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Abstract Carbon dioxide removal from the atmosphere and storage over long times scales in terrestrial and marine reservoirs is urgently needed to limit global warming and for sustainable management of the global carbon cycle. Ocean alkalinity enhancement by the artificial addition of carbonate minerals to the seafloor has been proposed as a method to sequester atmospheric CO2 and store it in the ocean as dissolved bicarbonate. Here, a reaction-transport model is used to scrutinize the efficacy of calcite addition and dissolution at a well-studied site in the southwestern Baltic Sea – a brackish coastal water body in northern Europe. We find that most calcite is simply buried without dissolution under moderate addition rates. Applying the model to other sites in the Baltic Sea suggests that dissolution rates and efficiencies are higher in areas with low salinity and undersaturated bottom waters. A simple box model predicts a tentative net CO2 uptake rate from the atmosphere of 3.2 megatonnes of carbon dioxide per year for the wider Baltic Sea after continually adding calcite to muddy sediments for 10 years. More robust estimates now require validation by field studies.

Sediment fluxes to the seafloor govern the fate of elements and compounds in the ocean and serve as a prerequisite for research on elemental cycling, benthic processes and sediment management strategies. To quantify these fluxes over seafloor areas, it is necessary to scale up sediment mass accumulation rates (MAR) obtained from multiple sample stations. Conventional methods for spatial upscaling involve averaging of data or spatial interpolation. However, these approaches may not be sufficiently precise to account for spatial variations of MAR, leading to poorly constrained regional sediment budgets. Here, we utilize a machine learning approach to scale up porosity and 210Pb data from 145 and 65 stations, respectively, in the Skagerrak. The models predict the spatial distributions by considering several predictor variables that are assumed to control porosity and 210Pb rain rates. The spatial distribution of MAR is based on the predicted porosity and existing sedimentation rate data. Our findings reveal highest MAR and 210Pb rain rates to occur in two parallel belt structures that align with the general circulation pattern in the Skagerrak. While high 210Pb rain rates occur in intermediate water depths, the belt of high MAR is situated closer to the coastlines due to lower porosities at shallow water depths. Based on the spatial distributions, we calculate a total MAR of 34.7 Mt yr-1 and a 210Pb rain rate of 4.7 · 1014 dpm yr-1. By comparing atmospheric to total 210Pb rain rates, we further estimate that 24% of the 210Pb originates from the local atmospheric input, with the remaining 76% being transported laterally into the Skagerrak. The updated MAR in the Skagerrak is combined with literature data on other major sediment sources and sinks to present a tentative sediment budget for the North Sea, which reveals an imbalance with sediment outputs exceeding the inputs. Substantial uncertainties in the revised Skagerrak MAR and the literature data might close this imbalance. However, we further hypothesize that previous estimates of suspended sediment inputs into the North Sea might have been underestimated, considering recently revised and elevated estimates on coastal erosion rates in the surrounding region of the North Sea.

Recent studies have begun to explore the potential of enhanced benthic weathering (EBW) in the Baltic Sea as a measure for climate change mitigation. To augment the understanding of EBW under seasonally changing conditions, this study aims to investigate weathering processes under anoxia to hypoxia in corrosive bottom waters, which reflect late summer conditions in the Baltic Sea. Dunite and calcite were added to sediment cores retrieved from Eckernförde Bay (Western Baltic Sea) with a constant flow-through of deoxygenated, CO2-enriched Baltic Sea bottom water. The addition of both materials increased benthic alkalinity release by 2.94 μmol cm−2 d−1 (calcite) and 1.12 μmol cm−2 d−1 (dunite), compared to the unamended control experiment. These excess fluxes are significantly higher than those obtained under winter conditions. The comparison with bottom water oxygen concentrations emphasizes that highest fluxes of alkalinity were associated with anoxic phases of the experiment. An increase in Ca and Si fluxes showed that the enhanced alkalinity fluxes could be attributed to calcite and dunite weathering. First order rate constants calculated based on these data were close to rates published in previous studies conducted under different conditions. This highlights the suitability of these proxies for mineral dissolution and justifies the use of these rate constants in modeling studies investigating EBW in the Baltic Sea and areas with similar chemical conditions. Generally stable pH profiles over the course of the experiment, together with the fact that the added minerals remained on the sediment surface, suggest that corrosive bottom waters were the main driving factor for the dissolution of the added minerals. These factors have important implications for the choice of mineral and timing for EBW as a possible marine carbon dioxide removal method in seasonally hypoxic to anoxic regions of the Baltic Sea.

Enhanced mineral dissolution in the benthic environment is currently discussed as a potential technique for ocean alkalinity enhancement (OAE) to reduce atmospheric CO2 levels. This study explores how biogeochemical processes affect the dissolution of alkaline minerals in surface sediments during laboratory incubation experiments. These involved introducing dunite and calcite to organic-rich sediments from the Baltic Sea under controlled conditions in an oxic environment. The sediment cores were incubated with Baltic Sea bottom water. Findings reveal that the addition of calcite increased the benthic alkalinity release from 0.4 μmol cm−2 d−1 (control) to 1.4 μmol cm−2 d−1 (calcite) as well as other weathering products such as calcium. However, these enhanced fluxes returned to lower fluxes after approximately 4 weeks yet still higher than the un-amended controls. Microbial activity appeared to be the primary driver for lowering pore water pH and thus enhanced weathering. In several sediment cores, pH profiles taken at the start of the experiments indicated activity of sulfur oxidizing Beggiatoa spp, which was verified by RNA-profiling of 16S rRNA genes. The pH profiles transitioned to those commonly associated with the activity of cable bacteria as the experiments progressed. The metabolic activity of cable bacteria would explain the significantly lower pH values (~5.6) at sediment depths of 1–3 cm, which would favor substantial calcite dissolution. However, a high abundance of cable bacteria was not reflected in 16S rRNA sequence data. Total alkalinity (TA) fluxes in these cores increased by a factor of ~3, with excess TA/calcium ratios indicating that the enhanced flux originated from calcite dissolution. The dissolution of dunite or the potential formation of secondary minerals could not be identified due to the strong natural flux of silicic acid, likely due to biogenic silica dissolution. Furthermore, no accumulation of potentially harmful metals such as nickel was observed, as highlighted as a potential risk in other studies concerning OAE. Given the complexity of sediment chemistry and changes of the benthic conditions induced by the incubation, it remains challenging to distinguish between natural and enhanced mineral weathering. Further investigation, including the identification of suitable tracers for mineral dissolution, are necessary to assess the feasibility of benthic weathering as a practical approach for OAE and climate change mitigation.

High alkalinity values observed in coastal seas promote the uptake of CO2 from the atmosphere. However, the alkalinity budget of coastal areas and marginal seas is poorly understood, even though some of the recently observed alkalinity enhancement can be ascribed to riverine fluxes and anaerobic processes in shelf sediments. Here, we investigate the alkalinity budget of the Baltic Sea to identify previously unrecognized alkalinity sources. We quantify the generation of alkalinity and dissolved calcium (Ca) in this marginal sea applying simple mass balance calculations. Using this approach, we identify alkalinity and Ca sources of approximately 324 Gmol yr-1 and 122 Gmol yr-1, respectively, that cannot be ascribed to the riverine input. The magnitude of the Ca source suggests that a major fraction of the excess alkalinity (244 Gmol yr-1) is induced by the dissolution of calcium carbonate (CaCO3). A review of available field data shows that carbonate-bearing rocks at the coast and the seabed of the Baltic Sea are rapidly eroded and may provide sufficient CaCO3 to close the Ca budget. Hence, dissolution of eroded CaCO3 is the most likely source for the Ca enrichment observed in Baltic Sea water. This hypothesis is supported by mass accumulation rates of sediments derived from radioisotope data that are evaluated to derive a basin-wide rate of mud to muddy sand accumulation at the bottom of the Baltic Sea. The resulting value (139 Tg yr-1) exceeds current estimates of riverine particle fluxes into the Baltic Sea by more than one order of magnitude and confirms that rates of till erosion are sufficiently high to account for the Ca and most of the alkalinity excess in Baltic Sea water. Finally, we show that deliberate addition of CaCO3 to sediments deposited in the Baltic Sea could neutralize significant amounts of CO2 and help to achieve net-zero greenhouse gas emissions in the Baltic region.

Enhanced weathering of mafic and ultra-mafic minerals has been suggested as a strategy for carbon dioxide removal (CDR) and a contribution to achieve a balance between global CO2 sources and sinks (net zero emission). This study was designed to assess CDR by dissolution of ultramafic sand (UMS) in artificial seawater (ASW). Fine grained UMS with an olivine content of ~75% was reacted in ASW for up to 134 days at 1 bar and 21.5–23.9°C. A decline in total alkalinity (TA) was observed over the course of the experiments. This unexpected result indicates that TA removal via precipitation of cation-rich authigenic phases exceeded the production of TA induced by olivine dissolution. The TA decline was accompanied by a decrease in dissolved inorganic carbon and Ca concentrations presumably induced by CaCO3 precipitation. Temporal changes in dissolved Si, Ca, Mg, and TA concentrations observed during the experiments were evaluated by a numerical model to identify secondary mineral phases and quantify rates of authigenic phase formation. The modeling indicates that CaCO3, FeOOH and a range of Mg-Si-phases were precipitated during the experiments. Chemical analysis of precipitates and reacted UMS surfaces confirmed that these authigenic phases accumulated in the batch reactors. Nickel released during olivine dissolution, a potential toxic element for certain organisms, was incorporated in the secondary phases and is thus not a suitable proxy for dissolution rates as proposed by earlier studies. The overall reaction stoichiometry derived from lab experiments was applied in a box model simulating atmospheric CO2 uptake in a continental shelf setting induced by olivine addition. The model results indicate that CO2 uptake is reduced by a factor of 5 due to secondary mineral formation and the buffering capacity of seawater. In comparable natural settings, olivine addition may thus be a less efficient CDR method than previously believed.

The sluggish water mass transport in the deeper North Pacific Ocean complicates the assessment of formation, spreading and mixing of surface, intermediate and deep-water masses based on standard hydrographic parameters alone. Geochemical tracers sensitive to water mass provenance and mixing allow to better characterize the origin and fate of the prevailing water masses. Here, we present dissolved neodymium (Nd) isotope compositions (εNd) and concentrations ([Nd]) obtained along a longitudinal transect at ∼180°E from ∼7°S to ∼50°N. The strongest contrast in Nd isotope signatures is observed in equatorial regions between surface waters (εNd ∼0 at 4.5°N) and Lower Circumpolar Deep Water (LCDW) prevailing at 4500 m depth (εNd = −6.7 at 7.2°N). The Nd isotope compositions of equatorial surface and subsurface waters are strongly influenced by regional inputs from the volcanic rocks surrounding the Pacific, which facilitates the identification of the source regions of these waters and seasonal changes in their advection along the equator. Highly radiogenic weathering inputs from Papua-New-Guinea control the εNd signature of the equatorial surface waters and strongly alter the εNd signal of Antarctic Intermediate Water (AAIW) by sea water-particle interactions leading to an εNd shift from −5.3 to −1.7 and an increase in [Nd] from 8.5 to 11.0 pmol/kg between 7°S and 15°N. Further north in the open North Pacific, mixing calculations based on εNd, [Nd] and salinity suggest that this modification of the AAIW composition has a strong impact on intermediate water εNd signatures of the entire region allowing for improved identification of the formation regions and pathways of North Pacific Intermediate Water (NPIW). The deep-water Nd isotope signatures indicate a southern Pacific origin and subsequent changes along its trajectory resulting from a combination of water mass mixing, vertical processes and Nd release from seafloor sediments, which precludes Nd isotopes as quantitative tracers of deep-water mass mixing. Moreover, comparison with previously reported data indicates that the Nd isotope signatures and concentrations below 100 m depth essentially remained stable over the past decades, which suggests constant impacts of water mass advection and mixing as well as of non-conservative vertical exchange and bottom release.