Description: A prominent two-step rise in atmospheric CO2 marked the end of the last glacial. The steps coincided with climatic intervals Heinrich Stadial 1 (HS1) and the Younger Dryas (YD). Records of 231Pa/230Th on sediment cores bathed by NADW, revealed a rapid reduction of the Atlantic Meridional Overturning Circulation (AMOC), during these intervals. It was argued that a weakened AMOC would have significantly reduced the efficiency of the biological pump and thus might have contributed to the rise in atmospheric CO2. Despite playing an important role, this process fails to account for the enigmatic drop in atmospheric Δ14C and δ13C during HS1 that marks the first step of the CO2-rise. Increasing CO2-concentrations with a simultaneous drop in their Δ14C, call for the ventilation of an old and 14C-depleted carbon reservoir. In this respect, several studies point to the presence of very old, 14C-depleted deep-waters in the glacial Southern Ocean, which rejuvenated during the last deglaciation. However, the accumulation of 14C-depleted, carbon-rich waters in the deep Southern Ocean requires circulation patterns that significantly differ from todays. Here we present a combined set of 231Pa/230Th-, Rare Earth Element- and XRF-proxy records to understand the evolution of the South Pacific Overturning Circulation (SPOC) over the last 35,000 years. Our reconstructions are based on a transect of five sediment cores from the Southwest Pacific, covering the AAIW as well as the UCDW and LCDW. Our data show that throughout the last glacial the SPOC was significantly weakened. This reduction favored the observed accumulation of 14C-depleted CO2 in Circumpolar Deep Waters (CDW). Parallel to the HS1 increase of atmospheric CO2, the deep circulation picked up its pace and recovered toward the Holocene. This trend is in remarkable agreement with water mass radiocarbon reconstructions from the very same area, as well as with atmospherical changes in CO2, Δ14C and δ13C. Hence, we are confident that the Southern Ocean – represented here by the South Pacific – played the dominant role in the first rise in atmospheric CO2. In addition the observed deglacial SPOC strengthening may have supported the transport of warm CDW onto the shelf areas since the timing of retreating West Antarctic ice sheets is in good agreement with recent reconstructions.

Description: A method is presented for the chemical characterization of natural organic matter (NOM). We combined reversed-phase chromatographic separation of NOM with high resolution inductively coupled plasma mass spectrometry. A desolvation technique was used to remove organic solvent derived from the preceding chromatographic separation. We applied our method to solid-phase extracted marine dissolved organic matter samples from South Atlantic and Antarctic surface waters. The method provided a direct and quantitative determination of dissolved organic phosphorus and sulfur in fractions of differing polarity and also allowed simultaneous speciation studies of trace elements. Dissolved organic carbon/phosphorus and carbon/sulfur ratios for the different chromatographic fractions of our two samples ranged between 341–3025 for C/P and 11–1225 for C/S. Differences in elemental distribution between the fractions were attributed to different biochemical environments of the samples. Sulfur was exclusively found in one hydrophilic fraction, while uranium showed a strong affinity to the hydrophobic fractions. Our method was designed to be easily adapted to other separation techniques. The elemental information will deliver valuable information for ultrahigh resolution molecular analyses.