No description available.

The design of a computerized system for the estimation of uranium potential supply in the United States constitutes the primary objective of this dissertation. Once completed, this system performs for various levels of economic variables, such as prices, the estimation of potential uranium supply without requiring the appraisal by geologists, area by area, of undiscovered uranium endowment. The main components that form the system are explicit models of endowment, exploration, and production. These component models are derived from engineering and geological data, and together, they comprise the system. This system is unique in that it links physical attributes of endowment to time series of price and production. This linkage is made by simulating the activities of the U.S. uranium industry, activities (exploration, mine development, and production) that are involved in the transformation of endowment to potential supply. Uranium endowment is first generated by employing a crustal abundance model; a data file containing characteristics (tonnage, grade, depth, intra-deposit grade variation) of the discrete deposits that comprise the endowment is established by this model. An exploration model relates discoveries to exploration effect and deposit characteristics. Discovery yield for a given effort is linked to the relative "discoverability" of the deposits of the endowment as well as to the total exploration effort. An economic evaluation is performed on each discovery to determine whether or not the deposit can be developed and produced, given the stated level of the economic variables. The system then determines the magnitude of potential supply that could be forthcoming from all discoverable and exploitable deposits for the stated economic circumstances. Initially, the parameters of the system must be estimated. The approach employed for this estimation makes use of the time series information on uranium exploration and production activities. In essence, the system is used to simulate the past history of the U.S. uranium industry (period 1948-1978) and to generate industry statistics for these activities; the parameters selected are those values that cause the system to yield a time series that matches closely that which actually occurred.

Uranium has been mined for many years and used for fuel for nuclear reactors and materials for atomic weapons, ammunition, and armor. While the radioactivity associated with uranium mining has been linked to the development of lung and kidney cancers, and leukemia, little is known about the direct chemical genotoxicity of uranium. The overall hypothesis of the current research is that uranium can produce DNA damage by chemical genotoxicity mechanisms. Three specific aims were tested. In Aim 1, specific DNA lesions caused by direct interaction of uranium and DNA were investigated. Chinese Hamster Ovary cells (CHO) with mutations in various DNA repair pathways were exposed to 0 – 300 μM of soluble depleted uranium (DU) as uranyl acetate (UA) for 0 – 48 hr. Results indicate that UA readily enters CHO cells, with the highest concentration localizing in the nucleus. Clonogenics assay shows that UA is cytotoxic in each cell line with the greatest cytotoxicity in the base excision repair deficient EM9 cells and the nuclear excision repair deficient UV5 cells compared to the non-homologous end joining deficient V3.3 cells and the parental AA8 cells after 48 hr. This indicates that UA is forming DNA adducts that may be producing single strand breaks through hydrolysis rather than double strand breaks in CHO cells. Fast Micromethod® results indicate an increased amount of single strand breaks in the EM9 cells after 48 hr UA exposure compared to the V3.3 and AA8 cells. In Aim 2, the role of oxidative stress in producing DNA lesions was determined. Cellular oxidative stress has been implicated in the genotoxicity of many heavy metals as a mechanism of induced DNA damage. To investigate this possible mechanism, human bronchial epithelial cells (16HBE14o⁻) were exposed to 30 ppb (0.13 μM U) UA for 2 – 24 hr. UA did not significantly induce oxidative stress compared to untreated cells at 3 – 4 hr time points. These results suggest that cellular oxidative stress is not a major pathway of DU genotoxicity at low concentrations. In Aim 3, DNA damage response to uranium-induced DNA damage was investigated. It has been widely reported that metals can be genotoxic by inhibiting DNA repair. Cultured cells were co-exposed to 0.13 μM UA in the presence of 0 – 25 μM of etoposide for 0 – 48 hr. Results indicate that UA inhibited double strand break repair. Coexposures of etoposide and UA synergistically induced cytotoxicity compared to individual treatments and untreated cells. Co-exposed UA and etoposide treated 16HBE14o⁻ cells exhibited a decrease in phosphorylation of DNA repair proteins compared to etoposide treatments. Untreated and UA-treated 16HBE14o⁻ cells did not induce phosphorylation of DNA repair proteins. These results suggest that DU inhibits double strand break DNA repair at low concentrations in the presence of a known DNA double-strand damaging agent, etoposide. The inhibition of DNA repair by DU at environmentally relevant concentrations suggests a novel means by which uranium may exert its genotoxic effects. Results found at low dose exposures are not consistent with alterations seen with radioactivity, suggesting that the effects of uranium at low doses are due to its chemical genotoxic effects. Understanding how uranium reacts with DNA is important to better understand how this suspected carcinogen induces cancer and to help to elucidate mechanisms that produce cancers in people exposed to uranium.

Uranium contamination of groundwater from mining and milling operations is an environmental concern. Reductive precipitation of soluble and mobile hexavalent uranium (U(VI)) contamination to insoluble and immobile tetravalent uranium (U(IV)) constitutes the most promising remediation approach for uranium in groundwater. Previous research has shown that many microorganisms are able to catalyze this reaction in the presence of suitable electron-donors. The purpose of this work is to explore lowcost, effective alternatives for biologically catalyzed reductive precipitation of U(VI). Methanogenic granular sludge from anaerobic reactors treating industrial wastewaters was tested for its ability to support U(VI)-reduction. Due to their high microbial diversity, methanogenic granules displayed intrinsic activity towards U(VI)-reduction. Endogenous substrates from the slow decomposition of sludge biomass provided electron-equivalents to support efficient U(VI)-reduction without external electrondonors. Continuous columns with methanogenic granules also demonstrated sustained reduction for one year at high uranium loading rates. One column fed with ethanol, only enabled a short-term enhancement in the uranium removal efficiency, and no enhancement over the long term compared to the endogenous column. Nitrate, a common co-contaminant of uranium, remobilized previously deposited biogenic U(IV). U(VI) also caused inhibition to denitrification. An enrichment culture (EC) was developed from a zero-valent iron (Fe⁰)/sand packed-bed bioreactor. During 28 months, the EC enhanced U(VI)-reduction rates by Fe⁰ compared with abiotic Fe⁰ controls. Additional experiments indicated that the EC prevented the passivation of Fe⁰ surfaces through the use of cathodic H₂ for the reduction of Fe(III) in passivating corrosion mineral phases (e.g. magnetite) to Fe²⁺. This contributed to the formation of secondary minerals more enriched with Fe(II), which are known to be chemically reactive with U(VI). To determine the toxicity of U(VI) to different populations present in uranium contaminated sites, including methanogens, denitrifiers and uranium-reducers, experiments were carried out with anaerobic mixed cultures at increasing U(VI) concentrations. Significant inhibition to the presence of U(VI) was observed for methanogens and denitrifiers. On the other hand uranium-reducing microorganisms were tolerant to high U(VI) concentrations. The results of this dissertation indicate that direct microbial reduction of U(VI) and microbially enhanced reduction of U(VI) by Fe⁰ are promising approaches for uranium bioremediation.

No description available.

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.

Ce travail avait pour objectif d’étudier les effets de l’uranium sur le budget énergétique et la dynamique de population d’un micro-crustacé représentatif des écosystèmes aquatiques d’eau douce, Daphnia magna. L’étude expérimentale de la toxicité de l’uranium sur la physiologie (nutrition, respiration) et l’histoire de vie (survie, croissance, reproduction) deD. magna a été réalisée au travers d’expositions sur une, deux ou trois générations successives(F0, F1, F2), commencées avec des néonates issus de 1ère ou 5ème ponte, à des concentrations de0, 10, 25 et 75 μgU.L-1. Les résultats ont mis en évidence l’aggravation des effets au travers des générations (en partie liée à l’exposition des daphnies pendant l’embryogénèse) et la sensibilité plus forte des individus issus de 1ère ponte. Des réductions significatives des taux d’assimilation mesurés par méthode de marquage-traçage au 14C de la nourriture nous ont permis d’identifier un effet sur l’assimilation comme mode d’action de l’uranium, en accord avec les altérations importantes de la structure de la paroi du tube digestif révélées par microscopie optique.L’intégration des résultats dans un modèle de budget énergétique (DEBtox) a abouti à l’estimation de concentrations seuil sans effet (NEC) de 9.37, 8.21 et 2.31 μgU.L-1 au-delà desquelles le fonctionnement de l’organisme est altéré dans les générations F0, F1 et F2,respectivement. La combinaison du DEBtox avec des modèles matriciels a permis d’extrapoler les conséquences sur le taux de croissance asymptotique de la population (λ), critère plus pertinent dans un contexte écologique. Les simulations ont prédit une augmentation de l’impact de l’uranium au travers des générations avec une réduction de λ dans F0 et une extinction des populations pour des concentrations de 51-59 μgU.L-1 dans F1 et de 39-41 μgU.L-1 dans F2. Les simulations ont souligné l’importance de prendre en considération les individus les plus sensibles dans la détermination de la réponse des populations. / This work aimed to study effects of uranium on energy budget and population dynamicsin Daphnia magna a representative microcrustacean of freshwater ecosystems. An experimentalstudy of uranium toxicity on physiology (nutrition, respiration) and life history (survival, growthand reproduction) of D. magna was carried out, based on exposures over one, two or threesuccessive generations (F0, F1 and F2) started with neonates from 1st or 5th brood, at 0, 10, 25and 75 μgU.L-1. Results showed that toxic effects increased across generations (partially due todaphnid exposure during embryogenesis) and that individuals from 1st brood were moresensitive than individuals from 5th brood. Significant reductions in assimilation rates, measuredusing a radiotracing method with 14C-labelled food, allowed us to identify an effect onassimilation as the mode of action for uranium, in agreement with important damages in theintegrity of intestinal epithelium observed by optic microscopy. Integrating results in a dynamicenergy budget model (DEBtox) yielded estimated no effect concentrations (NEC) of 9.37, 8.21and 2.31 μgU.L-1 above which organism functions were altered in generations F0, F1 and F2,respectively. Combining DEBtox with matrix models allowed us to extrapolate consequences onasymptotic population growth rate (λ), a relevant endpoint in an ecological context. Simulationspredicted an increase in uranium impact across generations with reduction of λ in F0 andpopulation extinctions at 51-59 μgU.L-1 in F1 and 39-41 μgU.L-1 in F2. Simulations emphasizedthe importance of considering the most sensitive individuals while determining populationresponse

This thesis investigated uranium (U) migration behaviour at the Needle‟s Eye natural analogue site, located close to Southwick Water, South West Scotland. The results of this study are important for the prediction of U behaviour in the far-field environments of nuclear waste repositories over long time-scales. The Needle‟s Eye natural analogue site was selected because the processes involved in U mobilisation, the direction of water flow and the extent of retention of uranium in peaty soils had already been identified. To this end, previous results demonstrated that groundwater passing through the mineralisation oxidized U and transported it to the peaty area, where 80-90% of the released U has been retained. Sequential extraction of the peaty soils indicated that more than 90% of the solid phase U was bound to the organic fraction. However, in-depth characterisation of U associations within the soil porewaters and the peaty soils at this site was lacking. Therefore, the processes controlling the migration of uranium within this organic-rich system were the main focus of this study. There were five sampling trips carried out from 2007-2011, in which cave drip waters, bog waters and surface soil and soil core samples were selectively collected for analysis by a range of methods described below. The cave drip waters emerging from the mineralisation were oxidizing and slightly alkaline (7.6-7.8), U was mainly in truly dissolved (<3 kDa) forms (Ca2UO2(CO3)30, CaUO2(CO3)32- and UO2(CO3)22-). It is known that the formation of the ternary Ca-UVI-CO3 complexes inhibits the reduction of U and so it is likely that it is UVI that is present within the peaty soils and their associated porewaters. Sampling trip 1 quantified the U concentrations in cave waters and soil core porewaters. By 30 m from the cave, U concentrations in the soil porewaters had decreased by a factor of ~10. Ultrafiltration fractionated the colloidal fraction (3 kDa-0.2 μm) into large (100 kDa-0.2 μm), medium (30-100 kDa) and small (3-30 kDa) colloidal fractions. It was found that U was mainly associated with the large colloid (100 kDa-0.2 μm) but, with increasing distance from the mineralisation, the U distribution became bimodal with both large and small fractions being equally important. Iron (Fe) was exclusively associated with the large colloid fraction in the peaty soil porewaters. Gel electrophoresis and gel filtration, applied to study the interactions of U (and other elements) with humic substances (HS), showed that the associations were quite uniform with increasing depth of the cores and increasing distance from the U mineralisation. Uranium (and other elements including Fe) was associated with the largest humic molecules. Sampling trip 2 involved collection of three more soil cores and ultrafiltration again fractionated the total dissolved porewater into large, medium and small colloids. This time, the truly dissolved (<3 kDa) fraction was also analysed. Again, U was mainly associated with the large colloidal (100 kda-0.2 μm) fraction. With increasing distance and increasing depth, U was still predominantly associated with the large colloidal fraction, but the importance of the truly dissolved (<3 kDa) phase could not be neglected. At the same time, Fe was also mainly associated with the large colloidal fraction. The remainder of the experimental work on samples from trip 2 focused on determining the importance of U associations with both Fe and humic components of the solid phase. Sequential extraction of the whole soil mainly targeted different iron phases and found that U was mainly released in the sodium acetate and sodium dithionite solutions, which indicated U was associated with (i) Fe carbonates; and (ii) crystalline Fe oxides (e.g. goethite, hematite, and akaganetite). However, very little Fe was extracted in the “carbonate-bound” fraction and separate experiments showed that U was not associated with Fe carbonates but instead had been released from the surfaces of HS and humic-bound Fe surfaces. XRD spectroscopy showed that mineral compositions were in reasonable agreement with the sequential extraction results and SEM-EDX analysis indicated that U in the soil was generally not present in crystalline form, as only two particles with high U content were found after 4-hour searching. Exhaustive extraction of HS showed that >90% U was associated with organic substances, in agreement with previous work and novel experiments involving gel electrophoresis in conjunction with sequential extraction was used to study the relationships between U, Fe and the HS. It was demonstrated that ~20-25% U was weakly held by the HS or at humic-bound Fe surfaces, ~45% was incorporated into crystalline Fe oxides which were intimately associated with HS and the remainder was in the form of strong U-CO3-humic complexes. In sampling trip 3, U migration behaviour in the soil porewaters was the focus. A 30-m transect line, comprising seven0-5 cm soil samples, starting at the cave and passing through the peaty area towards the Southwick Water, was established. Soil porewaters from these surface soils were fractionated into colloidal (3 kDa-0.2 μm) fraction and truly dissolved (<3 kDa) phase. There was a major change in U speciation, from Ca2UO2(CO3)3 0,CaUO2(CO3)32- and UO2(CO3)22- in the truly dissolved fractions of waters close to the cave to a predominant association with the highly coloured colloidal fractions as soon as the boggy area was reached. With distance through the boggy area, it was clear that the colloidal U was being incorporated into the solid phase since porewater concentrations had decreased ~100-fold by 30 m from the cave. Ultrafiltration in conjunction with acetate extraction was then used to extract U from the porewater colloids isolated from a soil core (20 m from cave). In the organic-rich portion of the core (0-30 cm), ~60-70% U was colloidally associated and ~85-95% of this U was extracted from the colloidal fraction. This indicated that the interactions between U and the porewater colloids were weak. In sampling trip 4, U associations in the porewater colloids were still the main focus. Gel filtration of porewater colloids confirmed that U, Fe and humic colloids were intimately associated. It was concluded that although U in the cave drip water was mainly in truly dissolved forms, weak U----humic/Fe colloids were formed immediately when U entered the peaty area. In sampling trip 5, results for soil core porewaters showed that Fe in the whole core was mainly in the form of FeII. Thus strongly reducing conditions prevailed through the core which was situated within the peaty area. Combining the results from the five sampling trips, three zones within the peaty area were distinguished. Zone I was characterised by extremely high concentrations of dissolved HS and this was where the change in U speciation from dissolved to colloidal forms took place. Zone II contained most of the soil cores collected during this study and was characterised by strongly reducing conditions and moderate concentrations of HS. Colloidal U was removed to the solid phase as waters flow through this area. Zone III marks the transition to the saltmarsh. Focusing on Zone II, a conceptual model of U behaviour was developed: upon entering the peaty area, U is weakly held by very large humic-Fe colloids. These colloids are removed to the solid phase and over time the associations of U are transformed; some becomes incorporated into stable humic-bound crystalline oxides as a result of redox cycling of Fe, some becomes strongly complexed to HS and the remainder is weakly held by the HS and/or humic-bound Fe surfaces. The crystalline Fe oxides were transformed to Fe sulfides below 30 cm depth but the associated U was not transferred to these sulfides. Instead the weak associations became more important. In the wider context, since only UVI forms soluble complexes with acetate, UVI does not appear to be reduced even under the strongly reducing conditions encountered within waterlogged organic-rich soils. Initial interactions between UVI and porewater colloids appear to be weak but stronger interactions such as incorporation into Fe phases and complexation by HS occur once the colloids and associated U are removed to the solid phase. Waterlogged organic-rich soils appear to be a long-term sink for U but changing climatic conditions leading to the drying out of such soils may ultimately release U in association with smaller, more mobile organic-rich colloids.

Summary: This thesis is focused on mapping of contaminants released into the environment probably due to uranium mining. These chemical contaminants are used to reconstruct the sedimentary processes. In the thesis we evaluate geochemical situation in the catchment area in the locality Borecek (part of the municipality Ralsko) using the overbank sediments as sedimentary archives of pollution during the last decades by elements U, Ba, Zn, Ni and 226 Ra. A map of aerial survey of gamma activity was used to select the area of interest, for more accurate localisation we used a surface gamma spectrometry. On Borecek we retrieved ten depth profiles of alluvial sediments (up to 230 cm) and one in Mimon, all samples were subjected to X-ray fluorescence spectral analysis (XRF), across the floodplain we performed gamma wire logs. For interpretations of floodplains architecture electrical resistivity tomography (ERT) was used and selected profiles were analysed for the activity of 226 Ra and 210 Pb. Interrelation of 226 Ra and Ba proved that radiobarite is the main source of the gamma activity. 210 Pb / 226 Ra ratio was used as sediment age indicator. With enrichment factor (LEF), we performed chemostratigraphic correlation of the sediments, for that the concentration of the target elements is corrected for varying...

Summary: This thesis is focused on mapping of contaminants released into the environment probably due to uranium mining. These chemical contaminants are used to reconstruct the sedimentary processes. The aim of the thesis was both the geochemical assessment of the situation in the catchment area of the Ploucnice River in Boreček using the flood sediments from the research points as sedimentary archives pollution for last decades. With depth profiles, gamma wire log, XRF and enrichment factors (LEF), we have tried to perform chemostratigraphic correlation of the sediments. As target elements U, Ba, Zn and Ni were chosen, whose concentrations are related to the grain size of the sediment. Furthermore, the theory of secondary pollution is developed.