Σκοπός της παρούσας εργασίας, είναι η διερεύνηση των υδροχημικών παραμέτρων των κοκκωδών υδροφόρων της λεκάνης του Σπερχειού, καθώς και η πιθανή τροφοδοσία τους από τα ανθρακικά πετρώματα. Για το σκοπό αυτό πραγματοποιήθηκαν μετρήσεις στάθμης, καθώς και υδροχημικές αναλύσεις κύριων στοιχείων, ιχνοστοιχείων και σπάνιων γαιών. Γεωλογικά η περιοχή, στο βορειοανατολικό και νοτιοανατολικό τμήμα της ,δομείται από τους σχηματισμούς της Υποπελαγονικής ζώνης, στο νότιο από τους σχηματισμούς της ζώνης Παρνασσού-Γκιώνας και στο δυτικό από τους σχηματισμούς της ζώνης της Πίνδου. Οι Ολοκαινικές και Πλειο-πλειστοκαινικές αποθέσεις, δομούν το πεδινό τμήμα της λεκάνης και φιλοξενούν τον κύριο υδροφόρο ορίζοντα της περιοχής. Ο ελεύθερος αυτός υδροφόρος μεταπίπτει σε υπό πίεση, εξαιτίας της παρουσίας αργιλικών σχηματισμών, στα ανατολικά της περιοχής. Στα ορεινά τμήματα της λεκάνης, εντός των ανθρακικών σχηματισμών, αναπτύσσονται σημαντικοί υδροφόροι ορίζοντες. Με βάση τον πιεζομετρικό χάρτη της περιοχής προκύπτει ότι η διεύθυνση της ροής του υπόγειου νερού, είναι κυρίως ΒΑ-ΝΑ και o προσχωματικός υδροφόρος, τροφοδοτείται πλευρικά, από τους ανθρακικούς σχηματισμούς, που βρίσκονται νότια και βορειοανατολικά του πεδινού τμήματος. Τα υπόγεια νερά της περιοχής, ομαδοποιούνται σε τρεις κύριους υδροχημικούς τύπους: Ca-HCO3, Ca-Mg-HCO3 και (Ca)-Νa-Cl-(HCO3). Ο πρώτος υδροχημικός τύπος χαρακτηρίζει τα φρέσκα νερά της περιοχής, ο δεύτερος τα νερά που παρέμειναν για μεγαλύτερο χρονικό διάστημα στον υδροφόρο και εμπλουτίστηκαν σε Μg+2, και ο τρίτος τα νερά που δέχονται την επίδραση είτε της θάλασσας, είτε των θερμών νερών από μεγαλύτερα βάθη. Από τα αποτελέσματα των υδροχημικών αναλύσεων προέκυψε ότι στην πλειοψηφία τους τα δείγματα είναι κορεσμένα σε ασβεστίτη και δολομίτη. Eπίσης σε μία ομάδα δειγμάτων, διαπιστώθηκε απεμπλουτισμός σε Na, γεγονός που αποδόθηκε σε διαδικασίες ιοντοανταλαγής. Οι αυξημένες συγκεντρώσεις Fe, Mn, αποδόθηκαν στη διάλυση των ορυκτών του φλύσχη της Πίνδου, ενώ ο Zn και τα NΟ3 σε ανθρωπογενείς παρεμβάσεις (βιομηχανικά απόβλητα και λιπάσματα). Το As το Li και το Β συνδέονται με την παρουσία θερμών πηγών. Τέλος η μεθοδολογία των σπάνιων γαιών, επαλήθευσε τα αποτελέσματα της πιεζομετρίας αλλά και τα υδροχημικών αναλύσεων, ότι δηλαδή ο προσχωματικός υδροφόρος της περιοχής, τροφοδοτείται πλευρικά από τα ανθρακικά πετρώματα της περιοχής και συγκεκριμένα από τους ασβεστόλιθους της Υποπελαγονικής ζώνης και της ζώνης Παρνασσού-Γκιώνας. / In the frames of this study the hydrochemical parameters of porous aquifers at Sperchios basin, were investigated. Moreover their possible recharge by carbonate rocks was examined. Therefore, a series of water level measurements and a sampling campaign were carried out. The samples were analysed for main, trace and rare earth elements. Regarding the area’s geological setting, its northeastern and southeastern part is comprised of formations of the Subpelagonic Zone, its southern edge of Parnassos-Giona Zone and its western part of Pindos Zone. At the lowlands these formations are overlain by Holocene and Pleistocene deposits which host the most important aquifer of the region. It is an unconfined aquifer, which at the eastern part turns into a confined one, due to the presence of clay formations. Many important aquifers have been also developed in the basin’s carbonate formations. The region’s piezometric map at the southern area indicates that the main water flow direction is NE-SE. Moreover it points out that the carbonate formations recharge the porous aquifer. According to their hydrochemical characteristics groundwater can be divided into three main types: Ca-HCO3, Ca-Mg-HCO3 and (Ca)-Na-Cl-(HCO3). The first one is typical of the region’s fresh water, the second one indicates longer residence time of the water that was enriched in Mg+2 and the third one of water that was either influenced by sea water or hot springs. The elaboration of the hydrochemical data also showed that the majority of water samples are saturated in calcite and dolomite. There is also a depletion of certain samples in Na+ which was attributed to ion exchange processes. High Fe and Mn concentrations originate from the dissolution of Pindos Flysch minerals, As, Li and B to the presence of hot springs, while Zn and NO3 were related to human impact (industrial waste and fertilizers). The rare earth elements confirmed the original hypothesis, which was based on piezometric data and hydrochemical data analysis, that the region’s porous aquifer is laterally recharged by the carbonate rock formations of Subpelagonic and Parnassos-Giona Zone limestones.

The Round Top laccolith is considered to be one of the youngest laccoliths in a series of five known as the Sierra Blanca peaks, located in Hudspeth county, Texas. The laccolith is anomalous within the region in that it is peraluminous and enriched in HREEs, F, and U, and is comprised of intermingled discrete packages of various rhyolite types. The laccolith rhyolite varies in color from gray, purple, red, and tan, which combine locally to form distinct geometric mottled textures. The general composition of the rhyolite is 48-52% potassium feldspar, 28-30% quartz, 8-14% plagioclase feldspar, 4-5% annite biotite, 2-3% magnetite-hematite, 1% zircon, and 1% trace phases. The morphology of the trace phases suggests quenching of a late-stage volatile-rich vapor phase at the time of the laccolith formation. The rhyolite displays a wide array of unique mineralogical characteristics indicative to rapid emplacement and metastable crystallization conditions, including three-part quartz phenocrysts, hourglass sector-zoned potassium feldspars, and late-stage anhedral zircons. Unique accessory and trace phases include cassiterite, cerianite-(Ce), changbaiite, columbite, cryolite, tantalite, thorite, yttrofluorite, yttrocerite, and two unidentified minerals named (W) and (X). Initial alteration of the laccolith by high temperature volatile-rich vapor during the late stages of crystallization caused the partial dissolution of the feldspars and quartz. Subsequent quenching of this high temperature vapor phase produced the abundant interstitial, and pore filling REE-fluorides common to the laccolith. The variation in rhyolite color and the presence of the mottled textures are a direct result of partial oxidation of the laccolith by secondary fluids. The oxidizing fluids migrated within the laccolith along an extensive fracture network, altering the adjacent wallrock by oxidizing magnetite phenocrysts to hematite. The gray, purple, and red rhyolite types reflect an increase in turbidity caused by hematitic inclusions primarily within the pore spaces of the potassium feldspar portions of the groundmass. The tan rhyolite is locally restricted to the base of the laccolith and has been subjected to an intense degree of alteration independent of the other rhyolite types, primarily indicated by the conversion of feldspars to clay. Petrographic, microbeam, and geochemical studies have determined little variation in REE concentration between the three rhyolites of similar alteration intensity, but have indicated a depletion in LREEs within the more altered tan rhyolite. The average REE+Y content for the rhyolites sampled (n=11) ranges between 249 ppm and 518 ppm. The REE+Y concentrations between rhyolite samples of the same type show some variation, possibly indicating a correlation between alteration and REE+Y abundance and/or innate heterogeneity in the vapor phase during the initial laccolith formation. The magma emplaced at Round Top underwent a prolonged evolutionary process of fractionation/differentiation as evident by the unusual mineral assemblage and geochemical enrichment associated with the laccolith (e.g. extremely negative europium anomaly, and the positive La/Yb correlation). Future exploration for Round Top style REE-deposits should center within long-lived, tectonically active and complex regions where laccoliths are likely to exist. Specifically, exploration should focus on identifying the youngest laccolith in a felsic series, as this is the most likely to contain the greatest abundance of incompatible elements within the laccolithic group. The early alteration of feldspars by the high temperature vapor phase was crucial in the development of the REE+Y enrichment at Round Top. The feldspar dissolution provided abundant open pore space that was subsequently filled by the REE-fluorides. Thus, exploration should additionally seek laccoliths that have undergone a similar early alteration process, and expand to potential laccolith groups not yet exposed by erosional processes. / text

The Alnö Complex is a Late Precambrian alkaline and carbonatite intrusion (c. 30km2) into Early Proterozoic country rock that extends from the north east, to the north western shoulder of Alnö Island. Carbonatites are rare among volcanic provinces, with Oldoinyo Lengai of northern Tanzania being the only active carbonatite volcano in the world today. The high carbonate mineral volumes and rare earth element (REE) concentrations of carbonatites, in combination with the intrusive-extrusive nature of their suites contribute to the rarity of these rocks. Carbonatites, through their peculiar petrological and geochemical compositions, provide vital insights to the composition and condition of the Earth’s mantle. The genesis of the Alnö carbonatites and their relation to other lithological units at the complex is however, only partially understood. This stems from the epistemological division of carbonatites as having either a ‘magmatic’ or ‘reactive’ origin. This study focuses on sampled carbonatites from the Alnö Complex, employing an oxygen and carbon isotope approach on their native calcite, complemented with petrological and mineralogical methods in order to constrain petrogenesis. As a reference, oxygen and carbon isotope data of calcite from an earlier Alnö investigation as well as from an array of data from comparative alkaline complexes elsewhere are also discussed. The combined data and the derived findings support a scenario that is consistent with the ‘magmatic’ model wherein carbonatites have a primary mantle-derived origin, and prospectively stem from a parent magma akin to that of Oldoinyo Lengai, but have experienced a degree of silicate and sedimentary assimilation. The extraction of the Alnö carbonatites for their rare earth metals is a looming possibility due to the current volatility in the rare earth market. The risks and opportunities involved in this kind of natural resource extraction provide a context wherein sustainable development paradigms can be applied. The capacity of the Alnö environment to withstand the impact of development in the mining sector is discussed through a perspective of establishing a quarry, and quarry-related methods for rare earth extraction.

To explore whether the dispersion of sediments in the North Atlantic can be related to modern and past Atlantic Meridional Overturning Circulation (AMOC) flow speed, particle size distributions (weight%, Sortable Silt mean grain size) and grain-size separated (0–4, 4–10, 10–20, 20–30, 30–40 and 40–63 μm) Sm-Nd isotopes and trace element concentrations are measured on 12 cores along the flow-path of Western Boundary Undercurrent and in the central North Atlantic since the Last glacial Maximum (LGM). North Atlantic is a useful place to explore how size-specific sediment provenance is related to sedimentary inputs and deep-current advection because mantle-derived materials in Iceland is a unique sedimentary source compared to crustal-derived terranes in Europe, Greenland and North America. The four main processes transporting sediments from continents to the North Atlantic (bottom currents, turbidity currents, ice-rafting events, airborne inputs) can be well distinguished through the size-specific physical and geochemical records. When primarily advected by the bottom currents, Holocene sediments show that the finer-sized fractions (0–4, 4–10, 10–20 μm) were transported further, and the coarser size fraction (40–63 μm) matched local inputs. In the deep coretops (> 2700 m) proximal to southern Greenland, fine-slit size fraction (10–20 μm) instead of clay size fraction (0–4 μm) observed more Icelandic-material contribution. In the past, the 20–30, 30–40 and 40–63 μm particles in the shallower Iceland-proximal core (1249 m) reflect Icelandic composition variation due to the abrupt volcanic eruption around 13–9 ka; while in the deeper Iceland-proximal core (2303 m) they were sensitive to the changing bottom flow speed. Downstream in cores proximal to southern Greenland (> 2272 m) and eastern North America (3555 m), composition of the 20–63 μm sediments could be used as an indicator for the retreating of the Greenland and Laurentide Ice Sheets which affect the sediment accessibility of the covered geological terranes; while the 0–4, 4–10 and 10–20 μm particles were more sensitive towards the changing direction (northern-sourced or southern-sourced) and velocity of the bottom current. In the open North Atlantic, the composition of the 0–10 μm particles were less variable between the cold and warm climate intervals compared to the 10–63 μm particles, and the 30–40 and 40–63 μm size fractions were sensitive towards both ice-rafting events and bottom flow direction. During LGM, shallower and vigorous northern-sourced water (NSW) was observed overlaying the deeper southern-sourced water (SSW), with the boundary between 2133 to 2303 m in southern Iceland, and ~ 2272 m in southern Greenland. Reduced NSW occurred during Heinrich Stadial 1, until AMOC above ~ 3500 m recovered to vigorous modern-like version no later than ~ 13.5 ka. Sluggish overflow was observed in North Atlantic between 12.2–11.7 ka above ~ 3500 m. Reduction of Iceland-Scotland Overflow Water occurred around 9.7 ka, and started recovering to its modern vigorous no later than ~ 8.6 ka. These relative past AMOC strength variations (vigorous/sluggish) are firstly converted to actual bottom-current speed (in cm/s) using laminar advection model in this work: vertical settling velocity of particle having the most Icelandic contribution is calculated by Stokes’ Law, and the lateral deep-sea current speed is calculated when the vertical settling depth and the lateral advection distance of the particle traveled before settling are constrained. Primary modelling errors originating from temperature/salinity variations in past deep seawater, winnowing process in fine particles, basaltic-signature dilution by crustal input, and lateral advection pathways of Icelandic-material are further discussed, indicating relatively low modelling error (< ~ 10–20 %). The modelling results agree well with modern deep-sea current speed measurements and backtrack-trajectory eddy resolving model (Ocean model for the Earth Simulator, OFES18), indicating reasonable quantifications of past AMOC flow speeds.

Silicate melt inclusions (MI) are small samples of melt that are trapped during crystal growth at magmatic pressures and temperatures. The MI represent a sample of the melt that was isolated from the magma during host crystal growth. Thus, MI provide a valuable tool for constraining the magmatic history of igneous systems because they provide an unambiguous method to directly determine compositions of melts from which the host crystal grew. As such, coupled petrographic examination and geochemical analyses of MI and host crystals can reveal information about crystal/melt processes in igneous systems that are difficult (or impossible) to assess through conventional methods. Many studies have used MI to monitor large scale petrogenetic processes such as partial melting and fractional crystallization. The research presented below focuses on using MI to constrain processes that operate at the crystal/melt interface because MI are samples of melt that resided adjacent to the host crystal prior to entrapment as an inclusion. Chapter one addresses challenges associated with preparing small crystals containing MI for geochemical analysis. In chapter two trace element analyses of MI and the immediately adjacent host zircon crystals are used to determine zircon/melt partition coefficients. In chapter 3 the significance of boundary layer development adjacent to growing crystals is evaluated by comparing the trace element compositions of MI host crystals that have significantly different trace element mineral/melt partitioning behavior. / Ph. D.

With the development of new generation synchrotron facilities, the performances of various X-ray spectroscopies have become more advanced. In order to interpret the X-ray spectrum experiments of various novel materials related to transition metal and rare earth elements, new advanced theoretical methods are required. The present thesis incorporates four modus operandi based on the classic multiplet theory to study the core level X-ray spectroscopy of transition metal and rare earth element. The four approaches consist of new methods developed from classic multiplet approach to high level first-principles method assisted multiplet calculation. Some methods are selected from previous researches and some are invented by original researches. These methods are integrated together to form a complete set of multiplet computational methods. This set of multiplet computational methods can perform calculations on various X-ray spectroscopies such as XAS, XPS, XES and RIXS related to the core-level electron. These wide range of spectroscopic methods coupled to different multiplet theory approaches serve as efficient tools to understand the electronic structure of metal sites and their unique contribution to the physical/chemical properties of the materials. The thesis creatively improves the classic multiplet theory on several aspects: (1) the relation between crystal field parameters and local structure factors; (2) the difficulty of processing point group symmetry branching chain in low symmetric structure; (3) the first-principles calculation of semi-empirical parameters. Four modus operandi are presented in this thesis: the first is the classic multiplet theory consisting of the multiplet effect, crystal field effect and charge transfer effect via several semi-empirical parameters as description for these effects. The second level multiplet theoretical approach analyze the crystal field potential matrix in various symmetries according to the point group symmetry branching rules. Then the crystal field effect parameters used in classic multiplet theory are linked analytically to the specific structural factors such as bond length and angles. This approach is a good tool to study the structural distortion from higher to lower order symmetry with analysis of X-ray spectral feature changes in experiment. The third modus operandi adopts large cluster model consisting of point charges at equivalent atoms position to simulate the crystal field effect on the center metal site. This approach handles low order symmetric crystal field with long range effect in multiplet calculation in an easier way than the classic multiplet theory. The fourth modus operandi initially studies the system of interest in first-principles calculation for the electronic wavefunctions. Then the electronic wavefunctions are used to derive the maximally localized Wannier functions at metal/ligand sites. The analysis of these Wannier functions provide a lot of semi-empirical parameters required in the classic multiplet calculation approach in a first-principles way. This modus operandi has substantially resolved the problem of finding the best set of semi-empirical parameters to fit the calculated X-ray spectrum with experimental data. In order to study the core electrons of the light elements (such as C/N/O) around center metal ions, a theoretical calculation method used to study the core electrons' vibrationally-resolved X-ray spectroscopy is also introduced as a complementary research and applied to C1s core ionized XPS calculation as an example. / Med utvecklingen av nya generationens synkrotronanläggningar har prestandan för olika röntgenspektroskopier blivit mer avancerad. För att tolka röntgenspektrumexperiment av olika nya material relaterade till övergångsmetaller och sällsynta jordartsmetaller krävs nya avancerade teoretiska metoder. Denna avhandling inkorporerar fyra metoder baserade på den klassiska multiplettläran för att studera röntgenspektroskopi på kärnenerginivån för övergångsmetaller och sällsynta jordartsmetaller. De fyra metoderna består av nya metoder som utvecklats från den klassiska multiplettläran till multiplettberäkning med hjälp av högnivå-först-principer-metoder. Vissa metoder har valts från tidigare forskning och några har uppfunnits genom originalforskning. Dessa metoder integreras för att bilda en komplett uppsättning av multiplettberäkningsmetoder. Denna uppsättning av multiplettberäkningsmetoder kan utföra beräkningar av olika röntgenspektroskopier som XAS, XPS, XES och RIXS relaterade till elektroner på kärnenerginivån. Denna breda spektrum av spektroskopiska metoder som kopplas till olika multipletteteoretiska tillvägagångssätt fungerar som effektiva verktyg för att förstå den elektroniska strukturen hos metalliska platser och deras unika bidrag till materialets fysikaliska/kemiska egenskaper. Avhandlingen förbättrar på ett kreativt sätt den klassiska multiplettläran på flera områden: (1) förhållandet mellan kristallfältparametrar och lokala strukturfaktorer, (2) svårigheten med att hantera förgreningskedjor i punktgruppsymmetri för strukturer med låg symmetri, (3) först-principer-beräkning av semi-empiriska parametrar. Fyra metoder presenteras i denna avhandling: den första är den klassiska multiplettläran som omfattar multiplett-effekten, kristallfältseffekten och laddningsöverföringseffekten genom flera semi-empiriska parametrar som beskriver dessa effekter. Den andra multiplett-teoretiska tillvägagångssättet analyserar kristallfältspotensialmatrisen i olika symmetrier enligt reglerna för punktgruppsymmetri. Därefter kopplas de kristallfältseffektparametrar som används i den klassiska multiplettläran analytiskt till specifika strukturella faktorer som bindningslängd och vinklar. Detta tillvägagångssätt är ett bra verktyg för att studera strukturell distorsion från högre till lägre ordningssymmetri med analys av förändringar i röntgenspektrala funktionsändringar i experiment. Det tredje tillvägagångssättet använder en stor klustermetod som består av punktladdningar på ekvivalenta atompositioner för att simulera kristallfältsinverkan på metallcentralen. Detta tillvägagångssätt hanterar kristallfält med låg symmetri och lång räckvidd i multiplettberäkningar på ett enklare sätt än den klassiska multiplettläran. Det fjärde tillvägagångssättet studerar initialt det intressanta systemet med först-principer-beräkningar av elektronvågfunktioner. Därefter används dessa elektronvågfunktioner för att härleda maximalt lokaliserade Wannier-funktioner vid metall-/ligandpositioner. Analysen av dessa Wannier-funktioner ger många av de semi-empiriska parametrar som krävs i den klassiska multiplettberäkningsmetoden på ett först-principer-sätt. Detta tillvägagångssätt har i stor utsträckning löst problemet med att hitta den bästa uppsättningen semi-empiriska parametrar för att anpassa de beräknade röntgenspektrumen med experimentella data. För att studera de lättas elektroner (som C/N/O) runt centrala metalljoner introduceras även en teoretisk beräkningsmetod för att studera röntgenspektrum med vibrationell upplösning för kärnelektroner som ett kompletterande forskningsområde och tillämpas på beräkningar av C1s-kärnenerginivåns XPS som ett exempel. / <p>QC 2023-05-23</p>

L’augmentation de la consommation de ressources suscite des préoccupations quant à leur disponibilité. Ces dernières années, les organisations nationales et internationales ont défini l’approvisionnement durable des ressources et la mise en place d’une économie circulaire comme des objectifs centraux de leurs stratégies à court et long termes.Dans ce contexte, différentes approches méthodologiques relevant de l’Analyse du Cycle de Vie (ACV) sont utilisées pour caractériser l'impact de l'épuisement des ressources. Les approches actuelles fournissent néanmoins des visions partielles, car dépendantes de données disponibles limitées, et ne reflètent pas les défis de la société en lien avec cette question des ressources.La méthode et les facteurs nouvellement développés fournissent une vision plus exhaustive de la disponibilité des ressources et peuvent être utilisés dans des analyses du cycle de vie ou dans des approches d'économie circulaire. Ce travail fut produit en partenariat avec le cd2e et le pôle de compétitivité Team². Il a également été réalisé en collaboration avec le bureau d’études et d’expertise en ACV, Cycleco. / Increase in resource demand raises concerns over their availability. In the recent years, national and international institutions have targeted sustainable resource supply and new economy models (e.g. circular economy, etc.) as a goal of their short- and long-term strategies. In this context, different methodological approaches under Life Cycle Assessment (LCA) framework are used to address the impact of resource depletion. However, they provide partial visions, based on limited available data, and do not reflect society challenges related to the resources. The newly developed factors and the LCIA method provide a more exhaustive vision through the availability of resources and may be used in Life Cycle Assessment or circular economy approaches. This work is done in partnership with the cd2e and Team2 cluster. It is also carried out in collaboration with CYCLeco Life Cycle Assessment Experts.