The presence of the sea ice diatom biomarker IP25 in Arctic marine sediments has been used in previous studies as a proxy for past spring sea ice occurrence and as an indicator of wider palaeoenvironmental conditions for different regions of the Arctic over various timescales. The current study describes a number of analytical and palaeoceanographic developments of the IP25 sea ice biomarker. First, IP25 was extracted and purified from Arctic marine sediments. This enabled the structure of IP25 to be confirmed and enabled instrumental (GC-MS) calibrations to be carried out so that quantitative measurements could be performed with greater accuracy. Second, palaeo sea ice reconstructions based on IP25 and other biomarkers were carried out for a suite of sub-Arctic areas within the Greenland, Norwegian and Barents Seas, each of which represent contrasting oceanographic and environmental settings. Further, an evaluation of some combined biomarker approaches (e.g. the PIP25 and DIP25 indices) for quantifying and/or refining definitions of sea ice conditions was carried out. Temporally, particular emphasis was placed on the characterisation of sea ice conditions during the Younger Dryas and the Holocene. Some comparisons with other proxies (e.g. foraminifera, IRD) were also made. A study of a sediment core from Andfjorden (69.16˚N, 16.25˚E), northern Norway, provided unequivocal evidence for the occurrence of seasonal sea ice conditions during the Younger Dryas. The onset (ca. 12.9 cal. kyr BP) and end (ca. 11.5 cal. kyr BP) of this stadial were especially clear in this location, while in a study from the Kveithola Trough (74.52˚N, 16.29˚E), western Barents Sea, these transitions were less apparent. This was attributed to the presence of colder surface waters and the occurrence of seasonal sea ice both before and after this stadial at higher latitudes. Some regional differences regarding the severity of the sea ice conditions were also observed, although an overall general picture was proposed, with more severe sea ice conditions during the early-mid Younger Dryas and less sea ice observed during the late Younger Dryas. A shift in the climate towards ice-free conditions was recorded in northern Norway during the early Holocene (ca. 11.5 – 7.2 cal. kyr BP). Milder conditions were also observed during the Holocene in the western Barents Sea, with three main climate periods observed. During the early Holocene (ca. 11.7 – 9.5 cal. kyr BP), the position of the spring ice edge was close to the study area which resulted in high productivity during summers. During the mid-late Holocene (ca. 9.5 – 1.6 cal. kyr BP), sea ice was mainly absent due to an increased influence of Atlantic waters and northward movement of the Polar Front. During the last ca. 1.6 cal. kyr BP, sea ice conditions were similar to those of the present day. In addition to the outcomes obtained from the Norwegian-Barents Sea region, comparison of biomarker and other proxy data from 3 short cores from Kangerdlugssuaq Trough (Denmark Strait/SE Greenland) with historical climate observations allowed the development of a model of sea ice conditions which was then tested for longer time-scales. It is suggested that the IP25 in sediments from this region is likely derived from drift ice carried from the Arctic Ocean via the East Greenland Current and that two main sea surface scenarios have existed over the last ca. 150 yr. From ca. AD 1850 – 1910, near perennial sea ice conditions resulted in very low primary productivity, while from ca. AD 1910 – 1986, local sea ice conditions were less severe with increased drift ice and enhanced primary productivity. This two-component model was subsequently developed to accommodate different sea surface conditions that existed during the retreat of the Greenland Ice Sheet during the deglaciation (ca. 16.3 – 10.9 cal. kyr BP).

The West Pacific Warm Pool (WPWP) plays an important role in the global heat budget and global hydrologic cycle, so knowledge about its past variability would improve our understanding of global climate. Variations in WPWP precipitation are most notable during El Niño-Southern Oscillation events, when climate changes in the tropical Pacific impact rainfall not only in the WPWP, but around the globe. The stalagmite records presented in this dissertation provide centennial-to-millennial-scale constraints of WPWP precipitation during three distinct climatic periods: the Last Glacial Maximum (LGM), the last deglaciation, and the Holocene. In Chapter 2, the methodologies associated with the generation of U/Th-based absolute ages for the stalagmites are presented. In the final age models for the stalagmites, dates younger than 11,000 years have absolute errors of ±400 years or less, and dates older than 11,000 years have a relative error of ±2%. Stalagmite-specific 230Th/232Th ratios, calculated using isochrons, are used to correct for the presence of unsupported 230Th in a stalagmite at the time of formation. Hiatuses in the record are identified using a combination of optical properties, high 232Th concentrations, and extrapolation from adjacent U/Th dates. In Chapter 3, stalagmite oxygen isotopic composition (d18O) records from N. Borneo are presented which reveal millennial-scale rainfall changes that occurred in response to changes in global climate boundary conditions, radiative forcing, and abrupt climate changes. The stalagmite d18O records detect little change in inferred precipitation between the LGM and the present, although significant uncertainties are associated with the impact of the Sunda Shelf on rainfall d18O during the LGM. A millennial-scale drying in N. Borneo, inferred from an increase in stalagmite d18O, peaks at ~16.5ka coeval with timing of Heinrich event 1, possibly related to a southward movement of the Intertropical Convergence Zone (ITCZ). An inferred precipitation maximum (stalagmite d18O minimum) during the mid-Holocene in N. Borneo supports La Niña-like conditions and/or a southward migration of the ITCZ over the course of the Holocene as likely mechanisms for the observed millennial-scale trends. In Chapter 4, stalagmite Mg/Ca, Sr/Ca, and d13C records reflect hydrologic changes in the overlying karst system that are linked to a combination of rainfall variability and cave micro-environmental effects. Dripwater and stalagmite geochemistry suggest that prior calcite precipitation is a mechanism which alters dripwater geochemistry in slow, stalagmite-forming drips in N. Borneo. Stalagmite Mg/Ca ratios and d13C records suggest that the LGM climate in N. Borneo was drier and that ecosystem carbon cycling may have responded to the drier conditions. Large amplitude decadal- to centennial-scale variability in stalagmite Mg/Ca, Sr/Ca and d13C during the deglaciation may be linked to deglacial abrupt climate change events.

La transition entre le dernier épisode glaciaire et l'actuel interglaciaire (de 20 000 à 10 000 ans avant le présent) est caractérisée par de courtes et abruptes réorganisations du climat à différentes échelles. Sur l'Altiplano bolivien des paléolacs géants se développent et disparaissent en moins de 2000 ans. La dynamique des glaciers étant contrôlée par le climat, les dépôts laissés par les anciens glaciers constituent une des rares archives climatiques disponibles sur ce haut plateau aride. La méthode des âges d'exposition permet de reconstituer l'histoire des anciens glaciers. Cette thèse apporte de nouveaux outils méthodologiques pour le calcul de ces âges. Elle présente également de nouveaux âges couplés à des reconstructions climatiques. Ces résultats indiquent que la formation des paléolacs est concomitante de refroidissements moyens compris entre 2.5 et 4.5 C par rapport au présent et d'un apport accru d'humidité depuis l'Est, franchissant la Cordillère Orientale bolivienne / The transition between the last glacial maximum and the actual interstadial (from 20 to 12 ka before present) is characterized by short and abrupt climate reorganizations at different scales. Over the Bolivian Altiplano, giant palaeo-lakes wax and wane within 2000 years. The glaciers dynamics is controlled by the climate, making the deposits from the former glaciers one of the few climatic archives available on this arid plateau. The exposure age method enables to reconstruct the history of former glaciers. This thesis brings new tools for the calculation of these ages. It also presents new ages coupled with palaeo-climate reconstructions. These results indicates that the palaeo-lake formations are concomitant with mean coolings of 2.5 to 4.2°C compared to present and with an enhanced moist transport from the East, crossing the Bolivian Oriental Cordillera

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-04-03T16:44:03Z No. of bitstreams: 1 THIAGO ANDRADE DE SOUSA .pdf: 5768772 bytes, checksum: b3c4e1c52ed521e2c3772627711af6fa (MD5) / Made available in DSpace on 2017-04-03T16:44:03Z (GMT). No. of bitstreams: 1 THIAGO ANDRADE DE SOUSA .pdf: 5768772 bytes, checksum: b3c4e1c52ed521e2c3772627711af6fa (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica Ambiental. Niterói, RJ / Os sedimentos continentais depositados no fundo oceânico estão condicionados, majoritariamente, a evolução do clima, ao substrato geológico e ao tipo de transporte, sendo o transporte fluvial o de maior magnitude. Uma vez depositado, os sedimentos tornam-se registros do passado e carregam informações sob a forma de assinatura geoquímica. Os Elementos Terras Raras (ETR) apresentam um comportamento coerente ao longo de uma coluna sedimentar tornando-os útil nos estudos de proveniência sedimentar. Razões entre elementos maiores (Fe/Ca, por exemplo) são descritos na literatura como indicadores de reconstrução do aporto terrígeno. A geoquímica dos ETR e elementos maiores são determinados neste trabalho para o entendimento da dinâmica paleoclimática sobre o aporte e proveniência dos sedimentos da margem leste (Bacia de Santos) do Brasil, e as anomalias do Ce e Eu, confrontando técnicas analíticas distintas (ICP-MS e XRF core scanner) nos principais eventos abruptos (Younger Dryas e Heinrich events) ao longo dos últimos 45.000 anos. Igualmente é discutido a proveniência do material sedimentar por meio de razões entre Elementos Terras Raras leve (ETRL) e Elementos Terras Raras pesado (ETRP) comparando possíveis fontes disponíveis na literatura. O padrão de distribuição indica enriquecimento em ETRM sobre ETRL e ETRP em todos os eventos. Isso significa que a proveniência deste material, provavelmente, deve-se a uma única fonte. As concentrações dos ETRL são sempre maiores que ETRM e ETRP. Esse padrão é outro indicativo de fonte única do material sedimentar. O somatório das concentrações dos ETR durante o MIS 2 é sempre maior do que o MIS 1. O comportamento dos ETR durante os eventos Heinrich são bem similares. A média das concentrações dos ETR nestes eventos são superiores aos encontrados no MIS 1 – Interglacial. As análises das razões Fe/Ca e Ti/Ca pelas duas técnicas mostram-se coerentes e indicam maiores durante o MIS 2. Isto é devido ao aumento de chuvas na região (intensificação do SMAS), nível do mar regressivo (plataforma continental exposta) e por efeitos de diluição do carbonato marinho estimulada pela entrada de matéria orgânica. As razões Al/Si e Fe/K apresentam sinais distintos ao longo do testemunho deste estudo. O aumento de Si durante o MIS 2, em relação aos outros períodos, indica que o glacial foi menos úmido que o interglacial. O aumento de K dentro dos eventos Heinrich indica mudança no padrão de intemperismo continental devido aos episódios de chuvas e aumento no intemperismo químico nas bacias de drenagens. A anomalia do Ce é negativa em todos os períodos e indica condições oxidantes no ambiente deposicional ou oriundas de uma porção detrítica continental. A anomalia do Eu é ligeiramente positiva para todos os períodos. Isto é um indicativo de assimilação ou acúmulo de feldspato. Dados de cinco possíveis fontes para a proveniência do material foram extraídos da literatura. Os sedimentos de Cabo Frio apresentam fracionamento entre ETRL e ETRP próximos aos dados deste estudo. Entretanto, para a razão (Eu/Sm) observa-se boa correlação com fontes vindas da Patagônia e do Rio da Prata. Alguns autores apontam a pluma do Rio da Prata na contribuição sedimentar na região da Bacia de Santos. / The continental sediments deposited in the ocean floor are conditioned, mainly, to the evolution of the climate, the geological substrate and the type of transport, being the fluvial transport of the greater magnitude. Once deposited, the sediments become records of the past and carry information in a form of geochemical signature. Rare Earth Elements (REE) present a coercive behavior along a sedimentary column making them useful for studies of sedimentary origin. Ratios for larger elements (Fe/Ca, for example) are indicators of the reconstruction of the terrigenous port. The geochemistry of the ETR and major elements are determined in this work to understand the paleoclimatic dynamics on the contribution and provenance of the sediments of the eastern margin (Santos Basin) of Brazil, and the anomalies of the Ce and Eu, confronting different analytical techniques (ICP- MS and XRF core scanner) in the main abrupt events (Younger Dryas and Heinrich events) over the last 45,000 years. The origin of the sedimentary material is also discussed by means of ratios between Light Rare Earth Elements (LREE) and Heavy Rare Earth Elements (HREE) comparing possible sources available in the literature. The distribution pattern indicates MREE enrichment over LREE and HREE in all events. This means that the origin of this material, probably, is related to a single source. LREE concentrations are always higher than MREE and HREE. This pattern is another indicative of a single source of sedimentary material. The sum of REE concentrations during MIS 2 is always greater than MIS 1. The behavior of REE during Heinrich events is very similar. The mean REE concentrations in these events are higher than those found in MIS 1 - Interglacial. The analyses of Fe/Ca and Ti/Ca ratios are stronger than those observed during the investigation period (MIS) due to the regressive margin level (continental shelf exposed), and the effects of dilution of the marine carbonate stimulated by imput of organic matter. The Al/Si and Fe/K ratios show distinct signals over time during this study. The increase of Si during MIS 2, in relation to the other periods, indicates that the glacial was less humid than the interglacial. The increase of K within the Heinrich events indicates a change in the continental weather pattern due to rainfall episodes and increase in chemical weathering in the drainage basins. The Ce anomaly is negative at all periods and indicates oxidizing conditions in the depositional environment or from a continental detrital portion. The Eu anomaly is slightly positive for all periods. This is an indicative of assimilation or accumulation of feldspar. Data from five possible sources for a sample of the material was extracted from the literature. The Cabo Frio sediments show the fractionation between LREE and HREE. However, for a (Eu / Sm) ratio a good correlation is observed with sources coming from Patagonia and Rio de la Plata. Some authors point out a region of the River Plate and a sedimentary region in the region of the Santos Basin.

Testing Structural Changes Using Ratio Type Statistics Barbora Peštová Charles University in Prague, Faculty of Mathematics and Physics, Department of Probability and Mathematical Statistics, Czech Republic Abstract of the doctoral thesis We deal with sequences of observations that are naturally ordered in time and assume various underlying stochastic models. These models are parametric and some of the parameters are possibly subject to change at some unknown time point. The main goal of this thesis is to test whether such an unknown change has occurred or not. The core of the change point methods presented here is in ratio type statistics based on maxima of cumulative sums. Firstly, an overview of thesis' starting points is given. Then we focus on methods for detecting a gradual change in mean. Consequently, procedures for detection of an abrupt change in mean are generalized by considering a score function. We explore the possibility of applying the bootstrap methods for obtaining critical values, while disturbances of the change point model are considered as weakly dependent. Procedures for detection of changes in parameters of linear regression models are shown as well and a permutation version of the test is derived. Then, a related problem of testing a change in autoregression parameter is studied....

[pt] Umas das etapas mais complexas e críticas durante a construção de poços de petróleo é o processo de cimentação primária, definido como: O processo de instalação de cimento no anular entre o revestimento e a formação exposta ao poço [1]. Ela fornece isolamento zonal permanente para evitar contaminação ou migração de fluidos indesejáveis no anular, protege o revestimento da ocorrência de corrosão e fornece estabilidade hidráulica e mecânica para o revestimento ao longo da vida produtiva do poço de petróleo. Neste processo, ainda na etapa de perfuração, irregularidades na seção transversal (washouts) podem ser geradas como resultado de diversos colapsos parciais da seção do poço aberto em decorrência da presença de rochas pouco consolidadas da formação. Uma operação de cimentação primária bem sucedida dependerá se o sistema de fluidos espaçadores e a pasta de cimento deslocam de forma adequada e completa o fluido de perfuração do anular e washouts. Motivados por esse problema industrial, a presente dissertação usa um simulador numérico DNS (Direct Numerical Simulation) com o objetivo de analisar sistematicamente o comportamento hidrodinâmico e calcular a eficiência do deslocamento entre dois fluidos newtonianos miscíveis através de um anular contendo uma expansão seguida de uma contração abrupta. Investigamos como diferentes viscosidades e densidades dos fluidos, um injetado e outro deslocado, a miscibilidade entre eles, a taxa de injeção e a dimensão do washout retangular afetam o escoamento bifásico. Consideramos uma geometria axissimétrica durante processos de deslocamentos verticais, e as equações governantes são resolvidas em coordenadas cilíndricas, permitindo investigar diferentes aberturas anulares. Devido à miscibilidade entre os fluidos, nossos resultados preveem eficiências de deslocamento altíssimas, próximas a 100 Fluidos não-newtonianos são usualmente utilizados durante o processo industrial de cimentação primária de poços de petróleo. Contudo, as altas eficiências de deslocamentos encontradas em nossos resultados motivam estudos futuros sobre a influência da miscibilidade em deslocamentos de fluidos complexos. Estes resultados também motivam o uso de fluidos espaçadores para tentar controlar as propriedades de interface. Desta forma, é possível que a utilização de sistemas que se aproximem das condições reológicas e hidrodinâmicas de deslocamento entre fluidos newtonianos miscíveis poderá contribuir para um aumento da eficiência de deslocamento e, consequentemente, otimizar o processo de deslocamento de sistemas de fluidos, tendo em vista melhorias na integridade da cimentação de poços de petróleo. / [en] One of the most complex and critical stages during the construction ofoil wells is the primary cementing process, defined as the process of installingcement in the annulus between the casing and the exposed formation to thewell [1]. Primary cementing provides permanent zonal isolation to preventcontamination or migration of unwanted fluids in the annulus, protects thecasing from corrosion, and provides hydraulic and mechanical stability forthe casing throughout the productive life of the oil well. In this process,during the drilling stage, irregularities in the cross-section (washouts) can begenerated because of various partial collapses of the open wellbore section dueto the presence of poorly consolidated rocks in the formation. A successfulprimary cementing operation will depend on whether the spacer fluid systemand cement slurry adequately and completely displace the drilling fluid fromthe annulus and washouts.Motivated by this industrial problem, the present dissertation uses aDirect Numerical Simulation (DNS) numerical simulator to systematically analyze the hydrodynamic behavior and calculate the displacement efficiency between two miscible newtonian fluids through an annulus containing an expansion followed by an abrupt contraction. We investigate how different viscositiesand densities of the injected and displaced fluids, their miscibility, injectionrate, and the dimension of the rectangular washout affect the two-phase flow.We consider an axisymmetric geometry during vertical displacement processes,and the governing equations are solved in cylindrical coordinates, allowing theinvestigation of different annular clearances. Due to the miscibility betweenthe fluids, our results predict very high displacement efficiencies, close to 100Non-newtonian fluids are commonly used during the industrial processof primary cementing of oil wells. However, the high displacement efficienciesfound in our results motivate further studies on the influence of miscibilityin displacements of complex fluids. These results also encourage the use ofspacer fluids attempting to control the interfacial properties. Therefore, the useof systems that approximate the rheological and hydrodynamic conditions ofdisplacement between miscible newtonian fluids may contribute to an increasein displacement efficiency and, consequently, optimize the displacement processof fluid systems, aiming at improvements in the integrity of well cementing.