Radionuclides measured on three sediment cores from the Weddell Sea, Antarctica

High resolution 230Thex and 10Be and biogenic barium profiles were measured at three sediment gravity cores (length 605-850 cm) from the Weddell Sea continental margin. Applying the 230Thex dating method, average sedimentation rates of 3 cm/kyr for the two cores from the South Orkney Slope and of 2.4 cm/kyr for the core from the eastern Weddell Sea were determined and compared to delta18O and lithostratigraphic results. Strong variations in the radionuclide concentrations in the sediments resembling the glacial/interglacial pattern of the delta18O stratigraphy and the 10Be stratigraphy of high northern latitudes were used for establishing a chronostratigraphy. Biogenic Ba shows a pattern similar to the radionuclide profiles, suggesting that both records were influenced by increased paleoproductivity at the beginning of the interglacials. However, 230Thex0 fluxes (0 stands for initial) exceeding production by up to a factor of 4 suggest that sediment redistribution processes, linked to variations in bottom water current velocity, played the major role in controlling the radionuclide and biogenic barium deposition during isotope stages 5e and 1. The correction for sediment focusing makes the 'true' vertical paleoproductivity rates, deduced from the fluxes of proxy tracers like biogenic barium, much lower than previously estimated. Very low 230Thex0 concentrations and fluxes during isotope stage 6 were probably caused by rapid deposition of older, resedimented material, delivered to the Weddell Sea continental slopes by the grounded ice shelves and contemporaneous erosion of particles originating from the water column.

Radionuclides measured on 27 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

As part of the GEOTRACES Polarstern expedition ANT XXIV/3 (ZERO and DRAKE) we have measured the vertical distribution of 234Th on sections through the Antarctic Circumpolar Current along the zero meridian and in Drake Passage and on an EW section through the Weddell Sea. Steady state export fluxes of 234Th from the upper 100m, derived from the depletion of 234Th with respect to its parent 238U, ranged from 621±105 dpm/m**2/d to 1773±90 dpm/m**2/d. This 234Th flux was converted into an export flux of organic carbon ranging from 3.1-13.2 mmolC/m**2/d (2.1-9.0 mmolC/m**2/d) using POC/234Th ratio of bulk (respectively >50 µm) suspended particles at the export depth (100 m). Non-steady state fluxes assuming zero flux under ice cover were up to 23% higher. In addition, particulate and dissolved 234Th were measured underway in high resolution in the surface water with a semi-automated procedure. Particulate 234Th in surface waters is inversely correlated with light transmission and pCO2 and positively with fluorescence and optical backscatter and is interpreted as a proxy for algal biomass. High resolution underway mapping of particulate and dissolved 234Th in surface water shows clearly where trace elements are absorbed by plankton and where they are exported to depth. Quantitative determination of the export flux requires the full 234Th profile since surface depletion and export flux become decoupled through changes in wind mixed layer depth and in contribution to export from subsurface layers. In a zone of very low algal abundance (54-58 °S at the zero meridian), confirmed by satellite Chl-a data, the lowest carbon export of the ACC was observed, allowing Fe and Mn to maintain their highest surface concentrations (Klunder et al., this issue, Middag et al., this issue). An ice-edge bloom that had developed in Dec/Jan in the zone 60-65 °S as studied during the previous leg (Strass et al., in prep) had caused a high export flux at 64.5 °S when we visited the area two months later (Feb/March). The ice-edge bloom had then shifted south to 65-69 °S evident from uptake of CO2 and dissolved Fe, Mn and 234Th, without causing export yet. In this way, the parallel analysis of 234Th can help to explain the scavenging behaviour of other trace elements.

Radionuclides measured on 21 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

Drake Passage is a major route for many water masses from the strong Antarctic Circumpolar Current. During the ANTXXIV-3 expedition (in 2008) the vertical distributions of dissolved and size-fractionated particulate 231Pa and thorium isotopes (230Th, 232Th and 234Th) were investigated in order to better define the scavenging regimes and the effects of the oceanic circulation on the fate of particulate material and on the Pa-Th distributions in the water column. The reversible scavenging-model applied to both 230Th and 234Th, in the upper 1500 m depth, gives estimates of the particle dynamics (settling velocities S~ 500-1300 m/y, adsorption and desorption rate constants of 0.1-0.4 1/y and 1-6 1/y respectively). Particulate 234Th/230Th activity ratio shows a depth dependence, with decreasing ratio with increasing depth in agreement with previous studies, but no relationship with particle size was found. 231Pa and thorium isotope fractionation and partition coefficients were investigated with particle size vs depth and latitude and appear to vary horizontally following a North-South gradient. This suggests that both radionuclides are mostly bound to the fine suspended particles. At Drake Passage, the 230Thxs distribution is controlled by a southward upwelling of deep water (clearly visible on the vertical section of total 230Thxs, defined as dissolved + particulate concentrations) and reversible-scavenging processes (linear increase of 230Thxs with increasing depth) with North of the Southern ACC Front, higher settling velocities and less adsorption/desorption cycles, than South of it. Distributions of dissolved and total 231Paxs also reflect the influence of the North-South upwelling but somehow this effect appears to be limited to the upper 1500 m depth of the water column. Below this depth, 231Paxs vertical profiles exhibit contrasted concentrations, with some high dissolved activities in the deep water of the stations in the northern part of the ACC and not South of the ACC. These N-S differences in dissolved 231Paxs were attributed to the different origins and scavenging history of the deep Pacific waters flowing across Drake Passage. Here at North, radionuclides-rich deep water originates from the Central Pacific, while at South, deep water derives from the Southern Pacific in which the observed low radionuclides concentrations are attributed to high opal abundance. South of the Drake Passage, high dissolved and particulate activities of 230Th and 232Th confirmed the intrusion of 230Th-rich Weddell Sea Deep Water (WSDW) close to the Antarctic Peninsula.

Radionuclides in sediment cores from the higher latitudes

In this thesis it is shown that the cosmogenic radionuclide 10Be proved to be a sensitive stratigraphic tool for sediment cores from the Arctic Ocean with low or negligible content of biogenic carbonate, impeding a reliable 0180 stratigraphy. 10Be enables a stratigraphy of Arctic sediments comparable to the d18O stratigraphy Imbrie et al. [1984] in that high concentration of 10Be are related to interglacial stages in contrast to lower values during glacial periods. To use the °Be profile as dating tool it is necessary to investigate the sources and sinks as well as the pathways of this radiotracer. 10Be is produced in the upper atmosphere and transfered to the earth's surface by dry and wet deposition. Besides the atmospheric component there is an important input of 10Be with the rivers to the Arctic Ocean. I determined depositional 10Be fluxes in the shelf area of the Laptev Sea, which is characterized by a huge input of river water, the continental slope of the Laptev Sea, the central Arctic Ocean and the Norwegian- and Greenland Sea. The depositional 10Be fluxes of (20 ± 5) x 10**6 atoms/cm**2/a in the shelf area of the Laptev Sea are by two orders of magnitude higher than the recent atmospheric input (0.2 - 0.5) x 10**6 atoms/cm**2/a in Greenland. while the fluxes in the central Arctic Ocean are in the same range. Further I developed a model to reconstruct the pathways of radionuclides 230Th, 231Pa and 10Be in high northern latitudes. The modelling results were compared with the measured concentrations in the water column and the recent depositional fluxes. These results show that the recent pathways of these nuclides can be rebuild by this model. Thus we can apply this model to earlier oxygen isotope stages to find out which predominate conditions lead to the determined depositional fluxes.

Stable isotopes, radionuclides, and calculated sea surface temperature of two sediment cores in the Sicily Channel

The Eastern Mediterranean Transient (EMT) occurred in the Aegean Sea from 1988 to 1995 and is the most significant intermediate-to-deep Mediterranean overturning perturbation reported by instrumental records. The EMT was likely caused by accumulation of high salinity waters in the Levantine and enhanced heat loss in the Aegean Sea, coupled with surface water freshening in the Sicily Channel. It is still unknown whether similar transients occurred in the past and, if so, what their forcing processes were. In this study, sediments from the Sicily Channel document surface water freshening (SCFR) at 1910±12, 1812±18, 1725±25 and 1580±30 CE. A regional ocean hindcast links SCFR to enhanced deep-water production and in turn to strengthened Mediterranean thermohaline circulation. Independent evidence collected in the Aegean Sea supports this reconstruction, showing that enhanced bottom water ventilation in the Eastern Mediterranean was associated with each SCFR event. Comparison between the records and multi-decadal atmospheric circulation patterns and climatic external forcings indicates that Mediterranean circulation destabilisation occurs during positive North Atlantic Oscillation (NAO) and negative Atlantic Multidecadal Oscillation (AMO) phases, reduced solar activity and strong tropical volcanic eruptions. They may have recurrently produced favourable deep-water formation conditions, both increasing salinity and reducing temperature on multi-decadal time scales.

(Table 1) Radionuclides and ESR dating of sediment cores PS1535-10 and PS1535-8

ESR-spectra of foraminifera in arctic sediment cores display the [CO2]- -signal (g=2.0006). Research on the thermal behaviour of the [CO2]- -signal shows that both natural and artificial irradiation generates a precursor and a thermal unstable component of the [CO2]- -signal. The precursor can be transfered to the stable radical, and unstable radicals can be removed by heating. The signal-change by heating depends on the irradiation dose. Because of the varying response on thermal treatment, the dose-response curves show systematic differences depending on the applied procedure (single- or multi-aliquot method with or without heating). A model for the description of the [CO2]- -signal-change is presented. The combination of two exponential saturation functions seems to be an adequate analytical description of the dose-response curve of the [CO2]- -signal in foraminifera. Due to the limited thermal stability this signal can be used for dating foraminifera with ages up to about 190 ka.

Radionuclides of bulk and terrigenous surface sediments in the Southern Ocean

Sr and Nd isotopic compositions of Late Quaternary surface sediment and sediment cores from the south Atlantic and southeast Pacific sectors of the Southern Ocean are used to constrain the provenance and transport mechanisms of their terrigenous component. We report isotopic and mineralogical data for core samples from three localities, the Mid-Atlantic Ridge at 41°S and the northern and southern Scotia Sea. In addition, data for surface sediment samples from the south Atlantic and southeast Pacific sectors of the Southern Ocean are presented. The variations of Sr and Nd isotopic compositions of the bulk sediment samples in all cores were correlated with the magnetic susceptibility of the sediment and with the inferred glacial-interglacial stages. The isotopic data indicate that, during glacial periods, sediment was delivered from continental crust with a shorter residence time than that supplying material during interglacial periods. At the core site near the Mid-Atlantic Ridge, Nd isotopic, combined with mineralogical evidence indicates interglacial period deposition of a relatively high amount of kaolinite and silt with low epsilon-Nd values < -8. The material was probably supplied by North Atlantic Deep Water from low latitudes. For glacial periods, a high contribution of silt and clay with epsilon-Nd > -4.5, probably derived from southern South America, was indicated. The glacial-interglacial shift in sources may be due to either a decreasing influence of North Atlantic Deep Water during glacial times or by a larger contribution of glaciogenic detritus from southern South America. At the core site in the northern Scotia Sea, sediment of interglacial periods is dominated by smectite with epsilon-Nd < - 6 and silt with epsilon-Nd > -4. We suggest that smectite was derived from the Falkland shelf and silt was derived from the Argentinian shelf. During glacial periods, the Argentinian shelf was an important source for silt and chlorite with epsilon-Nd > -4. The contribution from the Falkland shelf seems to have remained similar during glacial and interglacial periods. Hydrographic transport by bottom currents and turbidites could account for the high glacial detrital flux. An evaluation of the significance of an aeolian contribution to deep sea sediment suggests that it plays only a minor role. In the southern Scotia Sea, the Antarctic Peninsula is considered an important source for young material with epsilon-Nd > -4, in particular during glacial periods. During interglacial periods, sediment supply from the Antarctic Peninsula was lower than during glacial times, resulting in a relatively high contribution of old material (epsilon-Nd < -8) from East Antarctica. Deep water currents and icebergs could account for the transport of the old component to the southern Scotia Sea. The accumulation rates of material from the various source regions for glacial times are in agreement with an increase in the strength of the Antarctic Circumpolar Current. The production rate and the circulation pattern of bottom water in the Weddell Sea appear to have remained similar over most of the last 150 kyr.

Activity concentrations of radionuclides in 5 short cores taken in 2007-2008 measured by ICP-MS and HPGe gamma spectrometry

Natural radionuclides and man-made 137Cs were analyzed in five short sediment cores taken in northern part of the Gulf of Eilat (Gulf of Aqaba) in order to provide information on sedimentation and mixing rates and sediment sources. The maximum estimates of sedimentation rates based on excess 210Pb were found to vary between 0.105 ± 0.020 and 0.35 ± 0.23 cm · year**-1. Even the lowest estimates are significantly higher than those expected from dust deposition, suggesting other sources and processes being responsible for most of the allochthonous material accumulation, including periodical floods following heavy rain events, internal erosion or triggers, like earthquakes. In 137Cs depth profiles no 1963 related nuclear weapon test maxima were found; instead, the activities decrease monotonically, suggesting that a major process leading to radionuclides' depth distribution might be mixing. The mixing rates calculated from 137Cs, excess 210Pb and excess 228Th reach values up to 2.18 ± 0.69 cm**2 · year**-1.

Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.