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Abstract: Swelling of shale in response to interaction with water is an important consideration within subsurface energy systems. In the case of waste disposal, swelling can provide important barriers around the waste and enhance the sealing ability of rocks. For shale gas exploration purpose, however, swelling may cause wellbore instability. Therefore, a careful study of shale swelling is critical for subsurface energy related applications. Here, the swelling effects of shale were imaged at nanoscale using an advanced synchrotron Transmission X-ray Microscopy (TXM) imaging technique for the first time, with a spatial resolution down to 40.9 nm. Organic matter and clays within the analysed sample were observed to display large swelling effects which resulted in a 50% reduction in porosity. Strain maps generated using Digital Volume Correlation (DVC) show deformation and significant strain were mostly localized to between the contact boundaries of sharp brittle minerals and softer organic matter and clays. This is the first study, to our knowledge, to directly image the swelling deformation of shale at the tens of nanometer scale and provide local information on the strain evolution.

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Abstract: Magnesium sulfate hydrates are considered important rock-forming minerals on the outer three Galilean moons of Jupiter (i.e., Europa, Ganymede, Callisto) and, alongside ferrous sulfate hydrates, are promising candidate minerals for the widespread sulfate deposits that occur in the equatorial region of Mars. In such extraterrestrial environments, these minerals experience extreme high-pressure conditions in the interiour of the Galilean moons and low temperature conditions on the surface of these moons and Mars. The aim of this thesis is to understand the structural stability, compressibility, and thermal expansion of these compounds in such extreme environments and aid their identification in ongoing and future space missions. Most magnesium sulfate hydrates lack accurate reference elastic tensors, which hinders their seismological identification in lander missions on the icy moons of the outer solar system, as envisioned for the near future. In this thesis, the accuracy of recent advancements in density functional theory to predict the compressibility and elastic constants of icy satellite candidate minerals (i.e., epsomite (MgSO₄·7H₂O), gypsum (CaSO₄·2H₂O), carbon dioxide (CO₂), and benzene (C₆H₆)) was assessed by benchmarking them against experimental reference data from the literature. Key findings are that density functional theory calculations do not yield elastic constants accurate enough to be used as a reference for the seismic exploration of icy moons. However, the bulk compressibility of such materials is very accurately reproduced by density functional theory, which was therefore used to predict the compressibility of the icy satellite candidate minerals starkeyite (MgSO₄·4H₂O) and cranswickite (MgSO₄·4H₂O). Knowledge of the compressibility of such minerals is critical to model mantle processes (e.g., salt diaprisim, plate tectonics, subduction) and the density structure of the outer three Galilean moons. The thermal expansion and structural stability of three sulfate minerals (i.e., rozenite (FeSO₄·4H₂O), starkeyite, and cranswickite) was characterised for the first time using neutron diffraction. Cranswickite transforms to starkeyite at 330 K, well above the maximum surface temperature of 308 K hitherto reported on Mars. Starkeyite likely undergoes a structural phase transition at around 245 K. The structure of this proposed low-temperature polymorph could not be determined but would be of great interest since the temperature drops below 245 K on equatorial Mars at night-time. Starkeyite was also studied by means of synchrotron X-ray diffraction but suffered radiation damage. No phase transition was observed in rozenite from 290 – 21 K, which contrasts with Raman data reported in the literature, where sharpening of vibrational modes upon cooling was misinterpreted as mode splitting and evidence for two phase transitions at temperatures relevant to the Martian surface. First-principles phonon frequency calculations provide evidence supporting the absence of vibrational mode splitting. A workflow to obtain reliable reference Raman spectra for space exploration was proposed and an optical centre stick for the simultaneous acquisition of neutron diffraction and Raman spectroscopy data at the HRPD instrument was commissioned. Lastly, the structure of a polymorph of hexahydrite (MgSO₄·6H₂O), most recently proposed in the literature, was shown to be unambiguously wrong.

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Abstract: Determination of mineral texture and diagenetic features in mudstones is crucial to reveal the history of their pore systems and provides key information to predict their future sealing ability, reactivity and storage capacity for sequestered CO2, hydrogen storage or nuclear waste disposal. To understand the spatial transport and storage of fluids, it is necessary to map the distribution of minerals and fractures in three dimensions (3D). This study proposes a novel, multi-scale three-dimensional (3D) imaging method, i.e., a combination of synchrotron- sourced micro- x-ray tomography and lab- sourced nano-tomography, to investigate the sedimentology and diagenetic features of the Bowland Shale, one of the most volumetrically important mudstone-dominated systems in the UK. Diagenetic minerals have been identified and characterised, including pyrite, calcite, kaolinite, illite, chlorite, dolomite, ankerite and authigenic quartz (micro-sized quartz and quartz overgrowths). Multi-scale 3D images provide detailed information about dolomite-ankerite zonation and carbonate dissolution pores. These features cannot be observed or quantified by conventional 2D methods, and they have not been reported in this subject area before. Using these results, potential reactions during carbon storage and other subsurface storage applications are predicted.

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Abstract: An understanding the organic matter (OM) in primitive interplanetary materials can provide us with important constraints on both the early solar system carbon cycle and incipient prebiotic synthesis before the origin of life. As a window to the past, primitive chondrites preserve the most pristine record of parent body, nebular and interstellar components and the occurrence of OM in them has been shown in both soluble (SOM) (1) and insoluble (IOM) (2) form. Total organic carbon (TOC) abundance reaches ~3-4 wt% in the most primitive carbonaceous chondrite (CCs) (3), such as Ivuna-type chondrites (CIs) – thus making them highly desirable for the OM studies, and relevant to the study of Asteroid 162173 Ryugu samples from the Hayabusa-2 mission. A combination of both SOM and IOM analysis of organic bulk meteorite separates together with in-situ analysis of OM have provided a comprehensive account of chondritic OM (4). In the case of in-situ analysis, the combination of both scanning (SEM) and transmission electron microscopy (TEM) together with soft X-Ray scanning transmission microscopy (STXM) have shown the presence of micron to submicron distinctive organic particles (OPs) (5). Carbon K-edge X-ray absorption near edge structure (XANES) has shown the aromatic-carbonyl-carboxyl chemical nature of these organic particles (5). In addition, aromatic-poorer and carboxylic-richer diffuse OM (6) within both amorphous and phyllosilicate occurs as well. As observation techniques are getting better, aberration corrected TEM coupled with electron energy loss spectroscopy (EELS) might provide the same results as carbon XANES, but with higher image magnification, rapid data acquisition and better accessibility. In this context, we present the results of a comparative carbon K-edge XANES and EELS study of CI meteorite Ivuna. An approximately 100 nm lamella of the Ivuna meteorite was prepared using focused ion beam (FIB)-SEM with the Helios 5 Hydra DualBeam (CEITEC, Masaryk University, Czechia) and analysed by TEM-EELS with the JEOL ARM200CF (ePSIC, Diamond Light Source, UK) and STXM-XANES at Beamline BL19A of the KEK Photon Factory, Japan. We observed that (I) XANES on samples that did not experience TEM-EELS are in agreement with the previous studies of aromatic-carbonyl-carboxylic macromolecular OPs and IOM, while (II) the TEM-EELS of OPs show aromatic-carbonyl functional chemistry but with amorphous carbon convoluting the carboxylic peak, and aromatic-poor spectra with a sharp carbonate peak in diffuse OM. The difference between XANES and EELS particularly in the diffuse OM can be interpreted by electron-beam damage. Thickness and e-beam damage leads to amorphous C formation in the OPs. In the case of more labile OM in the phyllosilicate, its change by heating and oxidation is expected.

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Abstract: NASA, ESA and the UK are collaborating on a Mars Sample Return (MSR) mission which aims to retrieve drill cores of Martian rock for terrestrial analysis, starting with the Mars2020 rover which landed successfully in Jezero Crater in Feb. 2021. Up to 30 samples, inside sealed titanium sample tubes, are planned to be returned to Earth in later missions. Due to the potential for back-contamination of Earth from possible extant life on Mars, strict contamination control measures must be taken for the purposes of planetary protection, as well as to prevent contamination of the samples by Earth’s environment. These measures place restrictions on the way measurements can be performed on the samples until they have been sterilised or judged safe. As the first step of scientific analysis, all samples will undergo a set of measurements called Pre-Basic Characterisation. Pre-BC will include weighing, X-ray CT, and magnetic measurements. These data along with Basic Characterisation data will be used to decide experimental plans for multi instrument analyses on the Mars samples. X-ray Diffraction (XRD) is currently planned for a later stage of sample analysis after the sample tubes have been opened due to limitations with conventional commercial X-ray diffractometers. [1, 2] While a conventional X-ray tube cannot provide an appropriate X-ray beam, a synchrotron source is capable of much higher intensities and precise wavelength selectivity. Synchrotron facilities also allow more suitable diffraction geometries for the size and shape of sample expected from MSR. We have carried out experiments with the help of Diamond Light Source’s I12-JEEP beamline to test the feasibility of XRD analysis of samples in sealed Mars2020 sample tubes and suitable instrument parameters for XRD of these samples. Titanium tubes were prepared as analogues to Mars2020 sample tubes. Three different geological analogues were used in place of the Mars samples: an Icelandic basaltic sand, a calcareous mudstone from Watchet Bay, UK, and a Devonian Fine Grained Sandstone, UK. Two different methods for preventing unwanted diffraction signal from the sample tube walls have also been tested: subtracting the diffraction spectrum of an empty tube from the tube-with-sample spectrum, and using energy-dispersive X-ray diffraction to exclude tube wall signal. We show that quantitative XRD phase analysis can be successfully carried out on returned Mars samples in unopened sample tubes using a synchrotron X-ray source, and thus could be included in the Pre-BC phase of returned sample science. This would provide mineralogical data much earlier in the sample science process, improving decision-making around sample science, curation, and handling.