Radiogenic lead (Pb) and neodymium (Nd) isotope compositions extracted from authigenic phases in marine sediments are sensitive tracers to reconstruct past ocean circulation and water mass mixing. Chemical reductive leaching of hydrogenetic ferromanganese oxyhydroxides from bulk sediments is the most practical way to recover past seawater Pb and Nd isotope signatures in the Southern Ocean, due to the scarcity of alternative archives. However, the leached signal could be compromised if substantial quantities of Pb and Nd were released from non-hydrogenetic sediment fractions during chemical extraction. Here we developed a very short 10-seconds leaching method to extract reliable seawater Pb and Nd isotope signals from sediments in the Atlantic sector of Southern Ocean. The effect of a previously recommended MgCl prewash, the role of chelate ligands in the leaching solution and length of leaching time were investigated. The results show that 10 seconds exposure time of sediments to reductive leaching extracted sufficient and more reliable hydrogenetic Pb and Nd compared with the commonly used 30-minute leaching approaches. The robustness of our improved leaching method was validated via direct comparison of Pb and Nd isotope signatures with actual seawater, porewater and corresponding sediment leachates from three stations in front of the Antarctic Filchner-Rønne Ice Shelf. Our findings suggest that in contrast previously studied sites on the West Antarctic continental shelf, the southern Weddell Sea shelf is not a location of pronounced benthic Nd fluxes to the water column.

Seawater rare earth element (REE) concentrations are increasingly applied to reconstruct water mass histories by exploiting relative changes in the distinctive normalised patterns. However, the mechanisms by which water masses gain their REE patterns are yet to be fully explained. To examine this, we collected water samples along the Extended Ellett Line (EEL), an oceanographic transect between Iceland and Scotland, and measured dissolved REE by offline automated chromatography (SeaFAST) and ICP-MS. The proximity to two continental boundaries, the incipient spring bloom coincident with the timing of the cruise, and the importance of deep water circulation in this climatically sensitive gateway region make it an ideal location to investigate sources of REE to seawater and the effects of vertical cycling and lateral advection on their distribution. The deep waters have REE concentrations closest to typical North Atlantic seawater and are dominated by lateral advection. Comparison to published seawater REE concentrations of the same water masses in other locations provides a first measure of the temporal and spatial stability of the seawater REE signature. We demonstrate the REE pattern is replicated for Iceland-Scotland Overflow Water (ISOW) in the Iceland Basin from adjacent stations sampled 16 years previously. A recently published Labrador Sea Water dissolved REE signature is reproduced in the Rockall Trough but shows greater light and mid REE alteration in the Iceland Basin, possibly due to the dominant effect of ISOW and/or continental inputs. An obvious concentration gradient from seafloor sediments to the overlying water column in the Rockall Trough, but not the Iceland Basin, highlights release of light and mid REE from resuspended sediments and pore waters, possibly a seasonal effect associated with the timing of the spring bloom in each basin. This study highlights the need for fully constrained REE sources and sinks, including the temporary nature of some sources, to achieve a balanced budget of seawater REE. In this contribution, I discuss some of the potential mechanisms and their implications for the longevity of the seawater REE signature.