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Glass corrosion in natural environments

Experiments carried out during the progress period are summarized. Experiments carried out involving glass samples exposed to solutions of Tris have shown the appearance of 'spikes' upon monitoring glass dissolution as a function of time. The periodic 'spikes' observed in Tris-based media were interpreted in terms of cracking due to excessive stress in the surface region of the glass. Studies of the interactions of silicate glasses with metal ions in buffered media were extended to systems containing Al. Caps buffer was used to establish the pH. The procedures used are described and the results are given. Preliminary studies were initiated as to the feasibility of adding a slowly dissolving solid compound of the additive to the glass-water system to maintain a supply of dissolved additive. It appears that several magnesium compounds have a suitable combination of solubility and affinity towards silicate glass surfaces to have a pronounced retarding effect on the extraction of uranium from the glass. These preliminary findings raise the possibility that introducing a magnesium source into geologic repositories for nuclear waste glass in the form of a sparingly soluble Mg-based backfill material may cause a substantial reduction in the extent of long-term glass corrosion. The studies described also provide mechanistic understanding of the roles of various metal solutes in the leachant. Such understanding forms the basis for developing long-term predictions of nuclear waste glass durability under repository conditions. From what is known about natural highly reduced glasses such as tektites, it is clear that iron is dissolved as ferrous iron with little or no ferric iron. The reducing conditions were high enough to cause metallic iron to exsolve out of the glass in the form of submicroscopic spherules. As the nuclear waste glass is much less reduced, a study was initiated on other natural glasses in addition to the nuclear waste glass. Extensive measurements were carried out on these glasses in order to characterize their magnetic properties. Results of these studies are described.

Thorpe, Arthur N.↗

Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

Barkatt, Aaron↗

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗

A Disc-Dominated and Clumpy Circumgalactic Medium of the Milky Way Seen in X-Ray Emission

The Milky Way galaxy is surrounded by a circumgalactic medium (CGM) that may play a key role in galaxy evolution as the source of gas for star formation and a repository of metals and energy produced by star formation and nuclear activity. The CGM may also be a repository for baryons seen in the early universe, but undetected locally. The CGM has an ionized component at temperatures near 2 x 10^6 K studied primarily in the soft X-ray band. Here we report a survey of the southern Galactic sky with a soft X-ray spectrometer optimized to study diffuse soft X-ray emission. The X-ray emission is best fit with a disc-like model based on the radial profile of the surface density of molecular hydrogen, a tracer of star formation, suggesting that the X-ray emission is predominantly from hot plasma produced via stellar feedback. Strong variations in the X-ray emission on angular scales of ~10 degrees indicate that the CGM is clumpy. Addition of an extended, and possibly massive, halo component is needed to match the halo density inferred from other observations.

P Kaaret↗

Safety aspects of nuclear waste disposal in space

Safety issues involved in the disposal of nuclear wastes in space as a complement to mined geologic repositories are examined as part of an assessment of the feasibility of nuclear waste disposal in space. General safety guidelines for space disposal developed in the areas of radiation exposure and shielding, containment, accident environments, criticality, post-accident recovery, monitoring systems and isolation are presented for a nuclear waste disposal in space mission employing conventional space technology such as the Space Shuttle. The current reference concept under consideration by NASA and DOE is then examined in detail, with attention given to the waste source and mix, the waste form, waste processing and payload fabrication, shipping casks and ground transport vehicles, launch site operations and facilities, Shuttle-derived launch vehicle, orbit transfer vehicle, orbital operations and space destination, and the system safety aspects of the concept are discussed for each component. It is pointed out that future work remains in the development of an improved basis for the safety guidelines and the determination of the possible benefits and costs of the space disposal option for nuclear wastes.

Rice, E. E.↗

Preliminary risk benefit assessment for nuclear waste disposal in space

This paper describes the recent work of the authors on the evaluation of health risk benefits of space disposal of nuclear waste. The paper describes a risk model approach that has been developed to estimate the non-recoverable, cumulative, expected radionuclide release to the earth's biosphere for different options of nuclear waste disposal in space. Risk estimates for the disposal of nuclear waste in a mined geologic repository and the short- and long-term risk estimates for space disposal were developed. The results showed that the preliminary estimates of space disposal risks are low, even with the estimated uncertainty bounds. If calculated release risks for mined geologic repositories remain as low as given by the U.S. DOE, and U.S. EPA requirements continue to be met, then no additional space disposal study effort in the U.S. is warranted at this time. If risks perceived by the public are significant in the acceptance of mined geologic repositories, then consideration of space disposal as a complement to the mined geologic repository is warranted.

Rice, E. E.↗

Analysis of space systems for the space disposal of nuclear waste follow-on study. Volume 1: Executive summary

The impact on space systems of three alternative waste mixes was evaluated as part of an effort to investigate the disposal of certain high-level nuclear wastes in space as a complement to mined geologic repositories. A brief overview of the study background, objectives, scope, approach and guidelines, and limitations is presented. The effects of variations in waste mixes on space system concepts were studied in order to provide data for determining relative total system risk benefits resulting from space disposal of the alternative waste mixes. Overall objectives of the NASA-DOE sustaining-level study program are to investigate space disposal concepts which can provide information to support future nuclear waste terminal storage programmatic decisions and to maintain a low level of research activity in this area to provide a baseline for future development should a decision be made to increase the emphasis on this option.

Source record↗

Analysis of space systems for the space disposal of nuclear waste follow-on study. Volume 2: Technical report

The space option for disposal of certain high-level nuclear wastes in space as a complement to mined geological repositories is studied. A brief overview of the study background, scope, objective, guidelines and assumptions, and contents is presented. The determination of the effects of variations in the waste mix on the space systems concept to allow determination of the space systems effect on total system risk benefits when used as a complement to the DOE reference mined geological repository is studied. The waste payload system, launch site, launch system, and orbit transfer system are all addressed. Rescue mission requirements are studied. The characteristics of waste forms suitable for space disposal are identified. Trajectories and performance requirements are discussed.

Source record↗

Risk Management of NASA Projects

Various NASA Langley Research Center and other center projects were attempted for analysis to obtain historical data comparing pre-phase A study and the final outcome for each project. This attempt, however, was abandoned once it became clear that very little documentation was available. Next, extensive literature search was conducted on the role of risk and reliability concepts in project management. Probabilistic risk assessment (PRA) techniques are being used with increasing regularity both in and outside of NASA. The value and the usage of PRA techniques were reviewed for large projects. It was found that both civilian and military branches of the space industry have traditionally refrained from using PRA, which was developed and expanded by nuclear industry. Although much has changed with the end of the cold war and the Challenger disaster, it was found that ingrained anti-PRA culture is hard to stop. Examples of skepticism against the use of risk management and assessment techniques were found both in the literature and in conversations with some technical staff. Program and project managers need to be convinced that the applicability and use of risk management and risk assessment techniques is much broader than just in the traditional safety-related areas of application. The time has come to begin to uniformly apply these techniques. The whole idea of risk-based system can maximize the 'return on investment' that the public demands. Also, it would be very useful if all project documents of NASA Langley Research Center, pre-phase A through final report, are carefully stored in a central repository preferably in electronic format.

Sarper, Hueseyin↗