Enhanced mineral dissolution in the benthic environment is currently discussed as a potential technique for ocean alkalinity enhancement (OAE) to reduce atmospheric carbon dioxide (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 anoxic to hypoxic environment. The sediment cores were incubated with Baltic Sea bottom water. Eight sediment cores were positioned vertically in a rack. Since the sediment surface was slightly oxidized by the bottom water (∼125 μmol l−1 upon recovery), the cores were left plugged on the top for 13 days to settle after recovery until the sediment surface was anoxic. To achieve chemical conditions that are expected in the natural system, 500l of retrieved sea water were degassed via bubbling with pure dinitrogen gas in batches of 100 l. Afterwards, between 50 and 60 l were transferred into an evacuated gas tight bag. After the transfer, pH and total alkalinity (TA) were measured to determine the dissolved inorganic carbon (DIC) of the water. Afterwards the DIC was increased via adding pure CO2 until a CO2 partial pressure (pCO2 ) of ∼2,300–∼3,300 μatm was established mimicking conditions prevailing in Boknis Eck during summer. Stirring heads were installed on the cores. To prevent the development of oxic conditions, it was ensured that as little gas phase as possible was left in the cores. Elimination of pelagic autotrophs, heterotrophs, and suspended particles was achieved by flushing the cores with modified bottom water for 2 days with a flow rate of 1.5 mml min−1. Afterwards, a continuous throughflow of 700 μl min−1 from the reservoir of modified bottom water was applied, leading to a residence time of ∼2.1 days inside the cores. For the experimental incubations, six cores received additions of alkaline materials, three with calcite (Cal1 - Cal3) and three cores with dunite (Dun1 - Dun3), leading to three replicates per treatment. Two control cores remained untreated (C1, C2). The amount of added substrate was based on the rain rate of particulate organic carbon observed in Boknis Eck (0.5 mmol cm−2 a−). The incubation lasted for 25 days. The volume of water in each core was determined at the end of the experiment via measuring the height of the water column after removing the stirring heads. At the end of the experiments, the bottom water was removed via suction and the cores were sliced for pore water analysis. The pore waters were recovered by centrifuging each respective sediment layer in 50 ml falcon tubes at 3000 rpm for 10 minutes. Afterwards, the supernatant water was transferred to polyethylene (PE) vials in an Ar-filled glove bag to minimize contact with oxygen. All samples were filtered through a 0.2 µm cellulose membrane filter and refrigerated in 25 ml ZinsserTM scintillation vials. TA samples (1 ml) were titrated with 0.02N HCl. For H2S, an aliquot of pore water was diluted. A 5 ml aliquot was frozen directly after the sampling procedure for later nutrient analysis. Nutrient measurements were performed either via manual photometric measurement (NH4) or using a Seal – AnalyticalTM QuAAtro autoanalyzer (PO43-). Samples for TA were analyzed directly after sampling by titration of 1 ml of bottom/pore water with 0.02N HCl. Titration was ended when a stable purple color appeared. During titration, the sample was degassed by continuous bubbling with nitrogen to remove any generated CO2 and H2S. The acid was standardized using an IAPSO seawater standard. Acidified sub-samples (30 μl suprapure HNO3- + 3 ml sample) were prepared for analyses of major and trace elements (Si, Na, K, Li, B, Mg, Ca, Sr, Mn, Ni and Fe) by inductively coupled plasma optical emission spectroscopy (ICP-OES, Varian 720-ES). For H2S, an aliquot of pore water was diluted with appropriate amounts of oxygen-free artificial seawater and the H2S was fixed by immediate addition of zinc acetate gelatin solution

Additional information regarding the experimental set-up: Laboratory: GEOMAR cool-lab (12.5 °C) Treatments, added to sediment core of 10 cm diameter: Dunite (4.4781 g, manufacturer Sibelco), Calcite (7.8618 g, manufacturer unknown). Baltic sea water sampled in Boknis Eck (Salinity: 21, Temperature: 4.2 °C) Start of the experiments: 2022-11-09T10:00* End of the experiments: 2022-12-04T09:45