Description: Trace elements play important roles as micronutrients in modulating marine productivity in the global ocean. The South Atlantic around 40° S is a prominent region of high productivity and a transition zone between the nitrate-depleted Subtropical Gyre and the iron-limited Southern Ocean. However, the sources and fluxes of trace elements to this region remain unclear. In this study, the distribution of the naturally occurring radioisotope 228Ra in the water column of the South Atlantic (Cape Basin and Argentine Basin) has been investigated along a 40° S zonal transect to estimate ocean mixing and trace element supply to the surface ocean. Ra-228 profiles have been used to determine the horizontal and vertical mixing rates in the near-surface open ocean. In the Argentine Basin, horizontal mixing from the continental shelf to the open ocean shows an eddy diffusion of Kx = 1.7 ± 1.4 (106 cm2 s−1) and an integrated advection velocity w = 0.6 ± 0.3 cm s−1. In the Cape Basin, horizontal mixing is Kx = 2.7 ± 0.8 (107 cm2 s−1) and vertical mixing Kz = 1.0–1.5 cm2 s−1 in the upper 600 m layer. Three different approaches (228Ra-diffusion, 228Ra-advection and 228Ra/TE-ratio) have been applied to estimate the dissolved trace-element fluxes from shelf to open ocean. These approaches bracket the possible range of off-shelf fluxes from the Argentine margin to be: 3.8–22 (× 103) nmol Co m−2 d−1, 7.9–20 (× 104) nmol Fe m−2 d−1 and 2.7–6.5 (× 104) nmol Zn m−2 d−1. Off-shelf fluxes from the Cape margin are: 4.3–6.2 (× 103) nmol Co m−2 d−1, 1.2–3.1 (× 104) nmol Fe m−2 d−1 and 0.9–1.2 (× 104) nmol Zn m−2 d−1. On average, at 40° S in the Atlantic, vertical mixing supplies 0.4–1.2 nmol Co m−2 d−1, 3.6–11 nmol Fe m−2 d−1, and 13–16 nmol Zn m−2 d−1 to the euphotic zone. Compared with atmospheric dust and continental shelf inputs, vertical mixing is a more important source for supplying dissolved trace elements to the surface 40° S Atlantic. It is insufficient, however, to provide the trace elements removed by biological uptake. Other inputs (e.g. particulate, or from winter deep-mixing) are required to balance the trace element budgets in this region.

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: Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES program as well as a proof-of-concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes, and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2=5.75 y), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange, and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn, and Zn inputs and exceed published estimates of atmospheric deposition by factors of ~3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.

Description: Continental shelves are a highly productive part of the oceans, playing a key role for both marine life and human activities. We know that they can easily be affected by a changing climate. They are also a particularly challenging system in marine trace element chemistry. The shelves are very strong sources for trace elements due to river runoff, dry deposition, submarine groundwater discharge (SGD), pore water fluxes, redox and salinity gradients, bioirrigation, and many other processes. These source terms, some of them extremely variable in space and time, are encountered by nearly equally strong and variable sink terms, like bioproductivity, precipitation reactions or fishing, just to name a few. The net flux is therefore a difference of two very large and variable terms, resulting in large uncertainties. In addition, discussing and quantifying individual parts of this budget is often problematic due to slightly different uses of terminology: is advective pore water flux the same as SGD? What are point sources, what are diffuse sources (and where does SGD stand here)? Where do you draw a boundary between suspended particle transport and sediment transport? This talk will aim to highlight a few of the main sources and sinks, uncertainties in their determination and challenges, as well as identifying areas where a closer look at definitions might help to improve our understanding of fluxes across the continental shelf.

Description: The precise determination of radium-226 (226Ra) in environmental samples is challenging due to its low con- centration. Seawater typically contains between 0.03 and 0.1 fg g−1 226Ra. Thus, this work addresses the need for an easy and precise methodology for 226Ra determination in seawater that may be applied routinely to a large number of samples. For this reason, a new analytical approach has been developed for the quantification of 226Ra in seawater via inductively coupled plasma mass spectrometry (ICP-MS). Analysis by single collector sector-field ICP-MS was shown to be convenient and reliable for this purpose once potential molecular interfer- ences were excluded by a combination of chemical separation and intermediate mass resolution analysis. The proposed method allows purification of Ra from the sample matrix based on preconcentration by MnO2 precipi- tation, followed by two-column separation using a cation exchange resin and an extraction chromatographic resin. The method can be applied to acidified and unacidified seawater samples. The recovery efficiency for Ra ranged between 90% and 99.8%, with precision of 5%, accuracy of 95.7% to 99.9%, and a detection limit of 0.033 fg g−1 (referring to the original concentration of seawater). The method has been applied to measure 226Ra concentrations from the North Sea and validated by analyzing samples from the central Arctic (GEOTRACES GN04). Samples from a crossover station (from GEOTRACES GN04 and GEOTRACES GN01 research cruises) were analyzed using alternative methods, and our results are in good agreement with published values.

Description: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 22 (2007): PA1216, doi:10.1029/2005PA001235.