Carbonate chemistry of intermediate waters in the Southwest Pacific Ocean since the Last Glacial Maximum

Shifts in ocean circulation and marine carbon storage likely played an important role in the termination of the last ice age, but the mechanisms driving these changes have not yet been fully explained. It has been suggested that a greater amount of CO2 was stored in the deep sea during glacial periods via the biologic pump and/or increased uptake by a more alkaline ocean. To quantify the relative roles of such processes, more constraints on past deep ocean alkalinity are needed. Here, we present a new record of deep water carbonate chemistry for the last 30,000 years derived from a sediment core located at 1,627 meters depth in New Zealand's Bay of Plenty. Today, this core site lies at the boundary between relatively fresh Antarctic/Tasman Intermediate Water (above), and Circumpolar Deep Water (below) with more corrosive Pacific Deep Water also intruding from the north. Trace element and stable isotopic composition of foraminiferal calcite (the epibenthic species Cibicidoides wuellerstorfi) reveal changes in bottom water carbonate chemistry during periods of atmospheric CO2 change. The boron to calcium ratio (B/Ca) in these shells indicates that deep water saturation (ΔCO32-) during the last glacial maximum (LGM) was only 5 μmol kg-1 less than the modern value of ~ 20 μmol/kg, consistent with previous work identifying the Pacific as a 'well-buffered' ocean basin on long timescales. However, reconstructed ΔCO32- values fluctuated by as much as 30 μmol/kg across the deglaciation, exhibiting the most pronounced changes between 17 and 13 ka. Together with shifts in carbon isotopes, these results imply changes in circulation and/or respired CO2 storage, and support a series of events in which major oceanographic changes are intimately linked with shifts in atmospheric circulation.