The A. Q. Khan nuclear supplier network constitutes the most severe loss of control over nuclear technology ever. For the first time in history all of the keys to a nuclear weapon*the supplier networks, the material, the enrichment technology, and the warhead designs--were outside of state oversight and control. This thesis demonstrates that Khan's nuclear enterprise evolved out of a portion of the Pakistani procurement network of the 1970s and 1980s. It presents new information on how the Pakistani state organized, managed, and oversaw its nuclear weapons laboratories. This thesis provides extensive documentation of command and control challenges faced by Pakistan and argues that Khan was largely a rogue actor outside of state oversight. The A. Q. Khan affair refutes more optimistic theories about the effects of nuclear proliferation. This case study indicates that states have a difficult time balancing an abstract notion of safety against pressing needs for organizational speed and flexibility. This thesis enumerates enabling institutional factors in Pakistan, which allowed Khan's enterprise to continue and flourish, and which might also be generalizable to other states of proliferation concern.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, in fulfilment of the requirements for the degree of Masters of Science. Johannesburg, 2017 / The monitoring of personnel for exposure to radioactive elements is a regulatory requirement for any nuclear installation and due to the nature of the research, the need for a non-invasive procedure for the monitoring for exposure to plutonium has been identified at the South African Nuclear Energy Corporation (NECSA). Historically, analyses of short-lived radioactive elements were performed by α-spectrometry. But due to the well documented drawbacks of the older generation of α-spectrometer analysis, Quadrupole Inductively Coupled Mass Spectrometry (Q-ICP-MS) was suggested as an alternative technique. A feasibility study was undertaken to determine whether sub-trace concentrations of plutonium in urine can be determined using a modern, standard Q-ICP-MS. A simplified One Variable at a Time (OVAT) approach was used to establish optimal analytical conditions starting from instrument setup and ending in sample preparation. The optimum sample preparation determined required 50 mL urine which underwent co-precipitation, wet-ashing and solid phase extraction using Tetra Valent Actinide (TEVA)-resin. Calibration standards ranged from 5 to 100 pg L-1 and the optimised method produced LOD’s of 0.2 pg L-1 and LOQ’s of 0.5 pg L-1. Sample intra-assay precision at 0.5- and 15 pg L-1 were 11.3% and 4.43% respectively, in the urine matrix. The bias was 8% and 0% at the same concentrations. The method was evaluated using samples from an international proficiency study and two out of the three tests that could be quantified passed specification. According to ISO 13528 a method is acceptable if two out of three tests pass. The method has been verified and a modern, standard Q-ICP-MS has been proven to be a suitable alternative to α-spectrometry with respect to sub-trace plutonium analysis. / MT 2017

"Radionuclides in particulate matter associated with outdoor and indoor dusts were analyzed to determine the form and concentration of radioactive isotopes present. These radioactive isotopes, such as Strontium 90, Cesium 137, and Uranium 235, consist of, or are sorbed onto fine particulate matter, (PM). The airborne dispersion of this fine particulate matter results in the facilitated transport of these sorbed or neat radionuclides. Sources of particulate-bound radioactive contaminants include fallout from weapons testing, accumulation of radon daughters, transport of soils containing naturally-occurring radioactive material, remediation of radiologically-contaminated sites, and nuclear material processing. Radiological contaminants in PM, may exist as trace contamination in homogenous collections of particles, but may also exist heterogeneously, as a small number of high-concentration radionuclides among a larger set of uncontaminated particles. A total of 114 samples of indoor and outdoor airborne dusts were collected from a former nuclear weapons production facility near Richland, WA, the Los Alamos National Laboratory, and the Yakama Indian Nation in Wapato, WA. Los Alamos, NM was also the site of the May 2000 Cerro Grande wildfire. The wildfire created very large amounts of airborne particulate matter, including smoke and soot. The area affected by open burning included 43,000 acres. At the national laboratory, greater than 7600 acres were affected, including some areas that were radiologically- contaminated, such as a U-238 ammunition firing area. (LANL, 2007) This introduces a potential source of hot particles in dusts and other archived particulate matter, which may remain in the environment. LANL Airborne radionuclide surveillance has historically found higher uranium levels during windy periods, and saw elevated air uranium levels associated with the Cerro Grande fire. (Ibid, p. 108) Dust samples were sieved to pass a 150 micron screen and analyzed by gamma spectroscopy. Samples with higher activity were analyzed by Scanning Electron Microscopy/Energy Dispersive X-ray analysis, SEM/EDS. The results of gamma spectroscopy and individual particle counts were compared to determine the degree of radioactive heterogeneity in each sample. Radioactive heterogeneity, isotopic distribution, and particle size can be related to the source of the radioactive PM. Radiological contaminants in particulate matter, (PM), may exist as trace contamination in homogenous collections of particles, but may also exist heterogeneously, as a small number of high-concentration radionuclides among a larger set of uncontaminated particles. Residential and source area dusts were collected from locations surrounding, and potentially impacted, by operational and remedial activities at the HNR. The dust samples were analyzed, by multiple means, in order to identify those with radiologically- contaminated particles. Samples with higher activity were further analyzed by Scanning Electron Microscopy/Energy Dispersive X-ray analysis, (SEM/EDS), to determine if the radiological contamination was homogenous or heterogeneous. Two case studies were followed. The method isolated and analyzed lead and bismuth from naturally occurring radioactive material in coal fly ash. The method isolated and fingerprinted thorium, and the rare earths cerium, lanthanum, samarium, neodymium, and gadolinium in sedimentary cerium monazite minerals, nuclear waste processing dusts, and fission waste products in a WWTP effluent channel."

Pyroprocessing, via electrorefining in a molten salt bath, is a promising treatment route for spent nuclear fuel reprocessing. In order to implement such a technology and ensure its safe operation it is vital to develop on-line techniques to understand and monitor the molten salt and its contents. These tools are technically challenging because of the high temperatures and corrosive environment experienced in molten salt media. Electrochemical, spectroscopic and spectroelectrochemical methods were developed and used to study actinide and fission product behaviour in molten LiCl-KCl eutectic. A spectroscopic furnace was designed and supporting methodology developed in order to allow the acquisition of reproducible quantitative data. The apparatus monitored the precipitation of NdCl3 by the addition of Li2CO3 and PrCl3 by the addition of Li2O in LiCl-KCl eutectic. The precipitates formed were identified as the respective LnOCl. In order to probe actinide behaviour in this hygroscopic medium, dry actinides chlorides were synthesised. The oxidation of uranium metal by BiCl3 in LiCl-KCl eutectic yielded UCl3 while neptunium and plutonium were prepared as Cs2AnCl6 via precipitation in concentrated aqueous HCl by addition of CsCl. The molar extinction coefficients for U(III), U(IV), Np(IV) and Pu(III) were obtained in LiCl-KCl eutectic at 450 áμ’C. The study of the Np(IV)/Np(III) couple via spectroelectrochemical techniques, enabled the determination of the Np(III) molar extinction coefficients. Uranium was studied in LiCl-KCl eutectic using square wave voltammetry, cyclic voltammetry and chronoabsorptometry. The electrochemical techniques benchmarked the results obtained by spectroelectrochemistry. The results from the different techniques were compared to and explained by determining the Gibbs energy and activation energy of U(III) and U(IV). It was concluded that all the mentioned techniques are suitable for the study of high temperature molten chlorides. Because of its capacity to gather numerous data parameters while minimising the number of experiments required and the quantity of material needed, spectroelectrochemical methods were highlighted as the most promising technique for future studies of radionuclides in high temperature melts.

Les réactions d'oxydoréduction de l'antimoine (V) et (III) avec la mackinawite (FeS) et du plutonium (III) et (V) avec plusieurs minéraux à fer(II) et des oxydes de fer(III) ont été étudiées dans des conditions d'anoxie. La spectroscopie d'absorption des rayons X fut utilisée pour l'analyse de l'état d'oxydation et de la structure locale du Sb et Pu associés à la phase solide. Après réaction avec la mackinawite, la chukanovite et la magnétite, PuO2, Pu(III) ou des mixtures des deux états d'oxydation ont été observé. A la surface de la magnétite un complexe tridenté du Pu(III) a pu être mis en évidence à l'aide des spectres EXAFS couplé à une simulation de Monte‐Carlo utilisant le code de calcul Feff. La quantité relative de Pu(III) est fonction de l'espèce minérale, du ratio solide/liquide, des valeurs pe et pH du système et, potentiellement, de la taille de particule et de la cristallinité de la phase solide de PuO2 en présence de laquelle le Pu(III) existe. Avec la mackinawite à pH 6,2 et à une occupation de surface de 67 nmol/m2 et avec la magnétite jusqu'à pH 8.4 et 56 nmol/m2 de Pu, uniquement du Pu(III) fut trouvé associé à la phase solide. Avec la maghémite contenant du fer(II) résiduel à pH6 Pu(III) et Pu(IV) était, probablement, présents dans des complexes de surfaces similaire à celui formé par le Pu(III) sur la magnétite. Dans les conditions expérimentales (couverture de surface ≤ 77 nmol/m2), aucune formation de PuO2 ne fut observé. Après réaction avec l'hématite et la goethite Pu(IV) était l'état d'oxydation prédominant associé à la phase solide. La sorption et la réduction du Sb(V) avec la mackinawite était fortement fonction du pH. A pH acide la sorption était rapide et Sb(V) fut complètement réduit en Sb(III), formant un complexe Sb(III)‐S3 probablement associé à la surface de la mackinawite. La réduction du Sb(V) était couplée à l'oxydation de la mackinawite et la greigite (Fe3S4) fut détectée par XRD. A pH basique, la sorption du Sb(V) est lente et la réduction vers le Sb(III) n'était complète qu'à des ratios de Sb/FeS très bas. Pour des valeurs plus élevé de Sb/FeS la sorption de Sb se faisait en partie par la réduction envers le complexe de Sb(III)‐S3 et en partie par une co‐précipitation avec le Fe(III). Il a pu être démontré que les minéraux à fer(II) peuvent effectivement contribuer à la réduction et à l'immobilisation de l'antimoine et du plutonium qui sont des contaminants environnementaux d'importance croissante.

The ability to quickly and accurately quantify fissile constituents in bulk materials remains essential to many aspects of nuclear forensics and for safeguarding nuclear materials and operations. This often entails the analysis of trace quantities of nuclear debris or effluents, and typically requires bulk sample digestion followed by actinide separation and mass spectrometry. Because destructive methods are time and labor intensive, efforts have been made to develop alternative nondestructive methods for this type of analysis. This work, performed at Oak Ridge National Laboratory at the High Flux Isotope Reactor (HFIR), seeks to utilize delayed neutron activation analysis on samples of interest containing multiple fissile constituents. Based on the variances in the fission product yields of individual fissile nuclides, this work utilizes methods of linear regression to derive a technique that allows for such analysis, forgoing chemical separation and using only a single irradiation and counting step. / text

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X-ray spectroscopic experiments, including X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS), were performed in a large energy range (60-9000 eV) on a variety of systems, probing different elements and orbitals. The systems can preferably be divided into three groups: Actinides, copper systems and amorphous materials. We studied oxidation states of Pu in PuO2 using a closed-source experimental setup, developed by us, to lower the safety restrictions associated with such experiments. The presence of Pu with higher oxidation state than Pu(IV) was found in polycrystalline PuO2. This is an important finding since Pu with higher oxidation states has higher solubility affecting the safety of a proposed undeground repository of spent nuclear fuel which can eventually be infiltrated by groundwater. In the proposed underground repository the molecular oxygen will vanish at some point due to microbial activity and mineral oxidation. At this stage sulfur is the most important candidate for causing copper corrosion. We studied Cu films and foils exposed to sulfide solutions at both Cu L2,3, Cu K and S L2,3 edges and found for example that S L2,3 XES is useful for distinguishing between different copper sulfides and Cu Kβ XES can be used to identify monovalent Cu compounds. Amorphous, zirconium containing alloys are potentially useful materials for future nuclear reactors. The electronic structure of such materials was also investigated.

Research report (M.S.)--University of Washington, 1971. / Typescript. "BNWL-1608, Special Distribution." "August 1971." Includes bibliographical references (p. 89-91).