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The Menez Gwen, Lucky Strike, Rainbow, TAG (Transatlantic Geotraverse) and Snake Pit hydrothermal vent fields on the Mid-Atlantic Ridge were revisited and resampled for geochemical investigation during the BIOBAZ 2013 and BICOSE 2014 research cruises. Geochemical analysis of the major and minor elements of the hydrothermal fluid and concentrations of gases extends and complements the existing dataset. Our results are consistent with values previously reported and fall within the range of the analytical error. This indicates that the hydrothermal vent field system has remained relatively stable over the last few decades. However, some differences were observed and (i) suggested a recent eruption at Menez Gwen, (ii) supported the occurrence of low-temperature serpentinisation in this same site, (iii) supported a change in the reaction zone or axial magma chamber (AMC) depth at Lucky Strike, (iv) an increase of the temperature at depth at Snake Pit and (v) supported the hypothesis of large seawater entrainment through the TAG hydrothermal mound. Besides, it is possible that small temporal and spatial scale processes may control a significant part of the geochemistry, owing to the fact that some variations in the data could not be interpreted. However, our investigation of the organic geochemistry represents a pioneering addition to research for Menez Gwen, Snake Pit and TAG and a much more comprehensive study for Lucky Strike and Rainbow. Concentrations for a wide variety of semi volatile organic compounds (SVOCs) were obtained for the first time at all sites. Our results showed that a great part of the total organic carbon (TOC) could not be allocated by the total SVOCs studied here, suggesting that other processes/sources of organic carbon remain to be identified. The TAG organic geochemistry seemed entirely based on thermogenic processes whereas mixed processes may occur at the other vent field. The presence of n-alkanes suggested the contribution of a low-temperatu

Understanding the dynamics and fate of methane (CH4) release from oceanic seepages on margins and shelves into the water column, and quantifying the budget of its total discharge at different spatial and temporal scales, currently represents a major scientific undertaking. Previous works on the fate of methane escaping from the seafloor underlined the challenge in both, estimating its concentration distribution and identifying gradients. In April 2019, the Envri Methane Cruise has been conducted onboard the R/V Mare Nigrum in the Western Black Sea to investigate two shallow methane seep sites at ∼120 m and ∼55 m water depth. Dissolved CH4 measurements were conducted with two continuous in-situ sensors: a membrane inlet laser spectrometer (MILS) and a commercial methane sensor (METS) from Franatech GmbH. Additionally, discrete water samples were collected from CTD-Rosette deployment and standard laboratory methane analysis was performed by gas chromatography coupled with either purge-and-trap or headspace techniques. The resulting vertical profiles (from both in situ and discrete water sample measurements) of dissolved methane concentration follow an expected exponential dissolution function at both sites. At the deeper site, high dissolved methane concentrations are detected up to ∼45 m from the seabed, while at the sea surface dissolved methane was in equilibrium with the atmospheric concentration. At the shallower site, sea surface CH4 concentrations were four times higher than the expected equilibrium value. Our results seem to support that methane may be transferred from the sea to the atmosphere, depending on local water depths. In accordance with previous studies, the shallower the water, the more likely is a sea-to-atmosphere transport of methane. High spatial resolution surface data also support this hypothesis. Well localized methane enriched waters were found near the surface at both sites, but their locations appear to be decoupled with the ones of the se

Pore water and sediment geochemistry in the western Black Sea were investigated on long Calypso piston core samples. Using this type of coring device facilitates the recovery of the thick sediment record necessary to analyze transport-reaction processes in response to the postglacial sea-level rise and intrusion of Mediterranean salt water 9 ka ago, and thus, to better characterize key biogeochemical processes and process changes in response to the shift from lacustrine to marine bottom water composition. Complementary data indicate that organic matter degradation occurs in the upper 15 m of the sediment column. However, sulfate reduction coupled with Anaerobic Methane Oxidation (AOM) is the dominant electron-accepting process and characterized by a shallow Sulfate Methane Transition Zone (SMTZ). Net silica dissolution, total alkalinity (TA) maxima and carbonate peaks are found at shallow depths. Pore water profiles clearly show the uptake of K+, Mg2+ and Na + by, and release of Ca2+ and Sr2+ from the heterogeneous lacustrine sediments, which is likely controlled by chemical reactions of silicate minerals and changes in clay mineral composition. Iron (Fe2+) and manganese (Mn2+) maxima largely coincide with Ca2+ peaks and suggest a close link between Fe2+, Mn2+ and Ca2+ release. We hypothesize that the Fe2+ maxima below the SMTZ result from deep Fe3+ reduction linked to organic matter degradation, either driven by DOC escaping from the shallow sulfate reduction zone or slow degradation of recalcitrant POC. The chemical analysis of dissolved and solid iron species indicates that iron is essentially associated with clay minerals, which suggests that microbial iron reduction is influenced by clay mineral composition and bioavailability of clay mineral-bound Fe(III). Overall, our study suggests that postglacial seawater intrusion plays a major role in shaping redox zonation and geochemical profiles in the lacustrine sediments of the Late Quaternary.

Hydrothermal vents are a recognized source of trace elements to the ocean inventory. Nevertheless, the contribution of slow-spreading ridges remains poorly resolved. To address this, high-resolution dissolved (<0.45 μm) iron (dFe) and manganese (dMn) samples were collected during the GEOTRACES HERMINE GApr07 process study at the Mid Atlantic Ridge. Samples were collected at nine stations, from the TAG vent site to 75 km south-southwest following the neutrally buoyant plume. Concentrations of dMn and dFe ranged from 71 ± 6 and 51 ± 2 nmol kg–1 right above the vent site to 0.43 ± 0.01 and 1.56 ± 0.02 nmol kg–1 at the most distal station, respectively. Using a 5-box model coupled with our data, we show that as the plume traveled away from the vent, aggregation processes controlled dFe concentrations in the first 2 km, with an aggregation rate averaging between 8.0 ± 0.6 and 0.11 ± 0.04 nmol L–1 d–1, respectively in the first and second kilometer. Aggregation, likely of small colloidal particles, led to partitioning of the size fractionated Fe pool, as 6% of the dFe was moved into the particulate size fraction. Further away, disaggregation processes became more prevalent, with rates ranging from 0.27 ± 0.02 to 0.008 ± 0.001 nmol L–1 d–1, enriching the dFe pool by 10%. The computed decrease of hydrothermal Fe within the neutrally buoyant plume was likely caused by flocculation of small Fe oxyhydroxide particles. This process resulted in Fe aggregate formation with radii estimated to range between 14 and 20 μm in the first km from TAG. Between 2 and 30 km from the vent site, the radii ranged between 2 and 4 μm.

Environmental sciences are expanding and are based on standardized and certified calibrations when measurements are required. When a gaseous composition is quantified, commercial standards are used. Here, we report on a two-component device for the preparation and injection of gas mixtures at the appropriate levels of pressure and volume. The two-component calibrator/injector can be used simultaneously or separately depending on the experimental objective but their combination is extremely effective for injecting gas mixtures at low concentrations. The quantity of gas introduced into a gas chromatograph with the injector can be adapted to the sensitivity of the detector or to avoid column overload. The calibrator provides for a large range of gas-mixture concentrations, from ppm to % mol/mol with an error of preparation of around 1% and an accuracy of less than 3%. This device prepares a variety of gas mixtures (hydrogen, methane and dioxide of carbon) which are compared with certified mixtures by means of gas chromatographic measurements. The results show good agreement between prepared and certified mixtures with a maximum difference of 2% which remains within the relative error of commercial stanard. In addition, the preparation of dissolved methane at different concentrations in seawater is presented as a direct application of the calibrator.

The study area is located at the transition between the northern end of the Tonga Trench and the North Fiji fracture zone, where tectonic movements are reputed to be the fastest in the world. To the southeast of Futuna Island, a broad area of volcanism occurs within a region characterized by a change in the tectonic fabric between a NE-SW oriented volcanic graben and the N-S oriented Alofi ridge. In 2010, the active volcano Kulo Lasi, which represents the most recent volcanic episode in the Futuna area, was discovered in the center of this extensive volcanic zone. Kulo Lasi is a 20 km diameter shield volcano that rises 400 m above the seafloor. It is composed of basaltic to trachy-andesitic lava with no obvious geochemical affinity with the Tonga subduction that occurs 500 km to the east. The central caldera is 5 km in diameter and 300 m deep and is located at a water depth of 1500 m. Diving operations with the submersible Nautile and high-resolution AUV mapping, have revealed the presence of numerous active and inactive hydrothermal fields on the floor and the walls of the caldera. Four tectono-volcanic stages can be distinguished at Kulo Lasi caldera. In stage 1, the shield volcano is built. Annular reverse faults develop at the summit and control circulation of water/rock-dominated hydrothermal fluids and high-temperature alteration of rocks along the nascent normal faults. Mixing of hydrothermal fluids with seawater is favored along normal superficial faults, leading to the formation of low-temperature Fe/Mn mineralization at the summit of the volcano. During stage 2, the caldera collapse, gradually revealing outcrops of the altered and mineralized zones formed during Stage 1. As the magma chamber cools and collapses, less heat is available. As a result, medium to low-temperature (<100 °C) Fe/Si deposits form on the floor of the caldera. In stage 3, refilling and ascent of the magma chamber at depth promote the uplift of a central resurgent dome devoid of recent

In this preliminary study, we investigate living (stained) foraminifera from the Sea of Marmara. We focus on the faunal composition and geochemical signatures (trace elements, carbon and oxygen stable isotopes) in foraminiferal tests at two deep-sea sites (329 and ~1240 m depth respectively). Documented by ROV observations and sampling, both study areas are heterogeneous (including bacterial mats and carbonate concretions), proximal to cold seeps and consist of dysoxic bottom water (O2<20 µmol/L). The prevailing dysoxia at both study areas restricts foraminiferal diversity to very low values (S<9, H’<0.97). Stress-tolerant species Bolivina vadescens and Globobulimina affinis dominate living faunas at both sites. The highest foraminiferal standing stock is recorded at the shallowest site underneath a spreading bacterial mat. No benthic foraminifera from either site possess geochemical signatures of methane seepage. Our biogeochemical results show that use of foraminiferal Mn/Ca ratios as a proxy for bottom water oxygenation depends strongly on regional physiography, sedimentary processes and water column structure.

“Headspace” technique is one of the methods for the onboard measurement of hydrogen (H2) and methane (CH4) in deep seawater. Based on the principle of an automatic headspace commercial sampler, a specific device has been developed to automatically inject gas samples from 300 ml syringes (gas phase in equilibrium with seawater). As valves, micro pump, oven and detector are independent, a gas chromatograph is not necessary allowing a reduction of the weight and dimensions of the analytical system. The different steps from seawater sampling to gas injection are described. Accuracy of the method is checked by a comparison with the “purge and trap” technique. The detection limit is estimated to 0.3 nM for hydrogen and 0.1 nM for methane which is close to the background value in deep seawater. It is also shown that this system can be used to analyze other gases such as Nitrogen (N2), carbon monoxide (CO), carbon dioxide (CO2) and light hydrocarbons.

The study area is close to the Wallis and Futuna Islands in the French EEZ. It exists on the western boundary of the fastest tectonic area in the world at the junction of the Lau and North-Fiji basins. At this place, the unstable back-arc accommodates the plate motion in three ways: (i) the north Fiji transform fault, (ii) numerous unstable spreading ridges, and (iii) large areas of recent volcanic activity. This instability creates bountiful opportunity for hydrothermal discharge to occur. Based on geochemical (CH4, TDM, 3He) and geophysical (nephelometry) tracer surveys: (1) no hydrothermal activity could be found on the Futuna Spreading Center (FSC) which sets the western limit of hydrothermal activity; (2) four distinct hydrothermal active areas were identified: Kulo Lasi Caldera, Amanaki Volcano, Fatu Kapa and Tasi Tulo areas; (3) extensive and diverse hydrothermal manifestations were observed and especially a 2D distribution of the sources. At Kulo Lasi, our data and especially tracer ratios (CH4/3He ~ 50×106 and CH4/TDM ~ 4.5) reveal a transient CH4 input, with elevated levels of CH4 measured in 2010, that had vanished in 2011 (Futuna 2), most likely caused by an eruptive magmatic event. By contrast at Amanaki, vertical tracer profiles and tracer ratios point to typical seawater / basalt interactions. Fatu Kapa is characterized by a substantial spatial variability of the hydrothermal water column anomalies, most likely due to widespread focused and diffuse hydrothermal discharge in the area. In the Tasi Tulo zone, the hydrothermal signal is characterized by a total lack of turbidity, although other tracer anomalies are in the same range as in nearby Fatu Kapa. The background data set revealed the presence of a Mn and 3He chronic plume due to the extensive and cumulative venting over the entire area. To that respect, we believe that the joined domain composed of our active area and the nearby active area discovered in the East by Lupton et al. (2012) highly co

The global mid-ocean ridge system, where tectonic plates diverge, is traditionally thought of as the largest single volcanic feature on the Earth. Yet, wide expanses of smooth sea floor in the easternmost part of the Southwest Indian Ridge in the Indian Ocean lacks the hummocky morphology that is typical for submarine volcanism. At other slow-spreading ridges, the sea floor can extend by faulting the existing lithosphere, along only one side of the ridge axis. However, the smooth sea floor in the easternmost Southwest Indian Ridge also lacks the corrugated texture created by such faulting. Instead, the sea floor is smooth on both sides of the ridge axis and is thought to be composed of altered mantle-derived rocks. Here we use side-scan sonar to image the sea floor and dredge samples to analyse the composition of two sections of the Southwest Indian Ridge, between 62 degrees 05'E and 64 degrees 40'E, where the sea floor formed over the past 11 million years. We show that the smooth floor is almost entirely composed of seawater-altered mantle-derived rocks that were brought to the surface by large detachment faults on both sides of the ridge axis. Faulting accommodates almost 100% of plate divergence and the detachment faults have repeatedly flipped polarity. We suggest that this tectonic process could also explain the exhumation of mantle-derived rocks at the magma-poor margins of rifted continents.