Coastal barium cycling at the West Antarctic Peninsula

Barium cycling in the ocean is associated with a number of processes, including the production and recycling of organic matter, freshwater fluxes, and phenomena that affect alkalinity. As a result, the biogeochemical cycle of barium offers insights into past and present oceanic conditions, with barium currently used in various forms as a palaeoproxy for components of organic and inorganic carbon storage, and as a quasi-conservative water mass tracer. However, the nature of the oceanic barium cycle is not fully understood, particularly in cases where multiple processes may be interacting simultaneously with the dissolved and particulate barium pools. This is particularly the case in coastal polar regions such as the West Antarctic Peninsula, where biological drawdown and remineralisation occur in tandem with sea ice formation and melting, glacial meltwater input, and potential fluxes from shelf sediments. Here, we use a high-precision dataset of dissolved barium (Bad) from a grid of stations adjacent to the West Antarctic Peninsula in conjunction with silicic acid (Si(OH)(4)), the oxygen isotope composition of water, and salinity measurements, to determine the relative control of various coastal processes on the barium cycle throughout the water column. There is a strong correlation between Bad and Si(OH)(4) present in deeper samples, but nevertheless persists significantly in surface waters. This indicates that the link between biogenic opal and barium is not solely due to barite precipitation and dissolution at depth, but is supplemented by an association between Bad and diatom tests in surface waters, possibly due to barite formation within diatom-dominated phytodetritus present in the photic zone. Sea-ice meltwater appears to exert a significant secondary control on barium concentrations, likely due to non-conservative biotic or abiotic processes acting as a sink for Bad within the sea ice itself, or sea-ice meltwater stimulating non-siliceous productivity that acts as a Bad sink. Meteoric water input, conversely, exerts little or no control on local barium levels, indicating that glacial meltwater is not a significant coastal source of barium to the West Antarctic Peninsula shelf waters.