocene and historical units typically record timescales of about 70 and 60 days, respectively. Barometric studies suggest that melts and crystals are likely stored and gradually transferred throughout an interconnected multi-tiered system that ultimately culminates in a mid-crustal reservoir(s) at about 6.8–7.5 ± 2.5 km depth, where final disaggregation by the carrier liquid took place. We argue that, as a result of extensional processes enhanced by rifting events, well-mixed melts got drawn into mid-crustal reservoir(s), causing crystal mush loosening and mobilization. In addition, we propose that more energy in the form of heat and/or melt supply was required in the early-Holocene to break up the dense mush fabric and convert it into an eruptible magma. Conversely, as evidenced by the diverse macrocryst content of the historical units and by the lack of gabbroic nodules, the system has become characterized by a less compact mush fabric since at least the middle-Holocene, such that fresh injection of melt would easily loosen and mobilize the mush, resulting in an eruption within a couple of months. This study provides evidence that along axial rift settings, rifting-related processes can help to “pull the mush apart” with no requirement for primitive magma injection as an eruption trigger. Furthermore, we provide evidence that in the Bárðarbunga-Veiðivötn volcanic system specifically, the time between mush disaggregation and eruption has decreased considerably with time, indicating shorter warning times before imminent eruptions.

Volatile elements (water, carbon, nitrogen, sulfur, halogens, and noble gases) played an essential role in the secular evolution of the solid Earth and emergence of life. Here we provide an overview of Earth's volatile inventories and describe the mechanisms by which volatiles are conveyed between Earth's surface and mantle reservoirs, via subduction and volcanism. Using literature data, we compute volatile concentration and flux estimates for Earth's major volatile reservoirs and provide an internally balanced assessment of modern global volatile recycling. Using a nitrogen isotope box model, we show that recycling of N (and possibly C and S) likely began before 2 Ga and that ingassing fluxes have remained roughly constant since this time. In contrast, our model indicates recycling of H2O(and most likely noble gases) was less efficient in the past. This suggests a decoupling of major volatile species during subduction through time, which we attribute to the evolving thermal regime of subduction zones and the different stabilities of the carrier phases hosting each volatile. ▪ This review provides an overview of Earth's volatile inventory and the mechanisms by which volatiles are transferred between Earth reservoirs via subduction. ▪ The review frames the current thinking regarding how Earth acquired its original volatile inventory and subsequently evolved through subduction processes and volcanism.

Mantle melting processes and the characteristics of the source lithologies are mostly derived from basalt compositions of the mid-ocean ridge system and from oceanic islands. However, these basalts are in most cases the products of crustal processes resulting from magma storage, mixing, differentiation and crustal interaction. In Iceland, magma mixing and homogenization in thoroughly stirred magma reservoirs appear to be the norm, leading to restricted variations of Sr and Nd isotope ratio for a given volcanic system. In contrast, more primitive basalts were erupted during the 2021 Fagradalsfjall eruption on the Reykjanes Peninsula with a large spread in isotope ratios. A strong negative correlation between Sr and Nd isotopes is observed from ratios that span a range from a depleted mantle composition to values akin to the Icelandic mantle such as that of the basalts of the Grímsvötn volcanic system. The isotope ratios are also correlated with the measured discharge rate during the eruption, with a depleted Sr isotope ratio appearing during the period of low discharge (around 5 m3/s) for the first month and a half of the eruption. In early May, the magma flux doubled and basalts with more radiogenic Sr isotope composition were produced. During the summer 2021, the Sr isotope ratios declined, due to lower proportions of melts from undepleted mantle source in the basalt mixture erupted. Whether the eruption ended when melts from the enriched mantle was exhausted or not remains to be elucidated, but clearly the highest eruption discharge rate resulted from melts of a more fertile mantle source.The variable proportions of depleted versus enriched melts in the eruption products demonstrate the absence of a magma reservoir in which homogenization could take place, and from which decreasing discharge rate with time would be expected. Instead, the initially low and steady and then increasing magma extrusion rate measured, strongly indicate direct mantle melt ascent to surface, which is also supported by the primitive mineralogy of the high-MgO basalt produced. Leaky-transform faults on the mid-ocean ridge system are characterized by eruptions of primitive basalts on intra-transform spreading centres (e.g. Garrett and Siqueiros fracture zones in the East Pacific). The Fagradalsfjall complex appears to be of similar nature, and the primitive magma and the important compositional and temporal variations demonstrate the effect of mantle source composition and associated processes on the eruption behaviour, as reflected in the magma discharge rate.

Recent Icelandic rifting events have illuminated the roles of centralized crustal magma reservoirs and lateral magma transport1–4, important characteristics of mid-ocean ridge magmatism1,5. A consequence of such shallow crustal processing of magmas4,5 is the overprinting of signatures that trace the origin, evolution and transport of melts in the uppermost mantle and lowermost crust6,7. Here we present unique insights into processes occurring in this zone from integrated petrologic and geochemical studies of the 2021 Fagradalsfjall eruption on the Reykjanes Peninsula in Iceland. Geochemical analyses of basalts erupted during the first 50 days of the eruption, combined with associated gas emissions, reveal direct sourcing from a near-Moho magma storage zone. Geochemical proxies, which signify different mantle compositions and melting conditions, changed at a rate unparalleled for individual basaltic eruptions globally. Initially, the erupted lava was dominated by melts sourced from the shallowest mantle but over the following three weeks became increasingly dominated by magmas generated at a greater depth. This exceptionally rapid trend in erupted compositions provides an unprecedented temporal record of magma mixing that filters the mantle signal, consistent with processing in near-Moho melt lenses containing 107–108 m3 of basaltic magma. Exposing previously inaccessible parts of this key magma processing zone to near-real-time investigations provides new insights into the timescales and operational mode of basaltic magma systems.

Global warming is increasing ocean temperatures, forcing marine organisms to respond to a suite of changing environmental conditions. The stable oxygen isotopic composition of otoliths is often used as an index of temperature exposure, but the accuracy of the resulting temperature reconstructions in wild, free-swimming Atlantic cod (Gadus morhua) has never been groundtruthed. Based on temperatures from data storage tags (DST) and corresponding salinity values, the stable oxygen isotope (δ18O) value was predicted for each month of tagging and compared with δ18Ootolith values measured in situ with secondary ion mass spectrometry (SIMS). Paired-sample Wilcoxon tests were applied to compare measured and predicted δ18O values. The difference between measured and predicted mean and maximum δ18Ootolith values was not significant, suggesting a good correspondence between SIMS-measured and DST-predicted δ18Ootolith values. However, SIMS-measured and predicted minimum δ18Ootolith values were significantly different (all samples: p < 0.01, coastal and frontal cod: p < 0.05), resulting in overestimation of maximum temperatures. Our results confirm that otoliths are well-suited as proxies for mean ambient temperature reconstructions. A possible matrix effect and the absence of a reliable aragonite standard for SIMS measurements appeared to cause a small divergence between measured and predicted δ18Ootolith values, which affected the estimation accuracy of absolute temperature. However, relative temperature changes were accurately estimated by SIMS-analyzed δ18Ootolith values.

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.

International audience; The element mercury (Hg) can develop large mass-independent fractionation (MIF) (Δ 199 Hg) due to photo-chemical reactions at Earth's surface. This results in globally negative Δ 199 Hg for terrestrial sub-aerially-derived materials and positive Δ 199 Hg for sub-aqueously-derived marine sediments. The mantle composition least affected by crustal recycling is estimated from high-3 He/ 4 He lavas from Samoa and Iceland, providing an average of Δ 199 Hg=0.00±0.10, Δ 201 Hg=-0.02±0.0.09, δ 202 Hg=-1.7±1.2; 2SD, N=11. By comparison, a HIMU-type lava from Tubuai exhibits positive Δ 199 Hg, consistent with altered oceanic crust in its mantle source. A Samoan (EM2) lava has negative Δ 199 Hg reflecting incorporation of continental crust materials into its source. Three Pitcairn lavas exhibit positive Δ 199 Hg which correlate with 87 Sr/ 86 Sr, consistent with variable proportions of continental (low Δ 199 Hg and high 87 Sr/ 86 Sr) and oceanic (high Δ 199 Hg and low 87 Sr/ 86 Sr) crustal material in their mantle sources. These observations indicate that MIF signatures offer a powerful tool for examining atmosphere-deep Earth interactions. Plain language summary: While Earth's mantle is continuously chemically and isotopically stirred by convection, some ocean island lavas preserve isotopic anomalies. Their most likely origin is the recycling of crustal material into Earth's mantle by subduction. A question is then whether these crustal materials originate from the ocean or the continents. By using mercury stable isotopic compositions, which have specific signatures in ocean and continent materials, we identify whether these anomalies are due to continental or oceanic crustal material in various ocean island basalts.

Carbon and other volatiles in the form of gases, fluids or mineral phases are transported from Earth's surface into the mantle at convergent margins, where the oceanic crust subducts beneath the continental crust. The efficiency of this transfer has profound implications for the nature and scale of geochemical heterogeneities in Earth's deep mantle and shallow crustal reservoirs, as well as Earth's oxidation state. However, the proportions of volatiles released from the forearc and backarc are not well constrained compared to fluxes from the volcanic arc front. Here we use helium and carbon isotope data from deeply sourced springs along two cross-arc transects to show that about 91 per cent of carbon released from the slab and mantle beneath the Costa Rican forearc is sequestered within the crust by calcite deposition. Around an additional three per cent is incorporated into the biomass through microbial chemolithoautotrophy, whereby microbes assimilate inorganic carbon into biomass. We estimate that between 1.2 × 108 and 1.3 × 1010 moles of carbon dioxide per year are released from the slab beneath the forearc, and thus up to about 19 per cent less carbon is being transferred into Earth's deep mantle than previously estimated.

Noble gas (He, Ne, Ar, Kr, Xe) compositions of mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) have been widely used to investigate the geochemical structure and evolution of Earth’s mantle. Many studies provide evidence for the existence of different mantle domains having distinctive chemical and noble gas signatures. Primordial mantle domains have isotopic signatures that have remained largely unmodified since the Earth’s formation, while recycled mantle domains have undergone extensive modification following chemical fractionation during melt extraction and magma degassing, mantle convection, and subduction recycling. Iceland represents a perfect natural laboratory to study the inventory of primordial and recycled noble gases within the mantle thanks to its particular location above a mid-ocean ridge and a mantle plume. In this hybrid setting, melts with a deep OIB-like mantle origin and with near-primordial mantle gas signatures interact and coexist with melts formed at shallower levels that exhibit MORB-like recycled mantle chemical characteristics. On Iceland, chemical and lithological mantle heterogeneities exist on both long and short length scales, and primordial and recycled noble gases signatures can both be present even in a single sample set. We investigated the spatial relationships between Iceland’s primordial and recycled mantle components by combining new high-precision noble gas (He, Ne, Ar, Kr, Xe) analyses of basaltic glass with a large existing dataset of noble gas data from subglacially erupted basalts collected across the Iceland. Here, we present noble gas data for the Western Volcanic Zone (WVZ), one of the most geologically interesting areas of Iceland. The data indicate a significant and consistent lateral variability in the noble gas signatures in relation to the distance from the plume centre. We discuss possible explanations for these variations, ways to improve our systematic understanding of mantle volatile distribution beneath Iceland, and outline future directions of this research.

Significance We report the discovery of anomalously high 3He/4He in “cold” geothermal fluids of central Panama, far from any active volcanoes. Combined with independent constraints from lava geochemistry, mantle source geochemical anomalies in Central America require a Galápagos plume contribution that is not derived from hotspot track recycling. Instead, these signals likely originate from large-scale transport of Galápagos plume material at sublithospheric depths. Mantle flow modeling and geophysical observations further indicate these geochemical anomalies could result from a Galápagos plume-influenced asthenospheric “mantle wind” that is actively “blowing” through a slab window beneath central Panama. The lateral transport of plume material represents a potentially widespread yet underappreciated mechanism that scatters enriched geochemical signatures in mantle domains far from plumes., It is well established that mantle plumes are the main conduits for upwelling geochemically enriched material from Earth's deep interior. The fashion and extent to which lateral flow processes at shallow depths may disperse enriched mantle material far (>1,000 km) from vertical plume conduits, however, remain poorly constrained. Here, we report He and C isotope data from 65 hydrothermal fluids from the southern Central America Margin (CAM) which reveal strikingly high 3He/4He (up to 8.9RA) in low-temperature (≤50 °C) geothermal springs of central Panama that are not associated with active volcanism. Following radiogenic correction, these data imply a mantle source 3He/4He >10.3RA (and potentially up to 26RA, similar to Galápagos hotspot lavas) markedly greater than the upper mantle range (8 ± 1RA). Lava geochemistry (Pb isotopes, Nb/U, and Ce/Pb) and geophysical constraints show that high 3He/4He values in central Panama are likely derived from the infiltration of a Galápagos plume–like mantle through a slab window that opened ∼8 Mya. Two potential transport mechanisms can explain the connection between the Galápagos plume and the slab window: 1) sublithospheric transport of Galápagos plume material channeled by lithosphere thinning along the Panama Fracture Zone or 2) active upwelling of Galápagos plume material blown by a “mantle wind” toward the CAM. We present a model of global mantle flow that supports the second mechanism, whereby most of the eastward transport of Galápagos plume material occurs in the shallow asthenosphere. These findings underscore the potential for lateral mantle flow to transport mantle geochemical heterogeneities thousands of kilometers away from plume conduits.

International audience; Nitrogen is the main constituent of the Earth's atmosphere, but its provenance in the Earth's mantle remains uncertain. The relative contribution of primordial nitrogen inherited during the Earth's accretion versus that subducted from the Earth's surface is unclear 1-6. Here we show that the mantle may have retained remnants of such primordial nitrogen. We use the rare 15 N 15 N isotopologue of N 2 as a new tracer of air contamination in volcanic gas effusions. By constraining air contamination in gases from Iceland, Eifel (Germany) and Yellowstone (USA), we derive estimates of mantle δ 15 N (the fractional difference in 15 N/ 14 N from air), N 2 / 36 Ar and N 2 / 3 He. Our results show that negative δ 15 N values observed in gases, previously regarded as indicating a mantle origin for nitrogen 7-10 , in fact represent dominantly air-derived N 2 that experienced 15 N/ 14 N fractionation in hydrothermal systems. Using two-component mixing models to correct for this effect, the 15 N 15 N data allow extrapolations that characterize mantle endmember δ 15 N, N 2 / 36 Ar and N 2 / 3 He values. We show that the Eifel region has slightly increased δ 15 N and N 2 / 36 Ar values relative to estimates for the convective mantle provided by mid-ocean-ridge basalts 11 , consistent with subducted nitrogen being added to the mantle source. In contrast, we find that whereas the Yellowstone plume has δ 15 N values substantially greater than that of the convective mantle, resembling surface components 12-15 , its N 2 / 36 Ar and N 2 / 3 He ratios are indistinguishable from those of the convective mantle. This observation raises the possibility that the plume hosts a primordial component. We provide a test of the subduction hypothesis with a two-box model, describing the evolution of mantle and surface nitrogen through geological time. We show that the effect of subduction on the deep nitrogen cycle may be less important than has been suggested by previous investigations. We propose instead that high mid-ocean-ridge basalt and plume δ 15 N values may both be dominantly primordial features. Differentiated bodies from our Solar System have rocky mantles with 15 N/ 14 N ratios within ±15‰ of modern terrestrial air 16,17. This is true for Earth's convective mantle, which has a δ 15 N value of approximately −5 ± 3‰, based on measurements from diamonds 5,18 and basalts that have been filtered for air contamination 3,11. Conversely, volatile-rich chondritic meteorites exhibit highly variable δ 15 N values between −20 ± 11‰ for enstatite chondrites and 48 ± 9‰ for CI carbonaceous chondrites 16,19. The distinct 15 N/ 14 N of rocky mantles relative to the chon-drites may reflect inheritance of N from a heterogeneous mixture of chondritic precursors 3. Alternatively, the relatively high 15 N/ 14 N values could be the result of evaporative losses 20 , or equilibrium partitioning of N isotopes between metal cores and rocky mantles 21,22. For Earth, plate tectonics allows for another interpretation 1. Geo-chemists have suggested that mantle δ 15 N values reflect subduction of nitrogen from the surface. Some of the evidence comes from studies of gases from mantle plumes. On Earth, mantle plumes with high 3 He/ 4 He ratios relative to mid-ocean-ridge basalts (MORBs) result from melting of relatively undegassed portions of the deep mantle 23. Nitrogen data are sparse, but plumes with both high and low 3 He/ 4 He values have δ 15 N values between 0 and +3‰ (refs. 2,4), higher than the values attributed to the convective mantle and similar to both sediments and altered oceanic crust (Extended Data Fig. 1) 12,13,15,24. One hypothesis is that the convective and deep mantle reservoirs both initially had identical but low enstatite chondrite-like δ 15 N values 6. Over geological time, these

Pre-print (óritrýnt handrit), Oceanic crust is a major transport medium of water into the mantle wedge and the convecting mantle. Yet, the water content of the oceanic crust remains uncertain. Active geothermal systems situated at on-land spreading centers provide a unique opportunity to study the hydration of the oceanic crust, with well constrained systems and boreholes reaching depths of >4 km. Here, we present hydrogen isotope data of geothermal fluids and altered basalt for three Icelandic geothermal systems: the meteoric water fed system at Krafla and the seawater fed systems at Reykjanes and Surtsey. The bulk rock δD values of altered and hydrated basalts from these localities, which exhibit significantly higher water contents (up to 8.9 wt.%) than magmatic (non-hydrated) basalts, vary greatly from −125 to −96 at Krafla, from −80 to −46 at Reykjanes and from −78 to −46 at Surtsey. The corresponding fluids have δD values of −84.1 to −81.1 at Krafla, −23.1 to −14.9 at Reykjanes and +2.1 to +4.3 at Surtsey. Comparison of isotope modeling results to the natural data reveals that hydration of the Icelandic crust and corresponding hydrogen isotopic characteristics are controlled by (1) the isotope composition of the source fluid, (2) isotope fractionation between the aqueous geothermal fluids and the alteration minerals formed, and (3) the type and quantity of alteration minerals formed. These factors in turn depend on the extent of fluid-rock interaction and temperature. Using the same modeling approach and expanding it to datasets available for the oceanic crust, we assessed the hydration state and δD values of the oceanic crust as a function of depth. We show that 1400 to 1650 Tg H2O/yr is added to the igneous oceanic crust upon alteration by seawater and that the upper part (, This project was financially supported by NordVulk, the International Continental Scientific Drilling Program (ICDP) through a grant to the SUSTAIN project, and the Icelandic Research Fund (project number: 163083-051). SAH acknowledges support from the Icelandic Research Fund (project number: 196139-051). HS Orka and Landsvirkjun kindly provided access to the drill cuttings. J. Cullen, T. Larson, R. Ólafsdóttir and Á.E. Sveinbjörnsdóttir are thanked for assistance during sample preparation and data acquisition. BIK is particularly grateful of being part of this project as without the project-related lab work she would have never met her future husband E.W. Marshall IV. We thank four anonymous reviewers for their constructive comments and suggestions to an earlier version of this manuscript. Louis Derry is thanked for careful editorial handling of this study.

Publisher's version (útgefin grein), Large volume effusive eruptions with relatively minor observed precursory signals are at odds with widely used models to interpret volcano deformation. Here we propose a new modelling framework that resolves this discrepancy by accounting for magma buoyancy, viscoelastic crustal properties, and sustained magma channels. At low magma accumulation rates, the stability of deep magma bodies is governed by the magma-host rock density contrast and the magma body thickness. During eruptions, inelastic processes including magma mush erosion and thermal effects, can form a sustained channel that supports magma flow, driven by the pressure difference between the magma body and surface vents. At failure onset, it may be difficult to forecast the final eruption volume; pressure in a magma body may drop well below the lithostatic load, create under-pressure and initiate a caldera collapse, despite only modest precursors., The research presented here has benefitted from extended visits of FS during a sabbatical term to, and discussion with scientists at, the University of Leeds, ISTerre University of Savoie Mont-Blanc, USGS Cascades Volcano Observatory, and Geological Survey of Japan. We acknowledge reviews by Philip Benson and Luca Caricchi that helped to significantly improve the paper, as well as reviews of an early version of the paper by two anonymous reviewers. Financial support from the H2020 project EUROVOLC funded by the European Commission is acknowledged (grant number 731070). F.S. acknowledges support from the University of Iceland Research Fund, and R.G. acknowledges partial support through NSF grant EAR-1464546. Fissure swarms, central volcanoes and caldera outlines shown in Fig. 1 are reproduced from publications referred to (refs. 42,76) with permissions from Elsevier, and we acknowledge the use of ArticDEM (ref. 77) to plot surface and ice topography shown in Fig. 1. COMET is the NERC Centre for the Observation and Modelling of Earthquakes, Volcanoes and Tectonics, a partnership between UK Universities and the British Geological Survey.

Rare high-(3)He/(4)He signatures in ocean island basalts (OIB) erupted at volcanic hotspots derive from deep-seated domains preserved in Earth’s interior. Only high-(3)He/(4)He OIB exhibit anomalous (182)W—an isotopic signature inherited during the earliest history of Earth—supporting an ancient origin of high (3)He/(4)He. However, it is not understood why some OIB host anomalous (182)W while others do not. We provide geochemical data for the highest-(3)He/(4)He lavas from Iceland (up to 42.9 times atmospheric) with anomalous (182)W and examine how Sr-Nd-Hf-Pb isotopic variations—useful for tracing subducted, recycled crust—relate to high (3)He/(4)He and anomalous (182)W. These data, together with data on global OIB, show that the highest-(3)He/(4)He and the largest-magnitude (182)W anomalies are found only in geochemically depleted mantle domains—with high (143)Nd/(144)Nd and low (206)Pb/(204)Pb—lacking strong signatures of recycled materials. In contrast, OIB with the strongest signatures associated with recycled materials have low (3)He/(4)He and lack anomalous (182)W. These observations provide important clues regarding the survival of the ancient He and W signatures in Earth’s mantle. We show that high-(3)He/(4)He mantle domains with anomalous (182)W have low W and (4)He concentrations compared to recycled materials and are therefore highly susceptible to being overprinted with low (3)He/(4)He and normal (not anomalous) (182)W characteristic of subducted crust. Thus, high (3)He/(4)He and anomalous (182)W are preserved exclusively in mantle domains least modified by recycled crust. This model places the long-term preservation of ancient high (3)He/(4)He and anomalous (182)W in the geodynamic context of crustal subduction and recycling and informs on survival of other early-formed heterogeneities in Earth’s interior.

The depth(s) of magma storage reservoirs beneath active volcanic regions may change with time. Determining the rates and causes of millennial-scale changes in magmatic system architecture is critical for the development of realistic time-integrated models of crustal evolution. Here we examine a suite of samples from the exceptionally well-exposed Bárðarbunga-Veiðivötn volcanic system in central Iceland in order to resolve the temporal evolution of magma storage conditions within one of Iceland’s most productive volcanic systems. We have measured the major and minor elemental composition of glass, mineral and melt inclusion from five erupted units that span a full glacial cycle, from a 500 μm), polymineralic clots and high-crystallinity nodules, consistent with derivation from crystal mush bodies. Macrocryst rims are in chemical equilibrium with their respective carrier melts, while macrocrysts cores are too primitive to have crystallized from these melts. Each sample records a distinct range of macrocryst compositions, indicating that the composition and/or eruptibility of stored crystal mush has changed with time. Macrocrysts from the oldest units are the most primitive, and the macrocryst compositional range becomes wider and, on average, more evolved, with time. Clinopyroxene-melt and melt-based (OPAM) geobarometers reveal temporally invariant crystallization conditions of 1.9–2.2 ± 0.7 (1σ) kbar pressure, corresponding to depths around 6.8–7.8 ± 2.5 km. All the samples also contain melt inclusions trapped at mid-crustal pressures of ∼2.6 kbar (9.6 km). In addition, melt inclusions hosted in most primitive olivines and plagioclases from subglacial and early Holocene eruptions preserve evidence of crystallization in a lower-crustal storage level(s) located at 17.5 km (4.9 kbar). This petrological record of deep crystallization may be linked to a surge in eruption rates, tapping of lower-crustal magma reservoirs, consistent with a crustal response associated with postglacial isostatic rebound. In contrast, the absence of a deep crystallization signature in the younger eruptive units may reflect lower magma production rates under steady-state conditions of the crust, and new magma pathways favouring melt storage in the mid-crust.

© 2019 Elsevier B.V. High-Fo olivine (Fo = Mg/(Mg+Fe) mol%) is an ideal proxy for establishing the compositions of primary melts and their mantle sources. This has been exploited in establishing lithological variations in the mantle source regions of oceanic basalts, including in Iceland. However, previous studies on Icelandic olivine lack spatial and temporal coverage. We present high-precision in-situ major, minor and trace element analyses of Fo-rich olivine from a suite of 53 primitive basalts erupted in the neovolcanic rift and flank zones of Iceland, as well as in older regions of Quaternary and Tertiary crust. Most of these samples have previously been analysed for 3He/4He, which ranges from 6.7 to 47.8 RA, the largest span reported for any oceanic island. By combining trace elemental variability with 3He/4He, we assess the extent of lithological variability in the Icelandic mantle plume. Trace-element ratios that are likely to preserve information about mantle source regions (e.g., Mn/Fe, Ni/(Mg/Fe), Ga/Sc, Zn/Fe and Mn/Zn) suggest a peridotitic mantle source in all rift-related volcanic regions, as well as in the off-rift flank zones of Öræfajökull and Snæfellsnes. However, a signal of a more pyroxenitic mantle lithology is clearly visible in olivine from the South Iceland Volcanic Zone, which represents the southward propagation of the Eastern Rift Zone, while olivine from Tertiary lavas suggests a mixed peridotite-pyroxenite source composition. We are able to identify four components present in the Icelandic mantle: a lithologically heterogeneous plume component with 3He/4He >MORB; a depleted MORB-like peridotite; an isotopically enriched MORB-like peridotite; and a peridotitic component with 3He/4He

Enriched mantle heterogeneities are widely considered to be generated through subduction, but the connections between specific subducted materials and the chemical signatures of mantle heterogeneities are not clearly defined. Boron is strongly isotopically fractionated at the surface and traces slab devolatilization, making it a potent tracer of previously subducted and recycled materials. Here, we present high-precision SIMS boron concentrations and isotope ratios on a comprehensive suite of quenched basaltic glasses from all neovolcanic zones in Iceland, two rhyolite glasses, and a set of primitive melt inclusions from central Iceland. Boron isotope ratios ( δ 11 B) in Icelandic basalts and melt inclusions range from −11.6‰ to −1.0‰, averaging −4.9‰, which is higher than mid-ocean ridge basalt (MORB; δ 11 B = − 7.1 ‰ ). Because the δ 11 B value of the Icelandic crust is low, the high δ 11 B compositions of the Icelandic lavas are not easily explained through crustal assimilation processes. Icelandic basalt glass and melt inclusion B/Ce and δ 11 B values correlate with trace element ratio indicators of the degree of mantle partial melting and mantle heterogeneity (e.g. Nb/Zr, La/Yb, Sm/Yb), which indicate that the boron systematics of basalts are controlled by mantle heterogeneity. Additionally, basalts with low B/Ce have high 206Pb/204Pb, further indicating mantle source control. These correlations can be used to deduce the boron systematics of the individual Icelandic mantle components. The enriched endmember within the Iceland mantle source has a high δ 11 B value and low B/Ce, consistent with the composition of “rehydrated” recycled oceanic crust. The depleted endmember comprises multiple distinct components with variable B/Ce, likely consisting of depleted MORB mantle and/or high 3He/4He mantle and two more minor depleted components that are consistent with recycled metasomatized mantle wedge and recycled slab gabbro. The compositions of these components place constraints on the devolatilization history of recycled oceanic crust. The high δ 11 B value and low B/Ce composition of the enriched component within the Iceland mantle source is inconsistent with a simple devolatilization process and suggests that the recycled oceanic crust component may have been isotopically overprinted by B-rich fluids derived from the underlying hydrated slab lithospheric mantle (i.e. “rehydration”). Further, the B/Ce and δ 11 B systematics of other OIBs can be used to constrain the devolatilization histories of recycled components on a global scale. Globally, most OIB B/Ce compositions suggest that recycled components have lost >99% of their boron, and their δ 11 B values suggest that rehydration may be a sporadic process, and not ubiquitous.

The distribution of helium isotope ratios (3He/4He) in Icelandic geothermal fluids, volcanic glasses and phyric lavas is investigated. Along with presenting a new helium isotope dataset using phyric lavas largely from off-rift regions, we compiled published data and constructed a database of all available helium isotope data from Iceland. The new dataset reveals an exceptionally high 3He/4He ratio from a phyric lava in NW-Iceland (47.5 RA, where RA is the 3He/4He ratio of air), which is among the highest values measured in any mantle-derived magma to date. Modifications of primary (i.e., mantle-derived) helium isotope ratios, due to additions of air-derived helium and He from radiogenic ingrowth, were evaluated and the database was filtered accordingly. The geographical information system ArcGIS (ESRI) was used to perform spatial analysis on the filtered database and the interpolation method, Natural Neighbor, was used to calculate representative helium isotope ratios for all parts of Iceland, including off-rift regions. The results show that helium isotope ratios for the whole of Iceland vary from 5.1 to 47.5 RA. However, this study allows for a fine-scale distinction to be made between individual rift segments and off-rift regions. The results clearly reveal that each rift zone has its own distinctive mean isotope signature: 12–17 RA in the Western Rift Zone, 8–11 RA in the Northern Rift Zone and 18–21 RA in the Eastern Rift Zone. Our isoscape map places new constraints on a previously inferred high-helium plateau region in central Iceland (Breddam et al., 2000). The plateau continues southward along the propagating Eastern Rift Zone and through to the South Iceland Seismic Zone and the Mid-Iceland belt. Its location coincides with many geological features, e.g., eruption rates, location of abandoned rift segments, seismic velocity and gravity anomalies. Such high helium isotope ratios have been associated with undegassed and primordial mantle sources that have been isolated in the lower mantle over Earth's history. Thus, high-helium domains throughout Iceland are interpreted to mark the loci of present and past plume conduits which help explain the considerable spatial variation in the sampling of a primordial mantle He component beneath the Iceland hotspot.

Carbon dioxide emissions from active subaerial volcanoes represent 20–50% of the annual global volcanic CO2 flux (Barry et al., 2014). Passive degassing of carbon from the flanks of volcanoes, and the associated accumulation of dissolved inorganic carbon (DIC) within nearby groundwater, also represents a potentially important, yet poorly constrained flux of carbon to the surface (Werner et al., 2019). Here we investigate sources and sinks of DIC in groundwaters in the Lassen Peak region of California. Specifically, we report and interpret the relative abundance and isotopic composition of helium (3He, 4He) and carbon (12C, 13C, 14C) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected 3He/4He values between 0.19 and 7.44 RA (where RA = air 3He/4He = 1.39 × 10−6), all in excess of the radiogenic production value (~0.05 RA), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (δ13C) vary between −12.6 and − 27.7‰ (vs. VPDB). Measured groundwater DIC/3He values fall in the range of 2.2 × 1010 to 1.1 × 1012. Using helium and carbon isotope data, we explore several conceptual models to estimate surface carbon contributions and to differentiate between DIC derived from soil CO2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use 14C to identify soil-derived DIC (assuming decadal-to-centennial groundwater ages and a soil CO2 14C activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent δ13C signature between −10.3 and − 59.3‰ (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/3He between 7.0 × 109 and 1.0 × 1012. These apparent δ13C and C/3He values are substantially isotopically lighter than and greater than canonical MORB values, respectively. We suggest that >95% of any external (non-soil-derived) DIC in groundwater must thus be non-mantle in origin (i.e., slab derived or assimilated organic carbon). We further investigate possible sources of external DIC to groundwater using two idealized conceptual approaches: a pure (unfractionated) source mixing model (after Sano and Marty, 1995) and a scenario that invokes fractionation due to calcite precipitation. Because the former model requires carbon contributions from an organic source component with unrealistically low δ13C (~ − 60‰), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial 14C activity. Thus, we cannot rule out the possibility that the true fraction of non-surface-derived DIC in these samples is lower or negligible, despite the pervasive mantle-derived He isotope signatures throughout the region. Following the 14C approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to ~2.2 × 106 kg/yr, which is lower than previous magmatic carbon flux estimates from the Lassen region ( Rose and Davisson, 1996 ). We find that the passive dissolved carbon flux could represent a maximum of ~4–18% of the total Lassen geothermal CO2 degassing flux (estimated to be ~3.5 × 107 kg/yr Rose and Davisson, 1996 ; Gerlach et al., 2008 ), which is still more than an order of magnitude smaller than soil gas CO2 flux estimates (7.3–11 × 107 kg/yr) for nearby volcanoes ( Sorey et al., 1998 ; Gerlach et al., 1999 ; Evans et al., 2002 ; Werner et al., 2014 ). We conclude that passive dissolved carbon fluxes should be combined with geothermal fluxes and soil gas fluxes to obtain a complete picture of volcanic carbon emissions globally. Our approach highlights the utility of measuring helium isotopes in concert with the full suite of noble gas abundances, tritium, δ13C and 14C, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.

Because of extensive volcanic production in Iceland during the Holocene, many of the early postglacial large-volume fissure lavas cannot be unambiguously traced to their eruptive craters solely by observations in the field. For example, the Bárðarbunga volcanic system has been suggested as a likely source of the large Holocene lava flows found in Bárðardalur valley, but this idea mainly relies on petrographic observations. We conducted a chemical and isotopic study of the lavas in Bárðardalur. For comparative purposes, we also targeted basement rocks of the Bárðarbunga central volcano, as well as several eruptive units in the region north of Vatnajökull. Based on a comparison of chemical and radiogenic isotope data of lavas from the Bárðardalur region and the eruptive units north of Vatnajökull and the Bárðarbunga central volcano, it appears most likely that the lavas of Bárðardalur valley belong to the Bárðarbunga volcanic system. These new data, and a compiled dataset for other selected volcanic systems of the NRZ, shed light on possible limitations when assigning erupted material to its source volcano by means of chemical composition. Furthermore, this study demonstrates that our understanding of the relative importance of the different processes at play during the petrogenesis of Icelandic basalts is likely to be greatly improved by multi-parameter datasets for geologically well-characterized eruptive units.

Publisher's version (útgefin grein)., Studies of short-lived radiogenic isotope systems and noble gas isotopic compositions of plume-derived rocks suggest the existence of primordial domains in Earth's present-day mantle. Tungsten-182 anomalies together with high 3He/4He in Phanerozoic rocks from large igneous provinces and ocean island basalts demonstrate the preservation of early-formed (within the first 60 Ma of solar system history) mantle domains tapped by modern mantle plumes. It has proven difficult to link the evidence for primordial domains with geochemical evidence for more recent processes, such as recycling. The Greenland-Iceland plume system, starting with eruptions of the Paleocene North Atlantic Igneous Province, is later manifested in the mid-Miocene to modern volcanic products of Iceland. Here, we report Pb isotopic compositions, μ182W (deviations in 182W/184W of a sample from a laboratory reference standard in parts per million), and 3He/4He, as well as highly siderophile element concentrations and Re-Os isotopic systematics of basaltic samples erupted at different times during the ~60 Ma history of the Greenland-Iceland plume. Paleocene samples from Greenland, representing the early stage of the mantle plume, are characterized by variable 3He/4He ranging from 7 to 48 R/RA (measured 3He/4He normalized to the atmospheric ratio) and an average μ182W of −4.0 ± 3.6 (2SD), within modern upper mantle-like values of 0 ± 4.5. The basalts from Iceland can be divided into two groups based on their Pb isotope compositions. One group, consisting mostly of Miocene basalts, is characterized by 206Pb/204Pb ranging from ~18.4 to 18.5, 3He/4He ranging from 17.8 to 40.2 R/RA, and μ182W values ranging from +1.7 to −9.1 ± 4.5. The other group, consisting mainly of Pleistocene and Holocene basalts, is characterized by higher 206Pb/204Pb, ranging from ~18.7 to 19.2, 3He/4He ranging from 7.9 to 25.7 R/RA, and μ182W values ranging from −0.6 to −11.7 ± 4.5. Collectively, the Greenland-Iceland suite examined requires mixing between a minimum of three mantle source domains characterized by distinct Pb-He-W isotopic compositions, in order to account for this range of isotopic data. The temporal changes in the isotopic data for these rocks appear to track the dominant contributing plume components as the system evolved. One of the domains is indistinguishable from the ambient upper oceanic mantle and contributed substantial material throughout the time progression. The other two domains are most likely primordial reservoirs that underwent limited de-gassing. Given the negative μ182W values in some rocks, one of these domains likely formed within the first 60 Ma of solar system history and is a major contributor to the youngest basalts. The isotopic characteristics of Greenland-Iceland plume-derived rocks reveal episodic changes in the source component proportions., This study was supported by NSF grant EAR-1624587 (to RJW and AMP). AMP acknowledges FWF grant V659-N29 . MJ acknowledges NSF grant EAR-1624840 , and MK acknowledges OCE-1259218 . We would like to thank Lotte M. Larsen and Asger K. Pedersen for providing the West Greenland samples, and Bernard Marty for the samples from East Greenland. We thank Catherine Chauvel for the editorial handling and Rita Parai, Dominique Weis, David Graham and an anonymous reviewer for the helpful and constructive comments on this and an earlier version of the manuscript.

Author(s): Willhite, Lori Nicole | Advisor(s): Jackson, Matthew G | Abstract: The Icelandic hotspot has erupted the highest terrestrial mantle-derived 3He/4He over a period spanning much of the Cenozoic, from the early-Cenozoic Baffin Island-West Greenland flood basalt province (49.8 RA), to the mid-Miocene lavas in northwest Iceland (40.2 to 47.5 RA), to Pleistocene lavas in Iceland’s neovolcanic zone (34.3 RA). This study provides a detailed geochemical data set—He-O-Sr-Nd-Hf-Pb isotopic compositions, as well as whole rock major and trace element concentrations—for a suite of 18 Baffin Island lavas. The Baffin Island lavas transited through and potentially assimilated variable degrees of Precambrian continental basement. We therefore use geochemical indicators sensitive to continental crust assimilation (whole rock Nb/Th, Ce/Pb, MgO) to identify the least crustally-contaminated lavas in the suite. Four lavas, identified as “least crustally-contaminated”, have high MgO (g15 wt.%) and Nb/Th and Ce/Pb ratios that fall within the mantle range (Nb/Th=15.6±2.6, Ce/Pb=24.3±4.3). These four lavas have 3He/4He up to 39.9 RA and mantle-like δ18O of 5.03 to 5.21‰, 87Sr/86Sr = 0.703008–0.703021, 143Nd/144Nd = 0.513094–0.513128, 176Hf/177Hf = 0.283265–0.283284, 206Pb/204Pb = 17.7560–17.9375, and are located on or near the 4.5 Ga Pb isotope geochron. The radiogenic isotopic compositions of the least crustally-contaminated Baffin Island lavas are offset to more geochemically depleted compositions compared to high-3He/4He lavas from Iceland, a shift that cannot be explained by continental crust assimilation in the Baffin suite. While Sr-Nd-Pb isotopic heterogeneity among high-3He/4He localities has been previously observed, this is an important observation of geochemically distinct high-3He/4He endmembers within a single hotspot. Additionally, the least crustally-contaminated primary melts from Baffin Island-West Greenland have higher mantle potential temperatures (1510 to 1630 °C) than global MORB primary magmas located far from hotspots (1320 to 1480 °C), which supports a hot, buoyant plume origin for these early Iceland plume lavas. These observations support the contention that the geochemically heterogeneous high-3He/4He domain is dense, located in the deep mantle, and sampled by only the hottest plumes.

Geothermal systems are complex environments where geochemical signatures are controlled by the influx of deep mantle fluids as well as near-surface processes that result from the high temperatures. Noble gas isotope ratios (e.g. 3He/4He, 20Ne/22Ne) are well-established tracers of deep mantle fluid provenance, and elemental fractionation of atmosphere-derived isotopes is widely used for tracing shallow processes such as solubility-dependent phase partitioning in groundwater and hydrocarbon fluids. Utilisation of these tracers for the latter purpose has been limited in geothermal systems, where they could be further extended to consider boiling and/or steam condensation. Here we report new noble gas isotope and abundance data for 21 vapour phase geothermal fluid samples collected from geothermal boreholes and naturally degassing fumaroles in Iceland. The samples were collected from active parts of the neovolcanic rift zone and include several key high-temperature geothermal localities of the Northern Rift Zone (NRZ), the Western Rift Zone (WRZ) and the Mid-Iceland Belt (MIB). Helium isotope ratios are MORB-like in the NRZ, whilst samples from the WRZ show values in excess of MORB, up to 15.9 Ra. Neon isotopes plot close to the air value, but may show a small plume mantle contribution. Argon isotopes show distinct mantle-derived 40Ar excesses (40Ar/36Ar up to 361.2), which to our knowledge are the largest measured anomalies in free geothermal fluids from Iceland. The atmosphere-derived noble gas signatures (20Ne, 36Ar, 84Kr) are consistent with high-temperature vapour-liquid phase partitioning. Atmosphere-derived xenon (130Xe) on the other hand is not consistent with the observations from the other atmosphere-derived noble gases, suggesting an additional complexity that likely relates to its unique sorption and bonding behaviour. We show that the abundance of 20Ne, 36Ar, 84Kr in the vapour phase is temperature-dependent, presenting a promising technique that can be used to estimate the temperature at which partitioning occurs in the subsurface. Using multiple noble gas species allows the effects of secondary atmospheric contamination to be corrected when using this method. We predict partitioning temperatures of 229 to 345 °C for the samples measured here, consistent with temperatures predicted using conventional geothermometers. The inert nature of the noble gases means that the technique presented here is not reliant on many of the assumptions that underpin conventional geothermometers. We suggest that this technique represents a novel and powerful geochemical tool to investigate the thermal properties of geothermal systems.

The chlorine isotope composition of Earth’s interior can place strong constraints on deep-Earth cycling of halogens and the origin of mantle chemical heterogeneity. However, all mantle-derived volcanic samples studied for Cl isotopes thus far originate from submarine volcanic systems, where the influence of seawater-derived Cl is pervasive. Here, we present Cl isotope data from subglacial volcanic glasses from Iceland, where the mid-ocean ridge system emerges above sea level and is free of seawater influence. The Iceland data display significant variability in δ 37 Cl values, from −1.8‰ to +1.4‰, and are devoid of regional controls. The absence of correlations between Cl and O isotope ratios and the lack of evidence for seawater-derived enrichments in Cl indicate that the variation in δ 37 Cl values in Icelandic basalts can be solely attributed to mantle heterogeneity. Indeed, positive correlations are evident between δ 37 Cl values and incompatible trace element ratios (e.g., La/Y), and long-lived radiogenic Pb isotope ratios. The data are consistent with the incorporation of altered lithosphere, including the uppermost sedimentary package, subducted into the Iceland mantle plume source, resulting in notable halogen enrichments in Icelandic basalts relative to lavas from adjacent mid-ocean ridges.

We report new nitrogen (N 2 ) abundance and isotope (δ 15 N) data for 43 subglacial basaltic glasses from the neovolcanic zones of Iceland, a key locality in studies of mantle plume geochemistry and crust–mantle processes. New helium and argon abundance and isotope data are also reported to supplement previous studies ( Furi et al., 2010 , Barry et al., 2014 ), allowing elemental ratios (e.g., N 2 / 40 Ar ∗ where 40 Ar ∗ = radiogenic 40 Ar) to be calculated. Subglacial basaltic glasses with N 2 > 2 μcm 3 STP/g show a wide range in δ 15 N values, from −2.91 to +11.96‰ (vs. Air), with values >6‰ only observed at one locality in the Eastern Rift Zone. Elemental ratios involving N 2 , i.e., N 2 / 3 He, and N 2 / 40 Ar ∗ , span several orders of magnitude from 2.5 × 10 5 to 9.0 × 10 7 , and 32.8 to 1.46 × 10 6 , respectively. In contrast, argon isotope ratios ( 40 Ar/ 36 Ar) are limited, ranging from air-like (∼298.6) values up to 1330. Glasses exhibit a wide range in helium isotope ratios (8–26 R A ), with clear distinctions between individual rift segments. A number of processes have extensively modified original mantle source N isotope and relative abundance compositions – most significantly air interaction, crustal contamination in some instances, and possibly degassing-induced fractionation. Under the assumption that the starting 4 He/ 40 Ar ∗ production ratio of Iceland mantle is identical to the depleted MORB mantle (DMM), a filtering protocol for the entire N dataset, based upon 40 Ar/ 36 Ar and 4 He/ 40 Ar ∗ ratios, was adopted to identify samples with unmodified δ 15 N values. Consequently, we identify 22 samples that define the Icelandic mantle N-isotope distribution (δ 15 N = −2.29 to +5.71‰). Using the filtered dataset, we investigate simple binary mixing scenarios involving N 2 / 3 He–N 2 / 40 Ar ∗ –δ 15 N variations to identify mantle end-member compositions. Mixing scenarios are consistent with a recycled component in the Iceland mantle source, defined by a high and heterogeneous δ 15 N end-member. Moreover, this end-member is coupled to the high 3 He/ 4 He signature, and is characterized by He depletion and/or the presence of excess N 2 . These features strongly suggest the presence of recycled crustal N-component(s) integrated into and/or entrained by the Iceland plume source. These new results reveal the highly heterogeneous nature of nitrogen in the hybrid Iceland plume source, consistent with models based on trace elements and radiogenic isotopes that advocate for significant heterogeneity of recycled crustal component(s) sampled by the Iceland plume. A relatively young age of the recycled crustal material (possibly Phanerozoic) is consistent with the association of positive δ 15 N values and high N 2 / 40 Ar ∗ ratios with constraints from radiogenic isotopes (e.g., Pb), thus indicating a relatively short time-interval (∼10 8 years) between subduction of crustal material and entrainment by the Iceland mantle plume.

Quartz formation processes in the Icelandic crust were assessed using coupled δ18O and δ30Si systematics of silica deposits formed over a wide temperature range (550 °C). Magmatic quartz reveals δ18O (-5.6 to +6.6 ‰) and δ30Si (-0.4 ± 0.2 ‰) values representative of mantle- and crustally-derived melts in Iceland. Hydrothermal quartz and silica polymorphs display a larger range of δ18O (-9.3 to +30.1 ‰) and δ30Si (-4.6 to +0.7 ‰) values. Isotope modelling reveals that such large variations are consistent with variable water sources and equilibrium isotope fractionation between fluids and quartz associated with secondary processes occurring in the crust, including fluid-rock interaction, boiling and cooling. In context of published δ18O and δ30Si data on hydrothermal silica deposits, we demonstrate that large ranges in δ30Si values coupled to insignificant δ18O variations may result from silica precipitation in a hydrothermal fluid conduit associated with near-surface cooling. While equilibrium isotope fractionation between fluids and quartz seems to prevail at high temperatures, kinetic fractionation likely influences isotope systematics at low temperatures., This project was financially supported by NordVulk and Landsvirkjun.

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

Volcanic systems represent a fundamental component of the neovolcanic zones in Iceland. They are composed of a central volcano and a fissure swarm, or a combination of the two. The 2014–2015 rifting event at the Bárðarbunga volcanic system produced basaltic lava approximately 40 km to the north of the central volcano, within a fissure swarm commonly attributed to the Askja volcanic system, highlighting the complex tectonic structure of a region, directly above the Iceland mantle plume. New analyses of Sr- and Nd-isotope ratios from the new lava (Holuhraun), and the underlying older Holuhraun lava, show that they have identical values to those of the Bárðarbunga-Veiðivötn lavas and tephra erupted during the Holocene. Moreover, comparison with published high-precision radiogenic isotope data, reveals that Holocene lavas and tephra from the Bárðarbunga and Askja systems are characterized by contrasting Sr- and Nd-isotope ratios, with the notable exception of the Þjórsárhraun lava and two early Holocene lavas from the extreme west and east of the Veiðivötn fissure swarm. The $^{87}$Sr/$^{86}$Sr and $^{143}$Nd/$^{144}$Nd isotope ratios can thus be utilized to define the provenance of lava flows north of the Vatnajökull ice cap, ascertaining that the large lava fields of Krepputunguhraun and Fjallsendahraun (Frambruni) must also have originated within the Bárðarbunga volcanic system.

The effusive six months long 2014-2015 Barðarbunga eruption (31 August-27 February) was the largest in Iceland for more than 200 years, producing 1.6 ± 0.3 km3 of lava. The total SO2 emission was 11 ± 5 Mt, more than the amount emitted from Europe in 2011. The ground level concentration of SO2 exceeded the 350 μg m−3 hourly average health limit over much of Iceland for days to weeks. Anomalously high SO2 concentrations were also measured at several locations in Europe in September. The lowest pH of fresh snowmelt at the eruption site was 3.3, and 3.2 in precipitation 105 km away from the source. Elevated dissolved H2SO4, HCl, HF, and metal concentrations were measured in snow and precipitation. Environmental pressures from the eruption and impacts on populated areas were reduced by its remoteness, timing, and the weather. The anticipated primary environmental pressure is on the surface waters, soils, and vegetation of Iceland.

Thermal fluids in Iceland range in temperature from < 10 °C to > 440 °C and are dominated by water (> 97 mol%) with a chloride concentration from < 10 ppm to > 20,000 ppm. The isotope systematics of the fluids reveal many important features of the source(s) and transport properties of volatiles at this divergent plate boundary. Studies spanning over four decades have revealed a large range of values for δD (− 131 to + 3.3‰), tritium (− 0.4 to + 13.8 TU), δ¹⁸O (− 20.8 to + 2.3‰),³He/⁴He (3.1 to 30.4 R[subscript A]), δ¹¹B (− 6.7 to + 25.0‰), δ¹³C[subscript ∑ CO₂](− 27.4 to + 4.6‰), ¹⁴C[subscript ∑ CO₂](+ 0.6 to + 118 pMC), δ¹³C[subscript CH₄](− 52.3 to − 17.8‰), δ¹⁵N (− 10.5 to + 3.0‰), δ³⁴S[subscript ∑ S− II] (− 10.9 to + 3.4‰), δ³⁴S[subscript SO₄](− 2.0 to + 21.2‰) and δ³⁷Cl (− 1.0 to + 2.1‰) in both liquid and vapor phases. Based on this isotopic dataset, the thermal waters originate from meteoric inputs and/or seawater. For other volatiles, degassing of mantle-derived melts contributes to He, CO₂ and possibly also to Cl in the fluids. Water-basalt interaction also contributes to CO₂ and is the major source of H₂S, SO₄, Cl and B in the fluids. Redox reactions additionally influence the composition of the fluids, for example, oxidation of H₂S to SO₄ and reduction of CO₂ to CH₄. Air-water interaction mainly controls N2, Ar and Ne concentrations. The large range of many non-reactive volatile isotope ratios, such as δ³⁷Cl and ³He/⁴He, indicate heterogeneity of the mantle and mantle-derived melts beneath Iceland. In contrast, the large range of many reactive isotopes, such as δ¹³C[subscript ∑ CO₂] and δ³⁴S[subscript ∑ S− II], are heavily affected by processes occurring within the geothermal systems, including fluid-rock interaction, depressurization boiling, and isotopic fractionation between secondary minerals and the aqueous and vapor species. Variations due to these geothermal processes may exceed differences observed among various crust and mantle sources, highlighting the importance and effects of chemical reactions on the isotope systematics of reactive elements. Keywords: Iceland; Isotopes; Thermal fluids; Volatiles

Publisher's version (útgefin grein), The 2014–2015 Holuhraun eruption, on the Bárðarbunga volcanic system in central Iceland, was one of the best-monitored basaltic fissure eruptions that has ever occurred, and presents a unique opportunity to link petrological and geochemical data with geophysical observations during a major rifting episode. We present major and trace element analyses of melt inclusions and matrix glasses from a suite of ten samples collected over the course of the Holuhraun eruption. The diversity of trace element ratios such as La/Yb in Holuhraun melt inclusions reveals that the magma evolved via concurrent mixing and crystallization of diverse primary melts in the mid-crust. Using olivine–plagioclase–augite–melt (OPAM) barometry, we calculate that the Holuhraun carrier melt equilibrated at 2.1±0.7 kbar (7.5±2.5 km), which is in agreement with the depths of earthquakes (6±1 km) between Bárðarbunga central volcano and the eruption site in the days preceding eruption onset. Using the same approach, melt inclusions equilibrated at pressures between 0.5 and 8.0 kbar, with the most probable pressure being 3.2 kbar. Diffusion chronometry reveals minimum residence timescales of 1–12 days for melt inclusionbearing macrocrysts in the Holuhraun carrier melt. By combining timescales of diffusive dehydration of melt inclusions with the calculated pressure of H2O saturation for the Holuhraun magma, we calculate indicative magma ascent rates of 0.12–0.29 m s−1. Our petrological and geochemical data are consistent with lateral magma transport from Bárðarbunga volcano to the eruption site in a shallow- to mid-crustal dyke, as has been suggested on the basis of seismic and geodetic datasets. This result is a significant step forward in reconciling petrological and geophysical interpretations of magma transport during volcano-tectonic episodes, and provides a critical framework for the interpretation of premonitory seismic and geodetic data in volcanically active regions., This work was supported by Natural Environment Research Council grants [NE/M021130/1] and [IMF548/1114]. DAN acknowledges support from the Alexander von Humboldt Foundation.