Bestimmung der Ionisationsenergie von Actinium und Ultraspurenanalyse von Plutonium mit resonanter Ionisationsmassenspektrometrie (RIMS)

ZusammenfassungDie Resonanzionisationsmassenspektrometrie (RIMS) verbindet hohe Elementselektivität mit guter Nachweiseffizienz. Aufgrund dieser Eigenschaften ist die Methode für Ultraspurenanalyse und Untersuchungen an seltenen oder schwer handhabbaren Elementen gut geeignet. Für RIMS werden neutrale Atome mit monochromatischem Laserlicht ein- oder mehrfach resonant auf energetisch hoch liegende Niveaus angeregt und anschließend durch einen weiteren Laserstrahl oder durch ein elektrisches Feld ionisiert. Die Photoionen werden in einem Massenspektrometer massenselektiv registriert.Ein Beispiel für die Anwendung von RIMS ist die präzise Bestimmung der Ionisationsenergie als fundamentale physikalisch-chemische Eigenschaft eines bestimmten Elements; insbesondere bei den Actinoiden ist die Kenntnis der Ionisationsenergie von Interesse, da es dort bis zur Anwendung der laser-massenspektroskopischer Methode nur wenige experimentelle Daten gab. Die Bestimmung der Ionisationsenergie erfolgt durch die Methode der Photoionisation im elektrischen Feld gemäß dem klassischen Sattelpunktsmodell. Im Experiment werden neutrale Atome in einem Atomstrahl mittels Laserlicht zunächst resonant angeregt. Die angeregten Atome befinden sich in einem äußeren, statischen elektrischen Feld und werden durch einen weiteren Laserstrahl, dessen Wellenlänge durchgestimmt wird, ionisiert. Das Überschreiten der Laserschwelle macht sich durch einen starken Anstieg im Ionensignal bemerkbar. Man führt diese Messung bei verschiedenen elektrischen Feldstärken durch und erhält bei Auftragen der Ionisationsschwellen gegen die Wurzel der elektrischen Feldstärke durch Extrapolation auf die Feldstärke Null die Ionisationsenergie.Im Rahmen dieser Arbeit wurde die Ionisationsenergie von Actinium erstmalig zu 43398(3) cm-1 º 5,3807(4) eV experimentell bestimmt. Dazu wurden Actiniumatome zunächst einstufig resonant mit einem Laser mit einer Wellenlänge von 388,67 nm auf einen Zustand bei 25729,03 cm-1 angeregt und anschließend mit Laserlicht mit einer Wellenlänge von ca. 568 nm ionisiert. Damit sind die Ionisationsenergien aller Actinoiden bis einschließlich Einsteinium mit Ausnahme von Protactinium bekannt. Als Atomstrahlquelle wird ein spezielles 'Sandwichfilament' benutzt, bei dem das Actinoid als Hydroxid auf eine Tantalfolie aufgebracht und mit einer reduzierenden Deckschicht überzogen wird. Das Actinoid dampft bei Heizen dieser Anordnung atomar ab. Bei den schwereren Actinoiden wurde Titan als Deckschicht verwendet. Um einen Actiniumatomstrahl zu erzeugen, wurde aufgrund der hohen Abdampftemperaturen statt Titan erstmals Zirkonium eingesetzt. Bei Protactinium wurde Thorium, welches noch stärkere Reduktionseigenschaften aufweist, als Deckmaterial eingesetzt. Trotzdem gelang es mit der 'Sandwichtechnik' nicht, einen Protactiniumatomstrahl zu erzeugen. In der Flugzeitapparatur wurde lediglich ein Protactinium-monoxidionensignal detektiert. Um ein erst seit kurzem verfügbares Fest-körperlasersystem zu explorieren, wurden zusätzlich noch die bekannten Ionisations-ener-gien von Gadolinium und Plutonium erneut bestimmt. Die gemessenen Werte stimmen mit Literaturdaten gut überein.Ferner wurde noch ein bestehender Trennungsgang für Plutonium aus Umweltproben auf die Matrices Meerwasser und Hausstaub angepasst und für die Bestimmung von Plutonium und dessen Isotopenzusammensetzung in verschiedenen Probenreihen mittels RIMS eingesetzt. Der modifizierte Trennungsgang ermöglicht das schnelle Aufarbeiten von großen Probenmengen für Reihenuntersuchungen von Plutoniumkontaminationen. Die ermittelten Gehalten an 239Pu lagen zwischen 8,2*107 Atome pro 10 l Meerwasserprobe und 1,7*109Atome pro Gramm Staubprobe.

Dissolved actinium in the ocean

The measurement of short-lived 223Ra often involves a second measurement for supported activities, which represents 227Ac in the sample. Here we exploit this fact, presenting a set of 284 values on the oceanic distribution of 227Ac, which was collected when analyzing water samples for short-lived radium isotopes by the radium delayed coincidence counting system. The present work compiles 227Ac data from coastal regions all over the northern hemisphere, including values from ground water, from estuaries and lagoons, and from marine end-members. Deep-sea samples from a continental slope off Puerto Rico and from an active vent site near Hawaii complete the overview of 227Ac near its potential sources. The average 227Ac activities of nearshore marine end-members range from 0.4 dpm/m**3 at the Gulf of Mexico to 3.0 dpm m? 3 in the coastal waters of the Korean Strait. In analogy to 228Ra, we find the extension of adjacent shelf regions to play a substantial role for 227Ac activities, although less pronounced than for radium, due to its weaker shelf source. Based on previously published values, we calculate an open ocean 227Ac inventory of 1.35 * 1018 dpm 227Acex in the ocean, which corresponds to 37 moles, or 8.4 kg. This implies a flux of 127 dpm/m**2/y from the deep-sea floor. For the shelf regions, we obtain a global inventory of 227Ac of 4.5 * 10**15 dpm, which cannot be converted directly into a flux value, as the regional loss term of 227Ac to the open ocean would have to be included. Ac has so far been considered to behave similarly to Ra in the marine environment, with the exception of a strong Ac source in the deep-sea due to 231Paex. Here, we present evidence of geochemical differences between Ac, which is retained in a warm vent system, and Ra, which is readily released [Moore, W.S., Ussler, W. and Paull, C.K., 2008-this issue. Short-lived radium isotopes in the Hawaiian margin: Evidence for large fluid fluxes through the Puna Ridge. Marine Chemistry]. Another potential mechanism of producing deviations in 227Ac/228Ra and daughter isotope ratios from the expected production value of lithogenic material is observed at reducing environments, where enrichment in uranium may occur. The presented data here may serve as a reference for including 227Ac in circulation models, and the overview provides values for some end-members that contribute to the global Ac distribution.

Radiological aspects of petroleum exploration and production in the sultanate of Oman

This thesis is a study of naturally occurring radioactive materials (NORM) activity concentration, gamma dose rate and radon (222Rn) exhalation from the waste streams of large-scale onshore petroleum operations. Types of activities covered included; sludge recovery from separation tanks, sludge farming, NORM storage, scaling in oil tubulars, scaling in gas production and sedimentation in produced water evaporation ponds. Field work was conducted in the arid desert terrain of an operational oil exploration and production region in the Sultanate of Oman. The main radionuclides found were 226Ra and 210Pb (238U - series), 228Ra and 228Th (232Th - series), and 227Ac (235U - series), along with 40K. All activity concentrations were higher than the ambient soil level and varied over several orders of magnitude. The range of gamma dose rates at a 1 m height above ground for the farm treated sludge had a range of 0.06 0.43 µSv h 1, and an average close to the ambient soil mean of 0.086 ± 0.014 µSv h 1, whereas the untreated sludge gamma dose rates had a range of 0.07 1.78 µSv h 1, and a mean of 0.456 ± 0.303 µSv h 1. The geometric mean of ambient soil 222Rn exhalation rate for area surrounding the sludge was mBq m 2 s 1. Radon exhalation rates reported in oil waste products were all higher than the ambient soil value and varied over three orders of magnitude. This study resulted in some unique findings including: (i) detection of radiotoxic 227Ac in the oil scales and sludge, (ii) need of a new empirical relation between petroleum sludge activity concentrations and gamma dose rates, and (iii) assessment of exhalation of 222Rn from oil sludge. Additionally the study investigated a method to determine oil scale and sludge age by the use of inherent behaviour of radionuclides as 228Ra:226Ra and 228Th:228Ra activity ratios.

Theoretical study on properties of new isotope (265)Bh

The properties of nuclei belonging to the newly observed a-decay chain starting from (265)Bh have been studied. The axially deformed relativistic mean-field calculation with the force NL-Z2 has been performed in the blocked BCS approximation. Some ground state properties such as binding energies, deformations, spins, and parities, as well as Q-values of the alpha-decay for this decay chain have been calculated and compared with known experimental data. Good agreement is found. The single-particle spectrum of the nucleus (265)Bh is studied and some new magic numbers are found, while the magnitudes of the shell gaps in superheavy nuclei are much smaller than those of nuclei before the actinium region, and the Fermi surfaces are close to the continuum. Thus the superheavy nuclei are usually not stable. The alpha-decay lifetimes in the (265)Bh decay chain are evaluated by different formulae, and compared with experimental data. The methods which give good agreement with the data are selected.

(Table 2) Concentrations of natural radioactive elements in Black Sea sediments from DSDP Hole 42-381

A description is given of a gamma-ray spectrometer complex consisting of four interchangeable, low-background NaI(Tl) crystals that operate simultaneously. The system is used in determination of concentrations of natural radioactive elements and sedimentation rates of bottom sediments by the ionium method. Three detector sizes are used, depending on amount of material available: 80x80; 100x100, and 150x150. The system is operated clockwise and data are brought out on a punch tape; results are computer-processed. Examples are shown of the complex use in determining sedimentation rates of bottom sediments in the Southeast Pacific and concentrations of natural radioactive elements in DSDP Hole 381.

Radionuclides measured on water bottle samples

Actinium is one of the rarest naturally occurring elements on earth. We measured its longest-lived isotope 227Ac (half-life 21.77 yr) for the first time in the water column of the Southeast Pacific, the Central Arctic, the Antarctic Circumpolar Current (ACC) and the Weddell Gyre (WG). Besides the profile in the Southeast Pacific, which confirms earlier findings about the role of diapycnal mixing for 227Ac distribution, we found three other different types of vertical profiles. These profiles point to a prominent role of advection for 227Ac distribution, especially in the Southern Ocean. Depending on the type of profile found, 227Ac is proposed as a tracer for different oceanographic questions. In the Southern Ocean, up to 4.93±0.32 dpm/m**3 227Ac is found close to the sea floor, which is the highest concentration ever observed in the ocean. Close to the sea surface in the WG, 0.46±0.05 dpm/m**3 227Acex (227Ac in excess of its progenitor 231Pa) is detected. We use 227Acex there to determine the upwelling velocity in the Eastern WG to be about 55 m/yr. In the ACC, Upper and Lower Circumpolar Deep Water (UCDW and LCDW) are found to differ clearly in their 227Acex activity. High 227Acex activities are therefore a promising tracer for recent inputs of LCDW to the sea surface, which may help to understand the role of deep upwelling for iron inputs into Antarctic surface waters. The expected release of 227Ac is compared with 228Ra to make sure that the large near-surface excess in the water column of the Southern Ocean is not due to lateral inputs by isopycnal mixing. Data from the Central Arctic and from a transect across the ACC confirm that 228Ra and 227Acex differ strongly in their sources. The first measurements of 227Ac on suspended matter (less than 1.7% of total 227Ac close to the sea floor) indicate that the particle reactivity of 227Ac is negligible in the open ocean, in agreement with earlier findings [Y. Nozaki, Nature 310 (1984) 486-488]. Despite the extremely low concentrations of 227Ac, new measurement techniques [W.S. Moore, R. Arnold, J. Geophys. Res. 101 (1996) 1321-1329] point to a comfortable and comparably simple determination of 227Ac in the future. Finally, 227Acex may become a widely used deep-sea specific tracer.