A new generation of medical grade Cf-252 sources was developed in 2002 at the Oak Ridge National Laboratory (ORNL). The combination of small size and large activity of these Cf-252 sources makes them suitable to be used with the conventional high-dose-rate (HDR) remote afterloading systems for interstitial brachytherapy. A recent in-water calibration experiment showed that the measured gamma dose rates near the new source are slightly greater than the neutron dose rates; contradicting the well established neutron-to-gamma dose ratio of approximately 2:1 at locations near a Cf-252 brachytherapy source. Specifically, the MCNP-predicted gamma dose rate is a factor of two higher than the measured gamma dose rate at the distance of 1 cm, and the differences between the two results gradually diminish at distances farther away from the source. To resolve this discrepancy, we updated the source gamma spectrum by including in the ORIGEN-S data library the experimentally measured Cf-252 prompt gamma spectrum as well as the true Cf-252 spontaneous fission yield data to explicitly model delayed gamma emissions from fission products. We also investigated the bremsstrahlung x-rays produced by the beta particles emitted from fission-product decays. The results show that the discrepancy of gamma dose rates is mainly caused by the omission of the bremsstrahlung x-rays in the MCNP runs. By including the bremsstrahlung x-rays, the MCNP results show that the gamma dose rates near a new Cf-252 source agree well with the measured results and that the gamma dose rates are indeed greater than the neutron dose rates. The calibration experiment also showed discrepancies between the experimental and computational neutron dose profiles obtained. Specifically the MCNP-predicted neutron dose rates were ~25% higher than the measured neutron dose rates at all distances. In attempting to resolve this discrepancy the neutron emission rate was verified by the National Institute of Standards and Technology (NIST) and an experiment was performed to explore the effects of bias voltage on ion chamber charge collection. So far the discrepancies between the computational and experimental neutron dose profiles have not been resolved. Further study is needed to completely resolve this issue and some suggestions on how to move forward are given.

There are a variety of uses for reference neutron fields including detector response and dosimeter studies. The Georgia Institute of Technology has a 252Cf spontaneous fission source and an AmBe (α, n) source available for use in its research programs. In addition, it has iron, lead, beryllium, tantalum, heavy water, and polyethylene spheres to modify the neutron energy distributions from these neutron sources. This research characterized the neutron leakage spectra from the source inside spherical shells using a Bonner sphere spectrometer. All the neutron fields measured were also computed with a Monte Carlo code to determine the neutron fluence rate and ambient dose equivalent rate. The comparison of experimental data and calculations are used to provide further insight into the neutron spectra as modified by the spheres. The characterization of these modified sources will provide data to assist in using the resulting neutron fields in other research activities. To measure each neutron field combination, one of the two sources was placed in the center of an attenuating sphere. The neutron field was first measured at a variety of source-to-detector distances with a Bonner Sphere System. The spectrometer measurements, specifically the count rates of the different Bonner spheres, as a function of distance from the source is fitted to obtain corrections for room-scatter and air-scatter of neutrons using the Eisenhauer, Schwartz, and Johnson method. Using these corrections, the count rates free of room return is obtained at 1 m from the source and unfolded using the BUMS software to obtain the reported fluence and dose equivalent rates. These results are compared to those generated by the Monte Carlo Neutral Particle (MCNP) code. Models were made in MCNP for each of the source and moderating sphere combinations. The neutron fluence and dose rates were tallied during the MCNP simulation. The unfolded experimental data and the MCNP calculations showed good agreement for most of source-attenuating sphere combinations, thereby reinforcing the experimental results.

L’acquisition de données structurales et thermodynamiques relatives à des systèmes actinides (An(III), Pu(IV) Pa(V))–acides organiques polyfonctionnels (citrique, NTA, DTPA), en solution aqueuse, vise à une meilleure compréhension des interactions actinides-ligands essentielle à l’optimisation de procédés de séparation, de décorporation, et également à l’évaluation de la sûreté des sites de stockage de déchets radioactifs. Le comportement du protactinium pentavalent à l’échelle des traces en présence des anions citrates et NTA a fait l’objet d’études systématiques par extraction liquide-liquide dans le système TTA/Toluène/HClO₄/NaClO₄/Pa(V)/ligands. Après avoir déterminé l’ordre limite des complexes (3 pour Pa(V)-Cit et 2 pour Pa(V)-NTA), les constantes de formation associées à chaque espèce ont pu être calculées. L’étude multi-technique (électrophorèse capillaire et spectrofluométrie laser) sur la complexation des An(III) par le DTPA, réalisée à plusieurs pH, a permis de mettre en évidence la coexistence des complexes mono-protoné (AnHDTPA–) et déprotoné. (AnDTPA²–) pour des solutions acides et faiblement acides. Une réinterprétation des données de la littérature, en considérant les deux complexes, a permis de faire converger les valeurs des constantes de complexation des espèces qui étaient jusqu’à maintenant dispersées. L’étude thermodynamique a ensuite été complétée par une étude théorique (calculs DFT). La structure des complexes protoné et non protoné et le mode de coordination du Curium ont ainsi été établis. L’étude exploratoire sur la complexation du Pu(IV) par le DTPA dans des conditions de pH proches du milieu biologique a nécessité le développement d’un protocole expérimental en trois étapes : protection de Pu(IV) contre l’hydrolyse avec NTA (pH faible), augmentation du pH vers des conditions neutres, compétition entre la complexation de Pu(IV) par le NTA et le DTPA. Les expériences préliminaires réalisées entre pH 1,5 et 3,5 par électrophorèse capillaire (EC-ICP-MS), semblent indiquer l’existence d’effet cinétique ou/et l’existence d’un complexe mixte. Les interprétations faites lors de cette étude exploratoire sont à confirmer. / A thorough knowledge of the chemical properties of actinides is now required in a wide variety of fields: extraction processes involved in spent fuel reprocessing, groundwater in the vicinity of radioactive waste packages, environmental and biological media in the case of accidental release of radionuclides. In this context, the present work has been focused on the complexation of Am(III), Cm(III), Cf(III), Pu(IV) and Pa(V) with organic ligands: DTPA, NTA and citric acid. The complexation of pentavalent protactinium with citric and nitrilotriacetic acids was studied using liquid-liquid extraction with the element at tracer scale (CPa < 10-10M). The order and the mean charge of each complex were determined from the analysis of the systematic variations of the distribution coefficient of Pa(V) as function of ligand and proton concentration. Then, the apparent formation constants related of the so-identified complexes were calculated. The complexation of trivalent actinides with DTPA was studied by fluorescence spectroscopy (TRLFS) and capillary electrophoresis (CE-ICP-MS). The coexistence of the mono-protonated and non-protonated complexes (AnHDTPA– and AnDTPA²–) in acidic media (1.5 ≤ pH ≤ 3.5) was shown unambiguously. Literature data have been reinterpreted by taking into account both complexes and a consistent set of formation constants of An(III)-DTPA has been obtained. The experimental study was completed by theoretical calculations (DFT) on Cm-DTPA system. The coordination geometry of Cm in CmDTPA²- and CmHDTPA- including water molecules in the first coordination sphere has been determined as well as interatomic distances. Finally, a study on the complexation of Pu(IV) with DTPA was initiated in order to more closely mimic physiological conditions. A three-step approach was proposed to avoid plutonium hydrolysis: i/ complexation of Pu(IV) with (NTA) in order to protect Pu(IV) from hydrolysis (at low pH) ii/ increase of pH toward neutral conditions and iii/ competition between the complexation of Pu with NTA and with DTPA. The preliminary experiments performed with CE-ICP-MS in the pH range 1.5 - 3.5 tend to indicate kinetic effect or/and the presence of mixed complex.

L'acquisition de données structurales et thermodynamiques relatives à des systèmes actinides (An(III), Pu(IV) Pa(V))-acides organiques polyfonctionnels (citrique, NTA, DTPA), en solution aqueuse, vise à une meilleure compréhension des interactions actinides-ligands essentielle à l'optimisation de procédés de séparation, de décorporation, et également à l'évaluation de la sûreté des sites de stockage de déchets radioactifs. Le comportement du protactinium pentavalent à l'échelle des traces en présence des anions citrates et NTA a fait l'objet d'études systématiques par extraction liquide-liquide dans le système TTA/Toluène/HClO₄/NaClO₄/Pa(V)/ligands. Après avoir déterminé l'ordre limite des complexes (3 pour Pa(V)-Cit et 2 pour Pa(V)-NTA), les constantes de formation associées à chaque espèce ont pu être calculées. L'étude multi-technique (électrophorèse capillaire et spectrofluométrie laser) sur la complexation des An(III) par le DTPA, réalisée à plusieurs pH, a permis de mettre en évidence la coexistence des complexes mono-protoné (AnHDTPA-) et déprotoné. (AnDTPA²-) pour des solutions acides et faiblement acides. Une réinterprétation des données de la littérature, en considérant les deux complexes, a permis de faire converger les valeurs des constantes de complexation des espèces qui étaient jusqu'à maintenant dispersées. L'étude thermodynamique a ensuite été complétée par une étude théorique (calculs DFT). La structure des complexes protoné et non protoné et le mode de coordination du Curium ont ainsi été établis. L'étude exploratoire sur la complexation du Pu(IV) par le DTPA dans des conditions de pH proches du milieu biologique a nécessité le développement d'un protocole expérimental en trois étapes : protection de Pu(IV) contre l'hydrolyse avec NTA (pH faible), augmentation du pH vers des conditions neutres, compétition entre la complexation de Pu(IV) par le NTA et le DTPA. Les expériences préliminaires réalisées entre pH 1,5 et 3,5 par électrophorèse capillaire (EC-ICP-MS), semblent indiquer l'existence d'effet cinétique ou/et l'existence d'un complexe mixte. Les interprétations faites lors de cette étude exploratoire sont à confirmer.