928 resultados para rare earth element
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The final stage of Brasiliano/Pan-African orogeny in the Borborema Province is marked by widespread plutonic magmatism. The Serra da Macambira Pluton is an example of such plutonism in Seridó Belt, northeastern Borborema Province, and it is here subject of geological, petrographic, textural, geochemical and petrogenetic studies. The pluton is located in the State of Rio Grande do Norte, intrusive into Paleoproterozoic orthogneisses of the Caicó Complex and Neoproterozoic metassupracrustal rocks of the Seridó Group. Based upon intrusion/inclusion field relationships, mineralogy and texture, the rocks are classified as follows: intermediate enclaves (quartz-bearing monzonite and biotite-bearing tonalite), porphyritic monzogranite, equigranular syenogranite to monzogranite, and late granite and pegmatite dykes. Porphyritic granites and quartz-bearing monzonites represent mingling formed by the injection of an intermediate magma into a granitic one, which had already started crystallization. Both rocks are slightly older than the equigranular granites. Quartz-bearing monzonite has K-feldspar, plagioclase, biotite, hornblende and few quartz, meanwhile biotite-bearing tonalite are rich in quartz, poor in K-feldspar and hornblende is absent. Porphyritic and equigranular granites display mainly biotite and rare hornblende, myrmekite and pertitic textures, and zoned plagioclase pointing out to the relevance of fractional crystallization during magma evolution. Such granites have Rare Earth Elements (REE) pattern with negative Eu anomaly and light REE enrichment when compared to heavy REE. They are slight metaluminous to slight peraluminous, following a high-K calc-alkaline path. Petrogenesis started with 27,5% partial melting of Paleoproterozoic continental crust, generating an acid hydrous liquid, leaving a granulitic residue with orthopyroxene, plagioclase (An40-50), K-feldspar, quartz, epidote, magnetite, ilmenite, apatite and zircon. The liquid evolved mainly by fractional crystallization (10-25%) of plagioclase (An20), biotite and hornblende during the first stages of magmatic evolution. Granitic dykes are hololeucocratic with granophyric texture, indicating hypabissal crystallization and REE patterns similar to A-Type granites. Preserved igneous textures, absence or weak imprint of ductile tectonics, association with mafic to intermediate enclaves and alignment of samples according to monzonitic (high-K calcalkaline) series all indicate post-collisional to post-orogenic complexes as described in the literature. Such interpretation is supported by trace element discrimination diagrams that place the Serra da Macambira pluton as late-orogenic, probably reflecting the vanishing stages of the exhumation and collapse of the Brasiliano/Pan-African orogen.
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The tin dioxide is an n-type semiconductor, which exhibits varistor behavior with high capacity of absorption of energy, whose function is to restrict transitory over-voltages without being destroyed, when it is doped with some oxides. Varistors are used in alternated current fields as well as in continuous current, and it can be applied in great interval of voltages or in great interval of currents. The electric properties of the varistor depend on the defects that happen at the grain boundaries and the adsorption of oxygen. The (98.90-x)%SnO2.0.25%CoO+0.75%MnO2+0.05%Ta2O5+0.05%Tr2O3 systems, in which Tr=La or Nd. Current-voltage measurements were accomplished for determination of the non-linear coefficient were studied. SEM microstructure analysis was made to evaluate the microstructural characteristics of the systems. The results showed that the rare-earth oxides have influenced the electrical behavior presented by the system. (C) 2002 Kluwer Academic Publishers.
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Pós-graduação em Ciência e Tecnologia de Materiais - FC
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This study is concerned with speciation and fractionation of the rare earth elements (REE) and calcium (Ca) in aqueous solutions. The aim is to investigate the chemical states and physical sizes in which these elements can be present. The REE (including neodymium) and Ca have contrasting geochemical behavior in aqueous solutions. Ca is a major dissolved element, while the REE are trace components and highly reactive with aquatic particles. The major interests of the five papers included in this thesis are the following: · Papers I and V deal with the behavior of neodymium (Nd) and its isotopes in the Kalix River and some marine waters. · The diffusive gradients in thin-films (DGT) method is developed for measuring Ca and Mg in Paper II. · Paper III presents a speciation and fractionation study of Ca in the Kalix and Amazonian rivers. · The rare earth elements and their carrier phases are investigated in the Kalix river in Paper IV. For most elements a detailed study of speciation and fractionation can not be performed using only one method. This is due to the overall heterogeneity of the material, considering both size and chemical composition, which is present in aquatic solutions. During this project the aquatic geochemistry of the REE and Ca has been studied using mainly three methods; cross-flow filtration (CFF), field-flow fractionation (FFF) and diffusive gradients in thin-films (DGT). Field work has to a large part been conducted in the Kalix River, in northern Sweden, which is one of the last pristine river systems in Europe. Some field work has also been conducted in the Baltic Sea and the Arctic Ocean. Results from Amazonian rivers are also presented. These are the main conclusions from this work: The DGT technique works equally well for measuring Ca and Mg in natural waters as previously reported for trace metal. A significant colloidal phase for Ca could be detected in the Kalix River and in different Amazonian rivers. This was concluded independently using both CFF and FFF. Variations in REE signatures in the Kalix River suggests two different pathways for the REE during weathering and release form soil profiles and transport in the river. No significant variation in Nd-isotopic composition could be detected in the Kalix River although concentrations varied by a factor of ~10. This suggests that there is one major source for Nd in the river although different pathways for the REE may exist. A study of Nd in the Kalix River, the Baltic Sea and the Arctic Ocean showed that the isotopic compositions in the diffusible fractions were similar to water samples. However, the relative amount of diffusible Nd increased with salinity, probably reflecting the lower concentration of colloidal and particulate material in marine waters.
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Als paläoklimatische Archive können unter anderem Stalagmiten und Klappen von Ostrakoden herangezogen werden. Bisher gab es noch keine veröffentlichten Ergebnisse räumlich hochaufgelöster Spurenelementverteilungen in einzelnen Ostrakodenklappen. Das gleiche gilt für die Bestimmung radiogener Blei-Isotope in Stalagmiten. Um klimatische Prozesse vergangener Zeiten zu untersuchen, wurde eine neue LA-ICP-MS (Laserablations – Massenspektrometrie mit induktiv gekoppeltem Plasma) Technik für hochaufgelöste in-situ Messungen von Spurenelementen und Bleiisotopen entwickelt. rnrnZunächst wurden geeignete Materialien für die Kalibrierung der Technik untersucht; als Proben dienten die Silikatreferenzgläser BAM-S005-A und BAM-S005B der Bundesanstalt für Materialforschung und –prüfung (BAM). Die Homogenität dieser Referenzgläser wurde mit LA-ICP-MS und den anderen mikroanalytischen Methoden EPMA (Elektronenmikrosonde) und SIMS (Ionensonde) überprüft. Die Ergebnisse zeigten, dass alle Haupt- und die meisten Spurenelemente in beiden Gläsern selbst im Mikrometerbereich homogen verteilt sind. Ausnahmen sind einige Spurenelemente, wie Cs, Cl, Cr, Mo und Ni, die heterogen in den Gläsern verteilt sind. Die Hauptelementzusammensetzung von BAM-S005-A und BAM-S005-B wurde mit Hilfe der EPMA bestimmt, wobei die Ergebnisse die Referenzwerte des BAM-Zertifikats bestätigten. Mit Ausnahme von Sr, Ba, Ce und Pb, stimmten die LA-ICP-MS-Spurenelementwerte mit den zertifizierten Werten innerhalb der angegebenen Fehlergrenzen überein. Gründe für die Diskrepanz der vier oben erwähnten Elemente sind noch unklar, aber sind möglicherweise durch fehlerhafte Referenzwerte zu erklären. Zusätzlich wurden 22 Spurenelemente gemessen, deren Gehalte von BAM nicht zertifiziert wurden. Aufgrund dieser Untersuchungen konnte festgestellt werden, dass beide BAM-Gläser für mikroanalytische Anwendungen geeignet sind.rnrnUm neuartige paläoklimatische Proxies im Calcit von Ostrakoden aus tibetanischen Seesedimenten zu untersuchen, wurde die Spurenelementvariabilität in einzelnen Ostrakodenklappen durch eine neue LA-ICP-MS-Technik bestimmt. Klappen von Ostrakoden der drei Arten (Leucocytherella sinensis Huang, 1982, ?Leucocythere dorsotuberosa Huang, 1982 und ?L. dorsotuberosa f. postilirata sensu Pang, 1985) wurden aus zwei Sedimentkernen des Nam Co Sees auf dem Hochplateau von Tibet gewonnen. Zwei LA-ICP-MS-Varianten, Spot- bzw. Linienanalyse, wurden verwendet, um die Elementkonzentrationen der Spurenelemente Mg, Sr, Ba, U und die der Seltenen Erdelemente (SEE) in den Klappen einzelner Ostrakoden zu bestimmen. Die Ergebnisse zeigten, dass die Linienanalyse präzisere Daten als die Spotanalyse liefert und sie wurde daher vorgezogen. Signifikante Unterschiede in der Spurenelementzusammensetzung zwischen den verschiedenen Arten der Ostrakoden wurden nicht gefunden. Variationen der Elementverhältnisse Mg/Ca und Sr/Ca in den Klappen stimmen mit veröffentlichten Seenspiegelschwankungen während des Holozäns überein, was zeigt, dass Mg- und Sr-Messungen in den Ostrakoden zur Untersuchung paläohydrochemischer Prozesse in diesem Gebiet herangezogen werden kann. Die gute Korrelation, die in dieser Arbeit zwischen Ba/Ca und Sr/Ca gefunden wurde, ist ein Hinweis darauf, dass der Einbau von Ba und Sr in die Klappen durch den gleichen Mechanismus erfolgte. Eine mögliche Beziehung zwischen dem U/Ca-Verhältnis in den Ostrakoden und den Redoxbedingungen auf dem Boden des Sees in der Vergangenheit wird diskutiert. Relativ geringe und konstante La/Ca-Verhältnisse wurden festgestellt, deren Ursache möglicherweise entweder auf der SEE-Charakteristik des Seewassers, auf biologischen Prozessen in den Ostrakoden oder auf Kontamination von Fe-Mn und/oder organischen Substanzen beruhen. Weitere Untersuchungen an Proben aus diesem Gebiet, speziell Klappen von lebenden Ostrakoden, sind notwendig, um den Gehalt von Ba, U und den SEE in Ostrakoden als paläoklimatische Proxies von Umweltbedingungen zu verwenden.
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A swarm of minette and melanephelinite dikes is exposed over 2500 km2 in and near the Wasatch Plateau, central Utah, along the western margin of the Colorado Plateaus in the transition zone with the Basin and Range province. To date, 110 vertical dikes in 25 dike sets have been recognized. Strikes shift from about N80-degrees-W for 24 Ma dikes, to about N60-degrees-W for 18 Ma, to due north for 8-7 m.y. These orientations are consistent with a shift from east-west Oligocene compression associated with subduction to east-west late Miocene crustal extension. Minettes are the most common rock type; mica-rich minette and mica-bearing melanephelinite occurs in 24 Ma dikes, whereas more ordinary minette is found in 8-7 Ma dikes. One melanephelinite dike is 18 Ma. These mafic alkaline rocks are transitional to one another in modal and major element composition but have distinctive trace element patterns and isotopic compositions; they appear to have crystallized from primitive magmas. Major, trace element, and Nd-Sr isotopic data indicate that melanephelinite, which has similarities to ocean island basalt, was derived from small degree melts of mantle with a chondritic Sm/Nd ratio probably located in the asthenosphere, but it is difficult to rule out a lithospheric source. In contrast, mica-bearing rocks (mica melanephelinite and both types of minette) are more potassic and have trace element patterns with strong Nb-Ta depletions and Sr-Nd isotopic compositions caused by involvement with a component from heterogeneously enriched lithospheric mantle with long-term enrichment of Rb or light rare earth elements (REE) (epsilon Nd as low as - 15 in minette). Light REE enrichment must have occurred anciently in the mid-Proterozoic when the lithosphere was formed and is not a result of Cenozoic subduction processes. After about 25 Ma, foundering of the subducting Farallon plate may have triggered upwelling of warm asthenospheric mantle to the base of the lithosphere. Melanephelinite magma may have separated from the asthenosphere and, while rising through the lithosphere, provided heat for lithospheric magma generation. Varying degrees of interaction between melanephelinite and small potassic melt fractions derived from the lithospheric mantle can explain the gradational character of the melanephelinite to minette suite.
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Thirty-nine medium and fine grained sandstones from between 19,26 and 147,23 mbsf in the Cape Roberts-l core (CRP-1) were analysed for 10 major and 16 trace elements. Using whole-lock compositions, 9 samples were selected for analyses of mineral and glass grains by energy dispersive electron microscope. Laser-Ablation Mass-Spectrometry was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to examine their contribution to the bulk rock chemistry. Geochemical data reveal the major contribution played by the Granite Harbour Intrusives to the whole rock composition, even if a significant input is supplied by McMurdo volcanics and Ferrar dolerite pyroxenes McMurdo volcanics were studied in detail; they appeal to derive from a variety of litologies, and a dominant role of wind transpoitation from exposures of volcanic rocks may be inferred from the contemporary occurrence of different compositions at all depths. Only at 116.55 mbsf was a thin layer of tephra found, linked to an explosive eruption McMurdo volcanic rocks exhibit larger abundances at depths above 62 mbsf, in correspondence with the onset of volcanic activity in the McMurdo Sound area. From 62 mbsf to the bottom of the core, McMurdo volcanics are less abundant and probably issued from some centres in the McMurdo Sound region. However, available data do not allow the exclusion of wind transport from some eruptive centres active in north Victoria Land at the beginning of the Miocene Epoch.
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Sixty-four volcanic chists, sandstones and tephras between 5.95 and 618.19 meters below sea floor (mbsf) in the Cape Roberts Project cores 2 and 2A cores (CRP-2/2A) were examined for Cenozoic and Mesozoic volcanic components, using optical and Scanning Electron Microscopy. Minerals and glass shards in a selection of samples were analysed by electron microprobe fined with an EDAX detector. Laser-Ablation ICP-Mass-Spectrometry (ICP-MS) was used to determine rare earth elements and 14 additional trace elements in glass shards, pyroxenes and feldspars in order to pin-point the onset of McMurdo Volcanic Group (MVG) activity in the stratigraphic column. Pumices in tephra layers of peralkaline phonolite composition in Unit 7.2 -between 108 and 114 mbsf - were also analysed for trace elements by ICP-MS. This tephra unit is not reworked and its isotopic age (21.44 ± 0.05 Ma) is the age of deposition. The height of the eruptive column responsible for the deposition of the tephra was probably less than 8 km; the source was local, probably within 30 km from the drill site. Phonolite of unit 7.2 of CRP-2/2A has no direct petrogenetic relation with the peralkaline trachyte in the tephra-enriched layer of CRP-1 at 116.55 mbsf. Volcanic clasts and sand grains (glass shards, aegirine-augite, anorthoclase) related to Cenozoic activity of MVG were observed only starting from Unit 9.8, where they are dated at 24.22 ± 0.06 Ma at c. 280 mbsf. In this unit the lowest- occurring basaltic glass shard is found at 297.54 mbsf. Sampled McMurdo volcanics are generally vesicular and vary in composition from alkali basalt to trachyte and peralkaline phonolite. By contrast, below 320 mbsf, aphyric or slightly-porphyritic volcanic clasts become more abundant but they are all non-vesiculated, pigeconite and ilmenite-bearing basalts and dolerite of tholeiitic affinity. These rocks are considered to be related to lava flows and associated intrusions of Jurassic age (Kirkpatrick basalts and Ferrar dolerite). As in CRP-1, McMurdo volcanics appear to derive from a variety of lithologics. Besides glaciers, a dominant role of wind transportation from exposed volcanic rocks may be inferred from the contemporary occurrence of glass shards of different compositions at depths above 297.54 mbsf. These data confirm that the onset of magmatic activity in southern Victoria Land is considerably delayed (by about 24 Ma) with respect to northern Victoria Land.
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The basalts and oceanic andesites from the aseismic Ninetyeast Ridge display trachytic, vesicular and amygdaloidal textures suggesting a subaerial volcanic environment. The normative composition of the Ninetyeast Ridge ranges from olivine picriteto nepheline-normative alkaline basalt, suggesting a wide range of differentiation. This is further supported by the fractionation-differentiation trends displayed by transition metal trace elements (Ni, Cr, V and Cu). The Ninetyeast Ridge rocks are enriched in rare earth (RE) and large ion lithophile (LIL) elements and Sr isotopes (0.7043-0.7049), similar to alkali basalts and tholeiites from seamounts and islands, but different from LIL-element-depleted tholeiitic volcanic rocks of the recent seismic mid-Indian oceanic ridge. The constancy of 87Sr/86Sr ratios for basalts and andesites is compatible with a model involving fractional crystallization of mafic magma. The variation of 87Sr/86Sr ratios between 0.97 and 2.79 may possibly be explained in terms of a primordial hot mantle and/or chemically contrasting heterogeneous mantle source layers relatively undepleted in LIL elements at different periods in the geologic past. In general, the Sr isotopic data for rocks from different tectonic environments are consistent with a "zoning-depletion model" with systematically arranged alternate alkali-poor and alkali-rich layers in the mantle beneath the Indian Ocean.
Chemical composition and isotopic ratios of basic lavas from Iceland and the surrounding ocean floor
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Major and trace dement data are used to establish the nature and extent of spatial and temporal chemical variations in basalts erupted in the Iceland region of the North Atlantic Ocean. The ocean floor samples are those recovered by legs 38 and 49 of the Deep Sea Drilling Project. Within each of the active zones on Iceland there are small scale variations in the light rare earth elements and ratios such as K/Y: several central complexes and their associated fissure swarms erupt basalts with values of K/Y distinct from those erupted at adjacent centres; also basalts showing a wide range of immobile trace element ratios occur together within single vertical sections and ocean floor drill holes. Although such variations can be explained in terms of the magmatic processes operating on Iceland they make extrapolations from single basalt samples to mantle sources underlying the outcrop of the sample highly tenuous. 87Sr/86Sr ratios measured for 25 of the samples indicate a total range from 0.7028 in a tholeiite from the Reykjanes Ridge to 0.7034 in an alkali basalt from Iceland and are consistent with other published ratios from the region. A positive correlation between 87Sr/86Sr and Ce/Yb ratios indicates the existence of systematic isotopic and elemental variations in the mantle source region. An approximately fivefold variation in Ce/Yb ratio observed in basalts with the same 87Sr/86Sr ratio implies that different degrees and types of partial melting have been involved in magma genesis from a single mantle composition. 87Sr/86Sr ratios above 0.7028, Th/U ratios close to 4 and La/Ta ratios close to 10 distinguish most basalts erupted in this part of the North Atlantic Ocean from normal mid-ocean ridge basalt (N-type MORB) - although N-type MORB has been erupted at extinct spreading axes just to the north and northeast of Iceland as well as the presently active Iceland-Jan Mayen Ridge. Comparisons with the hygromagmatophile element and radiogenic isotope ratios of MORB and the estimated primordial mantle indicate that the mantle sources producing Iceland basalts have undergone previous depletion followed by more recent enrichment events. A veined mantle source region is proposed in preference to the mantle plume model to explain the chemical variations.
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Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO2 concentration in chert, often with final SiO2 >=98 wt%. This contrast in SiO2 (and Si/Al) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO2 concentrations and Si/Al ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO2, construct a chert composition which is essentially identical to observed SiO2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO2 concentration contrast seems caused by biogenic SiO2 dissolution and transport from the local adjacent host sediment and subsequent SiO2 reprecipitation in the chert. Along with SiO2, other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO/Al2O3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce/Ce* values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu/Eu* decreases slightly during formation of DSDP chert. Normative La/Yb is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE/Al ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.
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About 13 m of Cretaceous, tholeiitic basalt, ranging from normal (N-MORB) to transitional (T-MORB) mid-ocean-ridge basalts, was recovered at Ocean Drilling Program Site 843 west of the island of Hawaii. These moderately fractionated, aphyric lavas are probably representative of the oceanic basement on which the Hawaiian Islands were built. Whole-rock samples from parts of the cores exhibiting only slight, low-temperature, seawater alteration were analyzed for major element, trace element, and isotopic composition. The basalts are characterized by enrichment in the high field strength elements relative to N-MORB, by a distinct positive Eu anomaly, and by Ba/Nb and La/Nb ratios that are much lower than those of other crustal or mantle-derived rocks, but their isotope ratios are similar to those of present-day N-MORB from the East Pacific Rise. Hole 843A lavas are isotopically indistinguishable from Hole 843B lavas and are probably derived from the same source at a lower degree of partial melting, as indicated by lower Y/Nb and Zr/Nb ratios and by higher concentrations of light and middle rare earth elements and other incompatible elements relative to Hole 843B lavas. Petrographic and trace-element evidence indicates that the Eu anomaly was the result of neither plagioclase assimilation nor seawater alteration. The Eu anomaly and the enrichments in Ta, Nb, and possibly U and K relative to N-MORB apparently are characteristic of the mantle source. Age-corrected Nd and Sr isotopic ratios indicate that the source for the lavas recovered at ODP Site 843 was similar to the source for Southeast Pacific MORB. An enriched component within the Cretaceous mantle source of these basalts is suggested by their initial 208Pb/204Pb-206Pb/204Pb and epsilon-Nd-206Pb/204Pb ratios. The Sr-Pb isotopic trend of Hawaiian post-shield and post-erosional lavas cannot be explained by assimilation of oceanic crust with the isotopic composition of the Site 843 basalts.
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Petrographic and geochemical study of basalts in the Kerguelen Plateau basement revealed changes in composition and character of volcanism during development of this tectonovolcanic structure. The Kerguelen Plateau is one of the largest intraplate rises in the World Ocean. It started to form about 120 Ma ago. Age of basalts and overlying sediments shows that plateau formation was in the northwest direction. Basalts of the Kerguelen Plateau basement are products of tholeiitic melts in terms of geochemistry, but differ from mid-ocean ridge basalt (MORB). They are enriched in incompatible trace elements and rare earth elements (REE) relative to MORB, and degree of enrichment varies in basalts from different segments of the plateau. Composition of basalts does not directly depend on their age. Specific features of plateau magmatism are commonly explained in terms of a long-living deep magma plume, which variously interacted with a depleted upper mantle source at different stages of plateau formation. However, taking into account block morphology and deep structure of the plateau, one can suggest that plateau volcanism was initiated by a large fault. As the volcanism prograded to the northwest, depth of fault penetration into the mantle changed. Composition of basalts in the plateau basement was also governed by formation depth of primary melts.
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In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.
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Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.