Ocean Alkalinity Research Articles

Ocean alkalinity enhancement approaches and the predictability of runaway precipitation processes: results of an experimental study to determine critical alkalinity ranges for safe and sustainable application scenarios

Abstract. To ensure the safe and efficient application of ocean alkalinity enhancement (OAE), it is crucial to investigate its impacts on the carbonate system. While modeling studies reported a sequestration potential of 3–30 Gt carbon dioxide (CO2) per year (Oschlies et al., 2023), there has been a lack of empirical data to support the applicability of this technology in natural environments. Recent studies have described the effect of runaway carbonate precipitation in the context of OAE, showing that calcium carbonate (CaCO3) formation was triggered if certain Ωaragonite saturation thresholds were exceeded. This effect could potentially lead to a net loss of the initially added alkalinity, counteracting the whole concept of OAE. The related precipitation can adversely affect the carbon storage capacity and may in some cases result in CO2 emissions. Experiments at the Espeland marine biological station (Bergen, Norway) were conducted to systematically study the chemical consequences of OAE deployment. The experiments lasted for 20–25 d to monitor the temporal development of carbonate chemistry parameters after alkalinity addition and the subsequent triggered carbonate precipitation process. Identified uniform patterns before and during the triggered runaway process can be described by empirical functional relationships. For approaches equilibrated to the CO2 concentration of the atmosphere, total alkalinity (TA) levels of up to 6500 µmol kg−1 remained stable without loss of total alkalinity (TA) for up to 20 d. Higher implemented TA levels, up to 11 200 µmol kg−1, triggered runaway carbonate formation. Once triggered, the loss of alkalinity continued until the Ωaragonite values leveled out at 5.8–6.0, still resulting in a net gain of 3600–4850 µmol kg−1 in TA. The non-CO2-equilibrated approaches, however, only remained stable for TA additions of up to 1000 µmol kg−1. The systematic behavior of treatments exceeding this level allows us to predict the duration of transient stability and the quantity of TA loss after this period. Once triggered, the TA loss continued in the non-CO2-equilibrated approaches until Ωaragonite values of 2.5–5.0 were reached, in this case resulting in a net loss of TA. To prevent a net loss of TA, treated water must be diluted below the time-dependent critical levels of TA and Ωaragonite within the identified transient stability duration. Identified stability and loss patterns of added TA depend on local environmental conditions impacting the carbonate system, such as salinity, temperature, biological activity, and particle abundance. Incorporating such stability and loss patterns into ocean biogeochemical models, which are capable of resolving dilution processes of treated and untreated water parcels, would, from a geochemical perspective, facilitate the prediction of safe local application levels of OAE. This approach would also allow an accurate determination of the fate of added alkalinity and a more realistic carbon storage potential estimation compared to the assessments that neglect carbonate system responses to OAE.

Carbon dioxide sequestration through mineralization from seawater: The interplay of alkalinity, pH, and dissolved inorganic carbon

Marine carbon dioxide removal technologies rely on the equilibration of the seawater with atmospheric CO2, where a pH increase can facilitate carbon dioxide removal either through increased absorption capacity of CO2, or precipitation of minerals. Here, we focus on explicitly defining the governing factors that influence seawater alkalinity with respect to CaCO3 mineralization and atmospheric CO2 uptake. We utilize an electrochemical setup and different water types, from near-shore Mediterranean seawater as well as Red Sea Salt water. The setup allows us to separate mineralization from alkalinity enhancement via an electrochemical membrane cell, and a second compartment with controlled environment, where the interplay of ion concentration, precipitation, pH, DIC concentration, and total alkalinity are evaluated. The effect of sparging additional carbon dioxide before, and after the precipitation of CaCO3 was evaluated while utilizing both a mild pH swing (from, ∼8.3 to ∼9.5), and a larger pH swing (from, ∼8.3 to ∼10.2). A thermodynamic model is presented defining the energy consumption to increase the pH, and the influence of Mg thereon is explicated. Furthermore, we detail theoretical aquatic chemistry simulations via PHREEQC to rationalize the observed intricate dynamics of the carbonate system in seawater. We end with a discussion of the implications of total alkalinity, pH, salt complexation, and carbon uptake capacity relevant to of all ocean alkalinity enhancement and marine based carbon dioxide removal systems, concluding that the carbon uptake capacity of water returned to the ocean must be verified in such technologies

Ocean Alkalinity Enhancement in Deep Water Formation Regions Under Low and High Emission Pathways

AbstractOcean Alkalinity Enhancement (OAE) is an ocean‐based Carbon Dioxide Removal (CDR) method to mitigate climate change. Studies to characterize regional differences in OAE efficiencies and biogeochemical effects are still sparse. As subduction regions play a pivotal role for anthropogenic carbon uptake and centennial storage, we here evaluate OAE efficiencies in the subduction regions of the Southern Ocean, the Northwest Atlantic, and the Norwegian‐Barents Sea region. Using the ocean biogeochemistry model FESOM2.1‐REcoM3, we simulate continuous OAE globally and in the subduction regions under high (SSP3‐7.0) and low (SSP1‐2.6) emission scenarios. The OAE efficiency calculated by two different metrics is higher (by 8%–30%) for SSP3‐7.0 than for SSP1‐2.6 due to a lower buffer factor in a high‐ world. All subduction regions show a CDR potential (0.23–0.31; PgC uptake per Pg alkaline material) consistent with global OAE for both emission scenarios. Calculating the efficiency as the ratio of excess dissolved inorganic carbon (DIC) to excess alkalinity shows that the Southern Ocean and the Northwest Atlantic are as efficient as the global ocean (0.79–0.85), while the Norwegian‐Barents Sea region has a lower efficiency (0.65–0.75). The subduction regions store a fraction of excess carbon below 1 km that is 1.9 times higher than the global ocean. The excess surface alkalinity and thus uptake and storage follow the mixed‐layer depth seasonality, with the majority of the excess flux occurring in summer at shallow mixed layer depths. This study therefore highlights that subduction regions can be efficient for OAE if optimal deployment strategies are developed.

Metrics for quantifying the efficiency of atmospheric CO2 reduction by marine carbon dioxide removal (mCDR)

Abstract Marine carbon dioxide removal (mCDR) is gaining interest as a tool to meet global climate goals. Because the response of the ocean–atmosphere system to mCDR takes years to centuries, modeling is required to assess the impact of mCDR on atmospheric CO2 reduction. Here, we use a coupled ocean–atmosphere model to quantify the atmospheric CO2 reduction in response to a CDR perturbation. We define two metrics to characterize the atmospheric CO2 response to both instantaneous ocean alkalinity enhancement (OAE) and direct air capture (DAC): the cumulative additionality (α) measures the reduction in atmospheric CO2 relative to the magnitude of the CDR perturbation, while the relative efficiency (ϵ) quantifies the cumulative additionality of mCDR relative to that of DAC. For DAC, α is 100% immediately following CDR deployment, but declines to roughly 50% by 100 years post-deployment as the ocean degasses CO2 in response to the removal of carbon from the atmosphere. For instantaneous OAE, α is zero initially and reaches a maximum of 40%–90% several years to decades later, depending on regional CO2 equilibration rates and ocean circulation processes. The global mean ϵ approaches 100% after 40 years, showing that instantaneous OAE is nearly as effective as DAC after several decades. However, there are significant geographic variations, with ϵ approaching 100% most rapidly in the low latitudes while ϵ stays well under 100% for decades to centuries near deep and intermediate water formation sites. These metrics provide a quantitative framework for evaluating sequestration timescales and carbon market valuation that can be applied to any mCDR strategy.

Synthesis of In Situ Marine Calcium Carbonate Dissolution Kinetic Measurements in the Water Column

AbstractCalcium carbonate (CaCO3) dissolution is an integral part of the ocean's carbon cycle. However, laboratory measurements and ocean alkalinity budgets disagree on the rate and loci of dissolution. In situ dissolution studies can help to bridge this gap, but so far published studies have not been utilized as a whole because they have not previously been compiled into one data set and lack carbonate system data to compare between studies. Here, we compile all published measurements of CaCO3 dissolution rates in the water column (11 studies, 752 data points). Combining World Ocean Atlas data (temperature, salinity) with the neural network CANYON‐B (carbonate system variables), we estimate seawater saturation state (Ω) for each rate measurement. We find that dissolution rates at the same Ω vary by 2 orders of magnitude. Using a machine learning approach, we show that while Ω is the main driver of dissolution rate, most variability can be attributed to differences in experimental design, above all bias due to (diffusive) transport and the synthetic or biogenic nature of CaCO3. The compiled data set supports previous findings of a change in the mechanism driving dissolution at Ωcrit = 0.8 that separates two distinct dissolution regimes: rslow = 0.29 · (1 − Ω)0.68(±0.16) mass% day−1 and rfast = 2.95 · (1 − Ω)2.2(±0.2) mass% day−1. Above the saturation horizon, one study shows significant dissolution that cannot solely be explained by established theories such as zooplankton grazing and organic matter degradation. This suggests that other, non‐biological factors may play a role in shallow dissolution.

Beyond the new normal for sustainability: transformative operations and supply chain management for negative emissions

PurposeThis paper aims to explore three operations and supply chain management (OSCM) approaches for meeting the 2 °C targets to counteract climate change: adaptation (adjusting to climatic impacts); mitigation (innovating towards low-carbon practices); and carbon-removing negative emissions technologies (NETs). We suggest that adaptation nor mitigation may be enough to meet the current climate targets, thus calling for NETs, resulting in the following question: How can operations and supply chains be reconceptualized for NETs?Design/methodology/approachWe draw on the sustainable supply chain and transitions discourses along with interview data involving 125 experts gathered from a broad research project focused on geoengineering and NETs. We analyze three case studies of emerging NETs (biochar, direct air carbon capture and storage and ocean alkalinity enhancement), leading to propositions on the link between OSCM and NETs.FindingsAlthough some NETs are promising, there remains considerable variance and uncertainty over supply chain configurations, efficacy, social acceptability and potential risks of unintended detrimental consequences. We introduce the concept of transformative OSCM, which encompasses policy interventions to foster the emergence of new technologies in industry sectors driven by social mandates but lack clear commercial incentives.Originality/valueTo the best of the authors’ knowledge, this paper is among the first that studies NETs from an OSCM perspective. It suggests a pathway toward new industry structures and policy support to effectively tackle climate change through carbon removal.

Potential of CO2 sequestration by olivine addition in offshore waters: A ship-based deck incubation experiment

Ocean alkalinity enhancement is considered as an effective atmospheric CO2 removal approach, but currently, little is known about the carbon sequestration potential of implementing olivine addition in offshore waters. We investigated the effect of olivine addition on the seawater carbonate system by carrying out a deck incubation experiment in the Northern Yellow Sea; the dissolution rate of olivine was calculated based on the increase in seawater alkalinity (TA), and the CO2 sequestration potential was evaluated. The results showed that the dissolution of olivine increased seawater TA and decreased partial pressure of CO2, resulting in oceanic CO2 uptake from the atmosphere through sea-air exchange; it also increased seawater pH and mitigated ocean acidification to a certain extent. The addition of 1 ‰ olivine had a more significant effect on the seawater carbonate system than 0.5 ‰ olivine addition. The average dissolution rate constant of olivine was 1.44 ± 0.15 μmol m−2 d−1. Assuming that olivine settles completely on the seabed due to gravity, the theoretically maximum amount of CO2 removed by applying 1 tonne of olivine per square meter area in the Northern Yellow Sea is only 2.0 × 10−4 t/m2. Therefore, when olivine addition is implemented in the offshore waters, it is necessary to consider reducing the olivine size, prolonging the settling time of olivine in the water column; and spreading olivine in well-mixed waters to prolong the residence time through repeated resuspension, thus increasing its potential in carbon sequestration.

Seafloor alkalinity enhancement as a carbon dioxide removal strategy in the Baltic Sea

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.

(Invited) EDAC Labs: Carbon Removal via Acid-Base Electrochemistry

EDAC Labs(https://edaclabs.com/) uses the electrochemical production of acid and base to decarbonize the world through conventional direct air capture, enabling carbon-negative mining, and by providing technology for other applications such as direct ocean capture, ocean alkalinity enhancement, and enhanced weathering. EDAC Labs’ electrosynthesizer device creates acid and base at reduced energy cost of conventional processes. For conventional direct air capture developers, EDAC Labs provides technology that is low cost and operates at ambient temperature and pressure. For direct ocean capture and ocean alkalinity enhancement developers, EDAC Labs supplies electrochemistry solutions to developers that lower project costs. For metal mines, EDAC Labs provides technology that extracts valuable metals while sequestering carbon to achieve carbon-negative mining. The acid is used to start the recovery of valuable metals from mine tailings, and the base is used to capture CO2 from air. The acid and base streams are then combined to extract metals that can be sold for applications such as batteries, and to create solid carbonates, which permanently store CO2. Figure 1

Design and Implementation of Iron-Based Electrochemical System for Simultaneous Carbon Capture and Hydrogen Gas Recovery

The catastrophic results of climate change and energy crisis, such as the rise in wildfires, floods, and ecosystem disruptions highlight the critical need of urgent and innovative global-scale solutions for carbon dioxide (CO2) removal (CDR). Ocean-based CDR methods, leveraging the ocean's capacity as a large sink to sequester up to 30% of emissions, offer a great promise. Yet, implementing and testing marine CO2 removal (mCDR) techniques such as ocean iron fertilization (OIF) or ocean alkalinity enhancement (OAE) face significant challenges. To overcome these challenges, a novel self-operating electrochemical technology is designed and presented in this work. The proposed technology, namely electrochemical OIF (EOIF), does not only combine OIF and OAE, but also recovers hydrogen gas (H2) from seawater, offering a promising solution for achieving quantifiable and transparent large-scale mCDR. The EOIF design s focused on employing Fe/Fe-producing anodes to eliminate the production of acids at the anode in traditional electrochemical OAE systems and replace it with Fe release, where the cathode can be made from naturally abundant cost-effective materials, such as carbon. The obtained results show that the EOIF system can be implemented to increase both the concentration of ferrous iron (Fe+2) by 0-0.5 mg/L, and the seawater pH by 8% (i.e., 25% decrease in the hydrogen ions concentration). It also offers the flexibility to optimize the release of iron (Fe+2/Fe+3) by adjusting the magnitude of the electric current in the systems, as well as by optimizing the electrode material and geometry. In certain ocean regions, enhanced iron concentrations stimulate the naturally occurring biological carbon pump (BCP), leading to increased phytoplankton growth, CO2 uptake, and subsequent export of carbon to the deep ocean. Simultaneously, the system increases seawater alkalinity and the buffer capacity, enhancing CO2 solubility and storage in the shallow ocean through the solubility pump. The techno-economic assessment shows that the combined advantages of the EOIF system can lower the mCDR cost by more than 95% compared to the traditional methods. The obtained measurements demonstrate the scalability of EOIF and its ability to operate using solar energy at a lower cost. Overall, the proposed EOIF technology offers a practical, effective, and sustainable solution for addressing climate change and energy recovery on a large-scale.

Effects of grain size and seawater salinity on magnesium hydroxide dissolution and secondary calcium carbonate precipitation kinetics: implications for ocean alkalinity enhancement

Abstract. Understanding the impacts that mineral grain size and seawater salinity have on magnesium hydroxide (Mg(OH)2) dissolution and secondary calcium carbonate (CaCO3) precipitation is critical for the success of ocean alkalinity enhancement. We tested Mg(OH)2 dissolution kinetics in seawater using three Mg(OH)2 grain sizes (<63, 63–180 and >180 µm) at three salinities (∼36, ∼28 and ∼20). While Mg(OH)2 dissolution occurred more quickly the smaller the grain size, salinity did not significantly impact measured rates. Our results also demonstrate that grain size can impact secondary CaCO3 precipitation, suggesting that an optimum grain size exists for ocean alkalinity enhancement (OAE) using solid Mg(OH)2. Of the three grain sizes tested, the medium grain size (63–180 µm) was optimal in terms of delaying secondary CaCO3 precipitation. We hypothesise that in the lowest-grain-size experiments, the higher surface area provided numerous CaCO3 precipitation nuclei, while the slower dissolution of bigger grain sizes maintained a higher alkalinity and pH at the surface of particles, increasing CaCO3 precipitation rates and making them observable much more quickly than for the intermediate grain size. Salinity also played a role in CaCO3 precipitation, where the decrease in magnesium (Mg) allowed secondary precipitation to occur more quickly, similar in effect size to another known inhibitor, i.e. dissolved organic carbon (DOC). In summary, our results suggest that OAE efficiency as influenced by CaCO3 precipitation depends not only on seawater composition but also on the physical properties of the alkaline feedstock used.

Public attitudes and emotions toward novel carbon removal methods in alternative sociotechnical scenarios

Abstract Despite high expectations about the role of carbon removal in meeting global climate targets, many of the proposed techniques remain nascent. This is especially so for techniques with potential for large-scale, permanent removal of CO2, such as direct air carbon capture and storage (DACCS) and ocean alkalinity enhancement (OAE). In such a context, understanding public attitudes is crucial but challenging, since we do not have enough information about the sociotechnical configurations which might accompany such proposals over future timescales. Carbon removal at scale will not take place in a vacuum—it will co-evolve within political, social, economic, and legal structures which in turn will have a strong influence on public attitudes. This study used a nationally-representative survey (n = 1978) in the UK to test the impact of alternative sociotechnical systems on public attitudes to DACCS and OAE. Participants were randomly assigned to one of five scenario conditions, representing different forms of governance logic (top–down vs bottom–up) and market logic (planned vs liberal economy), plus one with minimal sociotechnical information. We find that the scenario condition significantly impacted perceptions of OAE, with participants preferring its implementation within a bottom–up, planned economy scenario, and rejecting scenarios which most closely resembled the status quo. There were no significant differences between scenarios for DACCS, suggesting that the technology may be more flexible across alternative sociotechnical arrangements. OAE arouses more negative emotions, particularly worry about impacts on ocean ecosystems, whereas DACCS arouses more hope. We found that climate worry is associated with stronger emotions—both positive and negative—toward both techniques, thus carbon dioxide removal (CDR) could be polarising for the most climate-worried, likely due to tensions between climate urgency and concerns about deterring emissions reductions. The most important criteria for future CDR deployment were deemed to be biodiversity, durability, and cost, with a strong discourse around the current cost-of-living crisis.

On the emission-path dependency of the efficiency of ocean alkalinity enhancement

Ocean alkalinity enhancement (OAE) deliberately modifies the chemistry of the surface ocean to enhance the uptake of atmospheric CO2. The chemical efficiency of OAE (the amount of CO2 sequestered per unit of alkalinity added) depends, among other factors, on the background state of the surface ocean, which will significantly change until the end of this century and beyond. Here, we investigate the consequences of such changes for the long-term efficiency of OAE. We show, using idealized and scenario simulations with an Earth system model, that under doubling (quadrupling) of pre-industrial atmospheric CO2 concentrations, the simulated mean efficiency of OAE increases by about 18% (29%) from 0.76 to 0.90 (0.98). We find that only half of this effect can be explained by changes in the sensitivity of CO2 sequestration to alkalinity addition itself. The remainder is due to the larger portion of anthropogenic emissions taken up by a high-alkalinity ocean. Importantly, both effects are reversed if atmospheric CO2 concentrations were to decline due to large-scale deployment of land-based (or alternative ocean-based) carbon dioxide removal (CDR) methods. By considering an overshoot pathway that relies on large amounts of land-based CDR, we demonstrate that OAE efficiency indeed shows a strong decline after atmospheric CO2 concentrations have peaked. Our results suggest that the assumption of a constant, present-day chemical efficiency of OAE in integrated assessment modeling and carbon credit assignments could lead to economically inefficient OAE implementation pathways.

Magnesium hydroxide addition reduces aqueous carbon dioxide in wastewater discharged to the ocean

Ocean alkalinity enhancement (OAE) reduces the concentration of dissolved carbon dioxide (CO2) in seawater, leading to atmospheric carbon dioxide removal (CDR). Here we report laboratory experiments and a field-trial of alkalinity enhancement through addition of magnesium hydroxide to wastewater and its subsequent discharge to the coastal ocean. In wastewater, a 10% increase of average alkalinity (+0.56 mmol/kg) led to a 74% reduction in aqueous CO2 (−0.41 mmol/kg) and pH increase of 0.4 units to 7.78 (efficiency 0.73 molCO2/mol alkalinity). The alkalinization signal was limited to within a few metres of the ocean discharge, evident as 27.2 μatm reduction in CO2 partial pressure and 0.017 unit pH increase, and was consistent with rapid dilution of the alkali-treated wastewater. While this proof of concept field trial did not achieve CDR due to its small scale, it demonstrated the potential of magnesium hydroxide addition to wastewater as a CDR solution.

Carbon dioxide removal efficiency of iron and steel slag in seawater via ocean alkalinity enhancement

Ocean alkalinity enhancement (OAE) via the enhanced weathering of alkaline minerals is a promising carbon dioxide removal (CDR) technology. Theoretically, these includes iron and steel slags, although their dissolution kinetics in seawater are unknown. Here, we conducted lab-scale experiments to assess the alkalinity generation potential and dissolution kinetics of various slags in seawater. We show that the alkalinity generated per mass of iron slag was logarithmic, i.e., higher amounts of iron slag added had diminishing alkalinity returns. In contrast, the relatively quick dissolution of steel slags and their linear generation of alkalinity per mass of feedstock dissolved in seawater makes them better OAE candidates. Furthermore, despite the presence of potentially toxic metals in these feedstocks, their low to non-existent presence as dissolution products suggests that harmful concentrations should not be reached, at least for the slag tested here. Finally, if all steel slag produced annually was used for OAE, between 10 and 22 gigatonnes of CO2 could be captured cumulatively by 2,100, highlighting significant CDR potential by slags.

Marine carbon dioxide removal by alkalinization should no longer be overlooked

To achieve the Paris climate target, deep emissions reductions have to be complemented with carbon dioxide removal (CDR). However, a portfolio of CDR options is necessary to reduce risks and potential negative side effects. Despite a large theoretical potential, ocean-based CDR such as ocean alkalinity enhancement (OAE) has been omitted in climate change mitigation scenarios so far. In this study, we provide a techno-economic assessment of large-scale OAE using hydrated lime (‘ocean liming’). We address key uncertainties that determine the overall cost of ocean liming (OL) such as the CO2 uptake efficiency per unit of material, distribution strategies avoiding carbonate precipitation which would compromise efficiency, and technology availability (e.g., solar calciners). We find that at economic costs of 130–295 $/tCO2 net-removed, ocean liming could be a competitive CDR option which could make a significant contribution towards the Paris climate target. As the techno-economic assessment identified no showstoppers, we argue for more research on ecosystem impacts, governance, monitoring, reporting, and verification, and technology development and assessment to determine whether ocean liming and other OAE should be considered as part of a broader CDR portfolio.

Investigating the effect of silicate- and calcium-based ocean alkalinity enhancement on diatom silicification

Abstract. Gigatonne-scale atmospheric carbon dioxide removal (CDR) will almost certainly be needed to supplement the emission reductions required to keep global warming between 1.5–2 °C. Ocean alkalinity enhancement (OAE) is an emerging marine CDR method with the addition of pulverised minerals to the surface ocean being one widely considered approach. A concern of this approach is the potential for dissolution products released from minerals to impact phytoplankton communities. We conducted an experiment with 10 pelagic mesocosms (M1–M10) in Raunefjorden, Bergen, Norway, to assess the implications of simulated silicate- and calcium-based mineral OAE on a coastal plankton community. Five mesocosms (M1, M3, M5, M7, and M9) were enriched with silicate (∼ 75 µmol L−1 Na2SiO3), alkalinity along a gradient from 0 to ∼ 600 µmol kg−1, and magnesium in proportion to alkalinity additions. The other five mesocosms (M2, M4, M6, M8, M10) were enriched with alkalinity along the same gradient and calcium in proportion to alkalinity additions. The experiment explored many components of the plankton community, from microbes to fish larvae, and here we report on the influence of simulated mineral based OAE on diatom silicification. Macronutrients (nitrate and phosphate) limited silicification at the onset of the experiment until nutrient additions on day 26. Silicification was significantly greater in the silicate-based mineral treatment, with all genera except Cylindrotheca displaying an increase in silicification as a result of the increased concentration of dissolved silicate. In contrast to the effect of differences in dissolved silicate concentrations between the two mineral treatments, increases in alkalinity only influenced the silicification of two genera, Pseudo-nitzschia and Nitzschia. The four other genera (Arcocellulus, Cylindrotheca, Skeletonema, and Thalassiosira) investigated here displayed no significant changes in silicification as a result of alkalinity increases between 0 and 600 µmol kg−1 above natural levels. In summary, our findings illustrate that the enhancement of alkalinity via simulated silicate- and calcium-based methods has limited genus-specific impacts on the silicification of diatoms. This research underscores the importance of understanding the full breadth of different OAE approaches, their risks, co-benefits, and potential for interactive effects.

Ocean alkalinity enhancement using sodium carbonate salts does not lead to measurable changes in Fe dynamics in a mesocosm experiment

Abstract. The addition of carbonate minerals to seawater through an artificial ocean alkalinity enhancement (OAE) process increases the concentrations of hydroxide, bicarbonate, and carbonate ions. This leads to changes in the pH and the buffering capacity of the seawater. Consequently, OAE could have relevant effects on marine organisms and in the speciation and concentration of trace metals that are essential for their physiology. During September and October 2021, a mesocosm experiment was carried out in the coastal waters of Gran Canaria (Spain), consisting on the controlled variation of total alkalinity (TA). Different concentrations of carbonate salts (NaHCO3 and Na2CO3) previously homogenized were added to each mesocosm to achieve an alkalinity gradient between Δ0 to Δ2400 µmol L−1. The lowest point of the gradient was 2400 µmol kg−1, being the natural alkalinity of the medium, and the highest point was 4800 µmol kg−1. Iron (Fe) speciation was monitored during this experiment to analyse total dissolved iron (TdFe, unfiltered samples), dissolved iron (dFe, filtered through a 0.2 µm pore size filter), soluble iron (sFe, filtered through a 0.02 µm pore size filter), dissolved labile iron (dFe′), iron-binding ligands (LFe), and their conditional stability constants (KFeL′) because of change due to OAE and the experimental conditions in each mesocosm. Observed iron concentrations were within the expected range for coastal waters, with no significant increases due to OAE. However, there were variations in Fe size fractionation during the experiment. This could potentially be due to chemical changes caused by OAE, but such an effect is masked by the stronger biological interactions. In terms of size fractionation, sFe was below 1.0 nmol L−1, dFe concentrations were within 0.5–4.0 nmol L−1, and TdFe was within 1.5–7.5 nmol L−1. Our results show that over 99 % of Fe was complexed, mainly by L1 and L2 ligands with kFe′L′ ranging between 10.92 ± 0.11 and 12.68 ± 0.32, with LFe ranging from 1.51 ± 0.18 to 12.3 ± 1.8 nmol L−1. Our data on iron size fractionation, concentration, and iron-binding ligands substantiate that the introduction of sodium salts in this mesocosm experiment did not modify iron dynamics. As a consequence, phytoplankton remained unaffected by alterations in this crucial element.

Carbon Outwelling and Uptake Along a Tidal Glacier‐Lagoon‐Ocean Continuum

AbstractTidewater glaciers are highly vulnerable to climate change due to warming from both atmospheric and seawater sources. Most tidewater glaciers are rapidly retreating, but little is known about how glacial melting modifies coastal biogeochemical cycles. Here, we investigate carbonate and nutrient dynamics and fluxes in an expanding proglacial tidal lagoon connected to Europe's largest glacier in Iceland (Vatnajökull). The lagoon N:P:Si ratios (2:1:30) imply a system deficient in nitrogen. The large variations in the freshwater endmembers highlighted the complexity of resolving sources and transformations. The lagoon acted as a sink of dissolved inorganic carbon (DIC). Floating chamber incubations revealed a CO2 uptake of 26 ± 15 mmol m−2 d−1. Lagoon waters near the glacier had a 170% higher CO2 uptake than near the lagoon mouth, likely driven by primary production stimulated by nitrogen‐rich bottom water upwelling. The lateral DIC and total alkalinity (TA) flux rates (outwelling) from the lagoon to the ocean were −1.5 ± 0.1 (export to ocean) and 23 ± 5 mmol m−2 d−1 (import into the lagoon) respectively. All samples were undersaturated with respect to aragonite due to glacial meltwater dilution of TA and CO2 uptake. This implies dilution of oceanic alkalinity, lowering the nearshore buffering capacity against ocean acidification.

Regional potential of coastal ocean alkalinization with olivine within 100 years

The spreading of crushed olivine-rich rocks in coastal seas to accelerate weathering reactions sequesters atmospheric CO2 and reduces atmospheric CO2 concentrations. Their weathering rates depend on different factors, including temperature and the reaction surface area. Therefore, this study investigates the variations in olivine-based enhanced weathering rates across 13 regional coasts worldwide. In addition, it assesses the CO2 sequestration within 100 years and evaluates the maximum net-sequestration potential based on varying environmental conditions. Simulations were conducted using the geochemical thermodynamic equilibrium modeling software PHREEQC. A sensitivity analysis was performed, exploring various combinations of influencing parameters, including grain size, seawater temperature, and chemistry. The findings reveal significant variation in CO2 sequestration, ranging from 0.13 to 0.94 metric tons (t) of CO2 per ton of distributed olivine-rich rocks over 100 years. Warmer coastal regions exhibit higher CO2 sequestration capacities than temperate regions, with a difference of 0.4 t CO2/t olivine distributed. Sensitivity analysis shows that smaller grain sizes (10 µm) exhibit higher net CO2 sequestration rates (0.87 t/t) in olivine-based enhanced weathering across all conditions, attributed to their larger reactive surface area. However, in warmer seawater temperatures, olivine with slightly larger grain sizes (50 and 100 µm) displays still larger net CO2 sequestration rates (0.97 and 0.92 t/t), optimizing the efficiency of CO2 sequestration while reducing grinding energy requirements. While relying on a simplified sensitivity analysis that does not capture the full complexity of real-world environmental dynamics, this study contributes to understanding the variability and optimization of enhanced weathering for CO2 sequestration, supporting its potential as a sustainable CO2 removal strategy.