Description: Biogeochemical cycles of carbon, nutrients, and oxygen transmit mean states, trends and variations of the physical realm in coastal upwelling systems to their food webs and determine their role in regional budgets of greenhouse gases. This contribution focuses on biogeochemical processes in the northern Benguela Upwelling System (NBUS), where low oxygen levels in upwelling source water are a major influence on carbon and nutrient cycles. Based on measurements during numerous expeditions and results of 3-D regional ecosystem modeling (project GENUS; Geochemistry and Ecology of the Namibian Upwelling System) we here examine source water character, effects of low oxygen conditions on nutrient masses and ratios, and of diazotrophic N2-fixation on productivity of the system and its transition to the adjacent eastern South Atlantic. In available observations, the effects of denitrification in water and sediment and phosphate release from sediments are minor influences on nitrate:phosphate ratios of the system, and excess phosphate in aged upwelling water is inherited from upwelling source water. Contrary to expectation and model results, the low N:P ratios do not trigger diazotrophic N2-fixation in the fringes of the upwelling system, possibly due to a lack of seeding populations of Trichodesmium. We also examine the flux of carbon from the sea surface to either sediment, the adjacent sub-thermocline ocean, or to regenerated nutrients and CO2. Observed fluxes out of the surface mixed layer are significantly below modeled fluxes, and suggest that regeneration of nutrients and CO2 is unusually intense in the mixed layer. This contributes to very high fluxes of CO2 from the ocean to the regional atmosphere, which is not compensated for by N2-fixation. Based on observations, the NBUS thus is a significant net CO2 source (estimated at 14.8 Tg C a− 1), whereas the CO2 balance is closed by N2-fixation in the model. Methane concentrations were low in surface waters in on-line measurements during 1 expedition, and based on these our estimate for the emission of methane for the entire Benguela system is below 0.2 Tg CH4 a− 1.

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 • 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: 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 • 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.