Description: Presented is an example of the transport-reaction code (TRACTION) applied to the simulation of pore water species in the seawater mixing zone at Mercator Mud volcano in the Gulf of Cadiz. TRACTION was specifically designed to account for non-ideal transport effects in the presence of thermodynamic (e.g. salinity or temperature) gradients. The model relies on the most fundamental concept of solute diffusion, which states that the chemical potential gradient (Maxwell's model) rather than the concentration gradient (Fick's law) is the driving force for diffusion. In turn, this requires accounting for species interactions by applying Pitzer's method to derive species chemical potentials and Onsager coefficients instead of using the classical diffusion coefficients. Electrical imbalances arising from varying diffusive fluxes in multicomponent systems, like seawater, are avoided by applying an electrostatic gradient as an additional transport contribution.

Description: This dataset comprises porosity data from undisturbed reference sites sampled by a multiple corer (MUC) and disturbed push-cores (PUC), which were retrieved using the ROV Kiel 6000 (GEOMAR) during RV SONNE expedition SO239 in 2015. During this cruise, different European contract areas for the exploration of polymetallic nodules in the area of the Clarion-Clipperton Zone (CCZ) were visited (BGR, IOM, GSR, IFREMER), which are currently being explored in light of potential future deep-sea mining. The PUCs were taken in several small-scale disturbance tracks, which were created 1 day to 37 years before sampling for the simulation of deep-sea mining activities in the different exploration areas. The sampled disturbance tracks include 1-day- and 3-year-old EBS tracks (created with an Epibenthic sledge), 8-months- and 37-year-old dredge tracks, and a 20-year-old track from the Benthic Impact Experiment in the IOM area (IOM-BIE). The dataset was produces in the laboratories of the Alfred Wegener Institute (AWI) Bremerhaven, Germany.

Description: This dataset comprises solid-phase total organic carbon contents (TOC) and bulk sediment manganese contents from disturbed push-cores (PUC), which were retrieved using the ROV Kiel 6000 (GEOMAR) during RV SONNE expedition SO239 in 2015. During this cruise, different European contract areas for the exploration of polymetallic nodules in the area of the Clarion-Clipperton Zone (CCZ) were visited (BGR, IOM, GSR, IFREMER), which are currently being explored in light of potential future deep-sea mining. The PUCs were taken in several small-scale disturbance tracks, which were created 1 day to 37 years before sampling for the simulation of deep-sea mining activities in the different exploration areas. The sampled disturbance tracks include 1-day- and 3-year-old EBS tracks (created with an Epibenthic sledge), 8-months- and 37-year-old dredge tracks, and a 20-year-old track from the Benthic Impact Experiment in the IOM area (IOM-BIE). The dataset was produces in the laboratories of the Alfred Wegener Institute (AWI) Bremerhaven, Germany.

Description: Takahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well-defined subsurface seismic chimney structure ca. 80,500 m2 in area. Sub-seafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction-transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m−2 yr−1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m−2 yr−1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m−2 yr−1, respectively). A seep-wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation and benthic dissolved methane fluxes of 3.68 × 104 mol yr−1, 73.85 × 104 mol yr−1and 1.19 × 104 mol yr−1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.

Description: Mid-Oceanic ridge hydrothermal systems are in general significantly enriched in Ca due to leaching from the oceanic basement (albitization of anorthite), while Mg and SO4 are quantitatively removed by Mg-rich smectite and anhydrite formation respectively. During Meteor expedition 141 in September 2017 we sampled, close to a volcanic outcrop in the Terceira Rift (Azores, Central North Atlantic Ocean), pore fluids with a significantly different composition compared to typical Mid-Oceanic hydrothermal systems. Pore water Mg, SO4, and total alkalinity (TA) concentrations are significantly higher compared to seawater and a nearby reference core, while Ca concentrations stay at low values. The most straightforward way of interpreting the observed deviations is the dissolution of the prior hydrothermally formed high temperature (〉 240°C) mineral caminite (MgSO4·0.25Mg(OH)2·0.2H2O). This interpretation is corroborated by a thorough investigation of fluid isotope systems (δ26Mg, δ30Si, δ34S, δ44/42Ca, and 87Sr/86Sr). Caminite is known from mineral assemblages with e.g. anhydrite and forms only under specific conditions such as high fluid temperatures and in altered oceanic crust with only little fresh basaltic glass present, which are generally met in the Terceira Rift. To date, no signs of extensive caminite formation and/or dissolution have been reported, caminite has only been once described before in the nature by Haymon and Kastner (1986). Our study is the first indication of an abundant occurrence of caminite. The results imply that element recycling through caminite might play a presently unrecognized role in element budgets of hydrothermal systems. Haymon, R. M., and Kastner, M., 1986, Caminite; a new magnesium-hydroxide-sulfate-hydrate mineral found in a submarine hydrothermal deposit, East Pacific Rise, 21 degrees N: American Mineralogist, v. 71, no. 5-6, p. 819-825.

Description: We present a transport-reaction model (TRACTION) specifically designed to account for non-ideal transport effects in the presence of thermodynamic (e.g. salinity or temperature) gradients. The model relies on the most fundamental concept of solute diffusion, which states that the chemical potential gradient (Maxwell’s model) rather than the concentration gradient (Fick’s law) is the driving force for diffusion. In turn, this requires accounting for species interactions by applying Pitzer’s method to derive species chemical potentials and Onsager coefficients instead of using the classical diffusion coefficients. Electrical imbalances arising from varying diffusive fluxes in multicomponent systems, like seawater, are avoided by applying an electrostatic gradient as an additional transport contribution. We apply the model to pore water data derived from the seawater mixing zone at the submarine Mercator mud volcano in the Gulf of Cadiz. Two features are particularly striking at this site: (i) Ascending halite-saturated fluids create strong salinity (NaCl) gradients in the seawater mixing zone that result in marked chemical activity, and thus chemical potential gradients. The model predicts strong transport-driven deviations from the mixing profile derived from the commonly used Fick’s diffusion model, and is capable of matching well with the profile shapes observed in the pore water concentration data. Even better agreement to the observed data is achieved when ion pairs are transported separately. (ii) The formation of authigenic gypsum (several wt%) occurs in the surface sediments, which is typically restricted to evaporitic surface processes. Very little is known about the gypsum paragenesis in the subseafloor and we first present possible controls on gypsum solubility, such as pressure, temperature, and salinity (pTS), as well as the common ion and ion pairing effects. Due to leaching of deep diapiric salt, rising fluids of the MMV are saturated with respect to gypsum (as well as celestite and barite). Several processes that could drive these fluids towards gypsum supersaturation and hence precipitation were postulated and numerically quantified. In line with the varied morphology of the observed gypsum crystals, gypsum paragenesis at the MMV is likely a combination of two temperature-related processes. Gypsum solubility increases with increasing temperature, especially in strong electrolyte solutions and the first mechanism involves the cooling of saturated fluids along the geothermal gradient during their ascent. Secondly, local temperature changes, i.e. cooling during the transition from MMV activity towards dormancy results in the cyclic build-up of gypsum. The model showed that the interpretation of field data can be majorly misguided when ignoring non-ideal effects in extreme diagenetic settings. While at first glance the pore water profiles at the Mercator mud volcano would indicate strong reactive influences in the seawater mixing zone, our model shows that the observed species distributions are in fact primarily transport-controlled. The model results for SO4 are particularly intriguing, as SO4 is shown to diffuse into the sediment along its increasing (!) concentration gradient. Also, a pronounced gypsum saturation peak can be observed in the seawater mixing zone. This peak is not related to the dissolution of gypsum but is simply a result of the non-ideal transport forces acting on the activity profile of SO4 and Ca profiles.

Description: During R/V Meteor cruise 141/1, pore fluids of near surface sediments were investigated to find indications for hydrothermal activity in the Terceira Rift (TR), a hyper‐slow spreading center in the Central North Atlantic Ocean. To date, submarine hydrothermal fluid venting in the TR has only been reported for the D. João de Castro seamount, which presently seems to be inactive. Pore fluids sampled close to a volcanic cone at 2800 m water depth show an anomalous composition with Mg, SO4, and total alkalinity (TA) concentrations significantly higher than seawater and a nearby reference core. The most straightforward way of interpreting these deviations is the dissolution of the hydrothermally formed mineral caminite (MgSO4 0.25Mg(OH)2 0.2H2O). This interpretation is corroborated by a thorough investigation of fluid isotope systems (δ26Mg, δ30Si, δ34S, δ44/42Ca, and 87Sr/86Sr). Caminite is known from mineral assemblages with anhydrite, and forms in hydrothermal recharge zones only under specific conditions such as high fluid temperatures and in altered oceanic crust, which are conditions generally met at the TR. We hypothesize that caminite was formed during hydrothermal activity and is now dissolving during the waning state of the hydrothermal system, so that caminite mineralization is shifted out of its stability zone. Ongoing fluid circulation through the basement is transporting the geochemical signal via slow advection towards the seafloor.

Description: Typical Mid-Oceanic ridge hydrothermal systems are in general significantly enriched in Ca due to leaching from the magmatic basement (albitization of anorthite), while Mg and SO4 are quantitatively removed because of Mgrich smectite and anhydrite formation and further processes. In the Terceira Rift (TR), a hyper-slow spreading center in the Central North Atlantic Ocean, hydrothermal fluid venting is known to occur only at shallow intertidal water depths around the volcanogenic Azores Archipelago. Here, we show for the first time that hydrothermal fluid venting is active in the eastern TR at water depths of 2800 m. Pore fluids of a sediment core taken close to a volcanic cone, however, show that the fluid composition is significantly different from typical Mid-Oceanic hydrothermal systems. Pore water Mg, SO4, and total alkalinity (TA) concentrations are significantly higher compared to seawater and a nearby reference core. The most straightforward way of interpreting these excursions is the re-dissolution of the metastable mineral caminite (MgSO4 0.4Mg(OH)2 0.2H2O). Caminite is known from mineral assemblages with e.g. anhydrite and forms only under specific conditions such as high fluid temperatures and in altered oceanic crust with only few fresh basaltic glass present, which are generally met at the TR. Isotope measurements of �34S, �26Mg, 87Sr/86Sr, �88=86Sr, �44=42Ca and �30Si provide additional evidence for caminite as a source for Mg, SO4 and TA. The redissolution of the caminite is interpreted as a sign of cooling temperatures, which may indicate a waning state of the hydrothermal system. To date, no signs of extensive caminite formation and/or dissolution have been reported. Our study implies that element recycling through caminite might play a presently unrecognized role in element budgets of hydrothermal systems.

Description: One of the world‘s biggest manganese nodule fields on Earth is found in the Clarion-Clipperton Fracture Zone (CCZ) in the NE Pacific Ocean at 4-5 km water depth. Commercial deep-sea mining activities will affect the deep-sea environment1. We assess the recovery state of controlled anthropogenic disturbances within the CCZ which were created between 1 day and up to 37 years prior to sampling. Here, we present pore-water and solid-phase data of the upper 20 cm of sediment of disturbed sites in comparison with adjacent undisturbed reference sites. We focus on the impact of anthropogenic disturbances on the geochemical conditions of the sediments.