Description: The accumulation of gas hydrates in marine sediments is essentially controlled by the accumulation of particulate organic carbon (POC) which is microbially converted into methane, the thickness of the gas hydrate stability zone (GHSZ) where methane can be trapped, the sedimentation rate (SR) that controls the time that POC and the generated methane stays within the GHSZ, and the delivery of methane from deep-seated sediments by ascending pore fluids and gas into the GHSZ. Recently, Wallmann et al. (2012) presented transfer functions to predict the gas hydrate inventory in diffusion-controlled geological systems based on SR, POC and GHSZ thickness for two different scenarios: normal and full compacting sediments. We apply these functions to global data sets of bathymetry, heat flow, seafloor temperature, POC input and SR, estimating a global mass of carbon stored in marine methane hydrates from 3 to 455 Gt of carbon (GtC) depending on the sedimentation and compaction conditions. The global sediment volume of the GHSZ in continental margins is estimated to be 60–67 × 1015 m3, with a total of 7 × 1015 m3 of pore volume (available for GH accumulation). However, seepage of methane-rich fluids is known to have a pronounced effect on gas hydrate accumulation. Therefore, we carried out a set of systematic model runs with the transport-reaction code in order to derive an extended transfer function explicitly considering upward fluid advection. Using averaged fluid velocities for active margins, which were derived from mass balance considerations, this extended transfer function predicts the enhanced gas hydrate accumulation along the continental margins worldwide. Different scenarios were investigated resulting in a global mass of sub-seafloor gas hydrates of ~ 550 GtC. Overall, our systematic approach allows to clearly and quantitatively distinguish between the effect of biogenic methane generation from POC and fluid advection on the accumulation of gas hydrate, and hence, provides a simple prognostic tool for the estimation of large-scale and global gas hydrate inventories in marine sediments.

Description: This study focused on biogeochemical processes and microbial activity in sediments of a natural deep-sea CO2 seepage area (Yonaguni Knoll IV hydrothermal system, Japan). The aim was to assess the influence of the geochemical conditions occurring in highly acidic and CO2 saturated sediments on sulfate reduction (SR) and anaerobic methane oxidation (AOM). Porewater chemistry was investigated from retrieved sediment cores and in situ by microsensor profiling. The sites sampled around a sediment-hosted hydrothermal CO2 vent were very heterogeneous in porewater chemistry, indicating a complex leakage pattern. Near the vents, droplets of liquid CO2 were observed emanating from the sediments, and the pH reached approximately 4.5 in a sediment depth 〉 6 cm, as determined in situ by microsensors. Methane and sulfate co-occurred in most sediment samples from the vicinity of the vents down to a depth of 3 m. However, SR and AOM were restricted to the upper 7-15 cm below seafloor, although neither temperature, low pH, nor the availability of methane and sulfate could be limiting microbial activity. We argue that the extremely high subsurface concentrations of dissolved CO2 (1000-1700 mM), which disrupt the cellular pH homeostasis, and lead to end-product inhibition. This limits life to the surface sediment horizons above the liquid CO2 phase, where less extreme conditions prevail. Our results may have to be taken into consideration in assessing the consequences of deep-sea CO2 sequestration on benthic element cycling and on the local ecosystem state.

Description: A simple prognostic tool for gas hydrate (GH) quantification in marine sediments is presented based on a diagenetic transport-reaction model approach. One of the most crucial factors for the application of diagenetic models is the accurate formulation of microbial degradation rates of particulate organic carbon (POC) and the coupled formation of biogenic methane. Wallmann et al. (2006) suggested a kinetic formulation considering the ageing effects of POC and accumulation of reaction products (CH4, CO2) in the pore water. This model is applied to data sets of several ODP sites in order to test its general validity. Based on a thorough parameter analysis considering a wide range of environmental conditions, the POC accumulation rate (POCar in g/m2/yr) and the thickness of the gas hydrate stability zone (GHSZ in m) were identified as the most important and independent controls for biogenic GH formation. Hence, depth-integrated GH inventories in marine sediments (GHI in g of CH4 per cm2 seafloor area) can be estimated as: GHI=a ·POCar·GHSZb ·exp(−GHSZc/POCar/d)+e with a = 0.00214, b = 1.234, c = −3.339, d = 0.3148, e = −10.265. The transfer function gives a realistic first order approximation of the minimum GH inventory in low gas flux (LGF) systems. The overall advantage of the presented function is its simplicity compared to the application of complex numerical models, because only two easily accessible parameters need to be determined.

Description: A steady state box model was developed to estimate the methane input into the Black Sea water column at various water depths. Our model results reveal a total input of methane of 4.7 Tg yr−1. The model predicts that the input of methane is largest at water depths between 600 and 700 m (7% of the total input), suggesting that the dissociation of methane gas hydrates at water depths equivalent to their upper stability limit may represent an important source of methane into the water column. In addition we discuss the effects of massive short-term methane inputs (e.g. through eruptions of deep-water mud volcanoes or submarine landslides at intermediate water depths) on the water column methane distribution and the resulting methane emission to the atmosphere. Our non-steady state simulations predict that these inputs will be effectively buffered by intense microbial methane consumption and that the upward flux of methane is strongly hampered by the pronounced density stratification of the Black Sea water column. For instance, an assumed input of methane of 179 Tg CH4 d−1 (equivalent to the amount of methane released by 1000 mud volcano eruptions) at a water depth of 700 m will only marginally influence the sea/air methane flux increasing it by only 3%.

Description: In the eastern Black Sea, we determined methane (CH4) concentrations, gas hydrate volumes, and their vertical distribution from combined gas and chloride (Cl−) measurements within pressurized sediment cores. The total gas volume collected from the cores corresponded to concentrations of 1.2–1.4 mol CH4 kg−1 porewater at in-situ pressure, which is equivalent to a gas hydrate saturation of 15–18% of pore volume and amongst the highest values detected in shallow seep sediments. At the central seep site, a high-resolution Cl− profile resolved the upper boundary of gas hydrate occurrence and a continuous layer of hydrates in a sediment column of 120 cm thickness. Including this information, a more precise gas hydrate saturation of 22–24% pore volume could be calculated. This volume was higher in comparison to a saturation calculated from the Cl− profile alone, resulting in only 14.4%. The likely explanation is an active gas hydrate formation from CH4 gas ebullition. The hydrocarbons at Batumi Seep are of shallow biogenic origin (CH4 〉 99.6%), at Pechori Mound they originate from deeper thermocatalytic processes as indicated by the lower ratios of C1 to C2–C3 and the presence of C5.

Description: There has been a steady increase in interest in mining of deep-sea minerals in the Clarion–Clipperton Zone (CCZ) in the eastern Pacific Ocean during the last decade. This region is known to be one of the most eddy-rich regions in the world ocean. Typically, mesoscale eddies are generated by intense wind bursts channeled through gaps in the Sierra Madre mountains in Central America. Here, we use a combination of satellite and in situ observations to evaluate the relationship between deep-sea current variability in the region of potential future mining and eddy kinetic energy (EKE) in the vicinity of gap winds. A geometry-based eddy detection algorithm has been applied to altimetry sea surface height data for a period of 24 years, from 1993 to 2016, in order to analyze the main characteristic parameters and the spatiotemporal variability of mesoscale eddies in the northeast tropical Pacific Ocean (NETP). Significant differences between the characteristics of eddies with different polarity (cyclonic vs. anticyclonic) were found. For eddies with lifetimes longer than 1 d, cyclonic polarity is more common than anticyclonic rotation. However, anticyclonic eddies are larger in size, show stronger vorticity, and survive longer in the ocean than cyclonic eddies (often 90 d or more). Besides the polarity of eddies, the location of eddy formation should be taken into consideration when investigating the impacted deep-ocean region as we found eddies originating from the Tehuantepec (TT) gap winds lasting longer in the ocean and traveling farther distances in a different direction compared to eddies produced by the Papagayo (PP) gap winds. Long-lived anticyclonic eddies generated by the TT gap winds are observed to travel distances up to 4500 km offshore, i.e., as far as west of 110∘ W. EKE anomalies observed in the surface of the central ocean at distances of ca. 2500 km from the coast correlate with the seasonal variability of EKE in the region of the TT gap winds with a time lag of 5–6 months. A significant seasonal variability of deep-ocean current velocities at water depths of 4100 m was observed in multiple-year time series data, likely reflecting the energy transfer of the surface EKE generated by the gap winds to the deep ocean. Furthermore, the influence of mesoscale eddies on deep-ocean currents is examined by analyzing the deep-ocean current measurements when an anticyclonic eddy crosses the study region. Our findings suggest that despite the significant modulation of dominant current directions driven by the bottom-reaching eddy, the current magnitude intensification was not strong enough to trigger local sediment resuspension in this region. A better insight into the annual variability of ocean surface mesoscale activity in the CCZ and its effects on deep-ocean current variability can be of great help to mitigate the impact of future potential deep-sea mining activities on the benthic ecosystem. On an interannual scale, a significant relationship between cyclonic eddy characteristics and El Niño–Southern Oscillation (ENSO) was found, whereas a weaker correlation was detected for anticyclonic eddies.

Description: Due to its remoteness, the deep-sea floor remains an understudied ecosystem of our planet. The patchiness of existing data sets makes it difficult to draw conclusions about processes that apply to a wider area. In our study we show how different settings and processes determine sediment heterogeneity on small spatial scales. We sampled solid phase and porewater from the upper 10 m of an approximately 7.4×13 km2 area in the Peru Basin, in the southeastern equatorial Pacific Ocean, at 4100 m water depth. Samples were analyzed for trace metals, including rare earth elements and yttrium (REY), as well as for particulate organic carbon (POC), CaCO3, and nitrate. The analyses revealed the surprisingly high spatial small-scale heterogeneity of the deep-sea sediment composition. While some cores have the typical green layer from Fe(II) in the clay minerals, this layer is missing in other cores, i.e., showing a tan color associated with more Fe(III) in the clay minerals. This is due to varying organic carbon contents: nitrate is depleted at 2–3 m depth in cores with higher total organic carbon contents but is present throughout cores with lower POC contents, thus inhibiting the Fe(III)-to-Fe(II) reduction pathway in organic matter degradation. REY show shale-normalized (SN) patterns similar to seawater, with a relative enrichment of heavy REY over light REY, positive LaSN anomaly, negative CeSN anomaly, and positive YSN anomaly and correlate with the Fe-rich clay layer and, in some cores, also correlate with P. We therefore propose that Fe-rich clay minerals, such as nontronite, as well as phosphates, are the REY-controlling phases in these sediments. Variability is also seen in dissolved Mn and Co concentrations between sites and within cores, which might be due to dissolving nodules in the suboxic sediment, as well as in concentration peaks of U, Mo, As, V, and Cu in two cores, which might be related to deposition of different material at lower-lying areas or precipitation due to shifting redox boundaries.

Description: Using observational data, satellite altimeters, and reanalysis model products, we have investigated eddy-induced seawater anomalies and heat and salt transport in the northeastern tropical Pacific Ocean. An eddy detection algorithm (EDA) was used to identify eddy formation at the Mexican Tehuantepec Gulf (TT) in July 2018 during an unusually strong summer wind event. The eddy separated from the coast with a mean translation velocity of 11 cm s−1 and a mean radius of 115 km and traveled 2050–2400 km westwards off the Central American coast, where it was followed at approx 114∘ W and 11∘ N for oceanographic observation between April and May 2019. The in situ observations show that the major eddy impacts are restricted to the upper 300 m of the water column and are traceable down to 1500 m water depth. In the eddy core at 92 m water depth an extreme positive temperature anomaly of 8.2 ∘C, a negative salinity anomaly of −0.78 psu, a positive fluorescence anomaly of +0.8 mg m−3, and a positive dissolved oxygen concentration anomaly of 137 µmol kg−1 are observed. Compared with annual climatological averages in 2018, the water trapped within the eddy is estimated to transport an average positive westward zonal heat anomaly of 85×1012 W and an average westward negative salt anomaly of  kg s−1. The heat transport is the equivalent of 1 % of the total annual zonal eddy-induced heat transport at this latitude in the Pacific Ocean. Understanding the dynamics of long-lived mesoscale eddies that may reach the seafloor in this region of the Pacific Ocean is especially important in light of potential deep-sea mining activities that are being targeted on this area.