Coupled Thermo-Hydro-Mechanical and Chemical Analysis of Expansive Clay Subjected to Heating and Hydration

A fully coupled formulation combining reactive transport and an existing thermo-hydro-mechanical (THM) code is presented. Special attention has been given to phenomena likely to be encountered in clay barriers used as part of containment systems of nuclear waste. The types of processes considered include hydrolysis, complex formation, oxidation/reduction reactions, acid/base reactions, precipitation/dissolution of minerals and cation exchange. Both kinetically-controlled and equilibrium-controlled reactions have been incorporated. The total analytical concentrations (including precipitated minerals) are adopted as basic transport variables and chemical equilibrium is achieved by minimizing Gibbs Free Energy. The formulation has been incorporated in a general purpose computer code capable of performing numerical analysis of engineering problems. A validation exercise concerning a laboratory experiment involving the heating and hydration of an expansive compacted clay is described.     

Fast approximation algorithm for job sequencing with deadlines

The problem under consideration is to schedule jobs on a machine in order to minimize the sum of the penalties of delayed jobs. A “range-and-bound” method is proposed for finding a tight bound P? such that P?≤P1≤2P?, P1 being the minimal sum desired. The considered scheduling problem, for n jobs and accuracy ε > 0, is solved by a fully polynomial ε-approximation algorithm in $\text{O(n}{}^2\text{log n +}\text{n}{}^2\text{ε}\text{)}$ time and $\text{O(}\text{n}{}^2\text{ε}\text{)}$ space.     

Konzentrierung radioaktiver Jodidlösungen

Zur Bestimmung biologischer Wirkstoffe, die in äußerst geringen Konzentrationen in der Körperflüssigkeit vorkommen, werden im zunehmenden Maße radioaktive Indikatoren benutzt. Dazu sind spezifische Aktivitäten in den Größenbereichen 100 mCi/g–1000 mCi/g erforderlich. Derartige Markierungen mit Jodisotopen setzen Lösungen hoher radioaktiver Konzentration sowie hoher spezifischer Aktivität in bezug auf das Markierungsatom voraus.     

HNO and NO release from a primary amine-based diazeniumdiolate as a function of pH

The growing evidence that nitroxyl (HNO) has a rich pharmacological potential that differs from that of nitric oxide (NO) has intensified interest in HNO donors. Recently, the diazeniumdiolate (NONOate) based on isopropylamine (IPA/NO; Na[(CH(3))(2)CHNH(N(O)NO)]) was demonstrated to function under physiological conditions as an organic analogue to the commonly used HNO donor Angeli's salt (Na(2)N(2)O(3)). The decomposition mechanism of Angeli's salt is dependent on pH, with transition from an HNO to an NO donor occurring abruptly near pH 3. Here, pH is shown to also affect product formation from IPA/NO. Chemical analysis of HNO and NO production led to refinement of an earlier, quantum mechanically based prediction of the pH-dependent decomposition mechanisms of primary amine NONOates such as IPA/NO. Under basic conditions, the amine proton of IPA/NO is able to initiate decomposition to HNO by tautomerization to the nitroso nitrogen (N(2)). At lower pH, protonation activates a competing pathway to NO production. At pH 8, the donor properties of IPA/NO and Angeli's salt are demonstrated to be comparable, suggesting that at or above this pH, IPA/NO is primarily an HNO donor. Below pH 5, NO is the major product, while IPA/NO functions as a dual donor of HNO and NO at intermediate pH. This pH-dependent variability in product formation may prove useful in examination of the chemistry of NO and HNO. Furthermore, primary amine NONOates may serve as a tunable class of nitrogen oxide donor.     

Porosity variations in saline media caused by temperature gradients coupled to multiphase flow and dissolution/precipitation

We present a theoretical-numerical investigation of porosity variations induced by temperature gradients in unsaturated saline media. It is known that temperature variations cause humidity variations which lead to liquid flow towards and vapour flow away from the hot source. When this phenomenon occurs in saline media, the liquid is salt saturated brine, so that evaporation causes salt precipitation and an ensuing porosity reduction. Condensation of water causes salt dissolution and porosity increase. This process may be important in the case of heat generating waste because it suggests that selfsealing may take place near the waste. On the other hand, salt mass balance will lead to porosity increases in other zones.     

Inventory and characterization of important radionuclides for the safety of storage and disposal. Correlation with key radionuclides in typical waste streams

Beginning in 1991 (and continuing until 1995) a research program has been undertaken involving the participation of six Western European countries, focusing on the following main objectives: (i) comparison of operational analytical methods for long-lived radionuclides and application to real waste samples; (ii) improvement of existing procedures and/or development of some alternative analytical methods; (iii) computation of correlation factors between long-lived radionuclides and easily-measured key radionuclides, through the analysis of some of the main waste streams from the participants' countries. Some preliminary and significant results that have been obtained in the framework of this project are presented and discussed.     

Reductive immobilization of <Superscript>79</Superscript>Se by iron canister under simulated repository environment

To understand the fate of ⁷⁹Se in a repository-like environment, the interactions between iron canister surface with dissolved selenite (SeO₃ ²⁻) and selenate (SeO₄ ²⁻) in anaerobic solutions have been investigated. Se(IV) immobilization on iron surface was observed to be about 100 times faster than that of Se(VI) at same conditions. An iron surface coated with a FeCO₃ layer corrosion product is more reactive than a polished iron to immobilize Se(IV) and Se(VI). The reacted iron surfaces were analysed by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Raman spectrometry and micro-X-ray Absorption Spectroscopy (XAS). The result show that Se(IV) and Se(VI) were reduced and precipitated. The dominating phase was found to be FeSe_2.     

Nonisothermal multiphase flow of brine and gas through saline media

We propose a general formulation for nonisothermal multiphase flow of brine and gas through saline media. The balance equations include mass balance (three species), equilibrium of stresses and energy balance (total internal energy). Salt, water and air mass balance equations are established. The balance of salt allows the establishment of the equation for porosity evolution due to solid skeleton deformation, dissolution/precipitation of salt and migration of brine inclusions. Water and air mass balance equations are also obtained. Two equations are required for water: total water in the medium and water present in solid phase brine inclusions. The mechanical problem is formulated through the equation of stress equilibrium. Finally, the balance of internal energy is established assuming thermal equilibrium between phases. Some general aspects of the constitutive theory are also presented.     

Vapour Transport in Low Permeability Unsaturated Soils with Capillary Effects

A discussion of water phase change in unsaturated soils that develop capillary effects is first carried out in the paper. A distinction between the GR (geothermal reservoir) and the NUS (nonisothermal unsaturated soil) approaches is performed. Several aspects concerning advective and nonadvective fluxes of vapour are described secondly and some relationships concerning the case of mass motion in a closed system subjected to temperature gradients derived. Since the structure of unsaturated clays changes with moisture content, in order to correctly simulate the coupled phenomena induced by temperature gradients a model for intrinsic permeability as a function of humidity is required. A preliminary version of the model is presented and applied to interpret a laboratory test by means of a numerical simulation using CODE_BRIGHT