Industrial radioactive barite scale: suppression of radium uptake by introduction of competing ions

Incorporation of radioactive isotopes during the formation of barite mineral scale is a widespread phenomenon occurring within the oil, mining and process industries. In a series of experiments radioactive barite/celestite solid solutions (SSBarite-Celcstite) have been synthesized under controlled conditions by the counter diffusion of Ra-226, Ba2+, Sr24+ and SO42- ions through a porous medium (silica gel), to investigate inhibiting effects in Ra uptake associated with the introduction of a competing ion (Sr2+). From characterization studies, the particle size and the morphology of the crystals appear to be related to the initial [Sr]/[Ba] molar ratio of the starting solution. Typically, systems richer in Sr produce smaller sized crystals and clusters characterized by a lower degree of order. The activity introduced to the system is mainly incorporated in the crystals generated from the barite/celestite solid solution as suggested by the activity profiles of the hydrogel columns analysed by gamma-spectrometry. There is a relationship between the initial [Sr]/[Ba] molar ratio of the starting solution and the activity exhibited by the synthesized crystals. An effective inhibition of the Ra-226 uptake during formation of the crystals (SSBarite-Celestite) was obtained through the introduction of a competing ion (Sr2+): the higher the initial [Sr]/[Ba] molar ratio of the starting solution, the lower the intensity of the activity peak in the crystals. (C) 2003 Published by Elsevier Ltd.

Extraction behavior of the synergistic system 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine and 2-bromodecanoic acid using Am and Eu as radioactive tracers

In this study, the extraction properties of a synergistic system consisting of 2,6-bis-(benzoxazolyl)-4-dodecyloxylpyridine (BODO) and 2-bromodecanoic acid (HA) in tert-butyl benzene (TBB) have been investigated as a function of ionic strength by varying the nitrate ion and perchlorate ion concentrations. The influence of the hydrogen ion concentration has also been investigated. Distribution ratios between 0.03-12 and 0.003-0.8 have been found for Am(III) and Eu(HI), respectively, but there were no attempts to maximize these values. It has been shown that the distribution ratios decrease with increasing amounts of ClO4-, NO3-, and H+. The mechanisms, however, by which the decrease occurs, are different. In the case of increasing perchlorate ion concentration, the decrease in extraction is linear in a log-log plot of the distribution ratio vs. the ionic strength, while in the nitrate case the complexation between nitrate and Am or Eu increases at high nitrate ion concentrations and thereby decreases the distribution ratio in a non-linearway. The decrease in extraction could be caused by changes in activity coefficients that can be explained with specific ion interaction theory (SIT); shielding of the metal ions, and by nitrate complexation with Am and Eu as competing mechanism at high ionic strengths. The separation factor between Am and Eu reaches a maximum at similar to1 M nitrate ion concentration. Thereafter the values decrease with increasing nitrate ion concentrations.

Ionospheric ion and electron heating at the poleward boundary of a poleward expanding substorm-disturbed region

We present observations of a poleward propagating substorm-disturbed region which was observed by the European Incoherent SCATter (EISCAT) radar and the Svalbard International Monitor for Auroral Geomagnetic Effects (IMAGE) magnetometers in the postmidnight sector. The expansion of the disturbance was launched by a substorm intensification which started similar to 25 min after the initial onset, and similar to 10 min before the disturbance arrived over Svalbard. In association with the magnetic disturbance, a poleward expanding enduring enhancement in the F region electron temperature was observed, indicative of soft electron precipitation, with a narrow band of enhanced ion temperature straddling its poleward edge, indicative of fast ion flows and ion-neutral collisional heating. This electron temperature boundary was coincident with the poleward propagating electrojet current system detected by the high-latitude IMAGE magnetometer stations and is taken to be a proxy for the observation of a substorm auroral bulge. The electron temperature boundary is inferred to have a width comparable or less than one radar range gate (similar to 60 km transverse to the magnetic field), while the region of high ion temperature was found to be approximately three gates wide, extending approximately two gates (similar to 120 km) poleward of the electron temperature boundary, and approximately one gate (similar to 60 km) equatorward. The two-beam radar line-of-sight velocity data are found to be consistent with the existence of a layer of high-speed flow in the boundary, peaking at values similar to1.5-3 km s(-1), roughly consistent with the ion temperature data. The flow is directed either east or west along the boundary depending on the direction of the flow in the poleward region. We infer that the flow is deflected along and around the boundary of the substorm-disturbed region due to the high conductivity of the latter. Variations in the flow poleward of the boundary produced no discernible magnetic effects on the ground, confirming the low conductivity of the preboundary ionosphere.

EISCAT/CRRES observations: nightside ionospheric ion outflow and oxygen-rich substorm injections

We present combined observations made near midnight by the EISCAT radar, all-sky cameras and the combined released and radiation efects satellite (CRRES) shortly before and during a substorm. In particular, we study a discrete, equatorward-drifting auroral arc, seen several degrees poleward of the onset region. The arc passes through the field-aligned beam of the EISCAT radar and is seen to be associated with a considerable upflow of ionospheric plasma. During the substorm, the CRRES satellite observed two major injections, 17 min apart, the second of which was dominated by O+ ions. We show that the observed are was in a suitable location in both latitude and MLT to have fed O+ ions into the second injection and that the upward flux of ions associated with it was sufficient to explain the observed injection. We interpret these data as showing that arcs in the nightside plasma-sheet boundary layer could be the source of O+ ions energised by a dipolarisation of the mid- and near-Earth tail, as opposed to ions ejected from the dayside ionosphere in the cleft ion fountain.

EISCAT observations of ion composition and temperature anisotropy in the high-latitude F-region

The papers by Winser et al. [(1990) J. atmos. terr. Phys.52, 501] and Häggström and Collis [(1990) J. atmos. terr. Phys.52, 519] used plasma flows and ion temperatures, as measured by the EISCAT tristatic incoherent scatter radar, to investigate changes in the ion composition of the ionospheric F-layer at high latitudes, in response to increases in the speed of plasma convection. These studies reported that the ion composition rapidly changed from mainly O+ to almost completely (>90%) molecular ions, following rapid increases in ion drift speed by >1 km s−1. These changes appeared inconsisent with theoretical considerations of the ion chemistry, which could not account for the large fractions of molecular ions inferred from the obsevations. In this paper, we discuss two causes of this discrepancy. First, we reevaluate the theoretical calculations for chemical equilibrium and show that, if we correct the derived temperatures for the effect of the molecular ions, and if we employ more realistic dependences of the reaction rates on the ion temperature, the composition changes derived for the faster convection speeds can be explained. For the Winser et al. observations with the radar beam at an aspect angle of ϕ = 54.7° to the geomagnetic field, we now compute a change to 89% molecular ions in < 2 min, in response to the 3 km s−1 drift. This is broadly consistent with the observations. But for the two cases considered by Häggström and Collis, looking along the field line (ϕ = 0°), we compute the proportion of molecular ions to be only 4 and 16% for the observed plasma drifts of 1.2 and 1.6 km s−1, respectively. These computed proportions are much smaller than those derived experimentally (70 and 90%). We attribute the differences to the effects of non-Maxwellian, anisotropic ion velocity distribution functions. We also discuss the effect of ion composition changes on the various radar observations that report anisotropies of ion temperature.

Measuring ion temperatures and studying the ion energy balance in the high-latitude ionosphere

Data are presented for a nighttime ion heating event observed by the EISCAT radar on 16 December 1988. In the experiment, the aspect angle between the radar beam and the geomagnetic field was fixed at 54.7°, which avoids any ambiguity in derived ion temperature caused by anisotropy in the ion velocity distribution function. The data were analyzed with an algorithm which takes account of the non-Maxwellian line-of-sight ion velocity distribution. During the heating event, the derived spectral distortion parameter (D∗) indicated that the distribution function was highly distorted from a Maxwellian form when the ion drift increased to 4 km s−1. The true three-dimensional ion temperature was used in the simplified ion balance equation to compute the ion mass during the heating event. The ion composition was found to change from predominantly O4 to mainly molecular ions. A theoretical analysis of the ion composition, using the MSIS86 model and published values of the chemical rate coefficients, accounts for the order-of-magnitude increase in the atomic/molecular ion ratio during the event, but does not successfully explain the very high proportion of molecular ions that was observed.

Superthermal ion signatures of auroral acceleration processes

The retarding ion mass spectrometer on the Dynamics Explorer 1 spacecraft has generated a unique data set which documents, among other things, the occurrence of non-Maxwellian superthermal features in the auroral topside ionosphere distribution functions. In this paper, we provide a representative sampling of the observed features and their spatial morphology as observed at altitudes in the range from a few thousand kilometers to a few earth radii. At lower altitudes, these features appear at auroral latitudes separating regions of polar cap and subauroral light ion polar wind. The most common signature is the appearance of an upgoing energetic tail having conical lobes representing significant ion heat and number flux in all species, including O+. Transverse ion heating below the observation point at several thousand kilometers is clearly associated with O+ outflows. In some events observed, transverse acceleration apparently involves nearly the entire thermal plasma, the distribution function becomes highly anisotropic with T⊥ > T∥, and may actually develop a minimum at zero velocity, i.e., become a torus having as its axis the local magnetic field direction. At higher altitudes, the localized dayside source region appears as a field aligned flow which is dispersed tailward across the polar cap according to parallel velocity by antisunward convective flow, so that upflowing low energy O+ ions appear well within the polar cap region. While this flow can appear beamlike in a given location, the energy dispersion observed implies a very broad energy distribution at the source, extending from a few tenths of an eV to in excess of 50 eV. On the nightside, upgoing ion beams are found to be latitudinally bounded by regions of ion conics whose half angles increase with increasing separation from the beam region, indicating low altitude transverse acceleration in immediate proximity to, and below, the parallel acceleration region. These observations reveal a clear distinction between classical polar wind ion outflow and O+ enhanced superthermal flows, and confirm the importance of low altitude transverse acceleration in ionospheric plasma transport, as suggested by previous observations.

Projected length annealing of etched Sm-152 ion tracks in apatite

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Argon ion implantation inducing modifications in the properties of benzene plasma polymers

Benzene plasma polymer films were bombarded with Ar ions by plasma immersion ion implantation. The treatments were performed using argon pressure of 3 Pa and 70 W of applied power. The substrate holder was polarized with high voltage negative pulses (25 kV, 3 Hz). Exposure time to the immersion plasma, t, was varied from 0 to 9000 s. Optical gap and chemical composition of the samples were determined by ultraviolet-visible and Rutherford backscattering spectroscopies, respectively. Film wettability was investigated by the contact angle between a water drop and the film surface. Nanoindentation technique was employed in the hardness measurements. It was observed growth in carbon and oxygen concentrations while there was decrease in the concentration of H atoms with increasing t. Furthermore, film hardness and wettability increased and the optical gap decreased with t. Interpretation of these results is proposed in terms of the chain crosslinking and unsaturation. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Plasma immersion ion implantation of nitrogen into H13 steel under moderate temperatures

Ion implantation of nitrogen into samples of tempered and quenched H13 steel was carried out by plasma immersion technique. A glow discharge plasma of nitrogen species was the ion source and the negative high voltage pulser provided 10-12 kV, 60 mu s duration and 1.0-2.0 kHz frequency, flat voltage pulses. The temperatures of the samples remained between 300 and 450 degrees C, sustained solely by the ion bombardment. In some of the discharges, we used a N-2 + H-2 gas mixture with 1:1 ratio. PIII treatments as long as 3, 6, 9 and up to 12 h were carried out to achieve as thickest treated layer as possible, and we were able to reach over 20 mu m treated layers, as a result of ion implantation and thermal (and possibly radiation enhanced) diffusion. The nitrogen depth profiles were obtained by GDOS (Glow Discharge Optical Spectroscopy) and the exact composition profiles by AES (Auger Electron Spectroscopy). The hardness of the treated surface was increased by more than 250%, reaching 18.8 GPa. No white layer was seen in this case. A hardness profile was obtained which corroborated a deep hardened layer, confirming the high efficacy of the moderate temperature PIII treatment of steels. (c) 2005 Elsevier B.V. All rights reserved.

The effect of N+ ion energy on the properties of ion bombarded plasma polymer films

This work describes the influence of the ion bombardment on the electrical, optical and mechanical properties of polymer films deposited from radio-frequency plasmas of benzene. Irradiations were conducted using N+ at 5 x 10(19) ions/m(2), varying the ion energy, E-0, from 0 to 150 keV. Film elemental composition was determined by Rutherford backscattering spectroscopy. Electrical resistivity and hardness were obtained by the two-point probe and nanoindentation technique, respectively. Ultraviolet-visible spectroscopy was employed to investigate the optical constants of the samples. Etching rate was determined by exposure of the films to reactive oxygen plasmas. Ion bombardment induced gradual loss of H and increase in C and O concentrations with Eo. As a consequence the electrical, optical and mechanical properties were drastically affected. Interpretation of these results is proposed in terms of chain cross-linking and unsaturation. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Surface modification by metal ion implantation forming metallic nanoparticles in insulating matrix.

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We investigated nanocomposites produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. During the implantation, the excess of metal atom concentration above the solubility limit leads to nucleation and growth of metal nanoparticles, driven by the temperature and temperature gradients within the implanted sample including the beam-induced thermal characteristics. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), that can be estimated by computer simulation using the TRIDYN. This is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study suggests that the nanoparticles form a bidimentional array buried few nanometers below the substrate surface. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples showed the metallic nanoparticles formed in the insulating matrix. The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted. These experimental results were compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement was found between the experimental results and the predictions of the theory. It was possible to conclude, in all cases, that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

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.

Preparation of cold Mg + ion clouds for sympathetic cooling of highly charged ions at SPECTRAP

Die Elektronen in wasserstoff- und lithium-ähnlichen schweren Ionen sind den extrem starken elektrischen und magnetischen Feldern in der Umgebung des Kerns ausgesetzt. Die Laserspektroskopie der Hyperfeinaufspaltung im Grundzustand des Ions erlaubt daher einen sensitiven Test der Quantenelektrodynamik in starken Feldern insbesondere im magnetischen Sektor. Frühere Messungen an wasserstoffähnlichen Systemen die an einer Elektronenstrahl-Ionenfalle (EBIT) und am Experimentierspeicherring (ESR) der GSI Darmstadt durchgeführt wurden, waren in ihrer Genauigkeit durch zu geringe Statistik, einer starken Dopplerverbreiterung und der großen Unsicherheit in der Ionenenergie limitiert. Das ganze Potential des QED-Tests kann nur dann ausgeschöpft werden, wenn es gelingt sowohl wasserstoff- als auch lithium-ähnliche schwere Ionen mit einer um 2-3 Größenordnung gesteigerten Genauigkeit zu spektroskopieren. Um dies zu erreichen, wird gegenwärtig das neue Penningfallensystem SPECTRAP an der GSI aufgebaut und in Betrieb genommen. Es ist speziell für die Laserspektroskopie an gespeicherten hochgeladenen Ionen optimiert und wird in Zukunft von HITRAP mit nierderenergetischen hochgeladenen Ionen versorgt werden.rnrnSPECTRAP ist eine zylindrische Penningfalle mit axialem Zugang für die Injektion von Ionen und die Einkopplung eines Laserstrahls sowie einem radialen optischen Zugang für die Detektion der Fluoreszenz. Um letzteres zu realisieren ist der supraleitende Magnet als Helmholtz-Spulenpaar ausgelegt. Um die gewünschte Genauigkeit bei der Laserspektroskopie zu erreichen, muss ein effizienter und schneller Kühlprozess für die injizierten hochegeladenen Ionen realisiert werden. Dies kann mittels sympathetischer Kühlung in einer lasergekühlten Wolke leichter Ionen realisiert werden. Im Rahmen dieser Arbeit wurde ein Lasersystem und eine Ionenquelle für die Produktion einer solchen 24Mg+ Ionenwolke aufgebaut und erfolgreich an SPECTRAP in Betrieb genommen. Dazu wurde ein Festkörperlasersystem für die Erzeugung von Licht bei 279.6 nm entworfen und aufgebaut. Es besteht aus einem Faserlaser bei 1118 nm der in zwei aufeinanderfolgenden Frequenzverdopplungsstufen frequenzvervierfacht wird. Die Verdopplerstufen sind als aktiv stabilisierte Resonantoren mit nichtlinearen Kristallen ausgelegt. Das Lasersystem liefert unter optimalen Bedingeungen bis zu 15 mW bei der ultravioletten Wellenlänge und erwies sich während der Teststrahlzeiten an SPECTRAP als ausgesprochen zuverlässig. Desweiteren wurde eine Ionequelle für die gepulste Injektion von Mg+ Ionen in die SPECTRAP Falle entwickelt. Diese basiert auf der Elektronenstoßionisation eines thermischen Mg-Atomstrahls und liefert in der gepulsten Extraktion Ionenbündel mit einer kleinen Impuls- und Energieverteilung. Unter Nutzung des Lasersystems konnten damit an SPECTRAP erstmals Ionenwolken mit bis zu 2600 lasergekühlten Mg Ionen erzeugt werden. Der Nachweis erfolgte sowohl mittels Fluoreszenz als auch mit der FFT-ICR Technik. Aus der Analyse des Fluoreszenz-Linienprofils lässt sich sowohl die Sensitivität auf einzelne gespeicherte Ionen als auch eine erreichte Endtemperatur in der Größenordnung von ≈ 100 mK nach wenigen Sekunden Kühlzeit belegen.