Concurrent determination of U, Np, Pu, Am, and Cm in clay systems at ultra-trace levels with accelerator mass spectrometry

The geochemistry of actinides under reducing conditions in a deep geological nuclear waste repository is characterized by low solubility and strong sorption to mineral surfaces. The quantification of actinide migration (i.e. diffusion) at resulting concentration levels requires an analytical method able to determine actinide concentrations down to ultra-trace levels (≈fg g$^{-1}$). In the actual study, such an analytical procedure was tested by using accelerator mass spectrometry (AMS), one of the very few analytical techniques that can presently meet those requirements. Specimens simulating the sample matrix representative for a diffusion experiment in natural clay rock were produced by spiking clay rock powders (Opalinus Clay or Callovo-Oxfordian Clay) and aliquots of corresponding pore waters with the actinide nuclides $^{233}$U, $^{237}$Np, $^{244}$Pu, and $^{248}$Cm in amounts ranging from approximately 3 × 10$^{-19}$ to 5 × 10$^{-15}$ mol per sample (≈0.07–1000 fg per sample). The actinide nuclides were separated as group via Fe(OH)$_{3}$ co-precipitation and then analyzed sequentially with AMS. During such analysis a decrease in count rates by up to a factor of 6 was observed in high-matrix clay rock samples compared to low-matrix standard solutions. Since the chemical yield of the actinides in the Fe(OH)$_{3}$ co-precipitation step prior to analysis turned out to be quantitative, this observation must originate from a reduction of the sputter rate of the actinide nuclides in the AMS ion source, which can be described partly as a dilution effect. By determining chemical-ionization-yield factors, suitable non-isotopic tracers were identified for $^{237}$Np and $^{243}$Am. This allowed for the concurrent determination of all actinide nuclides at levels down to 3 × 10−19 mol per sample. Different actinides in a deep geological formation may be present in concentration ranges differing by orders of magnitude depending on their chemical form and solubility. Such concentration spreads were simulated by preparing clay rock/pore water samples where each individual sample contained $^{233}$U, $^{237}$Np, $^{244}$Pu, $^{243}$Am, and $^{248}$Cm at quantities ranging from approximately 3 × 10$^{-19}$ to 4 × 10$^{-15}$ mol per sample. The presented sample preparation procedure, in combination with the extraordinary detection sensitivity of AMS allows for the simultaneous determination of diffusion profiles of several actinides at ultra-trace levels within one experiment

Measurement of the stellar Ni 58 (n,γ) Ni 59 cross section with accelerator mass spectrometry

The Ni58(n,γ)Ni59 cross section was measured with a combination of the activation technique and accelerator mass spectrometry (AMS). The neutron activations were performed at the Karlsruhe 3.7 MV Van de Graaff accelerator using the quasistellar neutron spectrum at kT=25 keV produced by the Li7(p,n)Be7 reaction. The subsequent AMS measurements were carried out at the 14 MV tandem accelerator of the Maier-Leibnitz Laboratory in Garching using the gas-filled analyzing magnet system (GAMS). Three individual samples were measured, yielding a Maxwellian-averaged cross section at kT=30 keV of (σ)30keV = 30.4 (23)syst(9)stat mbarn. This value is slightly lower than two recently published measurements using the time-of-flight (TOF) method, but agrees within the uncertainties. Our new results also resolve the large discrepancy between older TOF measurements and our previous value

Developing Accelerator Mass Spectrometry Capabilities for Anthropogenic Radionuclide Analysis to Extend the Set of Oceanographic Tracers

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 $^{233}$U, $^{135}$Cs, $^{99}$Tc, and $^{90}$Sr, will become important for oceanographic tracer application due to their generally conservative behavior in ocean water. In particular, the isotope ratios $^{233}$U/$^{236}$U and $^{137}$Cs/$^{135}$Cs 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., $^{236}$U, $^{237}$Np, $^{239,240}$Pu, $^{241}$Am as well as the very rare $^{233}$U, 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 $^{237}$Np concentration reliably, a $^{236}$Np 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 $^{135}$Cs, $^{99}$Tc, and $^{90}$Sr. The corresponding setup is fully operational now and the isobar suppression factors of >10$^{5}$ achieved, in principle, allow for the detection of the mentioned radionuclides in the environment. Especially for $^{90}$Sr 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 $^{90}$Sr as well as for $^{135}$Cs analysis, respectively

Genetic variation in the serotonin transporter gene (5-HTTLPR, rs25531) influences the analgesic response to the short acting opioid Remifentanil in humans

<p>Abstract</p> <p>Background</p> <p>There is evidence from animal studies that serotonin (5-HT) can influence the antinociceptive effects of opioids at the spinal cord level. Therefore, there could be an influence of genetic polymorphisms in the serotonin system on individual variability in response to opioid treatment of pain. The serotonin transporter (5-HTT) is a key regulator of serotonin metabolism and availability and its gene harbors several known polymorphisms that are known to affect 5-HTT expression (e.g. 5-HTTLPR, rs25531). The aim of this study was to investigate if the triallelic 5-HTTLPR influences pain sensitivity or the analgesic effect of opioids in humans. 43 healthy volunteers (12 men, 31 women, mean age 26 years) underwent heat pain stimulations before and after intravenous injection of Remifentanil; a rapid and potent opioid drug acting on μ-type receptors. Subjects rated their perceived pain on a visual analogue scale (VAS). All participants were genotyped for the 5-HTTLPR and the rs25531 polymorphism. We recruited by advertising, with no history of drug abuse, chronic pain or psychiatric disorders.</p> <p>Results</p> <p>At baseline, there was no difference in pain ratings for the different triallelic 5-HTTLPR genotype groups. However, the opiod drug had a differential analgesic effect depending on the triallelic 5-HTTLPR genotype. Remifentanil had a significantly better analgesic effect in individuals with a genotype coding for low 5-HTT expression (S_A/S_Aand S_A/L_G) as compared to those with high expression(L_A/L_A), p < 0.02. The analgesic effect for the three different genotype groups was linear to degree of 5-HTT expression.</p> <p>Conclusion</p> <p>This is the first report showing an influence of the triallelic 5-HTTLPR on pain sensitivity or the analgesic effect of opioids in humans. Previously the 5-HTTLPR s-allele has been associated with higher risk of developing chronic pain conditions but in this study we show that the genotype coding for low 5-HTT expression is associated with a better analgesic effect of an opioid. The s-allele has been associated with downregulation of 5-HT1 receptors and we suggest that individuals with a desensitization of 5-HT1 receptors have an increased analgesic response to opioids during acute pain stimuli, but may still be at increased risk of developing chronic pain conditions.</p

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk