Total alkalinity during laboratory incubation experiments on enhanced benthic weathering in organic rich Baltic Sea sediments

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 (January - May 2022). 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. Eight sediment cores were placed in a rack in an upright position. The bottom water was carefully removed via suction and replaced with a known volume (1.5 l – 2.0 l) of filtered (0.2 µm) Baltic Sea bottom water in order to remove pelagic auto- and heterotrophs and suspended particles. The volume of water added depended on the height of sediment in each core which varied slightly due to the recovery method. After this procedure, a gaseous headspace of ca. 10 cm was left in each core. Furthermore, the cores were equipped with adjustable stirring heads that contained ports for inserting optodes to continuously record pH and oxygen (O2) concentrations in the overlying water. In order to prevent anoxic conditions developing, ambient air was bubbled into the water column. The water column in each core was slowly and continuously flushed with a constant throughflow of 40 µl min-1 from a single reservoir of bottom water. The residence time of the water inside the cores was thus about 4 to 5 weeks. Bottom water samples were taken from the outflow of each core over a time period of several hours. Thus, samples represent the average outflow over the respective time period. Sampling intervals increased from daily during the first two weeks to every three to four days and weekly towards the end of the experiment. All samples were filtered through a 0.2 µm cellulose membrane filter and refrigerated in 25 ml ZinsserTM scintillation vials. Samples for total alkalinity (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.