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At mid-ocean ridges (MORs), seawater carrying dissolved sulfate (SO4) infiltrates the oceanic crust. Hydrothermal fluid emissions from such systems have much lower δ34S and sulfur is mostly present as reduced sulfide, albeit in lower total sulfur concentrations than in seawater. This has been explained by anhydrite formation and sulfate reduction based on petrographic evidence and mass balance considerations. Here, we utilize the chemical and stable isotope (δ34S, δ18O) systematics in natural anhydrite and pyrite from various locations along the submarine and on-land section of the Mid-Atlantic ridge near Iceland to quantify the key variables that control anhydrite formation and sulfate recycling in the oceanic crust. Hydrothermal anhydrite exhibited δ34S values of +20.6 ± 1.0‰ and δ18O values between +2.4 to +25.3‰. Volcanogenic anhydrite in encrustations showed δ34S values of −1.7 to +21.4‰ and δ18O values between +1.4 and +38.0‰. Hydrothermal pyrite exhibited δ34S values ranging from +3.4 and +19.7‰. Comparison of the natural dataset with results from geochemical isotope modelling revealed that δ34S and δ18O values of anhydrite and pyrite were dependent on the isotope composition of the source fluid, extent of water–rock interaction, temperature, and redox conditions. Departures of δ34S and δ18O values in anhydrite from the source fluid were caused by progressive fluid-basalt interaction where lower δ34S and δ18O values reflected a change in sources of S and O from solely fluid to basaltic origin. The δ18O values of anhydrite were additionally affected by temperature. Quantitative formation of anhydrite mainly occurred at temperatures < 150 °C, whereas at elevated temperatures (>200 °C) reduction of seawater-sulfate to H2S and subsequent pyrite precipitation were found to limit anhydrite formation. Extending our calculations to the oceanic crust revealed that the majority of seawater-sulfate is sequestered into anhydrite (3–38 Tg S yr−1) in vicinity of MORs at < 200 °C at shallow depth (

Publisher's version, Supercritical fluids exist in the roots of many active high-temperature geothermal systems. Utilization of such supercritical resources may multiply energy production from geothermal systems; yet, their occurrence, formation mechanism, and chemical properties are poorly constrained. Flow-through experiments at 260°C and 400-420°C were performed to study the chemical and mineralogical changes associated with supercritical fluid formation near shallow magmatic intrusions by conductive heating and boiling of conventional subcritical geothermal fluids. Supercritical fluids formed by isobaric heating of liquid geothermal water had similar volatile element concentrations (B, C, and S) as the subcritical water. In contrast, mineral-forming element concentrations (Si, Na, K, Ca, Mg, and Cl) in the supercritical fluid were much lower. The results are consistent with the observed mineral deposition of quartz, aluminum silicates, and minor amount of salts during boiling. Similar concentration patterns have been predicted from geochemical modeling and were observed at Krafla, Iceland, for the IDDP-1 supercritical fluid discharge. The experimental results confirm previous findings that supercritical fluids may originate from conductive heating of subcritical geothermal reservoir fluids characterized by similar or lower elemental concentrations with minor input of volcanic gas., We would like to thank Ríkey Kjartansdóttir, Andri Ísak Thórhallsson, and Helgi Arnar Alfreðsson for their valuable help. This work was funded by the Swiss National Science Foundation (CRSII2_1418431/1, Sinergia COTHERM), Georg (11-04-003), and The Energy Research Fund of Landsvirkjun in 2018 and 2019.

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.

In this study we show that mineralogy was the primary control of metamorphic fluid flow in the well-studied metabasaltic sills in the SW Scottish Highlands. Here, basaltic sills have been partially carbonated by H2O–CO2 fluids at greenschist facies conditions. This has led to mineral zonation with carbonate-poor sill interiors separated from carbonate-rich sill margins by reaction fronts. Although deformation set the stage for metamorphic fluid flow in the SW Scottish Highlands by causing the preferred alignment of mineral grains, metamorphic fluid flow was not coupled with active deformation but occurred later utilizing the pre-existing mineral alignment as a means of accessing the sill interiors. The sills which were studied were partially carbonated with well-preserved reaction fronts. They were selected because (atypically for the SW Scottish Highlands) they are mineralogically heterogeneous making them ideal for a study of mineralogical controls of metamorphic fluid flow. Their mineralogical heterogeneity reflects chemical heterogeneity arising from magmatic flow differentiation and spilitization, which occurred before greenschist facies metamorphism. Magmatic flow differentiation resulted in parts of the sill containing large crystals with no preferred alignment. Large (up to 3 cm) plagioclase phenocrysts were concentrated in the sill interior whereas large (up to 1 cm) amphibole (after pyroxene) grains formed cumulate layers close to the sill margins. These large randomly oriented crystals were replaced by an interface-coupled dissolution–precipitation mechanism. Replacement is constant volume and with hydration and carbonation affecting the cores of these minerals while the rims are remained intact and unaltered. This finding points to intra-granular metamorphic fluid flow. In contrast inter-granular metamorphic fluid flow was facilitated by mineral alignment on different scales. Pre-metamorphic spilitization, produced layers of epidote called segregations, whereas regional deformation caused preferred alignment mainly of amphibole and chlorite. Epidote undergoes a series of volume changes during greenschist facies metamorphism. This created porosity which produced preferred pathways for metamorphic fluids affecting the advancement of fluid-driven reaction fronts. Preferred alignment of amphibole and chlorite also affected the advancement of reaction fronts. In this case, fluid flow was preferentially parallel to the foliation. In both cases, inter-granular metamorphic fluid flow utilized a pre-existing fabric albeit on different scales. These results show intra-granular metamorphic fluid flow in unfoliated rock and inter-granular metamorphic fluid flow in foliated rock. In both cases metamorphic fluid flow occurred after deformation controlled by pre-existing mineralogical heterogeneities, such as grain composition and shape anisotropy as well as preferred alignment of mineral grains.

Pre-print (óritrýnt handrit), Surtsey is a young volcanic island in the offshore extension of Iceland's southeast rift zone that grew from the seafloor during explosive and effusive eruptions in 1963–1967. In 1979, a cored borehole (SE-1) was drilled to 181 m depth and in 2017 three cored boreholes (SE-2a, SE-2b and SE-3) were drilled to successively greater depths. The basaltic deposits host a low-temperature (40–141 °C) seawater-dominated geothermal system. Surtsey provides an ideal environment to study water-rock interaction processes in a young seawater geothermal system. Elemental concentrations (SiO2, B, Na, Ca, Mg, F, dissolved inorganic carbon, SO4, Cl) and isotope contents (δD, δ18O) in borehole fluids indicate that associated geothermal waters in submarine deposits originated from seawater modified by reactions with the surrounding basalt. These processes produce authigenic minerals in the basaltic lapilli tuff and a corresponding depletion of certain elements in the residual waters. Coupling of measured and modelled concentrations investigates the effect of temperature and associated abundance of authigenic minerals on chemical fluxes from and to the igneous oceanic crust during low-temperature alteration. The annual chemical fluxes calculated at 50–150 °C range from −0.01 to +0.1×1012 mol yr−1 for SiO2, +0.2 to +129×1012 mol yr−1 for Ca, −129 to −0.8×1012 mol yr−1 for Mg and −21 to +0.4 × 1012 mol yr−1 for SO4 where negative values indicate chemical fluxes from the ocean into the oceanic crust and positive values indicate fluxes from the oceanic crust to the oceans. These flux calculations reveal that water-rock interaction at varying water-rock ratios and temperatures produces authigenic minerals that serve as important sinks of seawater-derived SiO2, Mg and SO4. In contrast, water rock interaction accompanied by dissolution of basaltic glass and primary crystal fragments provides a significant source of Ca. Such low-temperature alteration could effectively influence the elemental budget of the oceanic igneous crust and ocean waters. The modeling provides insights into water chemistries and chemical fluxes in low temperature MOR recharge zones. Surtsey also provides a valuable young analogue for assessing the chemical evolution of fluid discharge over the life cycles of seamounts in ridge flank systems., Funding for this project was provided by the University of Iceland Recruitment fund, the International Continental Scientific Drilling Program (ICDP) through a grant to the SUSTAIN project, the Icelandic Science Fund, ICF-RANNÍS, the Bergen Research Foundation and K.G. Jebsen Centre for Deep Sea Research at University of Bergen, Norway, the German Research Foundation (DFG), and DiSTAR, Federico II, University of Naples, Federico II, Italy. The University of Utah, USA and the two Icelandic power companies Reykjavík Energy and Landsvirkjun, contributed additional funds. The authors would like to thank P. Bergsten, A.M. di Stefano, C.F. Gorny, J. Gunnarsson-Robin, G.H. Guðfinsson, Þ. Högnadóttir, E.W. Marshall, R. Ólafssdóttir, D.B. Ragnarsson and Þ.M. Þorbjarnardóttir for their contribution and assistance during sampling, sample preparation, analyses and data evaluation. The authors would like to thank M. E. Böttcher for careful editorial handling. Two anonymous reviewers and J. Alt are thanked for their thoughtful and valuable reviews.

Supercritical fluids with temperatures of ~400–500 °C have been reported from several active geothermal fields worldwide. Although the utilization of such fluids may multiply power production from new and already exploited geothermal systems, the fluid origin and chemical controls on their composition remain unclear. We performed flow-through high-temperature (400–420 °C) experiments at 34–69 bar to study the chemical and mineralogical changes associated with supercritical fluid formation upon boiling of subcritical geothermal fluids of varying chemical composition. Based on geochemical modeling and laboratory results, we propose that an important mechanism of supercritical fluid formation is conductive heating and boiling of subcritical geothermal groundwater by a magmatic intrusion. Such supercritical fluids will display low concentrations of mineral-forming elements (Si, Na, K, Ca, Mg, Al), with their concentrations being controlled by the solubility of salts, oxides, and aluminum silicates in high-temperature (>400 °C) and low-density (ρ

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.

This thesis aims to provide a better understanding of the role of mountain building in the carbon cycle. The amount of CO2 released into the atmosphere due to metamorphic processes is largely unknown. To constrain the quantity of CO2 released, fluid-driven reactions in metamorphic rocks can be studied by tracking fluid-rock interactions along ancient fluid flow pathways. The thesis is divided into two parts: 1) modeling of fluid flow rates and durations within shear zones and fractures during greenschist- and blueschist-facies metamorphism and 2) the assessment of possible mechanisms of fluid infiltration into rocks during greenschist- to epidote-amphibolite-facies metamorphism and controlling chemical and mineralogical factors of reaction front propagation.On the island Syros, Greece, fluid-rock interaction was examined along a shear zone and within brittle fractures to calculate fluid flux rates, flow velocities and durations. Petrological, geochemical and thermodynamic evidence show that the flux of CO2-bearing fluids along the shear zone was 100-2000 times larger than the fluid flux in the surrounding rocks. The time-averaged fluid flow velocity and flow duration along brittle fractures was calculated by using a governing equation for one-dimensional transport (advection and diffusion) and field-based parameterization. This study shows that fluid flow along fractures on Syros was rapid and short lived.Mechanisms and controlling factors of fluid infiltration were studied in greenschist- to epidote-amphibolite-facies metabasalts in SW Scotland. Fluid infiltration into metabasaltic sills was unassisted by deformation and occurred along grain boundaries of hydrous minerals (e.g. amphibole) while other minerals (e.g. quartz) prevent fluid infiltration. Petrological, mineralogical and chemical studies of the sills show that the availability of reactant minerals and mechanical factors, e.g. volume change in epidote, are primary controls of reaction front propagation.

Analysis of the delta O-18 and delta C-13 values of carbonate rocks from Islay, Scotland reveals structural channelling of metamorphic fluids through the axial region of a major en echelon anticlinal fold system. Metamorphic fluid flow produced axial planar veins with higher vein density in the axial region of the fold. Fluid: rock ratios were more than 30: 1 within this axial region, at least four times greater than the regional mean ratio of 7.6 +/- 1.5:1 for carbonate rocks on Islay. This supports the interpretation that metamorphic fluids were channelled through the axial region of the Islay Anticline. Fluid: rock ratios were calculated using a model for coupled delta O-18 and delta C-13 exchange with a metamorphic fluid. The metamorphic fluid was calculated to have delta O-18 and delta C-13 values of 15.3 parts per thousand and -6.1 parts per thousand, respectively and X-CO2 of 0.2. This is in isotopic and chemical equilibrium with chlorite- and graphite-bearing metamudstones that are structurally below the folded metacarbonate rocks on Islay. Devolatilization of these metamudstones is therefore a likely source mechanism for this metamorphic fluid. Removal of the effects of metamorphic fluid flow on delta C-13 values recorded by metacarbonate rocks on Islay allows us to re-evaluate evidence used to reconstruct Neoproterozoic climate. This evidence includes a large negative delta C-13 excursion reported from the Lossit Limestone Formation. This unit underlies the Port Askaig Formation, which is dominated by diamictites that have been interpreted as glacial tillites. This 'Islay anomaly' has been correlated with other such anomalies worldwide and together with overlying tillites has been cited as evidence of major (worldwide) glaciation events. In this study, we show that the magnitude of this negative delta C-13 anomaly can partly be explained by exchange with metamorphic fluids. However, we also show that extremely negative delta C-13 values in the Bonahaven Dolomite Formation, which overlies the Port Askaig Formation and has been interpreted as a 'cap carbonate', cannot be attributed to metamorphic fluid flow.

In this study we investigate a group of metabasaltic sills from the SW Scottish Highlands metamorphosed at epidote-amphibolite facies conditions that provide useful insight into the mechanisms and characteristics of fluid infiltration during metamorphism. The sills are amphibole and garnet bearing and exhibit a strong foliation in the sill margins that developed pre- to syn-peak metamorphism. Fluid infiltration caused hydration and carbonation in the sills, expressed as (1) replacement of garnet and amphibole by chlorite and calcite and (2) replacement of amphibole and epidote to form chlorite and calcite. Using garnet-amphibole and garnet-chlorite geothermometers we show that these reactions occurred after peak metamorphism at T = 290 to 400 °C. Reaction textures show that the fluid infiltration into the sill that caused hydration and carbonation occurred in the absence of deformation. The fluid infiltration was mineralogically controlled with greater fluid access in areas of abundant fine-grained elongate minerals such as amphibole and chlorite. The replacement of garnet by chlorite most likely occurred by an interface-coupled dissolution-precipitation mechanism as evidenced by perfect pseudomorphic textures of garnet, porosity generation behind the reactive interface and fracturing ahead of this interface. Porosity generated in the product chlorite enhanced fluid access to the replacement front. The study shows that deformation was not required for extensive fluid infiltration and alteration during metamorphism. Fluid flow uses a pre-existing foliation to gain access to the rock, taking advantage of the anisotropic shape of the aligned minerals.

Two types of blue halo (types I and II) composed of blueschist-facies minerals are centered around a brittle, normal shear zone in greenschist-facies rocks on the island of Syros, Aegean Sea, Greece. The shear zone is steeply dipping and cuts a near-horizontal layer of greenschist-facies rocks (albite + epidote + actinolite + chlorite + quartz). Type I and II blue haloes are 0·3 m and c. 1 m wide respectively, and are seen on both sides of the shear zone. The inner type I haloes are composed of nearly pure glaucophane schist and were formed by metasomatic addition of Na2O and SiO2, and to a lesser extent of K2O and large ion lithophile elements (LILE), coupled with loss of CaO, Al2O3 and MnO. The outer type II haloes consist of a carbonated blueschist-facies assemblage (glaucophane + calcite + phengite + epidote + garnet + quartz). These experienced only slight metasomatic changes (i.e. addition of K2O and LILE), which cannot alone explain halo formation. We present petrological, geochemical and thermodynamic evidence that this assemblage was preserved at greenschist-facies conditions because XCO2 was elevated by flow of a CO2-bearing fluid along the shear zone, which was approximately contemporaneous with greenschist-facies hydration in the surrounding rocks. We further note that the flux of CO2-bearing fluid along the shear zone was rapid with respect to the fluid flux in the surrounding rocks. Mass-balance calculations reveal that the fluid flux within the shear zone was at least 100–2000 times greater than the fluid flux within the surrounding rocks. Mineral textures show greenschist-facies minerals replacing blueschist minerals in the type II haloes, supporting our interpretation that the blueschist-facies minerals were preserved during greenschist-facies retrogression. A simplified P–T vs XCO2 pseudosection confirms that preservation of carbonated blueschist can occur at greenschist-facies conditions in the presence of a CO2-bearing fluid.