Natural and Artificial Radionuclides as Tracers of Ocean Processes

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A 51-cm core (SBB-8-2012) from the depo-center of Santa Barbara Basin (SBB), California has been dated by 210Pb dating and varve counting, spanning a depositional history during 1815-2011 CE. A total of 89 AMS 14C measurements on samples from 66 horizons, including animal cartilage, shell and total organic carbon (TOC) in the sediments show apparent 14C ages between 500 and 4000 yr BP. Among these AMS dates, D14C values measured in 78 samples from 62 horizons vary in the range of -64.3‰ to -383.8‰. The 14CTOC ages much older than predicted from our sedimentation model are influenced by the input of terrigenous sediments, changes in ocean circulation, biological input and carbon remineralization. Three strong old 14CTOC excursions at 1964~69, 1884~87 and 1819~21 CE indicate higher old carbon input caused by some unusual events (e.g., oil spill, flood event and earthquake). On multi-decadal timescales, the D14CTOC shifts in three zones were mainly caused by changes in fossil carbon emission from the seafloor, fraction of marine productivity to terrigenous input of organic carbon (OC) and the atmospheric nuclear bomb testing input of 14C into the SBB. On interannual to decadal timescales, variations of D14CTOC correspond to El Niño-Southern Oscillation effects. During the La Niña period, stronger upwelling and northerly California Current bring nutrient-enriched water into SBB and lead to higher productivity hence more marine OC with higher D14CTOC. In addition, reduced terrigenous input of OC with lower D14C under less coastal rainfall during La Niña could further elevate the D14CTOC. Lower scanning XRF (K+Ti)/2 (indicating lower terrigenous input), higher scanning XRF Sr/Ti as well as acid-leachable elements (reflecting higher biogenic components), and higher D14CTOC occur during La Niña. During the El Niño period, the phenomena are opposite. Spectrum analyses of the Southern Oscillation Index (SOI) and the D14CTOC as well as the comparison of SOI and SBB-8-2012 records support our scenarios.

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Recent major advances in Accelerator Mass Spectrometry (AMS) at the Vienna Environmental Research Accelerator (VERA) regarding detection efficiency and isobar suppression have opened possibilities for the analysis of additional long-lived radionuclides at ultra-low environmental concentrations. These radionuclides, including 233U, 135Cs, 99Tc, and 90Sr, will become important for oceanographic tracer application due to their generally conservative behavior in ocean water. In particular, the isotope ratios 233U/236U and 137Cs/135Cs have proven to be powerful fingerprints for emission source identification as they are not affected by elemental fractionation. Improved detection efficiencies allowed us to analyze all major long-lived actinides, i.e., 236U, 237Np, 239,240Pu, 241Am as well as the very rare 233U, in the same 10 L water samples of a depth profile from the northwest Pacific Ocean. For this purpose, a simplified and very flexible chemical purification procedure based on extraction chromatography (a single UTEVA® column) was implemented which can be extended by a DGA® column for Am purification. The procedure was validated with the reference materials IAEA-381/385. With the additional increase in ionization efficiency expected for the extraction of actinides as fluoride molecules from the AMS ion source, a further reduction of chemical processing may become possible. This method was successfully applied to an exemplary set of air filter samples. In order to determine the quantitative 237Np concentration reliably, a 236Np spike material is being developed in collaboration with the University of Tsukuba, Japan. Ion-Laser Interaction Mass Spectrometry (ILIAMS), a novel technique for the efficient suppression of stable isobaric background, has been developed at VERA and provides unprecedented detection sensitivity for the fission fragments 135Cs, 99Tc, and 90Sr. The corresponding setup is fully operational now and the isobar suppression factors of >105 achieved, in principle, allow for the detection of the mentioned radionuclides in the environment. Especially for 90Sr analysis, this new approach has already been validated for selected reference materials (e.g., IAEA-A-12) and is ready for application in oceanographic studies. We estimate that a sample volume of only (1–3) L ocean water is sufficient for 90Sr as well as for 135Cs analysis, respectively.

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