Improved Separation of Pa from Th and U in Marine Sediments with TK400 Resin.

Protactinium-231 is a radionuclide of broad interest in paleoceanography and paleoclimatology. This study describes an improved method for the purification and separation of Pa from marine sediment samples using the new TK400 resin by TrisKem International. The focus lies on the improvement of the separation of the abundant 232Th from the Pa fraction of the sample, which would reduce the peak tailing from 232Th on masses 231 and 233 during ICP-MS measurement. Furthermore, the reusability of TK400 has been tested. For this purpose, the conventional method using Dowex AG1X8 for the separation and purification of Pa has been compared to methods using the TK400 resin. A combination of a Dowex AG1X8 prior to a TK400 column has shown most convincing results. Based on our results we suggest a new efficient procedural method of analyzing 231Pa from marine sediment samples using TK400. Chemical Pa yields for a Dowex-TK400 combination are highest compared to the Dowex only method. Furthermore, the 232Th/231Pa ratio of the Pa-fractions has been reduced by 1 order of magnitude compared to conventional methods with Dowex AG1X8. Additionally, the reusability of TK400 resin up to nine times has been proven. The usage of TK400 is only limited in the presence of samples with a high matrix load (e.g., Fe). Therefore, matrix from sediment samples needs to be removed (here using Dowex resin) before samples are loaded onto TK400. We also report a series of concentration measurements from standard reference materials (UREM-11, NIST 2702), which have been used for 233Pa calibration.

Multi-proxy constraints on Atlantic circulation dynamics since the last ice age.

Uncertainties persist in the understanding of the Atlantic meridional overturning circulation and its response to external perturbations such as freshwater or radiative forcing. Abrupt reduction of the Atlantic circulation is considered a climate tipping point that may have been crossed when Earth's climate was propelled out of the last ice age. However, the evolution of the circulation since the Last Glacial Maximum (22-18 thousand years ago) remains insufficiently constrained due to model and proxy limitations. Here we leverage information from both a compilation of proxy records that track various aspects of the circulation and climate model simulations to constrain the Atlantic circulation over the past 20,000 years. We find a coherent picture of a shallow and weak Atlantic overturning circulation during the Last Glacial Maximum that reconciles apparently conflicting proxy evidence. Model-data comparison of the last deglaciation-starting from this new, multiple constrained glacial state-indicates a muted response during Heinrich Stadial 1 and that water mass geometry did not fully adjust to the strong reduction in overturning circulation during the comparably short Younger Dryas period. This demonstrates that the relationship between freshwater forcing and Atlantic overturning strength is strongly dependent on the climatic and oceanic background state.

A global synthesis of high-resolution stable isotope data from benthic foraminifera of the last deglaciation.

We present the first version of the Ocean Circulation and Carbon Cycling (OC3) working group database, of oxygen and carbon stable isotope ratios from benthic foraminifera in deep ocean sediment cores from the Last Glacial Maximum (LGM, 23-19 ky) to the Holocene (<10 ky) with a particular focus on the early last deglaciation (19-15 ky BP). It includes 287 globally distributed coring sites, with metadata, isotopic and chronostratigraphic information, and age models. A quality check was performed for all data and age models, and sites with at least millennial resolution were preferred. Deep water mass structure as well as differences between the early deglaciation and LGM are captured by the data, even though its coverage is still sparse in many regions. We find high correlations among time series calculated with different age models at sites that allow such analysis. The database provides a useful dynamical approach to map physical and biogeochemical changes of the ocean throughout the last deglaciation.

Deglacial patterns of South Pacific overturning inferred from 231Pa and 230Th.

The millennial-scale variability of the Atlantic Meridional Overturning Circulation (AMOC) is well documented for the last glacial termination and beyond. Despite its importance for the climate system, the evolution of the South Pacific overturning circulation (SPOC) is by far less well understood. A recently published study highlights the potential applicability of the 231Pa/230Th-proxy in the Pacific. Here, we present five sedimentary down-core profiles of 231Pa/230Th-ratios measured on a depth transect from the Pacific sector of the Southern Ocean to test this hypothesis using downcore records. Our data are consistent with an increase in SPOC as early as 20 ka that peaked during Heinrich Stadial 1. The timing indicates that the SPOC did not simply react to AMOC changes via the bipolar seesaw but were triggered via Southern Hemisphere processes.

Atlantic deep water circulation during the last interglacial.

Understanding how the Atlantic Meridional Overturning Circulation (AMOC) evolved during crucial past geological periods is important in order to decipher the interplay between ocean dynamics and global climate change. Previous research, based on geological proxies, has provided invaluable insights into past AMOC changes. However, the causes of the changes in water mass distributions in the Atlantic during different periods remain mostly elusive. Using a state-of-the-art Earth system model, we show that the bulk of NCW in the deep South Atlantic Ocean below 4000 m migrated from the western basins at 125 ka to the eastern basins at 115 ka, though the AMOC strength is only slightly reduced. These changes are consistent with proxy records, and it is mainly due to more penetration of the AABW at depth at 115 ka, as a result of a larger density of AABW formed at 115 ka. Our results show that depth changes in regional deep water pathways can result in large local changes, while the overall AMOC structure hardly changes. Future research should thus be careful when interpreting single proxy records in terms of large-scale AMOC changes, and considering variability of water-mass distributions on sub-basin scale would give more comprehensive interpretations of sediment records.

Biological and physical controls in the Southern Ocean on past millennial-scale atmospheric CO2 changes.

Millennial-scale climate changes during the last glacial period and deglaciation were accompanied by rapid changes in atmospheric CO2 that remain unexplained. While the role of the Southern Ocean as a 'control valve' on ocean-atmosphere CO2 exchange has been emphasized, the exact nature of this role, in particular the relative contributions of physical (for example, ocean dynamics and air-sea gas exchange) versus biological processes (for example, export productivity), remains poorly constrained. Here we combine reconstructions of bottom-water [O2], export production and (14)C ventilation ages in the sub-Antarctic Atlantic, and show that atmospheric CO2 pulses during the last glacial- and deglacial periods were consistently accompanied by decreases in the biological export of carbon and increases in deep-ocean ventilation via southern-sourced water masses. These findings demonstrate how the Southern Ocean's 'organic carbon pump' has exerted a tight control on atmospheric CO2, and thus global climate, specifically via a synergy of both physical and biological processes.