Beschreibung: Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe) and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (〈0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3- and consistent with supply from remineralised sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf, and therefore is likely low enough to affect phytoplankton growth and species composition.

Beschreibung: 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.

Beschreibung: The Sr/Ca ratio of coral aragonite is used to reconstruct past sea surface temperature (SST). Twentyone laboratories took part in an interlaboratory study of coral Sr/Ca measurements. Results show interlaboratory bias can be significant, and in the extreme case could result in a range in SST estimates of 7°C. However, most of the data fall within a narrower range and the Porites coral reference material JCp- 1 is now characterized well enough to have a certified Sr/Ca value of 8.838 mmol/mol with an expanded uncertainty of 0.089 mmol/mol following International Association of Geoanalysts (IAG) guidelines. This uncertainty, at the 95% confidence level, equates to 1.5°C for SST estimates using Porites, so is approaching fitness for purpose. The comparable median within laboratory error is 〈0.5°C. This difference in uncertainties illustrates the interlaboratory bias component that should be reduced through the use of reference materials like the JCp-1. There are many potential sources contributing to biases in comparative methods but traces of Sr in Ca standards and uncertainties in reference solution composition can account for half of the combined uncertainty. Consensus values that fulfil the requirements to be certified values were also obtained for Mg/Ca in JCp-1 and for Sr/Ca and Mg/Ca ratios in the JCt-1 giant clam reference material. Reference values with variable fitness for purpose have also been obtained for Li/Ca, B/Ca, Ba/Ca, and U/Ca in both reference materials. In future, studies reporting coral element/Ca data should also report the average value obtained for a reference material such as the JCp-1.

Beschreibung: Decades ago, the analysis of ancient air – trapped deep inside of Antarctic glaciers – revealed an astonishing pattern of atmospheric CO2. Ever since we’ve first laid our eyes on these intriguing signals– alternating between glacial lows and interglacial highs – an overall question emerged: Where was the CO2 stored during the glacials and how was it released back to the atmosphere during deglacial transitions? In general, several carbon reservoirs like the terrestrial biosphere or permafrost soils might interact with, and drive the atmosphere on these glacial-interglacial timescales. By far the largest influence however, might come from the deep ocean. Today, this reservoir stores up to 60-times the carbon, of which is stored in the entire atmosphere. Hence, tiny changes in the oceanic C-cycle might have severe ramifications for atmospheric CO2-levels. Parallel to global CO2 atm, Antarctic temperatures rose, while the expanded ice shelves suffered from a massive deglacial collapse. The timing and succession of events pointed to the climatic role of the Southern Hemisphere in general and the Southern Ocean in particular and raised a second question: What was the physical process, which connected these deglacial events? Until today, the international community compiled numerous studies from terrestrial and marine (distal and proximal) archives to shed light onto this dynamic system. These studies revealed a closely connected system between Antarctic sea ice and ice shelves, deep-water and atmospheric circulation, oceanic stratification, the biological pump and also bipolar teleconnections. Here, we want to discuss the current scientific knowledge and present new isotopic data – measured on planktic and benthic foraminifers as well as bulk sediments – that show how Southern Ocean overturning circulation changed on glacial-interglacial timescales and influenced the residence times of circumpolar deep-waters as well as their transport onto the continental shelf regions. In combination with other parameters, the deglacial increase in Southern Ocean overturning represents a plausible link that might explain the parallel evolution of several deglacial climate parameters.

Beschreibung: 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.