Description: Highlights • Mega ebullition of biogenic methane from an abandoned offshore gas well, North Sea. • Evidence for midwater bubble plume intrusion, fallback, and short-circuiting of the plume. • Effective trapping of seabed released methane underneath the thermocline. • First observation of a spiral vortex methane plume and marginal turbulences. • Megaplumes appear less efficient in terms of vertical methane transport than previously thought. Abstract First direct evidence for ongoing gas seepage activity on the abandoned well site 22/4b (Northern North Sea, 57°55′ N, 01°38′ E) and discovery of neighboring seepage activity is provided from observations since 2005. A manned submersible dive in 2006 discovered several extraordinary intense seepage sites within a 60 m wide and 20 m deep crater cut into the flat 96 m deep seafloor. Capture and (isotope) chemical analyses of the gas bubbles near the seafloor revealed in situ concentrations of methane between 88 and 90%Vol. with δ13C–CH4 values around −74‰ VPDB, indicating a biogenic origin. Bulk methane concentrations throughout the water column were assessed by 120 Niskin water samples showing up to 400.000 nM CH4 in the crater at depth. In contrast, concentrations above the thermocline were orders of magnitude lower, with a median value of 20 nM. A dye tracer injection into the gas seeps revealed upwelling bubble and water motion with gas plume rise velocities up to ∼1 ms−1 (determined near the seabed). However, the dissolved dye did not pass the thermocline, but returned down to the seabed. Measurements of direct bubble-mediated atmospheric flux revealed low values of 0.7 ± 0.3 kty−1, much less than current state-of-the-art bubble dissolution models would predict for such a strong and upwelling in situ gas bubble flux at shallow water depths (i.e. ∼100 m). Acoustic multibeam water column imaging data indicate a pronounced 200 m lateral intrusion at the thermocline together with high methane concentration at this layer. A partly downward-orientated bubble plume motion is also visible in the acoustic data with potential short-circuiting in accordance to the dye experiment. This observation could partly explain the observed trapping of most of the released gas below the well-established thermocline in the North Sea. Moreover, 3D analyses of the multibeam water column data reveal that the upwelling plume transforms into a spiral expanding vortex while rising through the water column. Such a spiral vortex motion has never been reported before for marine gas seepage and might represent an important process with strong implication on plume dynamics, dissolution behavior, gas escape to the atmosphere, and is considered very important for respective modeling approaches.

Description: This study highlights the potential of using a low frequency multibeam echosounder for detection and visualization of shallow gas occurring several meters beneath the seafloor. The presence of shallow gas was verified in the Bornholm Basin, Baltic Sea, at 80 m water depth with standard geochemical core analysis and hydroacoustic subbottom profiling. Successively, this area was surveyed with a 95 kHz and a 12 kHz multibeam echosounder (MBES). The bathymetric measurements with 12 kHz provided depth values systematically deeper by several meters compared to 95 kHz data. This observation was attributed to enhanced penetration of the low frequency signal energy into soft sediments. Consequently, the subbottom geoacoustic properties contributed highly to the measured backscattered signals. Those appeared up to 17 dB higher inside the shallow gas area compared to reference measurements outside and could be clearly linked to the shallow gas front depth down to 5 meter below seafloor. No elevated backscatter was visible in 95 kHz MBES data, which in turn highlights the superior potential of low frequency MBES to image shallow sub-seafloor features. Small gas pockets could be resolved even on the outer swath (up to 65°). Strongly elevated backscattering from gassy areas occurred at large incidence angles and a high gas sensitivity of the MBES is further supported by an angular response analysis presented in this study. We conclude that the MBES together with subbottom profiling can be used as an efficient tool for spatial subbottom mapping in soft sediment environments.

Description: Extremely intense bubble plumes, like the North Sea 22/4b blowout megaplume (defined as more than 10(6) L day(-1)), create very strong upwelling flows (〉1 m s(-1)), which lead to detrainment of methane-enriched water, but leave direct bubble-mediated transport unaffected. Dissolved CH4 depth profiles and atmospheric measurements during a fall 2011 survey of the 22/4b site suggest strong constraint of seabed CH4 below the thermocline. Seabed bubbles were nearly pure CH4. The effect of the upwelling flow on the fate of bubble plume CH4 was investigated with a numerical bubble-propagation model. The model considered different representative bubble plume size distributions, phi, and a global (total) megaplume bubble size distribution, Phi, synthesized from video survey data and phi from the literature. Simulations showed that none of the literature plumes or variations in the upwelling flow could constrain CH4 sufficiently below the thermocline. Two new bubble megaplume processes were simulated, vortical bubble trapping (slow rise) and a hypothesized, enhanced bubble gas exchange, k(BE), an enhancement factor applied to the normal bubble gas exchange rate, k(B). The latter could arise from plume turbulence increasing bubble boundary-layer turbulence and thus its gas exchange. Observations could not be reproduced solely by slow rise, however, simulations with k(BE)similar to 6 reproduced observational constraints, as could weaker k(BE) in conjunction with slow rise. Field validation of k(BE) is needed given its implications for the fate of megaplume CH4 emissions (anthropogenic or natural) for stratified and unstratified conditions. kBE suggests marine CH4 geologic contributions to the atmosphere from all but shallow waters primarily arises from bubble plumes that are less than megaplume size.

Description: Understanding the upward motion of CO2 droplets or CH4 bubbles in oceanic waters is prerequisite to predict the vertical distribution of the two most important greenhouse gases in the water column after these have been released from the seabed. One of the key parameters governing the fate of droplets or bubbles dissolving into the surrounding seawater as they rise, is the terminal velocity, uT. The latter is strongly influenced by the ability of both compounds to form skins of gas hydrate, if pressure and temperature satisfy thermodynamic framework conditions. Experimental efforts aiming to elucidate the rise properties of CO2 droplets and CH4 bubbles and specifically the influence of hydrate skins open the possibility to obtain a parameterization of uT applicable to both hydrate-coated and pure fluid particles of CH4 and CO2. With the present study, we report on experimentally determined terminal velocities of single CH4 bubbles released to pressurized and temperature-regulated seawater. Hydrate skins were identified by high bubble sphericities and changed motion characteristics. Based on these experiments as well as published data on the rise of hydrate-coated and pure liquid CO2 droplets and physical principles previously successfully used for clean bubbles near atmospheric pressures, a new parameterization of uT is proposed. Model predictions show a good agreement with the data base established from the laboratory-based measurements.

Description: Four mud extrusions were investigated along the erosive subduction zone off Costa Rica. Active fluid seepage from these structures is indicated by chemosynthetic communities, authigenic carbonates and methane plumes in the water column. We estimate the methane output from the individual mud extrusions using two independent approaches. The first is based on the amount of CH4 that becomes anaerobically oxidized in the sediment beneath areas covered by chemosynthetic communities, which ranges from 104 to 105 mol yr− 1. The remaining portion of CH4, which is released into the ocean, has been estimated to be 102–104 mol yr− 1 per mud extrusion. The second approach estimates the amount of CH4 discharging into the water column based on measurements of the near-bottom methane distribution and current velocities. This approach yields estimates between 104–105 mol yr−1. The discrepancy of the amount of CH4 emitted into the bottom water derived from the two approaches hints to methane seepage that cannot be accounted for by faunal growth, e.g. focused fluid emission through channels in sediments and fractures in carbonates. Extrapolated over the 48 mud extrusions discovered off Costa Rica, we estimate a CH4 output of 20·106 mol yr− 1 from mud extrusions along this 350 km long section of the continental margin. These estimates of methane emissions at an erosional continental margin are considerably lower than those reported from mud extrusion at accretionary and passive margins. Almost half of the continental margins are described as non-accretionary. Assuming that the moderate emission of methane at the mud extrusions off Costa Rica are typical for this kind of setting, then global estimates of methane emissions from submarine mud extrusions, which are based on data of mud extrusions located at accretionary and passive continental margins, appear to be significantly too high.

Description: Tommeliten is a prominent methane seep area in the Central North Sea. Previous surveys revealed shallow gas-bearing sediments and methane gas ebullition into the water column. In this study, the in situ methane flux at Tommeliten is re-assessed and the potential methane transport to the atmosphere is discussed, with regards to the hydrographic setting and gas bubble modeling. We have compiled previous data, acquired new video and acoustic evidence of gas bubble release, and have measured the methane concentration, and its C-isotopic composition in the water column. Parametric subbottom sonar data reveal the three-dimensional extent of shallow gas and morphologic features relevant for gas migration. Five methane ebullition areas are identified and the main seepage area appears to be 21 times larger than previously estimated. Our video, hydroacoustic, subbottom, and chemical data suggest that 1.5106 mol CH4/yr (26 tons CH4/yr) of methane gas is being released from the seepage area of Tommeliten. Methane concentration profiles in the vicinity of the gas seeps show values of up to 268 nM (100 times background) close to the seafloor. A decrease in d13C-CH4 values at 40 m water depth indicates an unknown additional biogenic methane source within the well oxygenated thermocline between 30 and 40 m water depth. Numerical modeling of the methane bubbles due to their migration and dissolution was performed to estimate the bubble-derived vertical methane transport, the fate of this methane in the water column, and finally the flux to the atmosphere. Modeling indicates that less than 4% of the gas initially released at the seafloor is transported via bubbles into the mixed layer and, ultimately, to the atmosphere. However, because of the strong seasonality of mixing in the North Sea, this flux is expected to increase as mixing increases, and almost all of the methane released at the seafloor could be transferred into the atmosphere in the stormy fall and winter time.

Description: The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients kd, which were found to correlate linearly with the friction velocity, u★. The resulting kd/u★-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater

Description: Along the erosive convergent margin off Costa Rica a large number of mound-shaped structures exist built by mud diapirism or mud volcanism. One of these, Mound 12, an intermittently active mud volcano, currently emits large amounts of aqueous dissolved species and water. Chemosynthetic vent communities, authigenic carbonates, and methane plumes in the water column are manifestations of that activity. Benthic flux measurements were obtained by a video-guided Benthic Chamber Lander (BCL) deployed at a vent site located in the most active part of Mound 12. The lander was equipped with 4 independent chambers covering adjacent areas of the seafloor. Benthic fluxes were recorded by repeated sampling of the enclosed bottom waters while the underlying surface sediments were recovered with the lander after a deployment time of one day. One of the chambers was placed directly in the centre of an active vent marked by the occurrence of a bacterial mat while the other chambers were located at the fringe of the same vent system at a lateral distance of only 40 cm. A transport-reaction model was developed and applied to describe the concentration profiles in the pore water of the recovered surface sediments and the temporal evolution of the enclosed bottom water. Repeated model runs revealed that the best fit to the pore water and benthic chamber data is obtained with a flow velocity of 10 cm yr− 1 at the centre of the vent. The flux rates to the bottom water are strongly modified by the benthic turnover (benthic filter). The methane flux from below at the bacterial mat site is as high as 1032 μmol cm− 2 yr− 1, out of which 588 μmol cm− 2 yr− 1 is oxidised in the surface sediments by microbial consortia using sulphate as terminal electron acceptor and 440 μmol cm− 2 yr− 1 are seeping into the overlaying bottom water. Sulphide is transported to the surface by ascending fluids (238 μmol cm− 2 yr− 1) and is formed within the surface sediment by the anaerobic oxidation of methane (AOM, 588 μmol cm− 2 yr− 1). However, sulphide is not released into the bottom water but completely oxidized by oxygen and nitrate at the sediment/water interface. The oxygen and nitrate fluxes into the sediment are high (781 and 700 μmol cm− 2 yr− 1, respectively) and are mainly driven by the microbial oxidation of sulphide. Benthic fluxes were much lower in the other chambers placed in the fringe of the vent system. Thus, methane and oxygen fluxes of only 28 and 89 μmol cm− 2 yr− 1, respectively were recorded in one of these chambers. Our study shows that the aerobic oxidation of methane is much less efficient than the anaerobic oxidation of methane so that methane which is not oxidized within the sediment by AOM is almost completely released into the bottom water. Hence, anaerobic rather than aerobic methane oxidation plays the major role in the regulation of benthic methane fluxes. Moreover, we demonstrate that methane and oxygen fluxes at cold vent sites may vary up to 3 orders of magnitude over a lateral distance of only 40 cm indicating an extreme focussing of fluid flow and methane release at the seafloor.

Description: To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 μm/s and between 9.0 and 10.6 · 10−2 μm/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ± 0.5 mmol CO2/m2s and 0.37 ± 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies.

Description: The methane concentration and pCO2 in surface waters and the overlying marine air were continuously surveyed along the pathway of the Kuroshio, from the eastern coast of Honshu to Taiwan, and then across the eastern part of the East China and South China Seas in September of 1994. Off Honshu, the CH4 content was controlled by the confluence of the relatively CH4-poor waters of the Kuroshio and the Oyashio and the CH4-rich Tsugaru Warm Current, the latter carrying water into the Pacific Ocean with a methane content more than twice the equilibrium value with the atmospheric CH4 partial pressure. Along the Kuroshio, the surface water was supersaturated in methane with respect to the atmosphere by 10–15% and appears considerably enriched relative to open Pacific surface waters at same latitudes. The northeastern part of the South China Sea, part of the deep basin of this marginal sea, showed CH4 concentrations similar to those found in open-ocean waters. In contrast, highly variable oversaturations up to 700% were observed along the northwestern coast of Borneo, most probably related to known seepage from oil and gas deposits in this area. The pCO2 of surface water was higher than the atmospheric pCO2 throughout the area surveyed. However, the ΔpCO2 of the surface waters varied from close to 0 to more than 60 μatm. The observed oversaturation in areas influenced by the Kuroshio confirm that, during a short period in late summer, the surface waters of this current between Taiwan and Japan act as a moderate source for atmospheric CO2.