Torben Stichel

Online preconcentration ICP-MS analysis of rare earth elements in seawater

The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (∼pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available “seaFAST” system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2σ) of the technique to be estimated at <23% for all REEs and <15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired.

Spatio-temporal evolution of the West African monsoon during the last deglaciation

On the basis of a multi-proxy data set from the Gulf of Guinea (eastern equatorial Atlantic) we reconstruct the spatio-temporal evolution of the West African monsoon (WAM) and present evidence for a decoupling between latitudinal shifts of the rain belt and WAM intensification. The onset of deglacial monsoon invigoration at ∼16,600 years before present lagged northward migration of a weak rainfall zone by ∼2800 years. Conversely, during the Younger Dryas (YD) time interval, WAM precipitation was severely reduced but we find no evidence for a large-scale retreat of the rainfall front. This observation is not in agreement with the hypothesis of a large-scale shift of the intertropical convergence zone south of the tropical WAM region during the YD. Our results can be better reconciled with the newly emerging concept of a strong influence of Tropical Easterly and African Easterly Jets on modern WAM.

Neodymium in the oceans: a global database, a regional comparison and implications for palaeoceanographic research

The neodymium (Nd) isotopic composition of seawater has been used extensively to reconstruct ocean circulation on a variety of time scales. However, dissolved neodymium concentrations and isotopes do not always behave conservatively, and quantitative deconvolution of this non-conservative component can be used to detect trace metal inputs and isotopic exchange at ocean–sediment interfaces. In order to facilitate such comparisons for historical datasets, we here provide an extended global database for Nd isotopes and concentrations in the context of hydrography and nutrients. Since 2010, combined datasets for a large range of trace elements and isotopes are collected on international GEOTRACES section cruises, alongside classical nutrient and hydrography measurements. Here, we take a first step towards exploiting these datasets by comparing high-resolution Nd sections for the western and eastern North Atlantic in the context of hydrography, nutrients and aluminium (Al) concentrations. Evaluating those data in tracer–tracer space reveals that North Atlantic seawater Nd isotopes and concentrations generally follow the patterns of advection, as do Al concentrations. Deviations from water mass mixing are observed locally, associated with the addition or removal of trace metals in benthic nepheloid layers, exchange with ocean margins (i.e. boundary exchange) and/or exchange with particulate phases (i.e. reversible scavenging). We emphasize that the complexity of some of the new datasets cautions against a quantitative interpretation of individual palaeo Nd isotope records, and indicates the importance of spatial reconstructions for a more balanced approach to deciphering past ocean changes. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

Meteorology and oceanography of the Atlantic sector of the Southern Ocean—a review of German achievements from the last decade

In the early 1980s, Germany started a new era of modern Antarctic research. The Alfred Wegener Institute Helmholtz Centre for Polar and Marine Research (AWI) was founded and important research platforms such as the German permanent station in Antarctica, today called Neumayer III, and the research icebreaker Polarstern were installed. The research primarily focused on the Atlantic sector of the Southern Ocean. In parallel, the German Research Foundation (Deutsche Forschungsgemeinschaft, DFG) started a priority program ‘Antarctic Research’ (since 2003 called SPP-1158) to foster and intensify the cooperation between scientists from different German universities and the AWI as well as other institutes involved in polar research. Here, we review the main findings in meteorology and oceanography of the last decade, funded by the priority program. The paper presents field observations and modelling efforts, extending from the stratosphere to the deep ocean. The research spans a large range of temporal and spatial scales, including the interaction of both climate components. In particular, radiative processes, the interaction of the changing ozone layer with large-scale atmospheric circulations, and changes in the sea ice cover are discussed. Climate and weather forecast models provide an insight into the water cycle and the climate change signals associated with synoptic cyclones. Investigations of the atmospheric boundary layer focus on the interaction between atmosphere, sea ice and ocean in the vicinity of polynyas and leads. The chapters dedicated to polar oceanography review the interaction between the ocean and ice shelves with regard to the freshwater input and discuss the changes in water mass characteristics, ventilation and formation rates, crucial for the deepest limb of the global, climate-relevant meridional overturning circulation. They also highlight the associated storage of anthropogenic carbon as well as the cycling of carbon, nutrients and trace metals in the ocean with special emphasis on the Weddell Sea.

TAG Plume: Revisiting the Hydrothermal Neodymium Contribution to Seawater

We present results on the distribution of eNd and [Nd] from the TAG hydrothermal vent field and adjacent locations collected during the GEOTRACES GA03 cruise in October 2011. Our results show that Nd isotopes directly below and above the plume do not significantly deviate from average NADW (eNd = -12.3±0.2). Within the plume, however, isotope values are shifted slightly towards more radiogenic values up to eNd = -11.4. Interestingly at the same time a significant decrease in [Nd] along with rare earth element (REE) fractionation is observed, indicating enhanced scavenging within the plume despite the change in Nd isotopes. Elemental concentrations of Nd are reduced by 19.6 to 18.5 pmol/kg, coinciding with the maximum increase of mantle derived helium (xs3He) from 0.203 to 0.675 fmol/kg, resulting in an average 1.8 pmol/kg decrease in [Nd] relative to an expected linear increase with depth. The inventory loss of Nd within the plume sums up to 614 nmoles/m2, or 6 %, if a continuous increase of [Nd] with depth is assumed. Compared to BATS and the western adjacent station USGT11-14, the local inventory loss is even higher at 10 %. The tight relationship of xs3He increase and [Nd] decrease allows us to estimate scavenging rates at TAG suggesting 40 mol/yr are removed within the TAG plume. A global estimate using power output along ocean ridges yields an annual Nd removal of 3.44x106 mol/yr, which is about 71% of riverine and dust flux combined or 6 to 8% of the estimated global flux of Nd into the ocean. The change in Nd isotopic composition of up to 0.7 more radiogenic eNd values suggests an exchange process between hydrothermally derived particles and seawater in which during the removal process an estimated 1.1 mol/yr of hydrothermal Nd is contributed to the seawater at the TAG site. This estimate is only 0.1 % of the global Nd signal added to the ocean by boundary exchange processes at ocean margins, limiting the ability of changing the Nd isotopic composition on a global scale in contrast to the more significant estimated sink of elemental Nd in hydrothermal plumes from