OSL-thermochronometry of feldspar from the KTB borehole, Germany

The reconstruction of thermal histories of rocks (thermochronometry) is a fundamental tool both in Earth science and in geological exploration. However, few methods are currently capable of resolving the low-temperature thermal evolution of the upper ∼2 km of the Earth's crust. Here we introduce a new thermochronometer based on the infrared stimulated luminescence (IRSL) from feldspar, and validate the extrapolation of its response to artificial radiation and heat in the laboratory to natural environmental conditions. Specifically, we present a new detailed Na-feldspar IRSL thermochronology from a well-documented thermally-stable crustal environment at the German Continental Deep Drilling Program (KTB). There, the natural luminescence of Na-feldspar extracted from twelve borehole samples (0.1–2.3 km depth, corresponding to 10–70 °C) can be either (i) predicted within uncertainties from the current geothermal gradient, or (ii) inverted into a geothermal palaeogradient of 29 ± 2  °C km−1, integrating natural thermal conditions over the last ∼65 ka. The demonstrated ability to invert a depth–luminescence dataset into a meaningful geothermal palaeogradient opens new venues for reconstructing recent ambient temperatures of the shallow crust (<0.3 Ma, 40–70 °C range), or for studying equally recent and rapid transient cooling in active orogens (<0.3 Ma, >200 °C Ma−1 range). Although Na-feldspar IRSL is prone to field saturation in colder or slower environments, the method's primary relevance appears to be for borehole and tunnel studies, where it may offer remarkably recent (<0.3 Ma) information on the thermal structure and history of hydrothermal fields, nuclear waste repositories and hydrocarbon reservoirs.

Mineralogical and isotopic record of diagenesis from the Opalinus Clay formation at Benken, Switzerland: Implications for the modeling of pore-water chemistry in a clay formation

Argillaceous rocks are considered to be a suitable geological barrier for the long-term containment of wastes. Their efficiency at retarding contaminant migration is assessed using reactive-transport experiments and modeling, the latter requiring a sound understanding of pore-water chemistry. The building of a pore-water model, which is mandatory for laboratory experiments mimicking in situ conditions, requires a detailed knowledge of the rock mineralogy and of minerals at equilibrium with present-day pore waters. Using a combination of petrological, mineralogical, and isotopic studies, the present study focused on the reduced Opalinus Clay formation (Fm) of the Benken borehole (30 km north of Zurich) which is intended for nuclear-waste disposal in Switzerland. A diagenetic sequence is proposed, which serves as a basis for determining the minerals stable in the formation and their textural relationships. Early cementation of dominant calcite, rare dolomite, and pyrite formed by bacterial sulfate reduction, was followed by formation of iron-rich calcite, ankerite, siderite, glauconite, (Ba, Sr) sulfates, and traces of sphalerite and galena. The distribution and abundance of siderite depends heavily on the depositional environment (and consequently on the water column). Benken sediment deposition during Aalenian times corresponds to an offshore environment with the early formation of siderite concretions at the water/sediment interface at the fluctuating boundary between the suboxic iron reduction and the sulfate reduction zones. Diagenetic minerals (carbonates except dolomite, sulfates, silicates) remained stable from their formation to the present. Based on these mineralogical and geochemical data, the mineral assemblage previously used for the geochemical model of the pore waters at Mont Terri may be applied to Benken without significant changes. These further investigations demonstrate the need for detailed mineralogical and geochemical study to refine the model of pore-water chemistry in a clay formation.

Implementation and evaluation of permeability-porosity and tortuosity-porosity relationships linked to mineral dissolution-precipitation

Changes of porosity, permeability, and tortuosity due to physical and geochemical processes are of vital importance for a variety of hydrogeological systems, including passive treatment facilities for contaminated groundwater, engineered barrier systems (EBS), and host rocks for high-level nuclear waste (HLW) repositories. Due to the nonlinear nature and chemical complexity of the problem, in most cases, it is impossible to verify reactive transport codes analytically, and code intercomparisons are the most suitable method to assess code capabilities and model performance. This paper summarizes model intercomparisons for six hypothetical scenarios with generally increasing geochemical or physical complexity using the reactive transport codes CrunchFlow, HP1, MIN3P, PFlotran, and TOUGHREACT. Benchmark problems include the enhancement of porosity and permeability through mineral dissolution, as well as near complete clogging due to localized mineral precipitation, leading to reduction of permeability and tortuosity. Processes considered in the benchmark simulations are advective-dispersive transport in saturated media, kinetically controlled mineral dissolution-precipitation, and aqueous complexation. Porosity changes are induced by mineral dissolution-precipitation reactions, and the Carman-Kozeny relationship is used to describe changes in permeability as a function of porosity. Archie’s law is used to update the tortuosity and the pore diffusion coefficient as a function of porosity. Results demonstrate that, generally, good agreement is reached amongst the computer models despite significant differences in model formulations. Some differences are observed, in particular for the more complex scenarios involving clogging; however, these differences do not affect the interpretation of system behavior and evolution.

Experimental Characterization and Quantification of Cement-Bentonite Interaction using Core Infiltration Techniques Coupled with X-ray Tomography

Deep geological storage of radioactive waste foresees cementitious materials as reinforcement of tunnels and as backfill. Bentonite is proposed to enclose spent fuel canisters and as drift seals. Sand/bentonite (s/b) is foreseen as backfill material of access galleries or as drift seals. The emplacement of cementitious material next to clay material generates an enormous chemical gradient in pore-water composition that drives diffusive solute transport. Laboratory studies and reactive transport modeling predicted significant mineral alteration at and near interfaces, mainly resulting in a decrease of porosity in bentonite. The goal of this thesis was to characterize and quantify the cement/bentonite interactions both spatially and temporally in laboratory experiments. A newly developed mobile X-ray transparent core infiltration device was used to perform X-ray computed tomography (CT) scans without interruption of running experiments. CT scans allowed tracking the evolution of the reaction plume and changes in core volume/diameter/density during the experiments. In total 4 core infiltration experiments were carried out for this study with the compacted and saturated cores consisting of MX-80 bentonite and sand/MX-80 bentonite mixture (s/b; 65/35%). Two different high-pH cementitious pore-fluids were infiltrated: a young (early) ordinary Portland cement pore-fluid (APWOPC; K+–Na+–OH-; pH 13.4; ionic strength 0.28 mol/kg) and a young ‘low-pH’ ESDRED shotcrete pore-fluid (APWESDRED; Ca2+–Na+–K+–formate; pH 11.4; ionic strength 0.11 mol/kg). The experiments lasted between 1 and 2 years. In both bentonite experiments, the hydraulic conductivity was strongly reduced after switching to high-pH fluids, changing eventually from an advective to a diffusion-dominated transport regime. The reduction was mainly induced by mineral precipitation and possibly partly also by high ionic strength pore-fluids. Both bentonite cores showed a volume reduction and a resulting transient flow in which pore-water was squeezed out during high-pH infiltration. The outflow chemistry was characterized by a high ionic strength, while chloride in the initial pore water got replaced as main anionic charge carrier by sulfate, originating from gypsum dissolution. The chemistry of the high-pH fluids got strongly buffered by the bentonite, consuming hydroxide and in case of APWESDRED also formate. Hydroxide got consumed by mineral reactions (saponite and possibly talc and brucite precipitation), while formate being affected by bacterial degradation. Post-mortem analysis showed reaction zones near the inlet of the bentonite core, characterized by calcium and magnesium enrichment, consisting predominately of calcite and saponite, respectively. Silica got enriched in the outflow, indicating dissolution of silicate-minerals, identified as preferentially cristobalite. In s/b, infiltration of APWOPC reduced the hydraulic conductivity strongly, while APWESDRED infiltration had no effect. The reduction was mainly induced by mineral precipitation and probably partly also by high ionic strength pore-fluids. Not clear is why the observed mineral precipitates in the APWESDRED experiment had no effect on the fluid flow. Both s/b cores showed a volume expansion along with decreasing ionic strengths of the outflow, due to mineral reactions or in case of APWESDRED infiltration also mediated by microbiological activity, consuming hydroxide and formate, respectively. The chemistry of the high-pH fluids got strongly buffered by the s/b. In the case of APWESDRED infiltration, formate reached the outflow only for a short time, followed by enrichment in acetate, indicating most likely biological activity. This was in agreement to post-mortem analysis of the core, observing black spots on the inflow surface, while the sample had a rotten-egg smell indicative of some sulfate reduction. Post-mortem analysis showed further in both cores a Ca-enrichment in the first 10 mm of the core due to calcite precipitation. Mg-enrichment was only observed in the APWOPC experiment, originating from newly formed saponite. Silica got enriched in the outflow of both experiments, indicating dissolution of silicate-minerals, identified in the OPC experiment as cristobalite. The experiments attested an effective buffering capacity for bentonite and s/b, a progressing coupled hydraulic-chemical sealing process and also the preservation of the physical integrity of the interface region in this setup with a total pressure boundary condition on the core sample. No complete pore-clogging was observed but the hydraulic conductivity got rather strongly reduced in 3 experiments, explained by clogging of the intergranular porosity (macroporosity). Such a drop in hydraulic conductivity may impact the saturation time of the buffer in a nuclear waste repository, although the processes and geometry will be more complex in repository situation.

Encapsulation of caesium-loaded Ionsiv in cement

The microporous material Ionsiv is used for 137Cs removal from aqueous nuclear waste streams. In the UK, Cs-loaded Ionsiv is classed as an intermediate-level waste; no sentencing and disposal route is yet defined for this material and it is currently held in safe interim storage on several nuclear sites. In this study, the suitability of fly ash and blast furnace slag blended cements for encapsulation of Cs-Ionsiv in a monolithic wasteform was investigated. No evidence of reaction or dissolution of the Cs-Ionsiv in the cementitious environment was found by scanning electron microscopy and X-ray diffraction. However, a small fraction (<= 1.6 wt.%) of the Cs inventory was released from the encapsulated Ionsiv during leaching experiments carried out on hydrated samples. Furthermore, it was evident that K and Na present in the cementitious pore water exchanged with Cs and H in the Ionsiv. Therefore, cement systems lower in K and Na, such as slag based cements, showed lower Cs release than the fly ash based cements.

Pore depth evolution of a pyrochlore pellet

The long-term stability of ceramic materials that are considered as potential nuclear waste forms is governed by heterogeneous surface reactivity. Thus, instead of a mean rate, the identification of one or more dominant contributors to the overall dissolution rate is the key to predict the stability of waste forms quantitatively. Direct surface measurements by vertical scanning interferometry (VSI) and their analysis via material flux maps and resulting dissolution rate spectra provide data about dominant rate contributors and their variability over time. Using pyrochlore (Nd2Zr2O7) pellet dissolution under acidic conditions as an example, we demonstrate the identification and quantification of dissolution rate contributors, based on VSI data and rate spectrum analysis. Heterogeneous surface alteration of pyrochlore varies by a factor of about 5 and additional material loss by chemo-mechanical grain pull-out within the uppermost grain layer. We identified four different rate contributors that are responsible for the observed dissolution rate range of single grains. Our new concept offers the opportunity to increase our mechanistic understanding and to predict quantitatively the alteration of ceramic waste forms.

Performance of a transmutation advanced device for sustainable energy application

Preliminary studies have been performed to design a device for nuclear waste transmutation and hydrogen generation based on a gas-cooled pebble bed accelerator driven system, TADSEA (Transmutation Advanced Device for Sustainable Energy Application). In previous studies we have addressed the viability of an ADS Transmutation device that uses as fuel wastes from the existing LWR power plants, encapsulated in graphite in the form of pebble beds, cooled by helium which enables high temperatures (in the order of 1200 K), to generate hydrogen from water either by high temperature electrolysis or by thermochemical cycles. For designing this device several configurations were studied, including several reflectors thickness, to achieve the desired parameters, the transmutation of nuclear waste and the production of 100 MW of thermal power. In this paper new studies performed on deep burn in-core fuel management strategy for LWR waste are presented. The fuel cycle on TADSEA device has been analyzed based on both: driven and transmutation fuel that had been proposed by the General Atomic design of a gas turbine-modular helium reactor. The transmutation results of the three fuel management strategies, using driven, transmutation and standard LWR spent fuel were compared, and several parameters describing the neutron performance of TADSEA nuclear core as the fuel and moderator temperature reactivity coefficients and transmutation chain, are also presented

Evaluation of reactivity monitoring techniques at the Yalina – Booster subcritical facility

La gestión de los residuos radiactivos de vida larga producidos en los reactores nucleares constituye uno de los principales desafíos de la tecnología nuclear en la actualidad. Una posible opción para su gestión es la transmutación de los nucleidos de vida larga en otros de vida más corta. Los sistemas subcríticos guiados por acelerador (ADS por sus siglas en inglés) son una de las tecnologías en desarrollo para logar este objetivo. Un ADS consiste en un reactor nuclear subcrítico mantenido en un estado estacionario mediante una fuente externa de neutrones guiada por un acelerador de partículas. El interés de estos sistemas radica en su capacidad para ser cargados con combustibles que tengan contenidos de actínidos minoritarios mayores que los reactores críticos convencionales, y de esta manera, incrementar las tasas de trasmutación de estos elementos, que son los principales responsables de la radiotoxicidad a largo plazo de los residuos nucleares. Uno de los puntos clave que han sido identificados para la operación de un ADS a escala industrial es la necesidad de monitorizar continuamente la reactividad del sistema subcrítico durante la operación. Por esta razón, desde los años 1990 se han realizado varios experimentos en conjuntos subcríticos de potencia cero (MUSE, RACE, KUCA, Yalina, GUINEVERE/FREYA) con el fin de validar experimentalmente estas técnicas. En este contexto, la presente tesis se ocupa de la validación de técnicas de monitorización de la reactividad en el conjunto subcrítico Yalina-Booster. Este conjunto pertenece al Joint Institute for Power and Nuclear Research (JIPNR-Sosny) de la Academia Nacional de Ciencias de Bielorrusia. Dentro del proyecto EUROTRANS del 6º Programa Marco de la UE, en el año 2008 se ha realizado una serie de experimentos en esta instalación concernientes a la monitorización de la reactividad bajo la dirección del CIEMAT. Se han realizado dos tipos de experimentos: experimentos con una fuente de neutrones pulsada (PNS) y experimentos con una fuente continua con interrupciones cortas (beam trips). En el caso de los primeros, experimentos con fuente pulsada, existen dos técnicas fundamentales para medir la reactividad, conocidas como la técnica del ratio bajo las áreas de los neutrones inmediatos y retardados (o técnica de Sjöstrand) y la técnica de la constante de decaimiento de los neutrones inmediatos. Sin embargo, varios experimentos han mostrado la necesidad de aplicar técnicas de corrección para tener en cuenta los efectos espaciales y energéticos presentes en un sistema real y obtener valores precisos de la reactividad. En esta tesis, se han investigado estas correcciones mediante simulaciones del sistema con el código de Montecarlo MCNPX. Esta investigación ha servido también para proponer una versión generalizada de estas técnicas donde se buscan relaciones entre la reactividad el sistema y las cantidades medidas a través de simulaciones de Monte Carlo. El segundo tipo de experimentos, experimentos con una fuente continua e interrupciones del haz, es más probable que sea empleado en un ADS industrial. La versión generalizada de las técnicas desarrolladas para los experimentos con fuente pulsada también ha sido aplicada a los resultados de estos experimentos. Además, el trabajo presentado en esta tesis es la primera vez, en mi conocimiento, en que la reactividad de un sistema subcrítico se monitoriza durante la operación con tres técnicas simultáneas: la técnica de la relación entre la corriente y el flujo (current-to-flux), la técnica de desconexión rápida de la fuente (source-jerk) y la técnica del decaimiento de los neutrones inmediatos. Los casos analizados incluyen la variación rápida de la reactividad del sistema (inserción y extracción de las barras de control) y la variación rápida de la fuente de neutrones (interrupción larga del haz y posterior recuperación). ABSTRACT The management of long-lived radioactive wastes produced by nuclear reactors constitutes one of the main challenges of nuclear technology nowadays. A possible option for its management consists in the transmutation of long lived nuclides into shorter lived ones. Accelerator Driven Subcritical Systems (ADS) are one of the technologies in development to achieve this goal. An ADS consists in a subcritical nuclear reactor maintained in a steady state by an external neutron source driven by a particle accelerator. The interest of these systems lays on its capacity to be loaded with fuels having larger contents of minor actinides than conventional critical reactors, and in this way, increasing the transmutation rates of these elements, that are the main responsible of the long-term radiotoxicity of nuclear waste. One of the key points that have been identified for the operation of an industrial-scale ADS is the need of continuously monitoring the reactivity of the subcritical system during operation. For this reason, since the 1990s a number of experiments have been conducted in zero-power subcritical assemblies (MUSE, RACE, KUCA, Yalina, GUINEVERE/FREYA) in order to experimentally validate these techniques. In this context, the present thesis is concerned with the validation of reactivity monitoring techniques at the Yalina-Booster subcritical assembly. This assembly belongs to the Joint Institute for Power and Nuclear Research (JIPNR-Sosny) of the National Academy of Sciences of Belarus. Experiments concerning reactivity monitoring have been performed in this facility under the EUROTRANS project of the 6th EU Framework Program in year 2008 under the direction of CIEMAT. Two types of experiments have been carried out: experiments with a pulsed neutron source (PNS) and experiments with a continuous source with short interruptions (beam trips). For the case of the first ones, PNS experiments, two fundamental techniques exist to measure the reactivity, known as the prompt-to-delayed neutron area-ratio technique (or Sjöstrand technique) and the prompt neutron decay constant technique. However, previous experiments have shown the need to apply correction techniques to take into account the spatial and energy effects present in a real system and thus obtain accurate values for the reactivity. In this thesis, these corrections have been investigated through simulations of the system with the Monte Carlo code MCNPX. This research has also served to propose a generalized version of these techniques where relationships between the reactivity of the system and the measured quantities are obtained through Monte Carlo simulations. The second type of experiments, with a continuous source with beam trips, is more likely to be employed in an industrial ADS. The generalized version of the techniques developed for the PNS experiments has also been applied to the result of these experiments. Furthermore, the work presented in this thesis is the first time, to my knowledge, that the reactivity of a subcritical system has been monitored during operation simultaneously with three different techniques: the current-to-flux, the source-jerk and the prompt neutron decay techniques. The cases analyzed include the fast variation of the system reactivity (insertion and extraction of a control rod) and the fast variation of the neutron source (long beam interruption and subsequent recovery).

La roca magica: Uses of natural zeolites in agriculture and industry

For nearly 200 years since their discovery in 1756, geologists considered the zeolite minerals to occur as fairly large crystals in the vugs and cavities of basalts and other traprock formations. Here, they were prized by mineral collectors, but their small abundance and polymineralic nature defied commercial exploitation. As the synthetic zeolite (molecular sieve) business began to take hold in the late 1950s, huge beds of zeolite-rich sediments, formed by the alteration of volcanic ash (glass) in lake and marine waters, were discovered in the western United States and elsewhere in the world. These beds were found to contain as much as 95% of a single zeolite; they were generally flat-lying and easily mined by surface methods. The properties of these low-cost natural materials mimicked those of many of their synthetic counterparts, and considerable effort has made since that time to develop applications for them based on their unique adsorption, cation-exchange, dehydration–rehydration, and catalytic properties. Natural zeolites (i.e., those found in volcanogenic sedimentary rocks) have been and are being used as building stone, as lightweight aggregate and pozzolans in cements and concretes, as filler in paper, in the take-up of Cs and Sr from nuclear waste and fallout, as soil amendments in agronomy and horticulture, in the removal of ammonia from municipal, industrial, and agricultural waste and drinking waters, as energy exchangers in solar refrigerators, as dietary supplements in animal diets, as consumer deodorizers, in pet litters, in taking up ammonia from animal manures, and as ammonia filters in kidney-dialysis units. From their use in construction during Roman times, to their role as hydroponic (zeoponic) substrate for growing plants on space missions, to their recent success in the healing of cuts and wounds, natural zeolites are now considered to be full-fledged mineral commodities, the use of which promise to expand even more in the future.

Site characterization progress report, Yucca Mountain, Nevada : April 1, 1990-September 30, 1990.

"March 1991."

Letter report to Congress and the Secretary of Energy.

Mode of access: Internet.

Environmental assessment : reference repository location, Hanford site, Washington.

"DOE/RW-0070."

Environmental assessment, Davis Canyon Site, Utah.

At head of title: Nuclear Waste Policy Act (Section 112).

Measures: Monastery for an Atomic Priesthood; Hanford, WA

Thesis (Master's)--University of Washington, 2016-06

Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R'2O3)y(P2O5)1-(x+y), where (R, R') denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å-1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with 'dial-up' lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P-O and PO bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials. © 2013 The Owner Societies.