Production, radiochemical separation and chemical coupling of radioactive arsenic isotopes to synthesize radiopharmaceuticals for molecular imaging

Noninvasive molecular-imaging technologies are playing a keyrole in drug discovery, development and delivery. Positron Emission Tomography (PET) is such a molecular imaging technology and a powerful tool for the observation of various diseases. However, it is limited by the availability of agents with high selectivity to the target and a physical half-life of the used positron emitting nuclide which matches the biological half-life of the observed process. For the long lasting enrichment of antibodies in tumor tissue few suitable isotopes for PET imaging are currently available. The element arsenic provides a range of isotopes, which could be used for diagnosis and also for endoradiotherapy. This work describes the development of radiochemical separation procedures to separate arsenic isotopes in no-carrier-added (nca) purity from reactor or cyclotron irradiated targets, the development and evaluation of a labeling chemistry to attach these separated arsenic isotopes to monoclonal antibodies, the in vitro and in vivo evaluation of antibodies labeled with radioactive arsenic isotopes and the molecular imaging using small animal PET.

Development of glass-ceramics from combination of industrial wastes together with boron mining waste

The utilization of borate mineral wastes with glass-ceramic technology was first time studied and primarily not investigated combinations of wastes were incorporated into the research. These wastes consist of; soda lime silica glass, meat bone and meal ash and fly ash. In order to investigate possible and relevant application areas in ceramics, kaolin clay, an essential raw material for ceramic industry was also employed in some studied compositions. As a result, three different glass-ceramic articles obtained by using powder sintering method via individual sintering processes. Light weight micro porous glass-ceramic from borate mining waste, meat bone and meal ash and kaolin clay was developed. In some compositions in related study, soda lime silica glass waste was used as an additive providing lightweight structure with a density below 0.45 g/cm3 and a crushing strength of 1.8±0.1 MPa. In another study within the research, compositions respecting the B2O3–P2O5–SiO2 glass-ceramic ternary system were prepared from; borate wastes, meat bone and meal ash and soda lime silica glass waste and sintered up to 950ºC. Low porous, highly crystallized glass-ceramic structures with density ranging between 1.8 ± 0,7 to 2.0 ± 0,3 g/cm3 and tensile strength ranging between 8,0 ± 2 to 15,0 ± 0,5 MPa were achieved. Lastly, diopside - wollastonite (SiO2-Al2O3-CaO )glass-ceramics from borate wastes, fly ash and soda lime silica glass waste were successfully obtained with controlled rapid sintering between 950 and 1050ºC. The wollastonite and diopside crystal sizes were improved by adopting varied combinations of formulations and heating rates. The properties of the obtained materials show; the articles with a uniform pore structure could be useful for thermal and acoustic insulations and can be embedded in lightweight concrete where low porous glass-ceramics can be employed as building blocks or additive in cement and ceramic industries.

Development of a method for plasma - induced combustion of intermediate to low-level radioactive waste

This work demonstrates that the plasma - induced combustion of intermediate to low-level radioactive waste is a suitable method for volume reduction and stabilization. Weaknesses of existing facilities can be overcome with novel developments. Plasma treatment of LILW has a high economical advantage by volume reduction for storage in final repositories.

Speziation von Plutonium bei der Sorption und Diffusion in Opalinuston

Die vorliegende Arbeit wurde im Rahmen des BMWi-Verbundprojektes Wechselwirkung und Transport von Aktiniden im natürlichen Tongestein unter Berücksichtigung von Huminstoffen und Tonorganika – Wechselwirkung von Neptunium und Plutonium mit natürlichem Tongestein“ durchgeführt. Um die langfristige Sicherheit der nuklearen Endlager beurteilen zu können, muss eine mögliche Migration der radiotoxischen Abfälle in die Umwelt betrachtet werden. Wegen seiner langen Halbwertszeit (24000 a) leistet Pu-239 einen wesentlichen Beitrag zur Radiotoxizität abgebrannter Kernbrennstoffe in einem Endlager. Das redox-sensitive Pu tritt in Lösung unter umweltrelevanten Bedingungen in den Oxidationsstufen +III bis +VI auf und kann nebeneinander in bis zu vier Oxidationsstufen vorliegen. Tonsteinformationen werden als mögliches Wirtsgestein für Endlager hoch-radioaktiver Abfälle betrachtet. Deshalb sind ausführliche Informationen zur Mobilisierung und Immobilisierung des Pu durch/in das Grundwasser aus einem Endlager von besonderer Bedeutung. In dieser Arbeit wurden neue Erkenntnisse über die Wechselwirkung zwischen Pu und dem natürlichen Tongestein Opalinuston (OPA, Mont Terri, Schweiz) mit Hinblick auf die Endlagerung wärmeentwickelnder radioaktiver Abfälle in einem geologischen Tiefenlager gewonnen.rnDer Fokus der Arbeit lag dabei auf der Bestimmung der Speziation von Pu an der Mineraloberfläche nach Sorptions- und Diffusionsprozessen mittels verschiedener synchrotronbasierter Methoden (µ-XRF, µ-XANES/EXAFS, µ-XRD, XANES/EXAFS). rnDie Wechselwirkung zwischen Pu und OPA wurde zunächst in Batch- und Diffusionsexperimenten in Abhängigkeit verschiedener experimenteller Parameter (u.a. pH, Pu-Oxidationsstufe) untersucht. In Sorptionsexperimenten konnte gezeigt werden, dass einige Parameter (z.B. Temperatur, Huminsäure) einen deutlichen Einfluss auf die Sorption von Pu haben.rnDie Speziationsuntersuchungen wurden zum einen an Pulverproben aus Batchexperimenten und zum anderen an OPA-Dünnschliffen bzw. Diffusionsproben in Abhängigkeit verschiedener experimenteller Parameter durchgeführt. Die EXAFS-Messungen an der Pu LIII-Kante der Pulverproben ergaben, dass eine innersphäriche Sorption von Pu(IV) an Tongestein unabhängig von dem Ausgangsoxidationszustand des Plutoniums in Lösung stattgefunden hat. Durch die Kombination der ortsaufgelösten Methoden wurde erstmalig mittels μ-XRF die Verteilung von Pu und anderen in OPA enthaltenen Elementen bestimmt. µ-XANES-Spektren an Pu-Anreicherungen auf OPA-Dünnschliffen und in Diffusionsproben bestätigen, dass das weniger mobile Pu(IV) die dominierende Spezies nach den Sorptions- und Diffusionsprozessen ist. Darüber hinaus wurde zum ersten Mal ein Diffusionsprofil von Pu in OPA mittels µ-XRF gemessen. Die Speziationsuntersuchungen mittels μ-XANES zeigten, dass das eingesetzte Pu(V) entlang seines Diffusionspfades zunehmend zu Pu(IV) reduziert wird. Mit µ-XRD wurde Illit als dominierende Umgebung, in der Pu angereichert wurde, identifiziert und Siderit als eine redoxaktive Phase auftreten kann. Die Ergebnisse dieser Arbeit zeigen, dass die Sicherheit von OPA als Wirtsgestein eines Endlagers hoch-radioaktiver Abfälle positiv zu bewerten ist. rn

Transport of Hydraulic Fracturing Water and Wastes in the Susquehanna River Basin, Pennsylvania

The development of the Marcellus Shale gas play in Pennsylvania and the northeastern United States has resulted in significant amounts of water and wastes transported by truck over roadways. This study used geographic information systems (GIS) to quantify truck travel distances via both the preferred routes (minimum distance while also favoring higher-order roads) as well as, where available, the likely actual distances for freshwater and waste transport between pertinent locations (e. g., gas wells, treatment facilities, freshwater sources). Results show that truck travel distances in the Susquehanna River Basin are greater than those used in prior life-cycle assessments of tight shale gas. When compared to likely actual transport distances, if policies were instituted to constrain truck travel to the closest destination and higher-order roads, transport mileage reductions of 40-80% could be realized. Using reasonable assumptions of current practices, greenhouse gas (GHG) emissions associated with water and waste hauling were calculated to be 70-157 MT CO2 eq per gas well. Furthermore, empty so-called backhaul trips, such as to freshwater withdrawal sites or returning from deep well injection sites, were found to increase emissions by an additional 30%, underscoring the importance of including return trips in the analysis. The results should inform future life-cycle assessments of tight shale gases in managed watersheds and help local and regional governments plan for impacts of transportation on local infrastructure. (C) 2013 American Society of Civil Engineers.

Transferability of geoscientific information from various sources (study sites, underground rock laboratories, natural analogues) to support safety cases for radioactive waste repositories in argillaceous formations

In studies related to deep geological disposal of radioactive waste, it is current practice to transfer external information (e.g. from other sites, from underground rock laboratories or from natural analogues) to safety cases for specific projects. Transferable information most commonly includes parameters, investigation techniques, process understanding, conceptual models and high-level conclusions on system behaviour. Prior to transfer, the basis of transferability needs to be established. In argillaceous rocks, the most relevant common feature is the microstructure of the rocks, essentially determined by the properties of clay–minerals. Examples are shown from the Swiss and French programmes how transfer of information was handled and justified. These examples illustrate how transferability depends on the stage of development of a repository safety case and highlight the need for adequate system understanding at all sites involved to support the transfer.

Characterisation of Gas Transport Properties of the Opalinus Clay, a Potential Host Rock Formation for Radioactive Waste Disposal

The Opalinus Clay in Northern Switzerland has been identified as a potential host rock formation for the disposal of radioactive waste. Comprehensive understanding of gas transport processes through this low-permeability formation forms a key issue in the assessment of repository performance. Field investigations and laboratory experiments suggest an intrinsic permeability of the Opalinus Clay in the order of 10(-20) to 10(-21) m(2) and a moderate anisotropy ratio < 10. Porosity depends on clay content and burial depth; values of similar to 0.12 are reported for the region of interest. Porosimetry indicates that about 10-30 of voids can be classed as macropores, corresponding to an equivalent pore radius > 25 nm. The determined entry pressures are in the range of 0.4-10 MPa and exhibit a marked dependence on intrinsic permeability. Both in situ gas tests and gas permeameter tests on drillcores demonstrate that gas transport through the rock is accompanied by porewater displacement, suggesting that classical flow concepts of immiscible displacement in porous media can be applied when the gas entry pressure (i.e. capillary threshold pressure) is less than the minimum principal stress acting within the rock. Essentially, the pore space accessible to gas flow is restricted to the network of connected macropores, which implies a very low degree of desaturation of the rock during the gas imbibition process. At elevated gas pressures (i.e. when gas pressure approaches the level of total stress that acts on the rock body), evidence was seen for dilatancy controlled gas transport mechanisms. Further field experiments were aimed at creating extended tensile fractures with high fracture transmissivity (hydro- or gasfracs). The test results lead to the conclusion that gas fracturing can be largely ruled out as a risk for post-closure repository performance.

Thermal neutron capture effects in radioactive and stable nuclide systems

Neutron capture effects in meteorites and lunar surface samples have been successfully used in the past to study exposure histories and shielding conditions. In recent years, however, it turned out that neutron capture effects produce a nuisance for some of the short-lived radionuclide systems. The most prominent example is the 182Hf-182W system in iron meteorites, for which neutron capture effects lower the 182W/184W ratio, thereby producing too old apparent ages. Here, we present a thorough study of neutron capture effects in iron meteorites, ordinary chondrites, and carbonaceous chondrites, whereas the focus is on iron meteorites. We study in detail the effects responsible for neutron production, neutron transport, and neutron slowing down and find that neutron capture in all studied meteorite types is not, as usually expected, exclusively via thermal neutrons. In contrast, most of the neutron capture in iron meteorites is in the epithermal energy range and there is a significant contribution from epithermal neutron capture even in stony meteorites. Using sophisticated particle spectra and evaluated cross section data files for neutron capture reactions we calculate the neutron capture effects for Sm, Gd, Cd, Pd, Pt, and Os isotopes, which all can serve as neutron-dose proxies, either in stony or in iron meteorites. In addition, we model neutron capture effects in W and Ag isotopes. For W isotopes, the GCR-induced shifts perfectly correlate with Os and Pt isotope shifts, which therefore can be used as neutron-dose proxies and permit a reliable correction. We also found that GCR-induced effects for the 107Pd-107Ag system can be significant and need to be corrected, a result that is in contrast to earlier studies.

Fate and effects of drilling wastes in a shallow estuarine mesocosm

To address concerns expressed about the possible effect of drilling mud discharges on shallow, low-energy estuarine ecosystems, a 12 month study was designed to detect alterations in water quality and sediment geochemistry. Each drilling mud used in the study and sediments from the study site were analyzed in the laboratory for chemical and physical characteristics. Potential water quality impacts were simulated by the EPA-COE elutriation test procedure. Mud toxicity was measured by acute and chronic bioassays with Mysidopsis bahia, Mercenaria mercenaria, and Nereis virens.^ For the field study, a relatively pristine, shallow (1.2 m) estuary (Christmas Bay, TX) without any drilling activity for the last 30 years was chosen for the study site. After a three month baseline study, three stations were selected. Station 1 was an external control. At each treatment station (2, 3), mesocosms were constructed to enclose a 3.5 m$\sp3$ water column. Each treatment station included an internal control site also. Each in situ mesocosm, except the controls, was successively dosed at a mesocosm-specific dose (1:100; 1:1,000; or 1:10,000 v/v) with 4 field collected drilling muds (spud, nondispersed, lightly-treated, and heavily-treated lignosulfonate) in sequential order over 1.5 months. Twenty-four hours after each dose, water exchange was allowed until the next treatment. Station 3 was destroyed by a winter storm. After the last treatment, the enclosures were removed and the remaining sites monitored for 6 months. One additional site was similarly dosed (1:100 v/v) with clean dredged sediment from Christmas Bay for comparison between dredged sediments and drilling muds.^ Results of the analysis of the water samples and field measurements showed that water quality was impacted during the discharges, primarily at the highest dose (1:100 v/v), but that elevated levels of C, Cr (T,F), Cr$\sp{+3}$ (T, F), N, Pb, and Zn returned to ambient levels before the end of the 24 hour exposure period or immediately after water exchange was allowed (Al, Ba(T), Chlorophyll ABC, SS, %T). Barium, from the barite, was used as a geochemical tracer in the sediments to confirm estimated doses by mass balance calculations. Barium reached a maximum of 166x background levels at the high dose mesocosm. Barium levels returned to ambient or only slightly elevated levels at the end of the 6 month monitoring period due to sediment deposition, resuspension, and bioturbation. QA/QC results using blind samples consisting of lab standards and spiked samples for both water and sediment matrices were within acceptable coefficients of variation.^ In order to avoid impacts on water quality and sediment geochemistry in a shallow estuarine ecosystem, this study concluded that a minimal dilution of 1:1,000 (v/v) would be required in addition to existing regulatory constraints. ^