Extraterrestrial<Superscript>3</Superscript> He in marine polymetallic nodules: A potential method for measuring growth rate of nodules

The comparative measurements of helium isotope compositions between marine polymetallic nodules and their surrounding sediments, their magnetic fractions and bulk from C-C Zone of the East Pacific Basin are reported. The⁴He content and³He/⁴He ratio of polymetallic nodules and their surrounding sediments are extremely high; the³He,⁴ He concentrations and most³He/⁴He ratios of magnetic fractions in nodules and sediments are apparently higher than those in bulk. The helium isotope data points of nodules and sediments are all distributed along or closely to the mixing curve of the interplanetary dust particles (IDPs) and the terrigenous sediments in the chart of³He-³He/⁴He. In the same sampling site, the³He/⁴He ratios of nodules and their surrounding sediments are very similar, and the changes of both ratios are synchronous. It shows that the high³He/⁴He ratios in nodules and sediments may all result from IDPs. So, if the flux of extraterrestrial³He into the nodules and sediments is constant, the growth rate of polymetallic nodules and the sedimentation rate of sediments can be independently calculated according to the concentra-tion of extraterrestrial³He in nodules and sediments.     

Extraterrestrial ~3He in marine polymetallic nodules: a potential method for measuring growth rate of nodules

The comparative measurements of helium isotope compositions between marine poly-metallic nodules and their surrounding sediments, their magnetic fractions and bulk from C-C Zoneof the East Pacific Basin are reported. The ~4He content and ~3He/~4He ratio of polymetallic nodulesand their surrounding sediments are extremely high; the ~3He, ~4He concentrations and most~3He/~4He ratios of magnetic fractions in nodules and sediments are apparently higher than those inbulk. The helium isotope data points of nodules and sediments are all distributed along or closelyto the mixing curve of the interplanetary dust particles (IDPs) and the terrigenous sediments in thechart of ~3He-~3He/~4He. In the same sampling site, the ~3He/~4He ratios of nodules and their surround-ing sediments are very similar, and the changes of both ratios are synchronous. It shows that thehigh ~3He/~4He ratios in nodules and sediments may all result from IDPs. So, if the flux of extrater-restrial ~3He into the nodules and sediments is constant, the growth rate of polymetallic nodules andthe sedimentation rate of sediments can be independently calculated according to the concentra-tion of extraterrestrial ~3He in nodules and sediments.     

Detection of tritium and alpha decaying radionuclides in L/ILW by measurements of helium isotopes

As decay products, helium isotopes can clearly indicate the presence of tritium and alpha decaying isotopes in a closed system. This study presents the helium and neon measurements and their interpretation of long-term headspace gas investigations in L/ILW waste drums from Paks Nuclear Power Plant and closed vaults of the Radioactive Waste Treatment and Disposal Facility, Püspökszilágy, Hungary. Development of special sampling methods and preparation lines as well as isotope-analytical measurements of the headspace gas samples were done in the Hertelendi Laboratory of Environmental Studies in the ATOMKI. In the gas samples helium isotopes as well as neon isotopes have been determined mass spectrometrically. While neon content can be of atmospheric origin only, helium can be produced either by alpha decay (⁴He) or decay of tritium (³He). ³H/⁴He and He/Ne ratios have been used to determine the different origin of the helium isotopes. Helium isotope ratios always represented ³He enrichment in the headspace gases produced by the decay of the tritium in the waste. Using the recent ³He concentration in headspace gas the total amount of ³H restored in L/ILW vaults was estimated. The investigated seven different vaults were closed between 1979 and 1995 when they had been full with L/ILW. The calculated tritium activities based on the He measurements showed good agreement with the documented isotope inventory of the vaults. Typical tritium activity concentrations were between 0.1 and 10 Bq/L gas in the drums and between 10 and 1000 Bq/L gas in the vaults. Additionally, one drum showed a higher He/Ne ratio compared to air, which clearly indicates ⁴He excess, thus the presence an alpha source in the waste.     

Finite size effects in the evaporation rate of3He clusters

We have computed the density of states and the evaporation rate of³He clusters, paying special attention to finite size effects which modify the³He level density parameter and chemical potential from their bulk values. Ready-to-use liquid-drop expansions of these quantities are given.     

Depth-profiling of deuterium in steels: Preparation of calibration standards

The preparation of a set of standards for the calibration of the analysis of deuterium using the²H/³He, p/⁴He reaction is described. Important considerations in the selection of a suitable standard are that it should be stable under irradiation and be simple to prepare with ready control of the amount of analyte. These requirements were met by Ca/OH/₂ which was prepared by the replacement of hydrogen with its isotope in known proportions in the reaction of CaO with water.     

Hyperfine structure of the 33 P state of3He and isotope shift for the 23 S-33 P 0 transition

The hyperfine structure of the³He 1s 3p ³ P state and the³He-⁴He isotope shift is determined by high precision measurements of the 1s2s ³ S ₁-1s 3p ³ p ³ P _J transition frequencies near 389 nm. A direct frequency measurement is made without the need for wavelength calibration by tuning a single laser to the atomic frequency, and using a novel heterodyne method to observe beat frequencies with a stable reference laser. A fit to a theoretical model of hyperfine structure is used to determine the hyperfine shifts. Additional off-diagonal mixing effects are investigated to resolve a possible systematic discrepancy in the hyperfine intervals. The final isotope shift without hyperfine structure of 42184308±165 kHz is used to deduce an rms nuclear charge radius for³He of 1.956±0.042 fm. This is in good agreement with other values obtained from atomic isotope shift measurements, and a recent theoretical value of 1.958±0.006 fm. The present result helps to resolve substantial differences in the³He nuclear radius derived from electron-nuclear scattering measurements, and it provides a significant test of the nuclear three-body problem.     

Study on distribution of elements in deep-sea Pacific polymetallic nodules via two-dimensional mapping laser ionization orthogonal time-of-flight mass spectrometry

A newly developed two-dimensional mapping high irradiance laser ionization orthogonal time-of-flight mass spectrometer (LI-O-TOFMS) has been applied for the elemental mapping of polymetallic nodules. Two polymetallic nodule standards were used to demonstrate the efficacy of LI-O-TOFMS for the standardless semiquantitative analysis and the spatial distribution of elements in a deep-sea Pacific polymetallic nodule was mapped. It was found that the two groups of elements, Mn–Ni–Cu–Fe and Co–Si–Al, show clear element-dependent spatial relationships. It is hypothesized that these spatial distributions reflect the environmental and physico-chemical conditions during the nodule formation. LI-O-TOFMS is shown to be a powerful tool in elemental analysis of polymetallic nodules, with the detection limits down to 10^− 7 g/g and a dynamic range of 7 orders of magnitude. Based on the images acquired, the contents of elements and their relationships can be revealed visually.     

Analysis of lanthanides and actinides in sea sediments from the Gulf of Tehuantepec

Seawater contains trace elements in solution, such as lanthanides and uranium, which can act as natural tracers when they flocculate to form the sediments of the seabed. Uranium is a special case because it is a radioactive element with isotopic ratio close to 1.14 (²³⁴U/²³⁸U) in sea water. Uranium is also present in all fractions of sediments, although the isotopic ratio in each fraction takes a specific value depending on its origin and surrounding environment. This work has been conducted in order to analyze lanthanides and uranium in a core of sea sediments. It is focused on separating the fractions forming the layers along the depth profile of the core sample so as to determine the ²³⁴U/²³⁸U activity ratios in fractions of organic matter, aquatic life skeletons and dissolved minerals. The Neutron Activation Analysis showed the presence of U, Lu, Hf, Eu, Ce and Yb ranging up to 50 ppm while alpha spectrometry gave a series of ²³⁴U/²³⁸U activity ratios which are discussed on the basis of statistical analysis.     

Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets

Electron impact ionization of helium nano-droplets containing several 10⁴ He atoms and doped with CCl₄ or SF₆ molecules is studied with high-mass resolution. The mass spectra show significant clustering of CCl₄ molecules, less so for SF₆ under our experimental conditions. Positive ion efficiency curves as a function of electron energy indicate complete immersion of the molecules inside the helium droplets in both cases. For CCl₄ we observe the molecular parent cation CCl₄⁺ that preferentially is formed via Penning ionization upon collisions with He*. In contrast, no parent cation SF₆⁺ is seen for He droplets doped with SF₆. The fragmentation patterns for both molecules embedded in He are compared with gas phase studies. Ionization via electron transfer to He⁺ forms highly excited ions that cannot be stabilized by the surrounding He droplet. Besides the atomic fragments F⁺ and Cl⁺ several molecular fragment cations are observed with He atoms attached.     

Separation of lithium isotopes with the N3O2 trimerrifield peptide resin

A study on the separation of lithium isotopes was carried out with 1,13-dioxa-4,7,10-triazacyclopentadecane-4,7,10-trimerrifield peptide resin [N₃O₂3M]. The resin having N₃O₂ as an anchor group has a capacity of 0.2 meq/g dry resin. Upon column chromatography [0.1 cm (I.D)×30 cm (height)] using 1.0M NH₄Cl solution as an eluent, a single separation factor of 1.00104 was obtained from the elution curve and isotope ratios based on theGlueckauf theory. The heavier isotope,⁷Li concentrated in the resin phase, while the lighter isotope,⁶Li enriched in the solution phase.     

Rotational 1 → 0 transitions in muonic helium-hydrogen molecular ions due to external Auger process

Rotational J = 1 → J = 0 transitions in (Heμh)_J muonic molecular ions (where He and h are helium and hydrogen isotopes, respectively), induced by external Auger process in collision with hydrogen isotope atoms are considered. The obtained reaction rates, normalized to liquid hydrogen density, range between 3.4 · 10¹¹ s^-1 and 11.2 · 10¹¹ s^-1 for different isotope combinations. Rotational state populations of Heμh in hydrogen isotope-helium mixtures are also calculated.     

Density of states and evaporation rate of helium clusters

The density of states of⁴He clusters is calculated on the assumption that only surface vibrations are thermally excited. Results for mixed³He-⁴He and³He clusters are also given. The Weisskopf procedure is used to calculate the evaporation rates and the cooling laws of helium clusters at low temperatures.     

High accuracy determination of235U in nondestructive assay standards by gamma spectrometry

High precision gamma spectrometry measurements have been made on five sets of uranium isotope abundance reference materials for nondestructive assay (NDA). These sets are intended for international safeguards use as primary reference materials for the determination of the²³⁵U abundance in homogeneous uranium bulk material by gamma spectrometry. The measurements were made to determine the count rate uniformity of the²³⁵U 185.7 keV gamma-ray as well as the²³⁵U isotope abundance for each sample. Since the samples were packaged such that the U₃O₈ is infinitely thick for the 185.7 keV gamma-ray, the measured count rate was not dependent on the material density. In addition, the activity observed by the detector was collimated to simulate calibration conditions used to measure bulk material in the field. The sample-to-sample variations observed within the 5 sets of samples ranged between 0.005–0.11% (1s) with standard deviations of the mean ranging from 0.01–0.02%. This observed variation appears to be due predominantly to counting statistics and not to material inhomogeneity and/or packaging. The results of this study indicate that accuracy of²³⁵U determinations via gamma spectrometry, in the range of few hundredths of a percent (2), is achievable. The main requirement for achieving this level of accuracy is a set of standards whose²³⁵U isotope abundances are known to within 0.01% (2).     

Determination of129I in soils of Germany using radiochemical neutron activation analysis

At 5 sampling sites distributed throughout Germany the¹²⁹I concentrations in soils have been measured in individual depth intervals to a depth of 60 cm. These measurements are used to determine the total amount of¹²⁹I in a soil column of 60 cm depth. The data indicate that the¹²⁹I concentrations and the¹²⁹I/¹²⁷I isotope ratios are higher at the sampling locations near the coast compared to the sampling locations in Southern Germany. The total¹²⁹I inventories in the top 60 cm of soils are correlated with the¹²⁹I deposition through rainfall.     

A new nuclear spin selective reaction of molecular oxygen

During high-temperature (623–673 K) oxidation of polyarylenes (polypyromellitimide and polyphenylquinoxaline), the molecular oxygen is enriched in the¹⁸O nonmagnetic isotope and impoverished in the¹⁷O magnetic isotope. The isotope selection increases with the increase in the degree of conversion of oxygen. The spin-selective reaction responsible for the selection of the¹⁷O isotope is the addition of molecular oxygen to triplet exited aromatic fragments of macromolecules to give endoperoxides. This reaction, which is selective in terms of the electron spin, is also nuclear-spin selective resulting in a magnetic isotope effect. The selection of nonmagnetic isotopes,¹⁶O and¹⁸O, is caused by competition between the reversible and irreversible decomposition of endoperoxide and by the classical isotope effect in these reactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1402–1405, August, 1994.The authors are grateful to E. M. Galimov and I. V. Nikulina for high-quality isotope analyses and to the Russian Foundation for Basic Research for financial support (grant 93-03-5227).     

Quantum statistical effects in helium clusters

We discuss ground state and statistical properties of helium clusters with special emphasis to quantum statistical effects. We investigate the density of states of⁴He and³He clusters, their cooling due to evaporation as well as the role played by surface excitations in the superfluid motion.     

3He NMR: from free gas to its encapsulation in fullerene

The ³He nuclear magnetic shieldings were calculated for single helium atom, its dimer, simple models of fullerene cages (He@C_n), and single wall carbon nanotubes. The performances of several levels of theory (HF, MP2, DFT‐VSXC, CCSD, CCSD(T), and CCSDT) were tested. Two sets of polarization‐consistent basis sets were used (pcS‐n and aug‐pcS‐n), and an estimate of ³He nuclear magnetic shieldings in the complete basis set limit using a two‐parameter fit was established. Theoretical ³He results reproduced accurately previously reported theoretical values for helium gas, dimer, and helium probe inside several fullerene cages. Excellent agreement with experimental values was achieved. ³He nuclear magnetic shieldings of single helium atom approaching various points of benzene ring were tested, and an impact of ³He confinement within fullerene cages of different size on the ³He chemical shift was determined. Copyright © 2013 John Wiley & Sons, Ltd.     

Penning ionization electron spectrometry of hydrogen iodide

The energy spectra of electrons released in thermal energy ionizing collisions of metastable helium and neon atoms with hydrogen iodide have been measured with high resolution and low background. The electron spectra, obtained for a mixed He(2¹ S, 2³ S) beam, a pure He(2³ S) beam, and a mixed Ne(3s ³ P ₂,³ P ₀) beam, are all characterized by the formation of theX ²Π _i andA ²Σ⁺ states of HI⁺. For both He(2¹ S) + HI and He(2³ S) + HI the spectra exhibit some broad features in the medium electron energy range which are attributed to ionization from an additional charge exchanged potential surface (He⁺ + HI^?) in the entrance channel. For the first time, we have detected the low energy electrons in the He(2¹ S, 2³ S) spectra due to autoionization of I** atoms which result from energy transfer to highly excited, dissociative HI** Rydberg states. The HI⁺ (X)²Π_3/2:²Π_1/2 fine-structure branching ratios vary significantly with the ionizing agent in a similar way as for the isoelectronic, atomic target case xenon.     

Wavelength and isotopic shift measurements of the3S(3s 4s) −3P(3s 3p) MgI transitions

The wavelengths of the³S(3s 4s) ?³P(3s 3p) MgI transitions have been measured for the²⁴Mg isotope with a precision of ±2 × 10^?7; moreover the isotope shifts of the above transitions have been measured for the three natural Mg isotopes as well as the hyperfine constants of the³S(3s 4s) level of²⁵Mg. The measurements have been performed in a metastable atomic beam.     

New possibilities in isotope correlation analysis of spent nuclear fuel

Isotopic correlation analysis is believed to make possible quick and accurate determinations of nuclear fuel parameters for reactor operation, reprocessing, fuel management and nuclear safeguards. Correlation dependencies have been found between ratios of fission products on the one hand and isotope ratios of the heavy elements on the other hand. The use of the¹⁵⁴Eu/¹⁵⁵Eu ratio in correlation analysis was proposed by SMULEK. The scope of useful applications of this isotopic ratio has been further investigated. A quick and time-saving method to measure the¹⁵⁴Eu/¹⁵⁵Eu ratio has been elaborated. The atomic ratios have been found by internal calibration using the computer programme ABSINT. Beside this the atomic ratios of¹⁵⁴Eu/¹⁵⁵Eu as a function of nuclear fuel burn-up have been calculated using the computer programme ISOTOP. The correlation between the¹⁵⁴Eu/¹⁵⁵Eu ratio and nuclear fuel burn-up is best approximated by a quadratic function. Up to a burn-up of 1% fima a linear function can be used.