Description: Highlights • Records of seawater εNdεNd are highly unradiogenic across the OMT at Ceara Rise. • Strong influence of Amazon particulate Nd on seawater εNdεNd at Ceara Rise. • Point-sourced riverine Nd influences seawater far from continental shelf. • Regional sedimentary Nd flux can be confused with water mass mixing signals. Abstract Dissolved and particulate neodymium (Nd) are mainly supplied to the oceans via rivers, dust, and release from marine sediments along continental margins. This process, together with the short oceanic residence time of Nd, gives rise to pronounced spatial gradients in oceanic 143Nd/144Nd ratios (εNdεNd). However, we do not yet have a good understanding of the extent to which the influence of riverine point-source Nd supply can be distinguished from changes in mixing between different water masses in the marine geological record. This gap in knowledge is important to fill because there is growing awareness that major global climate transitions may be associated not only with changes in large-scale ocean water mass mixing, but also with important changes in continental hydroclimate and weathering. Here we present εNdεNd data for fossilised fish teeth, planktonic foraminifera, and the Fe–Mn oxyhydroxide and detrital fractions of sediments recovered from Ocean Drilling Project (ODP) Site 926 on Ceara Rise, situated approximately 800 km from the mouth of the River Amazon. Our records span the Mi-1 glaciation event during the Oligocene–Miocene transition (OMT; ∼23 Ma). We compare our εNdεNd records with data for ambient deep Atlantic northern and southern component waters to assess the influence of particulate input from the Amazon River on Nd in ancient deep waters at this site. εNdεNd values for all of our fish teeth, foraminifera, and Fe–Mn oxyhydroxide samples are extremely unradiogenic (εNd≈−15εNd≈−15); much lower than the εNdεNd for deep waters of modern or Oligocene–Miocene age from the North Atlantic (εNd≈−10εNd≈−10) and South Atlantic (εNd≈−8εNd≈−8). This finding suggests that partial dissolution of detrital particulate material from the Amazon (εNd≈−18εNd≈−18) strongly influences the εNdεNd values of deep waters at Ceara Rise across the OMT. We conclude that terrestrially derived inputs of Nd can affect εNdεNd values of deep water many hundreds of kilometres from source. Our results both underscore the need for care in reconstructing changes in large-scale oceanic water-mass mixing using sites proximal to major rivers, and highlight the potential of these marine archives for tracing changes in continental hydroclimate and weathering.

Description: Offshore western Svalbard plumes of gas bubbles rise from the seafloor at the landward limit of the gas hydrate stability zone (LLGHSZ; ∼400 m water depth). It is hypothesized that this methane may, in part, come from dissociation of gas hydrate in the underlying sediments in response to recent warming of ocean bottom waters. To evaluate the potential role of gas hydrate in the supply of methane to the shallow subsurface sediments, and the role of anaerobic oxidation in regulating methane fluxes across the sediment–seawater interface, we have characterised the chemical and isotopic compositions of the gases and sediment pore waters. The molecular and isotopic signatures of gas in the bubble plumes (C1/C2+ = 1 × 104; δ13C-CH4 = −55 to −51‰; δD-CH4 = −187 to −184‰) are similar to gas hydrate recovered from within sediments ∼30 km away from the LLGHSZ. Modelling of pore water sulphate profiles indicates that subsurface methane fluxes are largely at steady state in the vicinity of the LLGHSZ, providing no evidence for any recent change in methane supply due to gas hydrate dissociation. However, at greater water depths, within the GHSZ, there is some evidence that the supply of methane to the shallow sediments has recently increased, which is consistent with downslope retreat of the GHSZ due to bottom water warming although other explanations are possible. We estimate that the upward diffusive methane flux into shallow subsurface sediments close to the LLGHSZ is 30,550 mmol m−2 yr−1, but it is 〈20 mmol m−2 yr−1 in sediments further away from the seafloor bubble plumes. While anaerobic oxidation within the sediments prevents significant transport of dissolved methane into ocean bottom waters this amounts to less than 10% of the total methane flux (dissolved + gas) into the shallow subsurface sediments, most of which escapes AOM as it is transported in the gas phase.

Description: Highlights • Field-scale sub-seabed release experiment to simulate leakage from CO2 reservoir. • CO2 induces pronounced changes in pore water geochemistry. • Dissolution of minerals as a result of increased dissolved CO2 concentrations. • Changes in pore water geochemistry are transient and spatially restricted. • Levels of released metals are low and likely to have minor impact on benthic ecosystems. Abstract The potential for leakage of CO2 from a storage reservoir into the overlying marine sediments and into the water column and the impacts on benthic ecosystems are major challenges associated with carbon capture and storage (CCS) in subseafloor reservoirs. We have conducted a field-scale controlled CO2 release experiment in shallow, unconsolidated marine sediments, and documented the changes to the chemical composition of the sediments, their pore waters and overlying water column before, during and up to 1 year after the 37-day long CO2 release. Increased levels of dissolved inorganic carbon (DIC) were detected in the pore waters close to the sediment-seawater interface in sediments sampled closest to the subsurface injection point within 5 weeks of the start of the CO2 release. Highest DIC concentrations (28.8 mmol L−1, compared to background levels of 2.4 mmol L−1) were observed 6 days after the injection had stopped. The high DIC pore waters have high total alkalinity, and low δ13CDIC values (−20‰, compared to a background value of −2‰), due to the dissolution of the injected CO2 (δ13C = −26.6‰). The high DIC pore waters have enhanced concentrations of metals (including Ca, Fe, Mn) and dissolved silicon, relative to non-DIC enriched pore waters, indicating that dissolution of injected CO2 promotes dissolution of carbonate and silicate minerals. However, in this experiment, the pore water metal concentrations did not exceed levels considered to be harmful to the environment. The spatial extent of the impact of the injected CO2 in the sediments and pore waters was restricted to an area within 25 m of the injection point, and no impact was observed in the overlying water column. Concentrations of all pore water constituents returned to background values within 18 days after the CO2 injection was stopped.

Description: Highlights • Development of a marine monitoring system suitable for operational CCS is achievable. • Monitoring should be hierarchical, starting with anomaly detection. • Comprehensive baselines are required to support monitoring. Abstract The QICS controlled release experiment demonstrates that leaks of carbon dioxide (CO2) gas can be detected by monitoring acoustic, geochemical and biological parameters within a given marine system. However the natural complexity and variability of marine system responses to (artificial) leakage strongly suggests that there are no absolute indicators of leakage or impact that can unequivocally and universally be used for all potential future storage sites. We suggest a multivariate, hierarchical approach to monitoring, escalating from anomaly detection to attribution, quantification and then impact assessment, as required. Given the spatial heterogeneity of many marine ecosystems it is essential that environmental monitoring programmes are supported by a temporally (tidal, seasonal and annual) and spatially resolved baseline of data from which changes can be accurately identified. In this paper we outline and discuss the options for monitoring methodologies and identify the components of an appropriate baseline survey.