Description: At the Black Sea chemocline, oxygen- and sulfide-rich waters meet and form a niche for thiotrophic pelagic bacteria. Here we investigated an area of the Northwestern Black Sea off Crimea close to the shelf break, where the chemocline reaches the seafloor at around 150–170 m water depth, to assess whether thiotrophic bacteria are favored in this zone. Seafloor video transects were carried out with the submersible JAGO covering 20 km2 on the region between 110 and 200 m depth. Around the chemocline we observed irregular seafloor depressions, covered with whitish mats of large filamentous bacteria. These comprised 25–55% of the seafloor, forming a belt of 3 km width around the chemocline. Cores from the mats obtained with JAGO showed higher accumulations of organic matter under the mats compared to mat-free sediments. The mat-forming bacteria were related to Beggiatoa-like large filamentous sulfur bacteria based on 16S rRNA sequences from the mat, and visual characteristics. The microbial community under the mats was significantly different from the surrounding sediments and enriched with taxa affiliated with polymer degrading, fermenting and sulfate reducing microorganisms. Under the mats, higher organic matter accumulation, as well as higher remineralization and radiotracer-based sulfate reduction rates were measured compared to outside the mat. Mat-covered and mat-free sediments showed similar degradability of the bulk organic matter pool, suggesting that the higher sulfide fluxes and subsequent development of the thiotrophic mats in the patches are consequences of the accumulation of organic matter rather than its qualitative composition. Our observations suggest that the key factors for the distribution of thiotrophic mat-forming communities near to the Crimean shelf break are hypoxic conditions that (i) repress grazers, (ii) enhance the accumulation and degradation of labile organic matter by sulfate-reducers, and (iii) favor thiotrophic filamentous bacteria which are adapted to exploit steep gradients in oxygen and sulfide availability; in addition to a specific seafloor topography which may relate to internal waves at the shelf break.

Description: Marine sediments host large amounts of methane (CH4), which is a potent greenhouse gas. Quantitative estimates for methane release from marine sediments are scarce, and a poorly constrained temporal variability leads to large uncertainties in methane emission scenarios. Here, we use 2D and 3D seismic reflection, multibeam bathymetric, geochemical and sedimentological data to (I) map and describe pockmarks in the Witch Ground Basin (central North Sea), (II) characterize associated sedimentological and fluid migration structures, and (III) analyze the related methane release. More than 1500 pockmarks of two distinct morphological classes spread over an area of 225 km2. The two classes form independently from another and are corresponding to at least two different sources of fluids. Class 1 pockmarks are large in size (〉 6 m deep, 〉 250 m long, and 〉 75 m wide), show active venting, and are located above vertical fluid conduits that hydraulically connect the seafloor with deep methane sources. Class 2 pockmarks, which comprise 99.5 % of all pockmarks, are smaller (0.9‐3.1 m deep, 26‐140 m long, and 14‐57 m wide) and are limited to the soft, fine‐grained sediments of the Witch Ground Formation and possibly sourced by compaction‐related dewatering. Buried pockmarks within the Witch Ground Formation document distinct phases of pockmark formation, likely triggered by external forces related to environmental changes after deglaciation. Thus, greenhouse gas emissions from pockmark fields cannot be based on pockmark numbers and present‐day fluxes but require an analysis of the pockmark forming processes through geological time.

Description: Highlights • A mechanistic explanation is provided for the observed CO2 loss in the sediments. • Reactions of CO2 with the sediment lead to significant heating. • The observations were modeled including reactions and losses due to lateral transport. • CO2 leakage will lead to very local effects. Abstract We investigated the effect of an artificial CO2 vent (0.0015−0.037 mol s−1), simulating a leak from a reservoir for carbon capture and storage (CCS), on the sediment geochemistry. CO2 was injected 3 m deep into the seafloor at 120 m depth. With increasing mass flow an increasing number of vents were observed, distributed over an area of approximately 3 m. In situ profiling with microsensors for pH, T, O2 and ORP showed the geochemical effects are localized in a small area around the vents and highly variable. In measurements remote from the vent, the pH reached a value of 7.6 at a depth of 0.06 m. In a CO2 venting channel, pH reduced to below 5. Steep temperature profiles were indicative of a heat source inside the sediment. Elevated total alkalinity and Ca2+ levels showed calcite dissolution. Venting decreased sulfate reduction rates, but not aerobic respiration. A transport-reaction model confirmed that a large fraction of the injected CO2 is transported laterally into the sediment and that the reactions between CO2 and sediment generate enough heat to elevate the temperature significantly. A CO2 leak will have only local consequences for sediment biogeochemistry, and only a small fraction of the escaped CO2 will reach the sediment surface.

Description: Highlights • Surface sediments react quickly with leaking CO2 and release cations into porewaters. • Both carbonate and silicate mineral dissolution lead to neutralization of CO2 in the sediments. • During short-term exposure to CO2 no toxic substances were released from North Sea surface sediments. • Porewater composition can be used as a diagnostic indicator of CO2 leakage from storage reservoirs. Abstract Sub-seabed geological CO2 storage is discussed as a climate mitigation strategy, but the impact of any leakage of stored CO2 into the marine environment is not well known. In this study, leakage from a CO2 storage reservoir through near-surface sediments was mimicked for low leakage rates in the North Sea. Field data were combined with laboratory experiments and transport-reaction modelling to estimate CO2 and mineral dissolution rates, and to assess the mobilization of metals in contact with CO2-rich fluids and their potential impact on the environment. We found that carbonate and silicate minerals reacted quickly with the dissolved CO2, increasing porewater alkalinity and neutralizing about 5% of the injected CO2. The release of Ca, Sr, Ba and Mn was mainly controlled by carbonate dissolution, while Fe, Li, B, Mg, and Si were released from silicate minerals, mainly from deeper sediment layers. No toxic metals were released from the sediments and overall the injected CO2 was only detected up to 1 m away from seabed CO2 bubble streams. Our results suggest that low leakage rates of CO2 over short timescales have minimal impact on the benthic environment. However, porewater composition and temperature are effective indicators for leakage detection, even at low CO2 leakage rates.

Description: Fluid-escape structures within sedimentary basins permit pressure-driven focused fluid flow through inter-connected faults, fractures and sediment. Seismically-imaged chimneys are recognised as fluid migration pathways which cross-cut overburden stratigraphy, hydraulically connecting deeper strata with the seafloor. However, the geological processes in the sedimentary overburden which control the mechanisms of genesis and temporal evolution require improved understanding. We integrate high resolution 2D and 3D seismic reflection data with sediment core data to characterise a natural, active site of seafloor methane venting in the UK North Sea and Witch Ground Basin, the Scanner pockmark complex. A regional assessment of shallow gas distribution presents direct evidence of active and palaeo-fluid migration pathways which terminate at the seabed pockmarks. We show that these pockmarks are fed from a methane gas reservoir located at 70 metres below the seafloor. We find that the shallow reservoir is a glacial outwash fan, that is laterally sealed by glacial tunnel valleys. Overpressure generation leading to chimney and pockmark genesis is directly controlled by the shallow geological and glaciogenic setting. Once formed, pockmarks act as drainage cells for the underlying gas accumulations. Fluid flow occurs through gas chimneys, comprised of a sub-vertical gas-filled fracture zone. Our findings provide an improved understanding of focused fluid flow and pockmark formation within the sediment overburden, which can be applied to subsurface geohazard assessment and geological storage of CO2.

Description: Highlights • Inherent & added tracers were tested for CO2 leakage attribution & quantification. • Additionally, CO2 leakage was quantified directly by the inverted funnel-technique. • All tracers except 18O were capable of attributing the CO2 source. • In total, ∼43 % of total injected CO2 leaked across the seabed. To inform cost-effective monitoring of offshore geological storage of carbon dioxide (CO2), a unique field experiment, designed to simulate leakage of CO2 from a sub-seafloor storage reservoir, was carried out in the central North Sea. A total of 675 kg of CO2 were released into the shallow sediments (∼3 m below seafloor) for 11 days at flow rates between 6 and 143 kg d-1. A set of natural, inherent tracers (13C, 18O) of injected CO2 and added, non-toxic tracer gases (octafluoropropane, sulfur hexafluoride, krypton, methane) were used to test their applicability for CO2 leakage attribution and quantification in the marine environment. All tracers except 18O were capable of attributing the CO2 source. Tracer analyses indicate that CO2 dissolution in sediment pore waters ranged from 35 % at the lowest injection rate to 41% at the highest injection rate. Direct measurements of gas released from the sediment into the water column suggest that 22 % to 48 % of the injected CO2 exited the seafloor at, respectively, the lowest and the highest injection rate. The remainder of injected CO2 accumulated in gas pockets in the sediment. The methodologies can be used to rapidly confirm the source of leaking CO2 once seabed samples are retrieved.

Description: Highlights • Approaches for CO2 leakage detection, attribution and quantification monitoring exist. • Many approaches cover multiple monitoring tasks simultaneously. • Sonars and chemical sensors on ships or AUVs can cover large areas. • Newer, more specific technologies can detect, verify and quantify smaller, localised leaks. Environmental monitoring of offshore Carbon Capture and Storage (CCS) complexes requires robust methodologies and cost-effective tools to detect, attribute and quantify CO2 leakage in the unlikely event it occurs from a sub-seafloor reservoir. Various approaches can be utilised for environmental CCS monitoring, but their capabilities are often undemonstrated and more detailed monitoring strategies need to be developed. We tested and compared different approaches in an offshore setting using a CO2 release experiment conducted at 120 m water depth in the Central North Sea. Tests were carried out over a range of CO2 injection rates (6 - 143 kg d−1) comparable to emission rates observed from abandoned wells. Here, we discuss the benefits and challenges of the tested approaches and compare their relative cost, temporal and spatial resolution, technology readiness level and sensitivity to leakage. The individual approaches demonstrate a high level of sensitivity and certainty and cover a wide range of operational requirements. Additionally, we refer to a set of generic requirements for site-specific baseline surveys that will aid in the interpretation of the results. Critically, we show that the capability of most techniques to detect and quantify leakage exceeds the currently existing legal requirements.

Description: Highlights • All known observations for Area of Particular Environmental Interest 6 presented. • Assess morphology, sediments, nodules, oceanography, biogeochemistry and ecology. • APEI-6 partially representative of nearby exploration areas yet clear differences. • Present scientific synthesis and management implications for Clarion Clipperton Zone. To protect the range of habitats, species, and ecosystem functions in the Clarion Clipperton Zone (CCZ), a region of interest for deep-sea polymetallic nodule mining in the Pacific, nine Areas of Particular Environmental Interest (APEIs) have been designated by the International Seabed Authority (ISA). The APEIs are remote, rarely visited and poorly understood. Here we present and synthesise all available observations made at APEI-6, the most north eastern APEI in the network, and assess its representativity of mining contract areas in the eastern CCZ. The two studied regions of APEI-6 have a variable morphology, typical of the CCZ, with hills, plains and occasional seamounts. The seafloor is predominantly covered by fine-grained sediments, and includes small but abundant polymetallic nodules, as well as exposed bedrock. The oceanographic parameters investigated appear broadly similar across the region although some differences in deep-water mass separation were evident between APEI-6 and some contract areas. Sediment biogeochemistry is broadly similar across the area in the parameters investigated, except for oxygen penetration depth, which reached 〉2 m at the study sites within APEI-6, deeper than that found at UK1 and GSR contract areas. The ecology of study sites in APEI-6 differs from that reported from UK1 and TOML-D contract areas, with differences in community composition of microbes, macrofauna, xenophyophores and metazoan megafauna. Some species were shared between areas although connectivity appears limited. We show that, from the available information, APEI-6 is partially representative of the exploration areas to the south yet is distinctly different in several key characteristics. As a result, additional APEIs may be warranted and caution may need to be taken in relying on the APEI network alone for conservation, with other management activities required to help mitigate the impacts of mining in the CCZ.

Description: Bottom-water oxygen supply is a key factor governing the biogeochemistry and community composition of marine sediments. Whether it also determines carbon burial rates remains controversial. We investigated the effect of varying oxygen concentrations (170 to 0 μM O2) on microbial remineralization of organic matter in seafloor sediments and on community diversity of the northwestern Crimean shelf break. This study shows that 50% more organic matter is preserved in surface sediments exposed to hypoxia compared to oxic bottom waters. Hypoxic conditions inhibit bioturbation and decreased remineralization rates even within short periods of a few days. These conditions led to the accumulation of threefold more phytodetritus pigments within 40 years compared to the oxic zone. Bacterial community structure also differed between oxic, hypoxic, and anoxic zones. Functional groups relevant in the degradation of particulate organic matter, such as Flavobacteriia, Gammaproteobacteria, and Deltaproteobacteria, changed with decreasing oxygenation, and the microbial community of the hypoxic zone took longer to degrade similar amounts of deposited reactive matter. We conclude that hypoxic bottom-water conditions—even on short time scales—substantially increase the preservation potential of organic matter because of the negative effects on benthic fauna and particle mixing and by favoring anaerobic processes, including sulfurization of matter.