Thesis (M.S.)--University of North Carolina at Wilmington, 2003. / Vita.

Thesis (M.S.)--University of North Carolina at Wilmington, 2004. / Includes bibliographical references (leaves : [89]-95).

One of the more significant regional groupings to have emerged since the collapse of the Soviet Union is the wider Black Sea. Located at the jagged confluence of the Western, Orthodox and Muslim worlds, the region was quite frequently a violent meeting place, and thus instead of a bridge between civilizations, it has been a barrier. Even more compelling is how the presence of oil and gas has thrust the Black Sea into the world's view and contributed to the rush of external interest, and how this has helped develop a unique regional entity. Today, in an interconnected global economy, the region's position as a producer and conduit for fossil fuels makes it impossible to consider in isolation. More importantly, to succinctly define this dissertation's research question, it can be asked how does energy act as a transformational agent in the emergence of a Black Sea region? / Ph. D.

The thesis presents the results of a study of 1005 graffiti on 13th century Byzantine amphorae from a shipwreck in the Bay of Sudak near Novy Svet, Crimea, Ukraine. The primary goals of this thesis are 1) to provide an overview of the excavation and shipwreck, 2) to examine the importance of the Novy Svet wreck in terms of Black Sea maritime trade in the Late Byzantine period, 3) to present the data collected at the Center for Underwater Archaeology at the Taras Shevchenko National University in Kiev, Ukraine (CUA) about the graffiti inscribed on the Günsenin IV amphorae raised from the Novy Svet wreck and 4) to discuss the meaning and importance of the graffiti, both aboard the ship itself and in a more general context. The thesis introduces the results of the 2002-2008 underwater excavation seasons at Novy Svet. Excavators have identified a 13th century shipwreck filled with glazed ceramics and amphorae as a Pisan vessel sunk on August 14, 1277. The majority of the amphorae are Günsenin IV jars and have graffiti inscribed on them. Analysis of the graffiti focuses on the division of the marks into morphological categories, and identifying parallels for the specific forms at other archaeological sites. The graffiti are divided into 5 types; Greek/Cyrillic letters, Turkic runes, geometric or pictorial symbols, numerical designations, and Arabic letters. Their parallels speak to a multi-lingual, multi-ethnic trade network in the Black Sea that included Byzantine Greeks, Hellenized Bulgarians, and Arabs.

This dissertation analyses the phenomenon of regionalism around the Baltic and the Black Sea since the end of the Cold War with a comparative approach and by applying an extended neorealist theory that includes geopolitics and historical legacy. The main focus is regional organizations, the Council of the Baltic Sea States (CBSS) and the Black Sea Economic Cooperation (BSEC), which defines the geographical and political borders of the Baltic and the Black Sea region. These regional organizations are treated as international regimes. The three main varibales taken into consideration in this study are the distribution of power among the big states, the geographical location and the historical legacy that directly and indirectly affect the relations among the states in each region. These variables are consistently applied to the following  four sector analysed in this study: hard security, energy, economic development, and environment. While the last three sectors are areas of cooperation within the CBSS and the BSEC, hard security is not. Its inclusion in this study is because of the fact that it strongly affects the power relations among the states in the two regions and that it is strictly linked to the other three sectors. Although the CBSS and the BSEC have established ad hoc Working Groups with the aim to make cooperation working effectively, regional states cooperate to the extent that it brings relative gains according to the neorealist theory. The analysis shows that the two regimes created around the Balti and the Black Sea are ineffective despite the fact that the CBSS has managed to create stronger cooperative links among its members compared to the BSEC.

abstract: Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding of the diagenetic processes that may affect molybdenum and uranium isotopes entering the rock record. Using samples from the Black Sea water column, the first water column profile of 238U/235U variations from a modern euxinic basin has been measured. This profile allows the direct determination of the 238U/235U fractionation factor in a euxinic marine setting. More importantly however, these data demonstrate the extent of Rayleigh fractionation of U isotopes that can occur in euxinic restricted basins. Because of this effect, the offset of 238U/235U between global average seawater and coeval black shales deposited in restricted basins is expected to depend on the degree of local uranium drawdown from the water column, potentially complicating the interpretation 238U/235U paleorecords. As an alternative to the black shales typically used for paleoredox reconstructions, molybdenum and uranium isotope variations in bulk carbonate sediments from the Bahamas are examined. The focus of this work was to determine what processes, if any, fractionate molybdenum and uranium isotopes during incorporation into bulk carbonate sediments and their subsequent diagenesis. The results demonstrate that authigenic accumulation of molybdenum and uranium from anoxic and sulfidic pore waters is a dominant process controlling the concentration and isotopic composition of these sediments during early diagenesis. Examination of ODP drill core samples from the Bahamas reveals similar behavior for sediments during the first ~780ka of burial, but provides important examples where isolated cores and samples occasionally demonstrate additional fractionation, the cause of which remains poorly understood. / Dissertation/Thesis / Ph.D. Geological Sciences 2012

The northwestern (NW) continental shelf of the Black Sea undergoes seasonal hypoxia. The benthic environment, the exchanges at the water-sediment interface and the diagenetic reactions are influenced by this phenomenon. In the framework of the BENTHOX project, two field cruises were conducted on the shelf in spring 2016 and in summer 2017.The first part of this investigation concerned the study of the impact of low oxygen levels in bottom waters on the diagenetic reactions. The microprofilings of geochemical parameters and the flux measurements showed both spatial and temporal variabilities in the benthic compartment of the NW continental shelf for the two seasons studied. The areas closest to the coasts exhibited the most important fluxes of oxygen consumption and of sulfate. These regions were strongly influenced by riverine inputs inducing a higher productivity and in turn resulting in an increase in the fluxes of organic matter deposited on the seabed.The diagenetic reactions were impacted by seasonal deoxygenation in bottom waters. The oxic respiration was less important in the summer as reflected by the shallower penetration depth of dissolved oxygen. Since 1995, the diffusive oxygen uptake (DOU) reported during hypoxic period indicated that the concentration of dissolved oxygen played an important role in the benthic exchange fluxes. Furthermore, a shallower reduction of sulphate and of Mn- and Fe-oxides observed in the sediments evidenced the impact of low oxygen levels on the diagenetic cascade. As a consequence, the benthic mineralization of organic matter was affected. During summer 2017, the oxic mineralization of organic carbon was less important and the contribution of the reducing species to oxygen consumption increased. The anaerobic mineralization of organic matter became thus the dominant process during the period of deoxygenation.The second part concerned the study of the sulfur and iron cycling in the shelf sediments during the low oxygen event of summer 2017. The sediments from the station close to the mouth of the Danube and that near the Dnieper exhibited a signature of detrital material different from that of the upper crust. The inputs of organic matter, in particular transported by the rivers, could influence the signal. The sediments of the NW shelf investigated were however of marine origin.Following the sulfate reduction already observed and mentioned above, the hydrogen sulfides produced were rapidly consumed as suggested by the low concentrations of acid volatile sulfide (AVS) and of the dissolved sulfide. The presence of pyrite in the upper layers of the sediments close to the water-sediment interface was plausible because the formation of pyrite in the water column had been reported due to the higher resistance of pyrite to oxidation compared to AVS (Wijsman et al. 2001). A non steady-state deposition was observed as suggested by Wijsman et al. (1999). It was characterized by an abrupt drop in the pyrite content caused possibly by fluctuations in salinity, dissolved O2 concentrations and organic matter fluxes.The non-reactive iron constituted the principal fraction of the total iron present in the sediments. Its contribution fell in the range reported for the marine sediments of the continental margins. A spatial variation of the concentration of highly reactive iron was nevertheless observed. Near the Dnieper mouth, the contents of reactive iron were lower and could be attributed to the less important fluvial inputs, to the sorption and/or precipitation processes or yet to the reallocation of the reactive iron of the shelf deposits towards the sediments in deep and euxinic waters.The last part of this thesis concerned the biogeochemistry of metals (Fe, Mn, Zn, Cu, Ni, Hg, Co and Cd) during the early diagenesis and the assessment of enrichment and pollution of these metals in the sediments of the shelf. The results showed that trace metals are probably linked to iron and manganese oxides as well as to sulphides. Ni and Zn could be involved in adsorption onto and co-precipitation with Fe- and Mn-oxides. Cu seemed to be associated preferentially to sulphides but no clear correlation was found. The enrichment and pollution of these metals in the shelf sediments showed spatial variability. The Danube delta area was enriched in Ni, Cu and Zn while the Odessa region was enriched in Co and Cd. The pollution of shelf sediments ranged from “unpolluted” to “very highly polluted”. Since the late 20th century, the heavy metal contents in shelf sediments remained stable in the Odessa region but increased in the Danube delta area. / Le plateau continental du Nord-Ouest de la Mer Noire subit une hypoxie saisonnière. L'environnement benthique, l'échange à l'interface eau-sédiment et les réactions diagénétiques sont influencés par ce phénomène. Dans le cadre du projet BENTHOX, deux campagnes de prélèvement ont été menées sur le plateau au printemps 2016 et à l'été 2017 dans le but de comprendre ces changements.La première partie de cette recherche concerne l’impact des faibles concentrations en oxygène dans les eaux de fond sur les réactions diagénétiques. Les micro-profils de paramètres géochimiques et les mesures de flux ont montré des variabilités spatiales et temporelles dans le compartiment benthique pour les deux saisons étudiées. Les zones les plus proches des côtes ont présenté les flux les plus importants de consommation d'oxygène et de sulfate. Ces régions ont été fortement influencées par les apports fluviaux induisant une productivité plus élevée et entraînant à son tour une augmentation des flux de matière organique déposée sur le fond marin. Les réactions diagénétiques sont affectées par la désoxygénation saisonnière des eaux de fond. La respiration oxique etait moins importante en été comme en témoigne la profondeur de pénétration moins profonde de l’oxygène. Depuis 1995, l’absorption d’oxygène dissous (DOU) rapportée pendant la période limitée en oxygène a indiqué que la concentration d'oxygène dissous jouait un rôle important dans les flux d'échanges benthiques. De plus, une diminution de la profondeur à laquelle la réduction des sulfates et la réduction des oxydes métalliques témoigne de l'impact d'une faible concentration en oxygène sur la cascade diagénétique. En conséquence, la minéralisation benthique de la matière organique a été affectée. Au cours de l'été 2017, la minéralisation oxique du carbone a été moins importante et la contribution des espèces réductrices à la consommation d’oxygène a augmenté. La respiration anaérobie de la matière organique est ainsi devenue le processus dominant pendant la période d'hypoxie.La deuxième partie portait sur l'étude du cycle du soufre et du fer dans les sédiments du plateau lors de l'événement de faible teneur en oxygène de l'été 2017. Les sédiments de la station proche de l'embouchure du Danube et de celle du Dniepr présentaient une signature de matière détritique différente de celle de la croûte supérieure. Les apports de matière organique, notamment transportés par les rivières, pourraient influencer le signal. Les sédiments du plateau nord-ouest étudiés étaient cependant d'origine marine. Suite à la réduction du sulfate déjà observée et mentionnée ci-dessus, les sulfures d'hydrogène produits ont été rapidement consommés comme le suggèrent les faibles concentrations en sulfure acide volatil (AVS) et en sulfure dissous. La présence de pyrite dans les couches supérieures des sédiments près de l'interface eau-sédiment était plausible car la formation de pyrite dans la colonne d'eau avait été signalée en raison de la résistance plus élevée de la pyrite à l'oxydation par rapport à l'AVS (Wijsman et al. 2001). Un dépôt à l'état non stationnaire a été observé comme le suggèrent Wijsman et al. (1999). Elle a été caractérisée par une chute brutale de la teneur en pyrite causée peut-être par des fluctuations de salinité, des concentrations d'O2 dissous et des flux de matière organiqueLe fer non réactif constituait la fraction principale du fer total présent dans les sédiments. Sa contribution est tombée dans la gamme signalée pour les sédiments marins des marges continentales. Une variation spatiale de la concentration en fer hautement réactif a néanmoins été observée. Près de l'embouchure du Dniepr, les teneurs en fer réactif étaient plus faibles et pouvaient être attribuées aux apports fluviaux moins importants, aux processus de sorption et / ou de précipitation ou encore à la réallocation du fer réactif des dépôts du plateau vers les sédiments en profondeur et eaux euxiniques.La dernière partie de cette thèse concerne la biogéochimie des métaux (Fe, Mn, Zn, Cu, Ni, Hg, Co et Cd) lors de la diagenèse précoce et l'évaluation de l'enrichissement et de la pollution de ces métaux dans les sédiments du plateau. Les résultats ont montré que les métaux traces sont probablement liés aux oxydes de fer et de manganèse ainsi qu'aux sulfures. Ni et Zn pourraient être impliqués dans l'adsorption et la coprécipitation avec les oxydes de Fe et de Mn. Le Cu semble être associé préférentiellement aux sulfures mais aucune corrélation claire n'a été trouvée. L'enrichissement et la pollution de ces métaux dans les sédiments du plateau ont montré une variabilité spatiale. La zone du delta du Danube a été enrichie en Ni, Cu et Zn tandis que la région d'Odessa s'est enrichie en Co et Cd. La pollution des sédiments du plateau allait de « non polluée » à « très fortement polluée ». Depuis la fin du 20e siècle, la teneur en métaux lourds des sédiments du plateau est restée stable dans la région d'Odessa mais a augmenté dans la région du delta du Danube. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

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Doctorat en Sciences politiques et sociales / info:eu-repo/semantics/nonPublished