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Cited by 183CO2 Sequestration and Geologic InteractionsClimate Change and GeoengineeringMarine and coastal ecosystems

Stability of alkalinity in ocean alkalinity enhancement (OAE) approaches – consequences for durability of CO 2 storage

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Hartmann, Jens, Suitner, Niels, Lim, Carl, Schneider, Julieta, Marín-Samper, Laura, Arístegui, Javier, Renforth, Phil, Taucher, Jan +1 more·2023·Biogeosciences
DOI 10.5194/bg-20-781-2023

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Abstract

According to modelling studies, ocean alkalinity enhancement (OAE) is one of the proposed carbon dioxide removal (CDR) approaches with large potential, with the beneficial side effect of counteracting ocean acidification. The real-world application of OAE, however, remains unclear as most basic assumptions are untested. Before large-scale deployment can be considered, safe and sustainable procedures for the addition of alkalinity to seawater must be identified and governance established. One of the concerns is the stability of alkalinity when added to seawater. The surface ocean is already supersaturated with respect to calcite and aragonite, and an increase in total alkalinity (TA) together with a corresponding shift in carbonate chemistry towards higher carbonate ion concentrations would result in a further increase in supersaturation, and potentially to solid carbonate precipitation. Precipitation of carbonate minerals consumes alkalinity and increases dissolved CO 2 in seawater, thereby reducing the efficiency of OAE for CO 2 removal. In order to address the application of alkaline solution as well as fine particulate alkaline solids, a set of six experiments was performed using natural seawater with alkalinity of around 2400 µmol kgsw −1 . The application of CO 2 -equilibrated alkaline solution bears the lowest risk of losing alkalinity due to carbonate phase formation if added total alkalinity (ΔTA) is less than 2400 µmol kgsw −1 . The addition of reactive alkaline solids can cause a net loss of alkalinity if added ΔTA > 600 µmol kgsw −1 (e.g. for Mg(OH) 2 ). Commercially available (ultrafine) Ca(OH) 2 causes, in general, a net loss in TA for the tested amounts of TA addition, which has consequences for suggested use of slurries with alkaline solids supplied from ships. The rapid application of excessive amounts of Ca(OH) 2 , exceeding a threshold for alkalinity loss, resulted in a massive increase in TA ( > 20 000 µmol kgsw −1 ) at the cost of lower efficiency and resultant high pH values > 9.5. Analysis of precipitates indicates formation of aragonite. However, unstable carbonate phases formed can partially redissolve, indicating that net loss of a fraction of alkalinity may not be permanent, which has important implications for real-world OAE application. Our results indicate that using an alkaline solution instead of reactive alkaline particles can avoid carbonate formation, unless alkalinity addition via solutions shifts the system beyond critical supersaturation levels. To avoid the loss of alkalinity and dissolved inorganic carbon (DIC) from seawater, the application of reactor techniques can be considered. These techniques produce an equilibrated solution from alkaline solids and CO 2 prior to application. Differing behaviours of tested materials suggest that standardized engineered materials for OAE need to be developed to achieve safe and sustainable OAE with solids, if reactors technologies should be avoided.

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  • If dissolution is sufficiently rapid but transport of resulting alkalinity away from the grain surface is limited, supersaturation with respect to carbonate minerals may occur, leading to mineral precipitation (aragonite in seawater and calcite in freshwater).

    “If dissolution is sufficiently rapid but transport of resulting alkalinity away from the grain surface is limited, supersaturation with respect to carbonate minerals may occur, leading to mineral precipitation (aragonite in seawater and calcite in freshwater). 12-15”

    From A framework for understanding efficiency losses of Ocean Alkalinity Enhancement (2026) · cites this paper as [15]

    Split into 2 atoms — 0 confirmed, 2 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.

    Experimental — accuracy not yet measured

  • In an OAE context, the most likely minerals to precipitate include calcium carbonate (CaCO3) polymorphs and magnesium hydroxide (Mg(OH)2).

    “In an OAE context, the most likely minerals to precipitate include calcium carbonate (CaCO3) polymorphs and magnesium hydroxide (Mg(OH)2). 14,15,28,30-34”

    From A framework for understanding efficiency losses of Ocean Alkalinity Enhancement (2026) · cites this paper as [15]

    The Discussion (§4.1) describes amorphous calcium carbonate precipitation followed by transformation into aragonite or calcite, supporting the calcium-carbonate part of the claim. But the Methods (§2.3) and Results (§3.5) describe Mg(OH)2 (brucite) as a solid added to seawater to dissolve, not as one of the most likely minerals to precipitate. The paper does not establish that likelihood ranking. (LLM, conf=0.87)

    Experimental — accuracy not yet measured

  • Efficiency losses associated with mineral sinking and precipitation to solids may occur essentially immediately, over seconds to days, whereas losses to incomplete mineral dissolution and incomplete air-sea flux will gradually decrease over time, on the scale of years.

    “For example, efficiency losses associated with mineral sinking and precipitation to solids may occur essentially immediately, over the course of seconds to days, whereas losses to incomplete mineral dissolution, and incomplete air-sea flux will gradually decrease over time, on the scale of years. 15,59”

    From A framework for understanding efficiency losses of Ocean Alkalinity Enhancement (2026) · cites this paper as [15]

    Split into 2 atoms — 0 confirmed, 2 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.

    Experimental — accuracy not yet measured

  • Such precipitation may enter a runaway process, where more alkalinity is lost than the amount added.

    “Such precipitation may enter a runaway process, where more alkalinity is lost than the amount added. 11,14,15,30,48,49”

    From A framework for understanding efficiency losses of Ocean Alkalinity Enhancement (2026) · cites this paper as [15]

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Cited by

Sorted by citations

Authors
Hartmann, J., Suitner, N., Lim, C., Schneider, J., Marín-Samper, L., Arístegui, J., Renforth, P., Taucher, J., & Riebesell, U.
Affiliations
  • Universität Hamburg (DE)
  • University of Bremen (DE)
  • GEOMAR Helmholtz Centre for Ocean Research Kiel (DE)
  • Universidad de Las Palmas de Gran Canaria (ES)
  • Heriot-Watt University (GB)
Corresponding author
  • Hartmann, Jens
  • Suitner, Niels
ORCID
Venue
Biogeosciences
Publisher
Copernicus GmbH
Published
2023-02-20
Volume
20
Issue
4
Pages
781-802
ISSN
  • 1726-4170 (ISSN-L)
  • 1726-4189
DOI
10.5194/bg-20-781-2023
OpenAlex
W4321366460
Cited by
183
References
1
Citations by year
2026: 39 · 2025: 47 · 2024: 43 · 2023: 51 · 2022: 3
FWCI
15.00
Type
journal article
Language
en
Open access
Licence
Locations
  • Biogeosciences (publishedVersion, cc-by)
  • Helmholtz Centre for Ocean Research Kiel (GEOMAR) (acceptedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Funders
  • Horizon 2020
  • Deutsche Forschungsgemeinschaft (390683824)
Topics
  • Physical Sciences › Environmental Science › Environmental Engineering › CO2 Sequestration and Geologic Interactions
  • Physical Sciences › Environmental Science › Global and Planetary Change › Climate Change and Geoengineering
  • Physical Sciences › Earth and Planetary Sciences › Oceanography › Marine and coastal ecosystems
Keywords
ocean alkalinity enhancement, carbon dioxide removal, carbonate precipitation, aragonite, calcite, total alkalinity, calcium hydroxide, magnesium hydroxide, alkaline slurry, ocean acidification, pH increase, alkaline solution, seawater alkalinity

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