>Magister Scientiae - MSc / The present research deals with the characterization of the Lower Ecca Group in terms of sedimentology, mineralogy and organic geochemistry. A field study was conducted in order to characterize the sedimentology and thereby determine the environments of deposition of the Prince Albert, Whitehill and Collingham Formations. In addition, shale samples were subjected to geochemical and mineralogical analyses so as to ascertain its source rock properties. The study utilized X-ray diffraction (XRD), scanning electron microscopy with an energy dispersive spectrometer (SEM-EDS), total organic carbon (TOC) and Rock-Eval pyrolysis to determine the mineralogy and organic geochemistry of shale from the formations under investigation. The sedimentological investigation revealed that the upper Prince Albert Formation is dominated by shale with thin beds of carbonate. These shales are interpreted to have been deposited by suspension settling in a marine environment which was occasionally interrupted by deposition of carbonates that form in a shallow marine environment. The overlying Whitehill Formation consists predominantly of carbonaceous shale with relatively more resistant shale beds also present. The fine sediments are interpreted to have been deposited from suspension settling under anoxic bottom conditions which would favor the preservation of organic rich material. Deposition of the Whitehill Formation was followed by the Collingham Formation which is dominated by rhythmic deposits of shale and sandstone that are occasionally interrupted by tuff layers. The clay size sediments are interpreted to have been deposited from suspension settling which are interbedded with low density turbidite current deposits in a marine environment. Based on the findings of the field study, it is apparent that the Prince Albert and Collingham Formations were deposited in marine environments, with the Whitehill Formation being deposited in an anoxic environment. These environments are known to be dominated by phytoplanktonic organisms and algal debris, and as such shales deposited in these environments contain predominantly Type I (derived from algae) and II kerogen (derived from plankton). It can therefore be postulated that Type I and II kerogens are the dominant constituents of organic matter in the Lower Ecca Group shales. Mineralogically, the shales consist chiefly of kaolinite, smectite and illite clay minerals, which are derived from a combination of weathering of feldspars, and the alteration of other clay minerals. The latter being inferred from the existence of albite in all the studied shale samples, pyroclastic material observed in the field, as well as the occurrence of alteration along clay mineral edges.

Στόχος της παρούσας διατριβής είναι η μελέτη των ιζηματολογικών και γεωχημικών χαρακτηριστικών του νεογενούς σχηματισμού Μετόχια στην νήσο Γαύδο με κατεύθυνση την αναζήτηση πιθανών μητρικών πετρωμάτων υδρογονανθράκων. Στο πρώτο κεφάλαιο γίνεται βιβλιογραφική ανασκόπηση της γεωλογίας της περιοχής μελέτης καθώς και γενικότερα της λεκάνης Μεσσαρά-Γαύδου, περιγραφή της τομής δειγματοληψίας και τέλος της γεωδυναμικής και παλαιογεωγραφικής εξέλιξης της ευρύτερης περιοχής. Στο δεύτερο κεφάλαιο καταρχήν πραγματοποιείται μια επιγραμματική αναφορά των συνθηκών που απαιτούνται για την γένεση πεδίων υδρογονανθράκων και κατόπιν δίνεται έμφαση στα χαρακτηριστικά του οργανικού υλικού που εγκλωβίζεται στα ιζήματα και στον τρόπο δημιουργίας των μητρικών πετρωμάτων. Στο τρίτο κεφάλαιο περιγράφονται οι γεωχημικές αναλύσεις που πραγματοποιήθηκαν. Το κεφάλαιο αυτό χωρίζεται σε δυο μέρη. Στο πρώτο περιγράφεται η ανάλυση ανθρακικού ασβεστίου και τα αποτελέσματα της. Στο δεύτερο μέρος παρουσιάζονται βιβλιογραφικά δεδομένα του ολικού οργανικού άνθρακα από την περιοχής της Μεσσαρά και τα αποτελέσματα της ανάλυσης του ολικού οργανικού άνθρακα καθώς και τα χαρακτηριστικά του οργανικού υλικού που προέκυψαν από την παρούσα διατριβή. Στο τέταρτο κεφάλαιο γίνεται μια περιγραφή των μεθόδων κοκκομετρικής ανάλυσης που χρησιμοποιήθηκαν, η σύγκριση των μεθόδων, τα αποτελέσματα και η σύγκριση των αποτελεσμάτων που προέκυψαν. Τέλος στο πέμπτο κεφάλαιο παρουσιάζονται τα αποτελέσματα της παρούσας διατριβής. / The aim of this thesis is to study the sedimentological and geochemical characteristics of the Neogene Metochia formation on the island of Gavdos towards the exploration for potential hydrocarbon source rocks. The first chapter is a review of the geology of the study area and generally the geology of the Messara-Gavdos basin, a description of the sampling section and the geodynamic and paleogeographic evolution of the area. In the second chapter a brief review of the conditions required for the genesis of hydrocarbons fields is provided, and then the characteristics of the organic material trapped in sediments and how source rock being creating, is emphasised. In the third chapter the geochemical analysis don are described. This chapter is divided into two parts. First part describes the analysis of the total calcium carbonate and the results obtained. Second part presents bibliographical data for total organic carbon from Messara area samples and the results of the total organic carbon analysis derived from this thesis, as well as the characteristics of organic material of the studied samples. The fourth chapter describes the grain-size analysis methods used in this thesis, a comparison of these methods, the results obtained and a comparison of them. Finally in the fifth chapter the outcomes of this thesis are presented.

Les Taillis à Très Courte Rotation sont une culture destinée à produire des plaquettes de bois énergie. L'objectif de la thèse était d'étudier l'impact des TTCR sur le fonctionnement des sols et de proposer des indicateurs de qualité. Cinq prélèvements ont été effectués chaque printemps et automne entre 2010 et 2012 sur les sols de quatre couples de TTCR et bandes enherbées, d'une forêt alluviale et d'un agrosystème, localisés dans la vallée de l'Aisne. Les paramètres suivants ont été mesurés: matières organiques, carbone total, capacité d'échange cationique et éléments échangeables, phosphore disponible, minéralisation du carbone et de l'azote, biomasse, abondance et diversité des communautés lombriciennes, abondance relative et diversité des communautés fongiques et bactériennes, activités enzymatiques, caractérisations physiques et chimiques des matières organiques. 6 années après la mise en place des TTCR, les densités fongiques et lombriciennes, la respiration basale, l'activité laccase étaient plus élevées dans les TTCR par rapport à l'agrosystème. Ces modifications peuvent être reliées aux changements quantitatifs et qualitatifs des matières organiques (augmentation du C/N, diminution de l'indice hydrogène). L'azote et le phosphore semblent être limitant mais les retours importants et le turn over rapide de la MO viennent tamponner les fortes exportations. Ces mesures ont conduit à la définition d'indicateurs et aboutissent à la proposition de trois indices : fertilité, activité biologique, abondance et diversité des communautés biologiques. L'utilisation des courbes de réponses principales confirme l'effet positif des TTCR sur la qualité du sol, observée avec le calcul d'indices synthétiques / Short Rotation Coppices (SRC) are a crop system intended to produce energy wood chips. This thesis aimed at assessing the impact of SRC on soil functioning and proposing quality indicators. Five samplings were performed in spring and autumn between 2010 and 2012 on plots including four couples of SRC and grassland, an alluvial forest and an agrosystem, in the Aisne valley. The following parameters were monitored: organic matter, total carbon, cation capacity exchange, available phosphorus, carbon and nitrogen basal respiration, earthworm biomass, density and diversity, fungal and bacterial density and diversity, enzymatic activity, physical and chemical organic matter characterisations. 6 years after conversion to SRC, earthworm and fungal density, basal respiration and laccase activity were higher in SRC soil compared to conventional agrosystem. These changes can be linked to qualitative and quantitative organic matter evolutions (increase of the C/N ratio and decrease of hydrogen index). Nitrogen and phosphorus seemed to be limiting factors for SRC crop yields. However, soil nutrient return and the good turnover of organic matter can buffer strong exportations. The measured parameters led to indicator definition and proposition of three indices: fertility, biological activity, density and diversity of biological communities. Principal response curves confirmed the positive effect of SRC on soil quality as observed with synthetic indices calculation

Soil organic matter (SOM) is highly important for soil quality and the global carbon cycle. SOM content is influenced by a complex interplay of many different factors such as time, climate, parent material, vegetation, and others. The effect of time is often studied using the chronosequence approach using a set of study sites differing in age but comparable in other soil-forming factors. The effect of other factors can be studied by comparing two or more chronosequences. An important assumption of these approaches is that the SOM quantification methods produce comparable results both among sites of each sequence and among different sequences. In this thesis, I explored the key factors in SOM accumulation and dealt with SOM quantification methods. I studied SOM accumulation in two model situations - in post-mining sites after open-cast coal and oil shale mining and in landslides in the Western Carpathians. The results of this thesis are summarized in one book chapter accepted for publication and four papers, out of which three have been published and one is prepared for publication in an international journal with impact factor. The key factor affecting the rate of SOM accumulation after a major disturbance is time. The accumulation rates found in the first 40 to 100 years in both post-mining sites...

Les sols de montagne représentent d'importants réservoirs de carbone (C) potentiellement vulnérables aux changements climatiques et changements d'usage qui les affectent de manière amplifiée. Or la grande variabilité de ces milieux, leur faible accessibilité ainsi que le manque d'outils de mesure appropriés limitent nos connaissances qui restent aujourd'hui très fragmentaires en ce qui concerne les stocks, la chimie et la réactivité du carbone organique des sols (COS). Ces informations sont pourtant nécessaires pour appréhender l'évolution de ces sols et de leur C dans ce contexte de changements globaux. Les objectifs de ce travail de thèse étaient (i) d'accéder à une meilleure compréhension de la nature, de la stabilité et de la vulnérabilité du COS dans une mosaïque d'écosystèmes des Préalpes calcaires (massif du Vercors), (ii) de rechercher des outils de caractérisation rapides et fiables adaptés à l'étude et au suivi du COS à l'échelle du paysage, et enfin (iii) de proposer des indices pour l'évaluation et le suivi de la qualité des sols en milieu de montagne. Dans un premier temps, nous avons testé l'application de la pyrolyse Rock-Eval pour l'étude du COS à grande échelle sur un ensemble d'unités écosystémiques. Nous avons ensuite comparé la pyrolyse Rock-Eval à deux techniques classiques d'étude de la matière organique du sol (MOS) : le fractionnement granulodensimétrique de la MOS et la spectroscopie moyen infrarouge. Ces approches analytiques couplées nous ont permis de quantifier les stocks de C à l'échelle de la zone d'étude et d'expliquer la stabilité et la vulnérabilité du COS sous des angles variés. Les facteurs responsables des patrons observés dans les différentes unités écosystémiques sont discutés. Ce travail a également confirmé la pertinence de l'outil Rock-Eval pour répondre aux objectifs fixés. Parallèlement, des approches biologiques nous ont permis d'évaluer l'importance de la composante microbienne dans ces sols. Enfin, des indices évaluant le statut organique des sols (stockage de COS, fertilité des sols, vulnérabilité du COS) sont proposés pour constituer des outils de gestion et d'aide à la décision. / Mountain soils are major reservoirs of carbon (C), potentially vulnerable to climate and land use changes that affect them significantly. However, the great variability of these soils, their limited accessibility and the lack of appropriate measurement tools restrict our knowledge. Today, our comprehension of the biogeochemistry of mountain soils remains very incomplete regarding stocks, chemistry and reactivity of soil organic carbon (SOC). Yet this information is necessary to understand the evolution of soil carbon in the current context of global change. The objectives of this work were (i) to gain a better understanding of the nature, stability and vulnerability of SOC in a mosaic of ecosystems in a calcareous massif in the Alps (Vercors massif), (ii) to search for fast and reliable characterization tools, suitable for the study and monitoring of COS at the landscape scale, and (iii) to propose indicators for the assessment and monitoring of soil quality in mountain regions. As a first step, we tested the application of Rock-Eval pyrolysis for the study of COS at large-scale on a set of ecosystem units. Then, we compared the Rock-Eval approach to two conventional techniques for soil organic matter (SOM) study: the particle-size fractionation of SOM, and the mid-infrared spectroscopy. These coupled analytical approaches allowed us to quantify C stocks across the study area, and explain the stability and the vulnerability of COS at various angles. Factors responsible for the patterns observed in the different eco-units are discussed. This work also confirmed the relevance of the Rock-Eval tool to achieve our previous objectives. Biological approaches allowed us to assess the significance of microbial pool in these soils. Finally, indices assessing the status of SOM (SOC storage, soil fertility, vulnerability COS) were proposed and constituted interesting management tools for decision-makers.

Le bassin de Jaca (Pyrénées espagnoles) est un exemple classique de bassins d’avant pays, où les grandes lignes du remplissage sédimentaire, ainsi que la chronologie des failles ont été très étudiées. Il reste toutefois à mieux comprendre la paléo-hydrologie et l’histoire thermique du bassin, de manière à proposer un modèle de circulation des fluides pendant sa mise en place et sa déformation (Paléocène-Oligocène). Pour ce faire, ce travail propose d’analyser la répartition de la fracturation, d’étudier les conditions de formation des veines syn-tectoniques et de caractériser la maturité de la matière organique sur l’ensemble du paléobassin d’avant-pays de Jaca, des zones internes vers les zones externes.L’analyse pétrographique, géochimique et microthermométrique des veines montre que la grande majorité des fluides minéralisateurs sont à l’équilibre isotopique et thermique avec l’encaissant. Dans le détail, nous avons identifié 2 événements principaux de formation de veines dans la zone interne du bassin (Sierras Interiores), que nous proposons d’associer au fonctionnement des failles majeures dans le socle. Nous suggérons que les fluides circulent le long des niveaux de décollements et sont expulsés sur de courtes distances (< 10 km), au travers des réseaux de fractures, vers le bassin d’avant-pays. Le reste du bassin enregistre principalement des fluides locaux, parfois associés à l’infiltration d’eau météorique. L’analyse des températures d’enfouissement (50°C à 250°C), qui inclut des données de Δ47, montre une organisation N-S relativement homogène depuis les Sierras Interiores (fenêtre à gaz) jusqu’aux Sierras Exteriores (immature), avec des anomalies longitudinales marquées. Les modélisations thermiques 1D sur 9 puits virtuels suggèrent que les températures maximales vers les Sierras Interiores peuvent résulter d’un enfouissement sédimentaire, dont une grande partie est érodée actuellement. Nous proposons que ces parties érodées correspondent à des dépôts tardi-orogéniques conglomératiques déposés à proximité de la zone axiale. Les données suggèrent une répartition non homogène de ces dépôts selon un axe E-W, impliquant des transferts sédimentaires plus complexes qu’habituellement discutés. Au vu de nos résultats et des précédentes études, le modèle paléohydrologique et thermique du bassin de Jaca, et à plus grande échelle, de la chaîne plissée sud-pyrénéenne, est compartimenté à la fois dans l’espace et dans le temps, en lien avec à la propagation latérale et frontale de la déformation, qui contrôle l’ouverture du système. Le modèle paléohydrologique et thermique de la chaîne plissée sud-pyrénéenne constitue donc un potentiel analogue aux chaînes plissées dont le raccourcissement résulte d’une convergence oblique. / The Jaca basin (Spanish Pyrenees) is a classical example of a foreland basin, where the sedimentary filling and the calendar of thrust activation have been extensively studied. It remains to understand the paleohydrology and the thermal history of the basin, so as to provide a fluid flow model related to its formation and deformation (Paleoecene-Oligocene). To do this, this work proposes to analyze the distribution of fracturing, to study the conditions of formation of syn-tectonic veins and to characterize the maturity of organic matter throughout the Jaca foreland basin, from hinterland to external areas.Petrographical, geochemical and microthermometric analysis of veins show that the vast majority of mineralizing fluids are at the isotopic and thermal equilibrium with the host-rock. In detail, we identified two main events of vein precipitation in the inner part of the basin (Sierras Interiores), probably related to major basement thrust activations. We suggest that fluids flow along decollement levels and are expelled over short distances (<10 km), through fracture networks towards the foreland basin. The other part of the basin mainly record local fluids, sometimes associated with the infiltration of meteoric water. Analysis of burial temperatures (50 °C to 250 °C), which includes Δ47 data, shows a relatively homogeneous N-S organization from the Sierras Interiores (gas window) to Sierras Exteriores (immature), with strong longitudinal anomalies. Thermal 1D modelling of 9 virtual wells suggest that the maximum temperatures of Sierras Interiores result from sedimentary accumulation, whose a large amount is now eroded. We propose that this eroded thickness corresponds to late-orogenic conglomeratic deposits near the axial zone. The data suggest an inhomogeneous distribution of the deposits along an E-W axis, involving more complex sedimentary transfers than usually discussed. Given our results and previous studies, the paleohydrological and thermal model of the Jaca basin, and on a larger scale, of the South Pyrenean fold and thrust belt, is compartmentalized both in space and in time, in response to the propagation of and oblique deformational front, which controls the opening of the system. The paleohydrological and thermal model of the South Pyrenean fold and thrust belt is therefore a potential analogue to fold and thrust belt including shortening due to an oblique convergence.

Using a comparative spatial and temporal analysis on sediment cores from 8 lakes in the Mackenzie River Delta uplands region, NT, Canada, this study assessed how persistent organic pollutant (POP) deposition to lake sediments was affected by: (1) the presence of retrogressive thaw slumps on lake shores; and (2) changes occurring with increased autochthonous primary productivity. POPs examined included polychlorinated biphenyls (PCBs), penta- and hexachlorobenzenes (CBzs), and dichlorodiphenyltrichloroethane and metabolites (DDTs). Surface sediments of slump-affected lakes contained higher total organic carbon (TOC)-normalized POP concentrations than nearby reference lakes unaffected by thaw slumps. Inorganic sedimentation rates were positively related to contaminant concentrations, suggesting that the influx of siliciclastic material reducing organic carbon in slump-affected lake water indirectly results in higher concentrations of POPs on sedimentary organic matter. This explanation was corroborated by an inverse relationship between sedimentary POP concentrations and TOC content of the lake water. Deposition proxies of autochthonous carbon were not significantly correlated to POP fluxes of surface sediments, and historical profile fluctuations did not coincide with variation in POP deposition. Thus this study does not support the contention that algal-derived organic carbon increases the delivery of organic pollutants to sediments (the algal-scavenging hypothesis), as previously proposed for mercury. Higher POP concentrations observed in surface sediments of slump-affected lakes are best explained by simple solvent switching processes of hydrophobic contaminants onto a lower pool of available organic carbon when compared to neighbouring lakes unaffected by thaw slump development.

Using a comparative spatial and temporal analysis on sediment cores from 8 lakes in the Mackenzie River Delta uplands region, NT, Canada, this study assessed how persistent organic pollutant (POP) deposition to lake sediments was affected by: (1) the presence of retrogressive thaw slumps on lake shores; and (2) changes occurring with increased autochthonous primary productivity. POPs examined included polychlorinated biphenyls (PCBs), penta- and hexachlorobenzenes (CBzs), and dichlorodiphenyltrichloroethane and metabolites (DDTs). Surface sediments of slump-affected lakes contained higher total organic carbon (TOC)-normalized POP concentrations than nearby reference lakes unaffected by thaw slumps. Inorganic sedimentation rates were positively related to contaminant concentrations, suggesting that the influx of siliciclastic material reducing organic carbon in slump-affected lake water indirectly results in higher concentrations of POPs on sedimentary organic matter. This explanation was corroborated by an inverse relationship between sedimentary POP concentrations and TOC content of the lake water. Deposition proxies of autochthonous carbon were not significantly correlated to POP fluxes of surface sediments, and historical profile fluctuations did not coincide with variation in POP deposition. Thus this study does not support the contention that algal-derived organic carbon increases the delivery of organic pollutants to sediments (the algal-scavenging hypothesis), as previously proposed for mercury. Higher POP concentrations observed in surface sediments of slump-affected lakes are best explained by simple solvent switching processes of hydrophobic contaminants onto a lower pool of available organic carbon when compared to neighbouring lakes unaffected by thaw slump development.