Processes Driving Iron and Manganese Dispersal From the TAG Hydrothermal Plume (Mid-Atlantic Ridge): Results From a GEOTRACES Process Study

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

Inter-Comparison of the Spatial Distribution of Methane in the Water Column From Seafloor Emissions at Two Sites in the Western Black Sea Using a Multi-Technique Approach

Understanding the dynamics and fate of methane (CH 4 ) 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 CH 4 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 CH 4 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 seafloor seepages. This highlights the need of better understanding the processes responsible for the transport and transformation of the dissolved methane in the water column, especially in stratified water masses like in the Black Sea

Multidisciplinary investigation on cold seeps with vigorous gas emissions in the Sea of Marmara (MarsiteCruise): Strategy for site detection and sampling and first scientific outcome

MarsiteCruise was undertaken in October/November 2014 in the Sea of Marmara to gain detailed insight into the fate of fluids migrating within the sedimentary column and partially released into the water column. The overall objective of the project was to achieve a more global understanding of cold-seep dynamics in the context of a major active strike-slip fault. Five remotely operated vehicle (ROV) dives were performed at selected areas along the North Anatolian Fault and inherited faults. To efficiently detect, select and sample the gas seeps, we applied an original procedure. It combines sequentially (1) the acquisition of ship-borne multibeam acoustic data from the water column prior to each dive to detect gas emission sites and to design the tracks of the ROV dives, (2) in situ and real-time Raman spectroscopy analysis of the gas stream, and (3) onboard determination of molecular and isotopic compositions of the collected gas bubbles. The in situ Raman spectroscopy was used as a decision-making tool to evaluate the need for continuing with the sampling of gases from the discovered seep, or to move to another one. Push cores were gathered to study buried carbonates and pore waters at the surficial sediment, while CTD-Rosette allowed collecting samples to measure dissolved-methane concentration within the water column followed by a comparison with measurements from samples collected with the submersible Nautile during the Marnaut cruise in 2007. Overall, the visited sites were characterized by a wide diversity of seeps. CO2- and oil-rich seeps were found at the westernmost part of the sea in the Tekirdag Basin, while amphipods, anemones and coral populated the sites visited at the easternmost part in the Cinarcik Basin. Methane-derived authigenic carbonates and bacterial mats were widespread on the seafloor at all sites with variable size and distributions. The measured methane concentrations in the water column were up to 377 μmol, and the dissolved pore-water profiles indicated the occurrence of sulfate depleting processes accompanied with carbonate precipitation. The pore-water profiles display evidence of biogeochemical transformations leading to the fast depletion of seawater sulfate within the first 25-cm depth of the sediment. These results show that the North Anatolian Fault and inherited faults are important migration paths for fluids for which a significant part is discharged into the water column, contributing to the increase of methane concentration at the bottom seawater and favoring the development of specific ecosystems

Analysis of hydrogen and methane in seawater by “Headspace” method: Determination at trace level with an automatic headspace sampler

“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

A simple method for the preparation and injection of gas mixtures into a gas chromatograph using a two-component device

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

Extending the dataset of fluid geochemistry of the Menez Gwen, Lucky Strike, Rainbow, TAG and Snake Pit hydrothermal vent fields: Investigation of temporal stability and organic contribution

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-temperature fluid at all sites. An additional high-temperature organic matter degradation component was likely present at Menez Gwen and Lucky Strike. Our results also indicated that both abiogenic and biogenic processes produced organic compounds. Therefore, we suggest that a portion of the fatty acids at Menez Gwen and polyaromatic hydrocarbons (PAHs) at Rainbow may be derived from abiogenic processes, whereas biogenic processes could be responsible for the presence of n-fatty acids (n-FAs) at Lucky Strike and Rainbow. Moreover, organic geochemistry data appeared to be helpful in understanding some inorganic processes

A GC-SSIM-CRDS System: Coupling a Gas Chromatograph with a Cavity Ring-Down Spectrometer for Onboard Twofold Analysis of Molecular and Isotopic Compositions of Natural Gases during Ocean-Going Research Expeditions

Carbon dioxide (CO2) and methane (CH4) are two climate-sensitive components of gases migrating within sediments and emitted into the water column on continental margins. They are involved in several key biogeochemical processes entering into the global carbon cycle. In order to perform onboard measurements of both the molecular and stable carbon isotope ratios (δ13C) of CH4 and CO2 of natural gases during oceanic cruises, we have developed a novel approach coupling gas chromatography (GC) with cavity ring-down spectroscopy (CRDS). The coupled devices are connected to a small sample isotope module (SSIM) to form a system called GC-SSIM-CRDS. Small volumes of natural gas samples (<1 mL) are injected into the GC using a headspace autosampler or a gas-tight syringe to separate the chemical components using a Shincarbon ST packed column and for molecular quantification by thermal conductivity detection (TCD). Subsequently, CO2 from the sample is trapped in a 7 mL loop at 32 °C before being transferred to the CRDS analyzer for sequential determination of the stable carbon isotope ratios of CH4 and CO2 in 24 min. The loop is an open column (without stationary phase). This approach does not require the use of adsorbents or cooling for the trapping step. Optimization of the separation step prior to analysis was focused on the influence of two key separation factors 1) the flow of the carrier gas and 2) the temperature of the oven. Our analytical system and the measurement protocol were validated on samples collected from gas seeps in the Sea of Marmara (Turkey). Our results show that the GC-SSIM-CRDS system provides a reliable determination of the molecular identification of CH4 and CO2 in complex natural gases, followed by the stable carbon isotope ratios of methane and carbon dioxide

Effects of postglacial seawater intrusion on sediment geochemical characteristics in the Romanian sector of the Black Sea

Highlights • Geochemical analyses highlight multiple diagenesis processes occurring in the sediment. • Intense methane seepages and organic matter degradation contribute to the sulfate reduction. • Chemical of dissolved and mineral iron species indicate that iron is associated with clay minerals. • In response to seawater intrusion, ion exchange, dissolution and reverse weathering reactions change the composition of clay constituting the sediment. Abstract 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 plumes as hotspots for deep-ocean heterotrophic microbial biomass production

International audienceAbstract Carbon budgets of hydrothermal plumes result from the balance between carbon sinks through plume chemoautotrophic processes and carbon release via microbial respiration. However, the lack of comprehensive analysis of the metabolic processes and biomass production rates hinders an accurate estimate of their contribution to the deep ocean carbon cycle. Here, we use a biogeochemical model to estimate the autotrophic and heterotrophic production rates of microbial communities in hydrothermal plumes and validate it with in situ data. We show how substrate limitation might prevent net chemolithoautotrophic production in hydrothermal plumes. Elevated prokaryotic heterotrophic production rates (up to 0.9 gCm −2 y −1 ) compared to the surrounding seawater could lead to 0.05 GtCy −1 of C-biomass produced through chemoorganotrophy within hydrothermal plumes, similar to the Particulate Organic Carbon (POC) export fluxes reported in the deep ocean. We conclude that hydrothermal plumes must be accounted for as significant deep sources of POC in ocean carbon budgets