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.

Le but de cette étude est de retracer l’évolution de l’hydrologie dans la partie occidentale de l’Océan Pacifique subtropical en utilisant le proxy εNd analysé sur les foraminifères et sur les oxydes de ferromanganèse authigéniques dans les sédiments. Ceux-ci proviennent de carottes sédimentaires prélevées au nord de la Mer de Chine du Sud (MCS). Avant d’utiliser l’εNd dans les sédiments profonds de la MCS, 16 profils d’eau de mer, collectés au nord de la MCS et dans le Mer des Philippines, ont été analysés afin d’établir la distribution d’εNd des masses d’eau dans l’ouest du Pacifique tropical et dans la MCS, qui jusqu’à aujourd’hui n’était pas documentée. Les valeurs d’εNd des masses d’eau profondes et intermédiaires varient de -2,7 à -4,4 et augmentent légèrement avec la profondeur. Dans la mer des Philippines, les valeurs d’εNd de l’eau intermédiaire du Pacifique Nord (North Pacific Intermediate Water, NPIW) atteint -2.7±0.4 à moyenne profondeur (500 à 1400m). En-dessous de de 1800m, l’eau profonde Pacifique (Pacific Deep Water, PDW) est caractérisée par du Nd moins radiogénique (-4.1±0.5), indiquant l’intrusion de masses d’eau australes. Pour la plupart des stations du nord de la MCS, les masses d’eau en-dessous de 1500m (PDW) affichent des valeurs d’εNd homogènes (~ -4.1), similaires à celles de la PDW dans la Mer des Philippines. Les valeurs d'εNd pour l'eau intermédiaire de la mer de Chine du Sud (South China Sea Intermediate Water, SCSIW, 500-1500m) varient entre -3.0 et -3.9 dû au mélange vertical de la NPIW avec la PDW. Les valeurs d'εNd de l'eau de mer dans la MCS (-5.3 à -7.0) affichent des modifications locales dans des zones où l'eau s'écoule au-dessus de systèmes de dépôt sédimentaire. Ceci implique que "l'échange à la marge" avec des sédiments non radiogéniques (autour de -11) peut se produire dans le temps et dans l'espace sans modifier la composition isotopique du Nd de la PDW dans le Nord de la MCS. Dans un second temps, l’εNd extrait des foraminifères planctoniques G. ruber a été étudié sur la carotte MD05-2904, collectée à 2000m de profondeur sur la marge nord-ouest de la MCS. Cette étude a été conduite dans le but de retracer les variations hydrologiques depuis le Dernier Maximum Glaciaire (DMG) dans la partie occidentale du Pacifique Nord subtropical. Les enregistrements d'εNd ainsi obtenus couvrent les derniers 25 000 ans. Ils affichent une large gamme de valeurs de -4±0.2 à -6.7±0.3, suggérant d'importants changements dans la contribution de la NPDW (εNd=-4) et de la UCDW (Upper circumpolar Deep Water, εNd -6 to -8) dans la zone étudiée. Durant la déglaciation, les enregistrements d'εNd indiquent une diminution des excursions négatives de l'εNd impliquant une plus forte proportion de SSW (Southern-sourced Water) entre 17 et 15 ka BP ainsi qu'entre 10 et 8 ka BP. Ces intervalles de temps sont contemporains de l’évènement Heinrich 1 (HS1) et de l’Holocène inférieur. Les shifts négatifs centrés sur le HS1 coïncident avec un phénomène d'upwelling renforcé dans l'océan austral, associé à un déplacement vers le pôle des vents d'ouest. Ceci implique une augmentation de la formation de la SSW qui se propage dans l'Ouest du Pacifique subtropical. L'excursion négative de l'εNd durant l’Holocène inferieur (~10-8 cal ka BP) indique une plus grande proportion de SSW qui pourrait être associée avec une plus forte production de SSW, comme observé récemment dans l'atlantique Sud, et/ou avec une possible réduction de la NPIW. Nos données suggèrent que le schéma de circulation actuel dans la partie occidental du Pacifique subtropical s'est mis en place il y a 4600 ans. / The aim of this study is to reconstruct the evolution of the hydrology of the western subtropical North Pacific Ocean by using εNd proxy analysed on foraminifera and dispersed authigenic ferromanganese oxide precipitates in sediments from deep-sea cores collected in the northern SCS. Before using the εNd proxy on deep sea sediments of the SCS, Nd of 16 seawater profiles collected in the northern South China Sea (SCS) and the Philippine Sea were investigated to establish the εNd distribution of water masses along the tropical western Pacific and the SCS that, until now have not been documented. εNd values for mid- and deep-water masses of the Philippine Sea and the SCS range from -2.7 to -4.4 and generally increase slightly with water depth. In the Philippine Sea, εNd values for the North Pacific Intermediate Water (NPIW) reach- 2.7±0.4 at mid-depths (500 to 1400 m). Below ~1800 m, the Pacific Deep Water (PDW) is characterized by less radiogenic Nd (-4.1±0.5) indicating the instrusion of southern sourced water masses. For most of the stations in the Northern SCS, water masses below 1500m (PDW) display homogenous εNd values (~ -4.1) similar to those of the PDW in the Philippine Sea. εNd values for the South China Sea Intermediate Water (SCSIW, 500-1500m) vary from -3.0 to -3.9 as a result of the vertical mixing of the NPIW with the PDW in the SCS. Seawater εNd values for the SCS (~5.3 to -7.0) display local modification in areas where the water lies above sediment drift deposit systems. This implies that “boundary exchange” with unradiogenic sediments (around~11) may occur temporally and spatially and does not modify he Nd isotopic composition of the PDW in the Northern SCS. In a second step, seawater εNd extracted from cleaned planktonic foraminifera G. ruber has been investigated on core MD05-2904, collected at a deph of 2000m on the north-western margin of the SCS. This study was undertaken in order to reconstruct hydrological variations since the LGM in the western subtropical North Pacific. The εNd records obtained from foraminifera spanning the past 25kyr. Display a wide range of values, ranging from -4±0.2 to -6.7±0.3, suggesting important changes in the contribution of the NPDW (εNd=-4) and the UCDW (εNd -6 to -8) in the subtropical western Pacific. During the period of deglaciation, εNd records indicate a relative decrease in the negative excursions of the εNd implying a higher proportion of SSW during the time intervals 17-15 cal kyr BP and 10-8 cal kyr BP; these intervals are coeval with the HS1 and early Holocene. The negative shifts centered on the HS1coincide with an enhanced upwelling in the Southern Ocean, associated with a polewards shift of the southern westerlies, inducing an enhanced formation of the SSW that propagates to the subtropical western Pacific. The negative excursion of the εNd during the Early Holocene (~10-8 cal kyr BP) indicates a higher relative proportion of SSW that could be associate with higher production of the SSW, as has been recently observed in the South Atlantic, and/or with a possible reduction of the NPIW. Our data suggest that the present modern circulation pattern in the western subtropical Pacific Ocean was fully established after 4.6 cal kyr BP.