Anthrax spores, in weaponized form, are dangerous biological warfare agents. Handheld technology for the rapid detection of anthrax is greatly needed to improve national security. Methods to detect anthrax spores are diverse, with most taking at least an hour for positive identification. A viable option for rapid detection is analytical pyrolysis (AP), which produces chemicals containing taxonomical information (biomarkers). AP methods are reviewed and critically analyzed to show that reproducible detection of anthrax spores in a rapid manner (< 5 min) with a handheld device is not currently possible. A promising alternative to AP is the use of a catalyst to produce biomarkers from anthrax spores with improved selectivity and reproducibility. Catalytic materials having promise for this include platinum, nickel, and superacids. Experiments evaluating several of these materials are described. A biomarker mass spectral library was created, based on information available in the scientific literature, to facilitate analysis and identification of the biomarkers produced experimentally. The RAMFAC algorithm was used to deconvolute chromatographic peaks to produce clean mass spectra and match them against entries in the biomarker library. While the library is not complete, its use with the RAMFAC algorithm enabled detection of many important biomarkers in experiments involving catalytic breakdown of anthrax spores. Experimental results from preliminary tests of several catalysts are presented and discussed. Addition of catalysts in the form of platinum nanoclusters and superacids to bacterial spores in a commercial pyrolyzer effected an increase in the amount of biomarkers produced at mild conditions over traditional pyrolysis methods. Electroformed nickel mesh, on the other hand, demonstrated low catalytic activity for the production of biomarkers, likely due to poor contact of the spores with the mesh. Biomarkers similar to those published in the literature were observed, including dipicolinic acid, picolinic acid, propionamide, acetamide, diketopiperazines, fatty acids, furfuryl alcohol, and DNA bases. A statistically designed factorial study was used to determine the importance of temperature, spore loading, and nanocluster loading on the production of three important biomarkers. The relative importance of these variables differs for each of the three important biomarkers, suggesting they are produced by different reaction mechanisms.

This study introduces numerical frameworks for simulating the interactions within soil systems subjected to freezing and thawing processes, crucial for addressing geotechnical challenges in cold regions. By integrating robust thermo-hydro-mechanical (THM), this research offers a general understanding and specific insights into the deformation, thermal, and moisture transport behaviors of freezing-thawing soils. The first part of this study presents a soil freezing characteristic curve (SFCC) adaptable to various computational frameworks, including THM models. The SFCC, enhanced by an automatic regression scheme and a smoothing algorithm, accommodates the dynamic changes in soil properties due to phase transitions. This model effectively captures the unique behaviors of different soil types under freezing conditions, addressing key factors such as freezing temperature, compaction, and mechanical loading. Building on this foundation, the second framework employs the phase-field method (PFM) coupled with THM to model the behavior of ice-rich saturated porous media. This approach advances the field by enabling distinct representations of the mechanical behaviors of ice and soil through a diffused interface, introducing anisotropic responses as the soil undergoes freezing. By integrating a transversely isotropic plastic constitutive model for ice, this method provides a tool for capturing the phase transition processes and the resulting mechanical responses of frozen soil. The third part extends these methodologies to model thaw consolidation in permafrost regions using a THM framework combined with phase field methods. This model incorporates internal energy functions and a multiscale modified Cam-Clay model within a damage phase field framework, adept at capturing the simultaneous effects of phase change and particle rearrangement. Through validation against experimental scenarios, this model demonstrates its effectiveness in understanding the microstructural evolution and plastic softening in thaw-sensitive soils, which is vital for enhancing infrastructure resilience under thaw conditions. Together, these integrated approaches represent a leap in the modeling and simulation of geotechnical behaviors in cold regions, offering potential applications in predicting and mitigating the impacts of climate change on permafrost and other freeze-thaw affected terrains. / Thesis / Doctor of Science (PhD)

Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.

Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.

Après une dernière phase de forage et de stimulation hydraulique, le site expérimental de Soultz-sous-Forêts comporte désormais trois puits connectés à un réservoir géothermique profond (5 km). A l'avenir, du fait de la mise en place d'une unité de production électrique, seule la modélisation numérique renseignera sur l'état du réservoir. Une compréhension poussée des propriétés géométriques de ce dernier est donc incontournable. C'est ce que propose ce travail, notamment en étudiant la prise en compte de la zone endommagée dans les modèles de faille.<br />Au cours de cette étude, les propriétés physiques de la zone endommagée (porosité, perméabilité, surface spécifique, conductivité thermique) ont été mesurées à différentes échelles et sur des échantillons présentant des structures et des faciès d'altération variés. La combinaison de ces mesures, et leur intégration dans différents modèles numériques, a notamment permis de mettre en évidence l'impact de la zone endommagée sur les transferts de chaleur et de matière, ainsi qu'une évolution particulière de la géométrie du réseau poreux avec l'altération.

Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.

[Truncated abstract] Rocks, as the host to natural chains of coupled thermal, hydraulic and mechanical processes, are heterogeneous at a variety of length scales, and in their mechanical properties, as well as in the hydraulic and thermal transport properties. Rock heterogeneity affects the ultimate hydro-carbon recovery or geothermal energy production. This heterogeneity has been considered one important and difficult problem that needs to be taken into account for its effect on the coupled processes. The aim of this thesis is to investigate the effect of rock heterogeneity on multi-physical processes. A fully coupled finite element model, hereinafter referred to as a porosity-based model (PBM) was developed to characterise the thermal-hydraulic-mechanical (THM) coupling processes. The development of the PBM consists of a two-staged workflow. First, based on poromechanics, porosity, one of the inherent rock properties, was derived as a variant function of the thermal, hydraulic and mechanical effects. Then, empirical relations or experimental results, correlating porosity with the mechanical, hydraulic and thermal properties, were incorporated as the coupling effects. In the PBM, the bulk volume of the model is assumed to be changeable. The rate of the volumetric strain was derived as the difference of two parts: the first part is the change in volume per unit of volume and per unit of time (this part was traditionally considered the rate of volumetric strain); and the second is the product of the first part and the volumetric strain. The second part makes the PBM a significant advancement of the models reported in the literature. ... impact of the rock heterogeneity on the hydro-mechanical responses because of the requirement of large memory and long central processing unit (CPU) time for the 3D applications. In the 2D PBM applications, as the thermal boundary condition applied to the rock samples containing some fractures, the pore pressure is generated by the thermal gradient. Some pore pressure islands can be generated as the statistical model and the digital image model are applied to characterise the initial porosity distribution. However, by using the homogeneous model, this phenomenon cannot be produced. In the 3D PBM applications, the existing fractures become the preferential paths for the fluid flowing inside the numerical model. The numerical results show that the PBM is sufficiently reliable to account for the rock mineral distribution in the hydro-mechanical coupling processes. The applications of the statistical method and the digital image processing technique make it possible to visualise the rock heterogeneity effect on the pore pressure distribution and the heat dissipation inside the rock model. Monitoring the fluid flux demonstrates the impact of the rock heterogeneity on the fluid product, which concerns petroleum engineering. The overall fluid flux (OFF) is mostly overestimated when the rock and fluid properties are assumed to be homogeneous. The 3D PBM application is an example. As the rock is heterogeneous, the OFF by the digital core is almost the same as that by the homogeneous model (this is due to that some fractures running through the digital core become the preferential path for the fluid flow), and around 1.5 times of that by the statistical model.

Gelfill (GF) is made of tailings, water, binder and chemical additives (Fillset, sodium silicate gel). The components of GF are combined and mixed on the surface and transported (by gravity and/or pumping) to the underground mine workings, where the GF can be used for both underground mine support and tailings storage. Thermal (T), hydraulic (H), and mechanical (M) properties are important performance criteria of GF. The understanding of these engineering properties and their evolution with time are still limited due to the fact that GF is a new cemented backfill material. In this thesis, the evolution of the thermal, hydraulic, mechanical, and microstructural properties of small GF samples are determined. Various binder contents of Portland cement type I (PCI) are used. The GF is cured for 3, 7, 28, 90, and 120 days. It is found that the thermal, hydraulic and mechanical properties are time-dependent or affected by the degree of binder hydration index. Furthermore, a relationship is found between the compressive strength and the saturated hydraulic conductivity of the GF samples. The unsaturated hydraulic properties of GF samples have also been investigated. The outcomes show that unsaturated hydraulic conductivity is influenced by the degree of binder hydration index and binder content, especially at low suction ranges. Simple functions are proposed to predict the evolution of air-entry values (AEVs), residual water content, and fitting parameters from the van Genuchten model with the degree of hydration index (α). Furthermore, two columns are built to simulate the coupled thermo-hydro-mechanical (THM) behaviour of GF under drained and undrained conditions. The obtained results from the GF columns are compared with the small samples. It is observed that the mechanical properties, hydraulic properties (suction and water content), and temperature development are strongly coupled. The magnitude of these THM coupling factors is affected by the size of the GF. The findings also show that the mechanical, hydraulic and thermal properties of the GF columns are different from samples cured in plastic moulds.

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