Ocean Alkalinity Research Articles

Atmospheric CO2 over the Past 66 Million Years from Marine Archives

Throughout Earth's history, CO2 is thought to have exerted a fundamental control on environmental change. Here we review and revise CO2 reconstructions from boron isotopes in carbonates and carbon isotopes in organic matter over the Cenozoic—the past 66 million years. We find close coupling between CO2 and climate throughout the Cenozoic, with peak CO2 levels of ∼1,500 ppm in the Eocene greenhouse, decreasing to ∼500 ppm in the Miocene, and falling further into the ice age world of the Plio–Pleistocene. Around two-thirds of Cenozoic CO2 drawdown is explained by an increase in the ratio of ocean alkalinity to dissolved inorganic carbon, likely linked to a change in the balance of weathering to outgassing, with the remaining one-third due to changing ocean temperature and major ion composition. Earth system climate sensitivity is explored and may vary between different time intervals. The Cenozoic CO2 record highlights the truly geological scale of anthropogenic CO2 change: Current CO2 levels were last seen around 3 million years ago, and major cuts in emissions are required to prevent a return to the CO2 levels of the Miocene or Eocene in the coming century. ▪ CO2 reconstructions over the past 66 Myr from boron isotopes and alkenones are reviewed and re-evaluated. ▪ CO2 estimates from the different proxies show close agreement, yielding a consistent picture of the evolution of the ocean-atmosphere CO2 system over the Cenozoic. ▪ CO2 and climate are coupled throughout the past 66 Myr, providing broad constraints on Earth system climate sensitivity. ▪ Twenty-first-century carbon emissions have the potential to return CO2 to levels not seen since the much warmer climates of Earth's distant past.

Alkalinization Scenarios in the Mediterranean Sea for Efficient Removal of Atmospheric CO2 and the Mitigation of Ocean Acidification

It is now widely recognized that in order to reach the target of limiting global warming to well below 2°C above pre-industrial levels (as the objective of the Paris agreement), cutting the carbon emissions even at an unprecedented pace will not be sufficient, but there is the need for development and implementation of active Carbon Dioxide Removal (CDR) strategies. Among the CDR strategies that currently exist, relatively few studies have assessed the mitigation capacity of ocean-based Negative Emission Technologies (NET) and the feasibility of their implementation on a larger scale to support efficient implementation strategies of CDR. This study investigates the case of ocean alkalinization, which has the additional potential of contrasting the ongoing acidification resulting from increased uptake of atmospheric CO2 by the seas. More specifically, we present an analysis of marine alkalinization applied to the Mediterranean Sea taking into consideration the regional characteristics of the basin. Rather than using idealized spatially homogenous scenarios of alkalinization as done in previous studies, which are practically hard to implement, we use a set of numerical simulations of alkalinization based on current shipping routes to quantitatively assess the alkalinization efficiency via a coupled physical-biogeochemical model (NEMO-BFM) for the Mediterranean Sea at 1/16° horizontal resolution (~6 km) under an RCP4.5 scenario over the next decades. Simulations suggest the potential of nearly doubling the carbon-dioxide uptake rate of the Mediterranean Sea after 30 years of alkalinization, and of neutralizing the mean surface acidification trend of the baseline scenario without alkalinization over the same time span. These levels are achieved via two different alkalinization strategies that are technically feasible using the current network of cargo and tanker ships: a first approach applying annual discharge of 200 Mt Ca(OH)2 constant over the alkalinization period and a second approach with gradually increasing discharge proportional to the surface pH trend of the baseline scenario, reaching similar amounts of annual discharge by the end of the alkalinization period. We demonstrate that the latter approach allows to stabilize the mean surface pH at present day values and substantially increase the potential to counteract acidification relative to the alkalinity added, while the carbon uptake efficiency (mole of CO2 absorbed by the ocean per mole of alkalinity added) is only marginally reduced. Nevertheless, significant local alterations of the surface pH persist, calling for an investigation of the physiological and ecological implications of the extent of these alterations to the carbonate system in the short to medium term in order to support a safe, sustainable application of this CDR implementation.

Community responses of intertidal foraminifera to pH variations: a culture experiment with propagules

Calcifying organisms such as benthic foraminifera are susceptible to changes in ocean pH and alkalinity. Responses to these changes include variations in mortality, calcification rates or assemblage composition, which have been observed in field and experimental studies. Here we applied a growth experiment with benthic foraminiferal propagules under different pH conditions to gather insights into the effect of pH on the composition of grown assemblages. A homogeneous propagule assemblage from a local mudflat in Corfu Island (Greece) was exposed to a range of pH conditions (6.5, 7.2, 7.8 and 8.5) for 5 weeks. In a second experiment, the assemblages were first exposed to low and subsequently to high conditions for a total of 8 weeks. After termination of the experiments, we recorded high survivability and growth throughout the treatments. Analysis of the assemblage composition of the first experiments revealed a shift from porcelaneous dominated taxa in the higher pH treatments to an assemblage with higher numbers of agglutinated taxa in the lower pH treatments. Soft-shelled monothalamous species were common throughout. The second experiment revealed assemblages that were significantly dominated by porcelaneous taxa with monothalamous taxa being almost absent. The results of this study are congruent with other observations on changing assemblage compositions with changing pH from both laboratory and field studies. The fast response of the assemblages through activation of potentially dormant propagules adds insights into the mechanisms behind seasonal composition changes in naturally variable environments such as river estuaries. They also shed new light on possible effects of continuous decreases in ocean pH on shallow-water foraminiferal assemblages in future.

Removing Carbon Dioxide Through Ocean Alkalinity Enhancement and Seaweed Cultivation: Legal Challenges and Opportunities

Scientists increasingly agree that carbon dioxide removal will be needed, alongside deep emissions cuts, to stave off the worst impacts of climate change. A wide variety of technologies and strategies have been proposed to remove carbon dioxide from the atmosphere. To date, most research has focused on terrestrial-based approaches, but they often have large land requirements, and may present other risks and challenges. As such, there is growing interest in using the oceans, which have already absorbed more than a quarter of anthropogenic carbon dioxide emissions, and could become an even larger carbon sink in the future. This paper examines the international and U.S. legal frameworks applicable to two ocean-based carbon dioxide removal strategies—ocean alkalinity enhancement and seaweed cultivation. Ocean alkalinity enhancement involves adding alkalinity to ocean waters, either by discharging alkaline rocks or through an electrochemical process, which increases ocean pH levels and thereby enables greater uptake of carbon dioxide, as well as reducing the adverse impacts of ocean acidification. Seaweed cultivation involves the growing of kelp and other macroalgae to store carbon in biomass, which can then either be used to replace more greenhouse gas-intensive products or sequestered.

Preformed Properties for Marine Organic Matter and Carbonate Mineral Cycling Quantification

AbstractWe estimate preformed ocean phosphate, nitrate, oxygen, silicate, and alkalinity by combining a reconstruction of ventilation pathways in the ocean interior with estimates of submixed layer properties. These new preformed property estimates are intended to aid biogeochemical cycling studies and validation of modeled preformed property distributions and are available online. Analyses of net property accumulations (observed minus preformed properties) indicate net remineralization ratios in the ocean interior of [1 P]: [14.1 ± 0.6 N]: [−141 ± 12 O2]: [95 ± 25 Si]: [89 ± 9 TA]. These ratios imply that the interior ocean stores 1,300 (±230) PgC through organic matter remineralization and 540 (±60) PgC through carbonate mineral dissolution and that apparent oxygen utilization can overestimate the interior ocean oxygen consumption by ~25%. Further, only 4 (±1%) and 46 (±5%) of the total alkalinity accumulated from carbonate mineral dissolution are found in seawater that is supersaturated with respect to the aragonite and calcite mineral forms of calcium carbonate, respectively. These small excess alkalinity inventories are due to smaller volumes of the supersaturated water masses and shorter ventilation timescales, as carbonate mineral dissolution rates appear nearly independent of depth and saturation state.

Anthropogenic CO2 of High Emission Scenario Compensated After 3500 Years of Ocean Alkalinization With an Annually Constant Dissolution of 5 Pg of Olivine

The CO2 removal model inter-comparison (CDRMIP) has been established to approximate the usefulness of climate mitigation by some well-defined negative emission technologies. I here analyze ocean alkalinization in a high CO2 world (emission scenario SSP5-85-EXT++ and CDR-ocean-alk within CDRMIP) for the next millennia using a revised version of the carbon cycle model BICYCLE, whose long-term feedbacks are calculated for the next 1 million years. The applied model version not only captures atmosphere, ocean, and a constant marine and terrestrial biosphere, but also represents solid Earth processes, such as deep ocean CaCO3 accumulation and dissolution, volcanic CO2 outgassing, and continental weathering. In the applied negative emission experiment, 0.14 Pmol/yr of alkalinity—comparable to the dissolution of 5 Pg of olivine per year—is entering the surface ocean starting in year 2020 for either 50 or 5000 years. I find that the cumulative emissions of 6,740 PgC emitted until year 2350 lead to a peak atmospheric CO2 concentration of nearly 2,400 ppm in year 2326, which is reduced by only 200 ppm by the alkalinization experiment. Atmospheric CO2 is brought down to 400 or 300 ppm after 2730 or 3480 years of alkalinization, respectively. Such low CO2 concentrations are reached without ocean alkalinization only after several hundreds of thousands of years, when the feedbacks from weathering and sediments bring the part of the anthropogenic emissions that stays in the atmosphere (the so-called airborne fraction) below 4%. The efficiency of carbon sequestration by this alkalinization approach peaks at 9.7 PgC per Pmol of alkalinity added during times of maximum anthropogenic CO2 emissions and slowly declines to half this value 2000 years later due to the non-linear marine chemistry response and ocean-sediment processes. In other words, ocean alkalinization sequesters carbon only as long as the added alkalinity stays in the ocean. To understand the basic model behavior, I analytically explain why in the simulation results a linear relationship in the transient climate response (TCR) to cumulative emissions is found for low emissions (similarly as for more complex climate models), which evolves for high emissions to a non-linear relation.

The IOD Impacts on the Indian Ocean Carbon Cycle

AbstractThis paper examines the impacts of Indian Ocean Dipole (IOD) Mode on the upper ocean carbon cycle and its variability in the Indian Ocean with available biogeochemical observations and 60 years (1960–2019) of model outputs from a global ocean biogeochemical general circulation model. The upper ocean carbon cycle variability of the Indian Ocean is faithfully reproduced by the model when compared with available observations. The IOD leads to a substantial sea‐to‐air CO2 flux variability in the southeastern tropical Indian Ocean over a broad region (70–105°E, 0–20°S), with more focus near the coast of Java‐Sumatra due to the prevailing upwelling dynamics and associated westward propagating anomalies. The sea‐to‐air CO2 fluxes, surface ocean partial pressure of CO2 (pCO2), the concentration of dissolved inorganic carbon (DIC), and ocean alkalinity (ALK) range as much as ±1.0 mole m−2 year−1, ±20 μatm, ±35 μmole kg−1, and ±22 μmole kg−1 within 80–105°E, 0–10°S due to IOD. The DIC and ALK are significant drivers of pCO2 variability associated with IOD. The roles of temperature (T) and biology are found negligible. A relatively warm T and extremely high freshwater forcing make the southeastern tropical Indian Ocean carbon cycle variability submissive to DIC and ALK evolutions in contrast to the tropical eastern Pacific where changes in DIC and T dominate the pCO2 interannual variability. For the first time, this study provides a most comprehensive and extended analysis for the region while highlighting significant differences in carbon cycle variability of the eastern tropical Indian Ocean compared to that of the other parts of the global oceans.

Detectability of Artificial Ocean Alkalinization and Stratospheric Aerosol Injection in MPI‐ESM

AbstractTo monitor the success of carbon dioxide removal (CDR) or solar radiation management (SRM) that offset anthropogenic climate change, the forced response to any external forcing is required to be detectable against internal variability. Thus far, only the detectability of SRM has been examined using both a stationary and nonstationary detection and attribution method. Here, the spatiotemporal detectability of the forced response to artificial ocean alkalinization (AOA) and stratospheric aerosol injection (SAI) as exemplary methods for CDR and SRM, respectively, is compared in Max Planck Institute Earth System Model (MPI‐ESM) experiments using regularized optimal fingerprinting and single‐model estimates of internal variability, while working under a stationary or nonstationary null hypothesis. Although both experiments are forced by emissions according to the Representative Concentration Pathway 8.5 (RCP8.5) and target the climate of the RCP4.5 scenario using AOA or SAI, detection timescales reflect the fundamentally different forcing agents. Moreover, detectability timescales are sensitive to the choice of null hypothesis. Globally, changes in the CO2 system in seawater are detected earlier than the response in temperature to AOA but later in the case of SAI. Locally, the detection time scales depend on the physical, chemical, and radiative impacts of CDR and SRM forcing on the climate system, as well as patterns of internal variability, which is highlighted for oceanic heat and carbon storage.

A Mechanistic Study of Carbonic Anhydrase‐Enhanced Calcite Dissolution

AbstractCarbonic anhydrase (CA) has been shown to promote calcite dissolution (Liu, 2001,https://doi.org/10.1111/j.1755-6724.2001.tb00531.x; Subhas et al., 2017,https://doi.org/10.1073/pnas.1703604114), and understanding the catalytic mechanism will facilitate our understanding of the oceanic alkalinity cycle. We use atomic force microscopy (AFM) to directly observe calcite dissolution in CA‐bearing solution. CA is found to etch the calcite surface only when in extreme proximity (~1 nm) to the mineral. Subsequently, the CA‐induced etch pits create step edges that serve as active dissolution sites. The possible catalytic mechanism is through the adsorption of CA on the calcite surface, followed by proton transfer from the CA catalytic center to the calcite surface during CO2hydration. This study shows that the accessibility of CA to particulate inorganic carbon (PIC) in the ocean is critical in properly estimating oceanic CaCO3and alkalinity cycles.

Deep water [CO32−] and circulation in the south China sea over the last glacial cycle

Records of carbonate ion concentration ([CO32−]) and benthic carbon isotope (δ13C) have profound implications for exploring deep water circulation and global carbon cycle. However, information on the glacial-interglacial deep ocean [CO32−] changes is still limited, especially in the Pacific Ocean. Here, we present new deep water [CO32−] records of the last glacial cycle, reconstructed by the B/Ca ratios of benthic foraminifera Cibicidoides wuellerstorfi from two cores in the South China Sea (SCS). The deep water [CO32−] changes of the SCS display similar trends with that of the western Pacific as well as “Pacific-type” CaCO3 (%), suggesting that the deep water carbonate chemistry of the SCS may reflect that of the Pacific. Our results support that carbonate dissolution is the primary driver for “Pacific-type” CaCO3 preservation during the late Quaternary glacial cycles. At the marine isotope stage (MIS) 5a to MIS 4 transition, deep water [CO32−] decreased with an amplitude of ∼7 μmol/kg in the SCS, roughly consistent with that from the Pacific cores at 2300–4300 m water depth. Considering a greater oceanic alkalinity and stronger carbonate dissolution at that time, this implies that deep Pacific carbon storage increased. The gradients of deep water [CO32−] and δ13C between the Pacific and the SCS reduced during extreme glacials (e.g., MIS 2, 4 and 6) relative to interglacials (e.g., MIS 1 and 5e), indicating weakened deep ocean ventilation and more sluggish Pacific deep-water circulation. This change is also confirmed by meridional δ13C distributions in the western Pacific for the Holocene and the last glacial maximum (LGM), and further supported by climate simulations using a complex Earth System Model. Overall, our results suggest that the increased deep Pacific carbon storage correlated to increased oceanic alkalinity and more sluggish Pacific deep-water circulation would have contributed to the atmospheric CO2 decrease during the last glacial period.

Antacids for the Sea? Artificial Ocean Alkalinization and Climate Change

There is increasing urgency for large-scale deployment of carbon-removal approaches to help avoid passing critical climatic thresholds. Given the severe risks of many terrestrial methods at extremely large scales, there is a compelling need to also assess the potential of marine negative-emissions technologies, such as artificial ocean alkalinization.

Ocean Alkalinity, Buffering and Biogeochemical Processes.

Alkalinity, the excess of proton acceptors over donors, plays a major role in ocean chemistry, in buffering and in calcium carbonate precipitation and dissolution. Understanding alkalinity dynamics is pivotal to quantify ocean carbon dioxide uptake during times of global change. Here we review ocean alkalinity and its role in ocean buffering as well as the biogeochemical processes governing alkalinity and pH in the ocean. We show that it is important to distinguish between measurable titration alkalinity and charge balance alkalinity that is used to quantify calcification and carbonate dissolution and needed to understand the impact of biogeochemical processes on components of the carbon dioxide system. A general treatment of ocean buffering and quantification via sensitivity factors is presented and used to link existing buffer and sensitivity factors. The impact of individual biogeochemical processes on ocean alkalinity and pH is discussed and quantified using these sensitivity factors. Processes governing ocean alkalinity on longer time scales such as carbonate compensation, (reversed) silicate weathering, and anaerobic mineralization are discussed and used to derive a close‐to‐balance ocean alkalinity budget for the modern ocean.

Understanding Alkalinity to Quantify Ocean Buffering

Ocean alkalinity plays a major role in ocean’s carbon uptake, in buffering, and in calcium carbonate production and dissolution, and it impacts and is affected by various biogeochemical processes.

North Indian Ocean Circulation Since the Last Deglaciation as Inferred From New Elemental Ratio Records for Benthic Foraminifera Hoeglundina elegans

AbstractThe evolution of intermediate circulation in the northern Indian Ocean since the last deglaciation has been reconstructed from two marine cores located at intermediate depths off the southern tip of India (MD77‐191) and in the northern Bay of Bengal (BoB) (MD77‐176). Benthic foraminiferal δ13C, seawater carbonate ion concentration ([CO32−]) estimated from the Sr/Ca, and paleotemperature reconstructed on the basis of the Mg/Li of aragonite benthic species Hoeglundina elegans were used to trace the evolution of past intermediate‐deepwater masses and to constrain ocean‐atmosphere exchanges during the two‐stage increase in atmospheric CO2 across the last deglaciation. The intermediate water [CO32−] was mainly affected by changes in the ocean alkalinity inventory, associated with the modulation of atmospheric CO2 on glacial‐interglacial timescales. Higher benthic foraminiferal δ13C, depleted [CO32−], and decreased benthic‐planktonic 14C age offsets at intermediate water depths suggest a release of deep‐sea CO2 to the atmosphere through the Antarctic Intermediate Water (AAIW) in the Southern Ocean during the 17–15.2 and 12.6–10.5 cal kyr BP time intervals. In addition, the decreased H. elegans Mg/Li record seems to reflect an increased contribution of cold water mass during the 17–15.2 and 12.6–11.9 cal kyr BP intervals and throughout the Holocene. In contrast, two warm events occurred in the 15–13.3 and 11–10.3 cal kyr BP time intervals. During the late Holocene, a decrease in the intermediate water [CO32−] indicates a contribution to atmospheric CO2 rise since 8 cal kyr BP, due to the depleted global ocean alkalinity and/or the variations in surface productivity (at least for MD77‐191).

Effect of Organic Alkalinity on Seawater Buffer Capacity: A Numerical Exploration

Organic alkalinity is a poorly understood component of total titration alkalinity in aquatic environments. Using a numerical method, the effects of organic acid (HOA) and its conjugate base (OA−) on seawater carbonate chemistry and buffer behaviors, as well as those in a hypothetical estuarine mixing zone, are explored under both closed- and open-system conditions. The simulation results show that HOA addition leads to pCO2 increase and pH decrease in a closed system when total dissolved inorganic carbon (DIC) remains the same. If opened to the atmosphere (pCO2 = 400 µatm), CO2 degassing and re-equilibration would cause depressed pH compared to the unperturbed seawater, but the seawater buffer to pH change $$\left( {\beta _{{{\text{DIC}}}} \, = \left( {\frac{{\partial \ln \left( {\left[ {{\text{H}}^{ + } } \right]} \right)}}{{\partial {\text{DIC}}}}} \right)^{{ - 1}} } \right)$$ indicates that weaker organic acid (i.e., higher pKa) results in higher buffer capacity (greater βDIC) than the unperturbed seawater. In comparison, OA− (with accompanying cations) in the form of net alkalinity addition leads to pCO2 decrease in a closed system. After re-equilibrating with the atmosphere, the resulting perturbed seawater has higher pH and βDIC than the unperturbed seawater. If river water has organic alkalinity, pH in the estuarine mixing zone is always lower than those caused by a mixing between organic alkalinity-free river (at constant total alkalinity) and ocean waters, regardless of the pKa values. On the other hand, organic alkalinity with higher pKa provides slightly greater βDIC in the mixing zone, and that with lower pKa either results in large CO2 oversaturation (closed system) or reduced βDIC (in mid to high salinity in the closed system or the entire mixing zone in the open system). Finally, despite the various effects on seawater buffer through either HOA or OA− addition, destruction of organic molecules including organic alkalinity via biogeochemical reactions should result in a net CO2 loss from seawater. Nevertheless, the significance of this organic alkalinity, especially that comes from organic acids that are not accounted for under the currently recognized “zero proton level” (Dickson in Deep Sea Res 28:609–623, 1981), remains unknown thus a potentially interesting and relevant research topic in studying oceanic alkalinity cycle.

Comparative Assessment of Climate Engineering Scenarios in the Presence of Parametric Uncertainty

AbstractClimate engineering (CE) measures are increasingly discussed when dealing with the adverse impacts of climate change. While much research has focused on individual methods, few studies attempt to compare and rank the effectiveness of these measures. Furthermore, model uncertainties are seldom acknowledged and lesser still, estimated when CE scenarios are assessed. In this work, we quantify the variance in outcomes due to poorly constrained model parameters under several idealized CE scenarios. The four scenarios considered are (1) warming under the high emission scenario Representative Concentration Pathway 8.5 without CE applied and the same emission scenario with (2) afforestation,(3) solar radiation management, and (4) artificial ocean alkalinization. By considering the parametric uncertainty in model outputs, we demonstrate the problems with comparing these scenarios using a single parameter setting. Using statistical emulation, we estimate the probability distributions of several model outcomes. Based on such distributions, we suggest an approach to ranking the effectiveness of the scenarios considered according to their probability of avoiding climate thresholds.

Increased fluvial runoff terminated inorganic aragonite precipitation on the Northwest Shelf of Australia during the early Holocene

Inorganic precipitation of aragonite is a common process within tropical carbonate environments. Across the Northwest Shelf of Australia (NWS) such precipitates were abundant in the late Pleistocene, whereas present-day sedimentation is dominated by calcitic bioclasts. This study presents sedimentological and geochemical analyses of core data retrieved from the upper 13 meters of IODP Site U1461 that provide a high-resolution sedimentary record of the last ~15 thousand years. Sediments that formed from 15 to 10.1 ka BP are aragonitic and characterised by small needles (<5 µm) and ooids. XRF elemental proxy data indicate that these sediments developed under arid conditions in which high marine alkalinity favoured carbonate precipitation. A pronounced change of XRF-proxy values around 10.1 ka BP indicates a transition to a more humid climate and elevated fluvial runoff. This climatic change coincides with a shelf-wide cessation of inorganic aragonite production and a switch to carbonate sedimentation dominated by skeletal calcite. High ocean water alkalinity due to an arid climate and low fluvial runoff therefore seems to be a prerequisite for the formation of shallow water aragonite-rich sediments on the NWS. These conditions are not necessarily synchronous to interglacial periods, but are linked to the regional hydrological cycle.

CO2 Removal With Enhanced Weathering and Ocean Alkalinity Enhancement: Potential Risks and Co-benefits for Marine Pelagic Ecosystems

Humankind will need to remove hundreds of gigatons of carbon dioxide (CO2) from the atmosphere by the end of the twenty-first century to keep global warming below 2°C within the constraints of the global carbon budget. However, so far it is unclear if and how this could be achieved. A widely recognized idea is to accelerate weathering reactions of minerals that consume CO2 when they dissolve. Acceleration could be realized by pulverizing and distributing gigatons of these minerals onto land (termed “enhanced weathering (EW)”) or sea (termed “ocean alkalinity enhancement (OAE)”) thereby largely increasing their reactive surfaces. However, the desired consumption of atmospheric CO2 during dissolution would inevitably be accompanied by a release of mineral dissolution products (alkalinity, Si, Ca, Mg, Fe, Ni, and maybe others). Here, we approximate their maximum additions to assess potential consequences for pelagic communities (mainly primary producers) and the biogeochemical fluxes they control. Based on this assessment, we tentatively qualify the potential to induce positive and/or negative side effects to be high for Fe, Ni, Si, intermediate for alkalinity, and low for Ca and Mg. However, perturbation potentials are always higher at perturbation hotspots and would be different for EW than for OAE. Furthermore, ecological/biogeochemical consequences of EW/OAE largely depend on the minerals used. We hypothesize that mainly calcifiers would profit in a scheme where CaCO3 derivatives would be used due to beneficial changes in carbonate chemistry. Figuratively, this may turn the blue ocean into a white(r) ocean. When using silicates, the release of additional Si, Fe and Ni could benefit silicifiers and N2-fixers (cyanobacteria) and increase ocean productivity ultimately turning the blue ocean into a green(er) ocean. These considerations call for dedicated research to assess risks and co-benefits of mineral dissolution products on marine and other environments. Indeed, both EW and OAE could become important tools to realize CO2 removal at the planetary scale but associated risks and/or co-benefits should be revealed before deciding on their implementation.

What was the source of the atmospheric CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; increase during the Holocene?

Abstract. The atmospheric CO2 concentration increased by about 20 ppm from 6000 BCE to the pre-industrial period (1850 CE). Several hypotheses have been proposed to explain mechanisms of this CO2 growth based on either ocean or land carbon sources. Here, we apply the Earth system model MPI-ESM-LR for two transient simulations of climate and carbon cycle dynamics during this period. In the first simulation, atmospheric CO2 is prescribed following ice-core CO2 data. In response to the growing atmospheric CO2 concentration, land carbon storage increases until 2000 BCE, stagnates afterwards, and decreases from 1 CE, while the ocean continuously takes CO2 out of the atmosphere after 4000 BCE. This leads to a missing source of 166 Pg of carbon in the ocean–land–atmosphere system by the end of the simulation. In the second experiment, we applied a CO2 nudging technique using surface alkalinity forcing to follow the reconstructed CO2 concentration while keeping the carbon cycle interactive. In that case the ocean is a source of CO2 from 6000 to 2000 BCE due to a decrease in the surface ocean alkalinity. In the prescribed CO2 simulation, surface alkalinity declines as well. However, it is not sufficient to turn the ocean into a CO2 source. The carbonate ion concentration in the deep Atlantic decreases in both the prescribed and the interactive CO2 simulations, while the magnitude of the decrease in the prescribed CO2 experiment is underestimated in comparison with available proxies. As the land serves as a carbon sink until 2000 BCE due to natural carbon cycle processes in both experiments, the missing source of carbon for land and atmosphere can only be attributed to the ocean. Within our model framework, an additional mechanism, such as surface alkalinity decrease, for example due to unaccounted for carbonate accumulation processes on shelves, is required for consistency with ice-core CO2 data. Consequently, our simulations support the hypothesis that the ocean was a source of CO2 until the late Holocene when anthropogenic CO2 sources started to affect atmospheric CO2.

Climate engineering–induced changes in correlations between Earth system variables—implications for appropriate indicator selection

Climate engineering (CE) deployment would alter prevailing relationships between Earth system variables, making indicators and metrics used so far in the climate change assessment context less appropriate to assess CE measures. Achieving a comprehensive CE assessment requires a systematic and transparent reevaluation of the indicator selection process from Earth system variables. Here, we provide a first step towards such a systematic assessment of changes in correlations between Earth system variables following simulated deployment of different CE methods. We therefore analyze changes in the correlation structure of a broad set of Earth system variables for two conventional climate change scenarios without CE and with three idealized CE model experiments: (i) solar radiation management, (ii) large-scale afforestation, and (iii) ocean alkalinity enhancement. First, we investigate how the three CE scenarios alter prevailing correlations between Earth system variables when compared to an intermediate-high and a business-as-usual future climate change scenario. Second, we contrast the indicators identified for the non-CE climate change scenarios and the indicators identified when all five scenarios are considered. Finally, we use the identified indicator sets for an evaluation of the five climate change scenarios. We find that the additional indicators provide valuable information for the assessment of the CE measures, and their application hence allows for a more comprehensive and a comparative assessment of the mitigation and CE deployment scenarios.