Nd and Pb isotopes in ferromanganese crusts

The intensity of North Atlantic Deep Water (NADW) production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate. Here we present a new approach to reconstruct the overall strength of NADW export from the North Atlantic to the Southern Ocean over the past 14 Myr applying the deep water Nd and Pb isotope composition as recorded by ferromanganese crusts and nodules. We present the first long-term Nd and Pb isotope time series for deep Southern Ocean water masses, which are compared with previously published time series for NADW from the NW Atlantic Ocean. These data suggest a continuous and strong export of NADW, or a precursor of it, into the Southern Ocean between 14 and 3 Ma. An increasing difference in Nd and Pb isotope compositions between the NW Atlantic and the Southern Ocean over the past 3 Myr gives evidence for a progressive overall reduction of NADW export since the onset of Northern Hemisphere glaciation (NHG). The Nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37% depending on location.

Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Pb isotopes in individual sand-sized (>150 µm) ice-rafted feldspars deposited at subpolar North Atlantic Ocean Deep Sea Drilling Project Site 611 during the late Pliocene (Marine Isotope Stages, MIS, G6 through 100)

The onset of abundant ice-rafted debris (IRD) deposition in the Nordic Seas and subpolar North Atlantic Ocean 2.72 millions of years ago (Ma) is thought to record the Pliocene onset of major northern hemisphere glaciation (NHG) due to a synchronous advance of North American Laurentide, Scandinavian and Greenland ice-sheets to their marine calving margins during marine isotope stage (MIS) G6. Numerous marine and terrestrial records from the Nordic Seas region indicate that extensive ice sheets on Greenland and Scandinavia increased IRD inputs to these seas from 2.72 Ma. The timing of ice-sheet expansion on North America as tracked by IRD deposition in the subpolar North Atlantic Ocean, however, is less clear because both Europe and North America are potential sources for icebergs in this region. Moreover, cosmogenic-dating of terrestrial tills on North America indicate that the Laurentide Ice Sheet did not extend to ~39°N until 2.4 ±0.14 Ma, at least 180 ka after the onset of major IRD deposition at 2.72 Ma. To address this problem,we present the first detailed analysis of the geochemical provenance of individual sand-sized IRD deposited in the subpolar North Atlantic Ocean between MIS G6 and 100 (~2.72-2.52 Ma). IRD provenance is assessed using laser ablation lead (Pb) isotope analyses of single ice-rafted (>150 mm) feldspar grains. To track when an ice-rafting setting consistent with major NHG first occurred in the North Atlantic Ocean during the Pliocene intensification of NHG (iNHG), we investigate when the Pb-isotope composition (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb) of feldspars deposited at DSDP Site 611 first resembles that determined for IRD deposited at this site during MIS 100, the oldest glacial for which there exists convincing evidence for widespread glaciation of North America. Whilst Quaternary-magnitude IRD fluxes exist at Site 611 during glacials from 2.72 Ma, we find that the provenance of this IRD is not constant. Instead, we find that the Pb isotope composition of IRD at our study site is not consistent with major NHG until MIS G2 (2.64 Ma). We hypothesise that IRD deposition in the North Atlantic Ocean prior to MIS G2 was dominated by iceberg calving from Greenland and Scandinavia. We further suggest that the grounding line of continental ice on Northeast America may not have extended onto the continental shelf and calved significant numbers of icebergs to the North Atlantic Ocean during glacials until 2.64 Ma.

Nd, Sr and Pb isotopes and clay minerals in sediment cores from the Gulf of Cadiz and the Portuguese margin

The assemblages of marine sediments on the SW Iberian shelf have been controlled by contributions from distinct sources, which have varied in response to environmental changes since the Last Glacial Maximum (LGM). The rapid, decadal scale Mediterranean overturning circulation permits mixing of suspended particles from the entire Mediterranean Sea. They are entrained into the suspended particulate matter (SPM) carried by Mediterranean Outflow Water (MOW), which enters the eastern North Atlantic through the Strait of Gibraltar and spreads at intermediate depths in the Gulf of Cadiz and along the Portuguese continental margin. Other major sediment sources that have contributed to the characteristics and budget of SPM along the flow path of MOW on the SW Iberian shelf are North African dust and river-transported particles from the Iberian Peninsula. To reconstruct climate- and circulation-driven changes in the supply of sediments over the past ~23000 cal yr B.P., radiogenic Nd, Sr and Pb isotope records of the clay-size sediment fraction were obtained from one gravity core in the Gulf of Cadiz (577 m water depth) and from two gravity cores on the Portuguese shelf (1745 m, 1974 m water depth). These records are supplemented by time series analyses of clay mineral abundances from the same set of samples. Contrary to expectations, the transition from the LGM to the Holocene was not accompanied by strong changes in sediment provenance or transport, whereas Heinrich Event 1 (H1) and the African Humid Period (AHP) were marked by significantly different isotopic signatures reflecting changes in source contributions caused by supply of ice rafted material originating from the North American craton during H1 and diminished supply of Saharan dust during the AHP. The data also reveal that the timing of variations in the clay mineral abundances was decoupled from that of the radiogenic isotope signatures.

Terrane transfer during the Grenville orogeny: tracing the Amazonian ancestry of southern Appalachian basement through Pb and Nd isotopes

Whole rock Pb isotope data can be used to determine the provenance of different blocks within the Rodinia supercontinent, providing a test for paleogeographic reconstructions. Calculated isotopic values for the source region of the Grenville-deformed SW Amazon craton (Rondonia, Brazil), anchored by published U-Pb zircon ages, are compared to those from the Grenville belt of North America and Grenvillian basement inliers in the southern Appalachians. Both the SW Amazon craton and the allochthonous Blue Ridge/Mars Hill terrane are defined by a similar Pb isotopic signature, indicating derivation from an ancient source region with an elevated U/Pb ratio. In contrast, the Grenville Province of Laurentia (extending from Labrador to the Llano Uplift of Texas) is characterized by a source region with a distinctly lower, time-integrated U/Pb ratio. Published U-Pb zircon ages (ca. 1.8 Ga) and Nd model ages (1.4-2.2 Ga) for the Blue Ridge/Mars Hill terrane also suggest an ancient provenance very different from the rest of the adjacent Grenville belt, which is dominated by juvenile 1.3-1.5 Ga rocks. The presence of mature continental material in rocks older than 1.15 Ga in the Blue Ridge/ Mars Hill terrane is consistent with characteristics of basement rocks from the SW Amazon craton. High-grade metamorphism of the Blue Ridge/Mars Hill basement resulted in purging of U, consistent with observations of the rest of the North American Grenville province. In contrast, the Grenvillian metamorphic history of the Amazon appears to have been much more heterogeneous, with both U enrichment and U depletion recorded locally. We propose that the Blue Ridge/ Mars Hill portion of the Appalachian basement is of Amazonian provenance and was transferred to Laurentia during Grenvillian orogenesis after similar to1.15 Ga. The presence of these Amazonian rocks in southeastern Laurentia records the northward passage of the Amazon craton along the Laurentian margin, following the original collision with southernmost Laurentia at ca. 1.2 Ga. (C) 2004 Elsevier B.V. All rights reserved.

Nd, Pb and Sr isotopes in sediment cores from the Gulf of Cadiz and the Portuguese margin

Mediterranean Outflow Water (MOW) is characterised by higher temperatures and salinities than other ambient water masses. MOW spreads at water depths between 500 and 1500 m in the eastern North Atlantic and has been a source of salinity for the Atlantic Meridional Overturning Circulation in the North Atlantic. We used high-resolution Nd and Pb isotope records of past ambient seawater obtained from authigenic ferromanganese coatings of sediments in three gravity cores at 577, 1745 and 1974 m water depth in the Gulf of Cadiz and along the Portuguese margin complemented by a selection of surface sediments to reconstruct the extent and pathways of MOWover the past 23 000 years. The surface and downcore Nd isotope data from all water depths exhibit only a very small variability close to the present day composition of MOW but do not reflect the present day Nd isotopic stratification of the water column as determined from a nearby open ocean hydrographic station. In contrast, the Pb isotope records show significant and systematic variations, which provide evidence for a significantly different pattern of the MOW pathways between 20 000 and 12 000 years ago compared with the subsequent period of time.

Tracking the magmatic evolution of island arc volcanism : insights from a high-precision Pb isotope record of Montserrat, Lesser Antilles

The volcanic succession on Montserrat provides an opportunity to examine the magmatic evolution of island arc volcanism over a ∼2.5 Ma period, extending from the andesites of the Silver Hills center, to the currently active Soufrière Hills volcano (February 2010). Here we present high-precision double-spike Pb isotope data, combined with trace element and Sr-Nd isotope data throughout this period of Montserrat's volcanic evolution. We demonstrate that each volcanic center; South Soufrière Hills, Soufrière Hills, Centre Hills and Silver Hills, can be clearly discriminated using trace element and isotopic parameters. Variations in these parameters suggest there have been systematic and episodic changes in the subduction input. The SSH center, in particular, has a greater slab fluid signature, as indicated by low Ce/Pb, but less sediment addition than the other volcanic centers, which have higher Th/Ce. Pb isotope data from Montserrat fall along two trends, the Silver Hills, Centre Hills and Soufrière Hills lie on a general trend of the Lesser Antilles volcanics, whereas SSH volcanics define a separate trend. The Soufrière Hills and SSH volcanic centers were erupted at approximately the same time, but retain distinctive isotopic signatures, suggesting that the SSH magmas have a different source to the other volcanic centers. We hypothesize that this rapid magmatic source change is controlled by the regional transtensional regime, which allowed the SSH magma to be extracted from a shallower source. The Pb isotopes indicate an interplay between subduction derived components and a MORB-like mantle wedge influenced by a Galapagos plume-like source.

Estudos de metais pesados e isótopos de Pb nos sedimentos da Baía de Sepetiba baseados em geoquímica e na distribuição pelas possíveis áreas fontes

A Baia de Sepetiba é uma laguna costeira separada do oceano por uma ilha barreira. Localiza-se a 60 km da cidade do Rio de Janeiro, em uma importante região geoeconômica do Brasil. O objetivo deste trabalho foi avaliar a distribuição espacial da contaminação dos metais Cu, Pb, V, Cr, Cd, Co, Ni e Zn nos sedimentos da Baia. O mapa das concentrações elaborado pelo método de lixiviação permitiu caracterizar anomalias ao entorno da foz do Rio Guandu, na área da Coroa Grande, do Porto de Itaguaí, da Ilha do Martins, e anomalias ao longo de faixa com direção NW-SE. Os resultados das concentrações totais indicam contaminação por Zn, Cd, próximo a Ilha da Madeira com Pb e Cr associados e Cu e Zn na Restinga de Marambaia, com Ni, Pb e Cr associados. Os resultados dos isótopos de Pb para as razões de 206Pb/207Pb entre 1,23 e 1,27 representam os resíduos industriais e ocorrem em duas áreas: na parte leste da Restinga e entre as Ilhas de Jaguanum e Itacuruçá. A leste/sudeste destas ilhas foi reportada uma razão ainda mais alta (1.30), ainda não identificável na literatura. As correntes marinhas desempenham a redistribuição dos sedimentos e metais associados na Baia, com transporte de oeste para leste da pluma sedimentar descarregada pelos rios. Os principais causadores da poluição da Baia de Sepetiba são uma pilha de rejeito de Zn abandonada, resíduos industriais e domésticos não tratados de forma eficaz, poluentes atmosféricos de siderúrgicas e veículos, e por ventura resíduos de atividades navais e militares.

Traçadores isotópicos (Pb) e concentrações de metais em sedimentos superficiais: ferramentas na caracterização da poluição no setor oeste da baía de Sepetiba-RJ (SE do Brasil)

Este estudo teve como objetivo principal utilizar os teores de elementos-traço e análise isotópica de Pb (204Pb,206Pb,207Pb,208Pb) como ferramentas na caracterização da poluição da Baía de Sepetiba-RJ. As coletas de sedimento superficiais de fundo foram realizadas em três campanhas, em novembro de 2010, no setor oeste da Baía de Sepetiba RJ. A malha amostral é composta por 66 amostras (BSEP 001 a BSEP 066) coletadas com busca-fundo Van Veen. O pré-processamento das amostras ocorreu no Laboratório Geológico de Preparação de Amostras do Departamento de Geologia da Universidade do Estado do Rio de Janeiro. A digestão parcial das amostras de sedimento (< 0.072 mm) para obtenção do teor parcial dos elementos-traço (Ag, As, Cd, Co, Cr, Cu, Li, Mn, Ni, Pb, Sr, U, Zn) e de isótopo de Pb (lixiviação) foi executada no Laboratório de Geoquímica Analítica do Instituto de Geociências da UNICAMP e a leitura foi executada através do ICP-MS. Já as análises das concentrações totais dos elementos-traço (inclusive, Hg) e de isótopos de Pb (dissolução total) foram realizadas no laboratório ACTLABS (Ontário-Canadá) através do ICP Varian Vista. As leituras isotópicas foram feitas somente nas amostras que apresentaram concentrações parciais de Pb, acima de 0,5 g/g, totalizando 21 estações. Pôde-se constatar a existência de um enriquecimento de elementos-traço no setor oeste da Baía de Sepetiba. As médias dos teores totais de Ag (0,4 g/g), Cd (0,76 g/g), Cu (62,59 g/g), Li (43,29 g/g), Ni (16,65 g/g), Pb (20,08 g/g), Sr (389,64 g/g) e Zn (184,82 g/g) excederam os limites recomendados ou valores naturais. Isto pode ser reflexo da influência antrópica na região, principalmente relacionada à atividade de dragagem e à permanência dos resíduos de minério da desativada companhia de minério Ingá, na Ilha da Madeira. Os mapas de distribuição da concentração dos metais-traço destacaram a presença de vários sítios de deposição ao longo do setor oeste da baía de Sepetiba, com destaque para a região entre a porção centro oeste da Ilha de Itacuruça e o continente; Saco da Marambaia e Ponta da Pombeba; e porção oeste da Ponta da Marambaia. As razões isotópicas 206Pb/207Pb da área estudada variaram entre 1,163 a 1,259 para dissolução total e 1,1749-1,1877 para técnica de lixiviação, valores considerados como assinaturas de sedimentos pós-industriais ou comparados à assinatura de gasolina. Ainda sobre a técnica de lixiviação, destaca-se que os sedimentos superficiais do setor oeste (206Pb/207Pb: 1,1789) da baía de Sepetiba apresentaram uma assinatura uniforme e menos radiogênica do que setor leste (206Pb/207Pb: 1,2373 e 1,2110) desta baía. Através da assinatura isotópica de Pb encontrada nesta região é possível destacar a pouca contribuição das águas oceânicas para esse sistema, entretanto, a circulação interna intensa das águas da baía permite a homogeneização destas. O emprego destes tipos de ferramentas no monitoramento ambiental da área mostrou-se bastante eficiente, sendo importante a continuidade desta abordagem de pesquisa a fim de auxiliar na implementação de um plano de manejo local.

Litogeoquímica, geocronologia (U-Pb) e geoquímica isotópica (Sr-Nd) dos granitoides do Domínio Cambuci (Faixa Ribeira) na região limítrofe dos Estados do Rio de Janeiro e Espírito Santo

Os granitoides do Domínio Cambuci, na região limítrofe entre os estados do Rio de Janeiro e Espírito Santo, foram separados em quatro principais grupos: (1) Complexo Serra da Bolívia (CSB) - Ortogranulitos e Ortognaisses Heterogêneos; Ortognaisse Cinza Foliado; e charnockitos da Região de Monte Verde (2) Leucogranitos/leucocharnockitos gnaissificados da Suíte São João do Paraíso (SSJP) (3) Granito Cinza Foliado (4) Leucogranito isotrópico. O CSB é caracterizado pelo magmatismo de caráter calcioalcalino do tipo I, oriundo em ambiente de arco vulcânico (Suíte Monte Verde) e retrabalhamento crustal (ortogranulitos leucocráticos). O Ortogranulito esverdeado fino, é considerado no presente estudo como rocha do embasamento para o Terreno Oriental, cristalizada durante o paleoproterozoico - Riaciano (2184,3 21 Ma) e recristalizada durante o evento metamórfico Brasiliano no neoproterozoico - Edicariano (607,2 1,5 Ma), cuja idade TDM é de 2936 Ma. O Ortogranulito leucocrático médio cristalizou-se no neoproterozoico Edicariano (entre 592 e 609 Ma) e idade TDM ca. 2100 Ma, ao qual apresenta registro de herança no paleoproterozoico. A Suíte Monte Verde caracteriza-se por um magmatismo calcioalcalino e a Suíte Córrego Fortaleza, por um magmatismo calcioalcalino de alto K, ambas com assinatura de arco magmático. Registram dois pulsos magmáticos, em no Neoproterozoico - Edicarano: um em 592 2 Ma, idade do charnoenderbito, com idade TDM 1797 Ma, e outro em 571,2 1,8 Ma (injeção de um charnockitoide). Para todas as rochas do CSB são registradas feições protomiloníticas, miloníticas e localmente ultramiloníticas. Os dados geoquímicos indicam que os granitoides da SSJP são da série calcioalcalina de alto K, gerados no Neoproterozoico (idades que variam desde 610,3 4,7 Ma até, 592,2 1,3 Ma. As idades TDM revelam valores discrepantes para duas amostras: 1918 Ma e 2415 Ma, sugerindo que tenham sido geradas de diferentes fontes. O Granito Cinza Foliado é da Série Shoshonítica, metaluminoso do tipo I e, de ambiência tectônica de granitos intraplaca. Entretanto, poderiam ter sido fomados em ambiente de arco cordilheirano, havendo contaminação de outras fontes crustais. Fato este pode ser confirmado pelas as idades TDM calculadas ≈ 1429 1446 Ma. O Leucogranito isotrópico ocorre em forma de diques de direção NW, possui textura maciça e é inequigranular. Dados geoquímicos revelam que são granitoides metaluminosos do tipo I da série shoshonítica, e, de acordo com a ambiência tectônica, são granitos intraplaca. O Leucogranito Isotrópico representa o magmatismo pós-colisional ao qual ocorreu entre 80 a 90 Ma de anos após o término do evento colisional na região central da Faixa Ribeira. O Leucogranito Issotrópico cristalizou-se no cambriano (512,3 3,3 Ma e 508,6 2,2 Ma) e com idades TDM ca. 1900

Nd and Pb isotope signatures on the Southeastern South American upper margin: Implications for sediment transport and source rocks

Neodymium and lead isotope values in sediment samples were used to interpret sediment transport and source rocks on the Southeastern South American upper margin. The sediments of the Argentinian margin exhibit an average epsilon(Nd) value of -1.9, indicating the influence of the Andean rocks as sediment sources. Sediments from the Rio de La Plata estuary show an average epsilon(Nd) value of -9.6 which is similar to that of the Southern Brazilian Upper Margin. Finally, sediments of Southeastern Brazil, which are associated with the transport of the Brazil Current exhibit an average epsilon(Nd) of -13.0. The Pb isotope signatures also confirm the differentiation of source rocks in the sedimentation of the study area. In addition, Pb isotopes helped to establish the extent of the influence of the Rio de La Plata on the sedimentation of the Southern Brazilian margin. In terms of Pb isotopes the sediments from the Rio de La Plata estuary and Southern Brazil are more radiogenic than those of Southeastem Brazil and the Argentinian margin. (c) 2007 Elsevier B.V. All rights reserved.