The geochemistry of late Archaean microbial carbonate: Implications for ocean chemistry and continental erosion history

Trace element concentrations and combined Sr- and Nd-isotope compositions were determined on stromatolitic carbonates (microbialites) from the 2.52 Ga Campbellrand carbonate platform (South Africa). Shale-normalised rare earth element and yttrium patterns of the ancient samples are similar to those of modern seawater in having positive La and Y anomalies and in being depleted in light rare earth elements. In contrast to modem seawater (and microbialite proxies), the 2.52 Ga samples lack a negative Ce anomaly but possess a positive Eu anomaly. These latter trace element characteristics are interpreted to reflect anoxic deep ocean waters where, unlike today, hydrothermal Fe input was not oxidised, and scavenged and rare earth elements were not coprecipitated with Fe-oxyhydroxides. The persistence of a positive Eu anomaly in relatively shallow Campbellrand platform waters indicates a dramatic reversal from hydrothermally dominated (Archaean) to continental erosion-dominated (Phanerozoic) rare earth element flux ratio. The dominant hydrothermal input is also expressed in the initial Sr- and Nd-isotope ratios. There is collinear variation in Sr-Nd systematics, which range from primitive values (Sr-87/Sr-86 of 0.702386 and epsilon (Nd) of +2.1) to more evolved crustal ratios. Mixing calculations show that the range in trace element ratios (e.g., Y/Ho) and initial isotope ratios is not a result of contamination by trapped sediment, but that the chemical band isotopic variation reflects carbonate deposition in an environment where different water masses mixed. Calculated Nd flux ratios yield a hydrothermal input into the 2.52 Ga oceans one order of magnitude larger than continental input. Such a change in flux ratio most likely required substantially reduced continental inputs, which could, in turn, reflect a plate tectonic causation (e.g., reduced topography or expansion of epicontinental seas). Copyright (C) 2001 Elsevier Science Ltd.

Lamproites from Gaussberg, Antarctica: Possible transition zone melts of Archaean subducted sediments

Petrogenetic models for the origin of lamproites are evaluated using new major element, trace element, and Sr, Nd, and Pb isotope data for Holocene lamproites from the Gaussberg volcano in the East Antarctic Shield. Gaussberg lamproites exhibit very unusual Pb isotope compositions (Pb-206/Pb-204 = 17.44-17.55 and Pb-207/Pb-204 = 15.56-15.63), which in common Pb isotope space plot above mantle evolution lines and to the left of the meteorite isochron. Combined with very unradiogenic Nd, such compositions are shown to be inconsistent with an origin by melting of sub-continental lithospheric mantle. Instead, a model is proposed in which late Archaean continent-derived sediment is subducted as K-hollandite and other ultra-high-pressure phases and sequestered in the Transition Zone (or lower mantle) where it is effectively isolated for 2-3 Gyr. The high Pb-207/Pb-204 ratio is thus inherited from ancient continent-derived sediment, and the relatively low Pb-206/Pb-204 ratio is the result of a single stage of U/Pb fractionation by subduction-related U loss during slab dehydration. Sr and Nd isotope ratios, and trace element characteristics (e.g. Nb/Ta ratios) are consistent with sediment subduction and dehydration-related fractionation. Similar models that use variable time of isolation of subducted sediment can be derived for all lamproites. Our interpretation of lamproite sources has important implications for ocean island basalt petrogenesis as well as the preservation of geochemically anomalous reservoirs in the mantle.

Depleted arc volcanism in the Alboran Sea and shoshonitic volcanism in Morocco: geochemical and isotopic constraints on Neogene tectonic processes

Samples of volcanic rocks from Alboran Island, the Alboran Sea floor and from the Gourougou volcanic centre in northern Morocco have been analyzed for major and trace elements and Sr-Nd isotopes to test current theories on the tectonic geodynamic evolution of the Alboran Sea. The Alboran Island samples are low-K tholeiitic basaltic andesites whose depleted contents of HFS elements (similar to0.5xN-MORB), especially Nb (similar to0.2xN-MORB), show marked geochemical parallels with volcanics from immature intra-oceanic arcs and back-arc basins. Several of the submarine samples have similar compositions, one showing low-Ca boninite affinity. Nd-143/Nd-144 ratios fall in the same range as many island-arc and back-arc basin samples, whereas Sr-87/Sr-86 ratios (on leached samples) are somewhat more radiogenic. Our data point to active subduction taking place beneath the Alboran region in Miocene times, and imply the presence of an associated back-arc spreading centre. Our sea floor suite includes a few more evolved dacite and rhyolite samples with (Sr-87/Sr-86)(0) up to 0.717 that probably represent varying degrees of crustal melting. The shoshonite and high-K basaltic andesite lavas from Gourougou have comparable normalized incompatible-element enrichment diagrams and Ce/Y ratios to shoshonitic volcanics from oceanic island arcs, though they have less pronounced Nb deficits. They are much less LIL- and LREE-enriched than continental arc analogues and post-collisional shoshonites from Tibet. The magmas probably originated by melting in subcontinental lithospheric mantle that had experienced negligible subduction input. Sr-Nd isotope compositions point to significant crustal contamination which appears to account for the small Nb anomalies. The unmistakable supra-subduction zone (SSZ) signature shown by our Alboran basalts and basaltic andesite samples refutes geodynamic models that attribute all Neogene volcanism in the Alboran domain to decompression melting of upwelling asthenosphere arising from convective thinning of over-thickened lithosphere. Our data support recent models in which subsidence is caused by westward rollback of an eastward-dipping subduction zone beneath the westemmost Mediterranean. Moreover, severance of the lithosphere at the edges of the rolling-back slab provides opportunities for locally melting lithospheric mantle, providing a possible explanation for the shoshonitic volcanism seen in northern Morocco and more sporadically in SE Spain. (C) 2004 Elsevier B.V. All rights reserved.

Late Jurassic oceanic crust and Upper Cretaceous Caribbean plateau picritic basalts exposed in the Duarte igneous complex, Hispaniola

Four distinct rock units have been recognized near El Aguacate, in the Janico-Juncalito-La Vega area of the Duarte complex (Dominican Republic): (1) serpentinites crosscut by numerous diabasic dikes, (2) basalts interbedded with Late Jurassic ribbon cherts, (3) picrites and ankaramites relatively enriched in incompatible trace elements, and (4) amphibolites and gneissic amphibolites chemically similar to Oceanic Plateau Basalts. Similar Ar-Ar ages of late magmatic amphibole from a picrite, and hornblende from an amphibolite (86.1 +/- 1.3 Ma and 86.7 +/- 1.6 Ma, respectively), suggest that the Duarte picrites are contemporaneous with the Deep Sea Drilling Program Leg 15 and Ocean Drilling Program Leg 126 basalts drilled from the Caribbean oceanic plateau. These basalts are associated with sediments containing Late Cretaceous faunas. Sr, Nd, and Pb data show that enriched picrites and amphibolites are isotopically similar to mafic lavas from previously described Caribbean plateau and Galapagos hotspot basalts. Major element, trace element, and lead isotopic features of Late Jurassic basalts and diabases are consistent with those of normal oceanic crust basalt. However, these basalts differ from typical N-MORB because they have lower epsilon Nd ratios that plot within the range of Ocean Island Basalts. These rocks appear to represent remnants of the Caribbean Jurassic oceanic crust formed from an oceanic ridge possibly close to a hotspot. Later, they were tectonically juxtaposed with Late Cretaceous slices of the Caribbean-Colombian plateau.

MPI-DING reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

[1] We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties ( at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive ( isotope dilution) and comparative bulk ( e. g., INAA, ICPMS, SSMS) and microanalytical ( e. g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented.

Petrology and chemistry of the Chalten Plutonic Complex and implications on the magmatic and tectonic evolution of the Southernmost Andes (Patagonia) during the Miocene

Résumé Scientific:Pétrologie et Géochimie du Complexe Plutonique de Chaltén et les conséquences pour l'évolution magmatique et tectonique du Andes du Sud (Patagonia) pendant le MiocèneLe sujet de cette thèse est le Complexe Plutonique de Chaltén (CHPC), situé à la frontière entre le Chili et l'Argentine, en Patagonie (49°15'S). Ce complexe s'est mis en place au début du Miocène, dans un contexte de changements tectoniques importants. La géométrie et la vitesse de migration des plaques en Patagonie a été modifiée suite l'ouverture de la plaque Farallon il y a 25Ma (Pardo-Casas and Molnar 1987) et la subduction de la ride active du Chili sous la plaque sud-américaine il y a 14Ma (Cande and Leslie 1986). Les effets de cette reconfiguration tectonique sur la morphologie et le magmatisme de la plaque supérieure sont encore sujets à discussion. Dans ce contexte, un groupe d'intrusions miocènes - telle que le CHPC - est particulièrement intriguant, car en position transitionnelle entre le batholithe patagonien et l'arc volcanique cénozoïque et récent à l'ouest, et les laves de plateau de Patagonie à l'est (Fig. 1). A cause de leur position tectonique transitoire, ces plutons isolés hors du batholithe représentent un endroit clé pour comprendre les interactions entre la tectonique à large échelle et le magmatisme en Patagonie. Ici, je présente de nouvelles données de terrain, petrologiques, géochimiques et géochronologiques dans le but de caractériser la nature du CHPC, qui était largement inconnu avant cette étude, dans le but de tester l'hypothèse de migration de l'arc et erosion par subduction.Les résultats de l'investigation géochimique (chapitre 2) montrent que le CHPC n'est qu'un exemple parmi les plutons isolés d'arrière arc ave une composition calco-alcaline caractéristique, c-à-d une signature d'arc. La plupart de ces plutons isolés ont une composition alcaline. Le CHPC, contrairement, a une signature calco-alcaline avec Κ intermédiaire, tel que le batholithe patagonien et la plupart des roches volcaniques quaternaires liées à l'arc le long des Andes.De nouvelles données géochronologiques U-Pb de haute précision sur des zircons, acquis par TIMS, sur le CHPC donnent des âges entre 17.0 et 16.4Ma. Les âges absolus sont en accord avec la séquence intrusive déduite des relations de terrain (chapitre 1). Ces données sont les premières contraintes d'âge U-Pb sur le CHPC. Elles montrent clairement que l'histoire magmatique du CHPC n'a pas de lien direct avec la subduction de la ride à cette latitude (Cande and Leslie 1986), car le complexe est au moins 6Ma plus ancien.Une comparaison en profondeur avec les autres intrusions d'âge Miocène en Patagonie révèlent - pour la première fois - une évolution temporelle intéressante. Il y a une tendance E-W distincte au magmatisme calco-alcalin entre 20-16Ma avec une diminution de l'âge vers l'est - le CHPC est l'expression la plus orientale de cette tendance. Je suggère que la relation espace-temps reflète une migration vers l'est (vers le continent) de l'arc magmatique. Je propose que le facteur principal contrôlant cette migration est la subduction rapide suite à la reconfiguration de la vitesse des plaques tectoniques après l'ouverture la plaque Farallon (à ~26Ma) qui résulterait en une déformation importante ainsi qu'à des taux élevés d'érosion dans la fosse de subduction.Les rapports d'isotopes radiogéniques (Pb, Sr, Nd) élevés, une signature 6018 basse et un rapport Th/La élevé sont des paramètres distinctifs pour les roches mafiques du CHPC. Le modèle isotopique présenté (chapitre 2) suggère que cette signature reflète une contamination de la source, dans le coin de manteau, plutôt qu'une contamination crustale. La signature des éléments en trace du CHPC indiquent que le coin de manteau a été contaminé par des composés terrigènes, le plus vraisemblablement par des sédiments paléozoïques.Les travaux de terrain, la pétrographie et la géothermobarométrie ont été utilisés dans le but de comprendre l'histoire interne du CHPC (chapitre 3). Ces données suggèrent deux niveaux distincts de cristallisation : l'un dans la croûte moyenne (6 à 4.5kbar) et l'autre à un niveau peu profond (3.5 à 2kbar). La modélisation isotopique AFC de la contamination crustale indique des taux variables d'assimilation, qui ne sont pas corrélés avec le degré de différenciation. Cela suggère que différents volumes de magma se sont différenciés en profondeur, de façon indépendante. Cela implique que le CHPC se serait formés en plusieurs puises de magmas provenant d'au moins trois sources différentes. Les textures des granodiorites et des granites indiquent des teneurs élevées en cristaux avant la mise en place et, par conséquent, des températures d'emplacement faibles. Les observations de terrain montrent que les roches mafiques sont déformées, alors que ce n'est pas le cas pour les granodiorites et granites (plus jeunes). La déformation des roches mafiques est encore sujet de recherche, afin de savoir si elle est liée à la déformation régionale en régime compressif ou à l'emplacement lui-même. Cependant, la mise en place de grand volume de magma felsique riche en cristaux suggère un régime d'extension.Scientific Abstract:Petrology and chemistry of the Chaltén Plutonic Complex and implications on the magmatic and tectonic evolution of the Southernmost Andes (Patagonia) during the MioceneThe subject of this thesis is the Chaltén Plutonic Complex (CHPC) located at the frontier between Chile and Argentina in Patagonia (at 49° 15 'Southern latitude). This complex intruded during early Miocene in a context of major tectonics changes. The plate geometry of Patagonia has been modified by changes in the plate motions after the break up of the Farallôn plate at 25Ma (Pardo-Casas and Molnar 1987) and by the subduction of the Chile spreading Ridge beneath South-America at 14 Ma (Cande and Leslie 1986). The effects of this tectonic setting on the morphology and the magmatism of the overriding plate are a matter of on-going discussion. Particularly intriguing in this context is a group of isolated Miocene intrusions - like the CHPC - which are located in a transitional position between the Patagonian Batholith and the Cenozoic and Recent volcanic arc in the West, and the Patagonian plateau lavas in the East (Fig. 1). Due to their transient tectonic position these isolated plutons outside the batholith represent a key to understanding the interaction between global-scale tectonics and magmatism in Patagonia. Here, I present new field, penological, geochemical and geochronological data to characterize the nature of the CHPC, which was largely unknown before this study, in order to test the hypothesis of time- transgressive magmatism.The results of the geochemical investigation (Chapter 2) show that the CHPC is only one among these isolated back-arc plutons with a characteristic calc-alkaline composition, i.e. arc signature. Most of these isolated intrusives have an alkaline character. The CHPC, in contrast, has a medium Κ calc-alkaline signature, like the Patagonian batholith and most of the Quaternary arc-related volcanic rocks along the Andes.New high precision TIMS U-Pb zircon dating of the CHPC yield ages between 17.0 to 16.4 Ma. The absolute ages support the sequence of intrusion relations established in the field (Chapter 1). These data are the first U-Pb age constraints on the CHPC, and clearly show that the magmatic history of CHPC has no direct link to the subduction of the ridge, since this complex is at least 6 Ma older than the time of collision of the Chile ridge at this latitude (Cande and Leslie 1986).An in-depth comparison with other intrusion of Miocene age in Patagonia reveals - for the first time - an interesting temporal pattern. There is a distinct E-W trend of calc-alkaline magmatism between 20-16 Ma with the younging of ages in the East - the CHPC is the easternmost expression of this trend. I suggest that this time-space relation reflects an eastward (landward) migration of the magmatic arc. I propose that main factor controlling this migration is the fast rates of subduction after the major reconfigurations of the plate tectonic motions after the break up of the Farallôn Plate (at -26 ) resulting in strong deformation and high rates of subduction erosion.High radiogenic isotope ratios (Pb, Sr, Nd) ratios, low 5018 signature and high Th/La ratios in mafic rocks are distinctive features of the CHPC. The presented isotopic models (Chapter 2) suggest that this signature reflects source contamination of the mantle wedge rather than crustal contamination. The trace element signature of the CHPC indicates that the mantle wedge was contaminated with a terrigenous component, most likely from Paleozoic sediments.Fieldwork, petrography and geothermobarometry were used to further unravel the internal history of the CHPC (Chapter 3). These data suggest two main levels of crystallization: one a mid crustal levels (6 to 4.5 kbar) and other a shallow level (3.5 to 2 kbar). Isotopic AFC modeling of crustal contamination indicate variable rates of assimilation, which are not correlated with the degree of differentiation. This suggests that different batches of magma differentiate independently at depths. This implies that the CHPC would have formed by several pulses of magmas from at least 3 different sources. Textures of granodiorites and granites indicate a high content of crystals previous to the emplacement and consequently low emplacement temperatures. Field observations show that the mafic rocks are deformed, whereas the (younger) granodiorites and granites are not. It is still subject of investigation whether the deformation of the mafic rocks is related to regional deformation during a compressional regime or to the emplacement it self. However, the emplacement of huge amount of crystal rich felsic magmas suggests an extensional regime.Résumé Grand PublicPétrologie et Géochimie du Complexe Plutonique de Chaltén et les conséquences pour l'évolution magmatique et tectonique du Andes du Sud (Patagonia) pendant le MiocèneLe Complexe Plutonique de Chaltén (CHPC) est un massif montagneux situé à 49°S à la frontière entre le Chili et l'Argentine, en Patagonie (région la plus au sud de l'Amérique du Sud). Il est composé de montagnes qui peuvent atteindre plus de 3000 mètres d'altitude, telles que le Cerro Fitz Roy (3400m) et le Cerro Torre (3100m). Ces montagnes sont composées de roches plutoniques, c.-à-d. des magmas qui se sont refroidis et ont cristallisés sous la surface terrestre.La composition chimique de ces roches montre que les magmas, qui ont formé ce complexe plutonique, font partie d'un volcanisme d'arc. Celui-ci se forme lorsqu'une plaque océanique plonge sous une plaque continentale. Les géologues appellent ce processus « subduction ». Dans un tel scénario, le manteau terrestre, qui se fait prendre entre ces deux plaques, fond pour former ainsi du magma. Ce magma remonte à travers la plaque continentale vers la surface. Si celui-ci atteint la surface, il forme les roches volcaniques, comme par exemple des laves. S'il n'atteint pas la surface, le magma se refroidit pour former finalement les roches plutoniques.Le long de la marge ouest d'Amérique du Sud, la plaque Nazca - qui se situe au sud-est de la plaque océanique pacifique - passe en dessous de la plaque d'Amérique du Sud. La bordure ouest du sud de la plaque sud-américaine a également été affectée par d'autres processus tectoniques, tels que des changements dramatiques dans les déplacements de plaques (il y a 25Ma) et la collision de la ride du Chili (depuis 15 Ma jusqu'à aujourd'hui). Ces caractéristiques tectoniques et magmatiques font de cette région un haut lieu pour les géologues. La plaque Nazca, s'est formée suite à l'ouverture d'une plaque océanique plus ancienne, il y a 25Ma. Cette ouverture est liée aux vitesses de subduction les plus rapides jamais connues. La ride du Chili est l'endroit où le sol de l'Océan Pacifique s'ouvre, formant deux plaques océaniques : les plaques Nazca et Antarctique. La ride du Chili subducte sous la plaque sud-américaine depuis 15Ma, en association avec la formation de grands volumes de magma ainsi que des changements morphologiques importants. La question de savoir lequel de ces changements tectoniques globaux affecte la géologie et la géographie de Patagonie a été, et est encore, discutée pendant de nombreuses années. De nombreux chercheurs suggèrent que la plupart des caractéristiques morphologiques et magmatiques en Patagonie sont liés à la subduction de la ride du Chili, mais cette suggestion est encore débattue comme le montre notre étude.Le batholithe de Patagonie du sud (SPB) est un énorme massif composé de roches plutoniques et il s'étend tout au long de la côte ouest de Patagonie (au sud de 47°S). Ces roches correspondent certainement aux racines d'un ancien arc volcanique, qui a été soulevé et érodé. Le CHPC, ainsi que d'autres petites intrusions dans la région, se situe dans une position exotique, à 100km à l'est du SPB. Certains chercheurs suggèrent que ces intrusions pourraient être liées à la subduction de la ride du Chili.Afin de débattre de cette problématique, nous avons utilisé différentes méthodes géochronologiques pour déterminer l'âge du CHPC et le comparer (a) à l'âge des roches intrusives similaires du SPB et (b) à l'âge de la collision de la ride du Chili. Dans ce travail, nous prouvons que le CHPC s'est formé au moins 7Ma avant la collision avec la ride du Chili. Sur la base des âges du CHPC et de la composition chimique de ses roches et minéraux, nous proposons que le CHPC fait partie d'un arc volcanique ancien. La migration de l'arc volcanique plus profondément dans le continent résulte de la grande vitesse de subduction entre 25 et lOMa. Des caractéristiques évidentes pour un tel processus - telles qu'une déformation importante et une vitesse d'érosion élevée - peuvent être rencontrées tout au long de la bordure ouest de l'Amérique du sud.

Construction mechanisms and thermal evolution of upper crustal intrusions : the Saint-Jean-du-Doigt bimodal intrusion (Brittany, France)

Understanding the emplacement and growth of intrusive bodies in terms of mechanism, duration, ther¬mal evolution and rates are fundamental aspects of crustal evolution. Recent studies show that many plutons grow in several Ma by in situ accretion of discrete magma pulses, which constitute small-scale magmatic reservoirs. The residence time of magmas, and hence their capacities to interact and differentiate, are con¬trolled by the local thermal environment. The latter is highly dependant on 1) the emplacement depth, 2) the magmas and country rock composition, 3) the country rock thermal conductivity, 4) the rate of magma injection and 5) the geometry of the intrusion. In shallow level plutons, where magmas solidify quickly, evi¬dence for magma mixing and/or differentiation processes is considered by many authors to be inherited from deeper levels. This work shows however that in-situ differentiation and magma interactions occurred within basaltic and felsic sills at shallow depth (0.3 GPa) in the St-Jean-du-Doigt (SJDD) bimodal intrusion, France. This intrusion emplaced ca. 347 Ma ago (IDTIMS U/Pb on zircon) in the Precambrian crust of the Armori- can massif and preserves remarkable sill-like emplacement processes of bimodal mafic-felsic magmas. Field evidence coupled to high precision zircon U-Pb dating document progressive thermal maturation within the incrementally built ioppolith. Early m-thick mafic sills (eastern part) form the roof of the intrusion and are homogeneous and fine-grained with planar contacts with neighboring felsic sills; within a minimal 0.8 Ma time span, the system gets warmer (western part). Sills are emplaced by under-accretion under the old east¬ern part, interact and mingle. A striking feature of this younger, warmer part is in-situ differentiation of the mafic sills in the top 40 cm of the layer, which suggests liquids survival in the shallow crust. Rheological and thermal models were performed in order to determine the parameters required to allow this observed in- situ differentiation-accumulation processes. Strong constraints such as total emplacement durations (ca. 0.8 Ma, TIMS date) and pluton thickness (1.5 Km, gravity model) allow a quantitative estimation of the various parameters required (injection rates, incubation time,...). The results show that in-situ differentiation may be achieved in less than 10 years at such shallow depth, provided that: (1) The differentiating sills are injected beneath consolidated, yet still warm basalt sills, which act as low conductive insulating screens (eastern part formation in the SJDD intrusion). The latter are emplaced in a very short time (800 years) at high injection rate (0.5 m/y) in order to create a "hot zone" in the shallow crust (incubation time). This implies that nearly 1/3 of the pluton (400m) is emplaced by a subsequent and sustained magmatic activity occurring on a short time scale at the very beginning of the system. (2) Once incubation time is achieved, the calculations show that a small hot zone is created at the base of the sill pile, where new injections stay above their solidus T°C and may interact and differentiate. Extraction of differentiated residual liquids might eventually take place and mix with newly injected magma as documented in active syn-emplacement shear-zones within the "warm" part of the pluton. (3) Finally, the model show that in order to maintain a permanent hot zone at shallow level, injection rate must be of 0.03 m/y with injection of 5m thick basaltic sills eveiy 130yr, imply¬ing formation of a 15 km thick pluton. As this thickness is in contradiction with the one calculated for SJDD (1.5 Km) and exceed much the average thickness observed for many shallow level plutons, I infer that there is no permanent hot zone (or magma chambers) at such shallow level. I rather propose formation of small, ephemeral (10-15yr) reservoirs, which represent only small portions of the final size of the pluton. Thermal calculations show that, in the case of SJDD, 5m thick basaltic sills emplaced every 1500 y, allow formation of such ephemeral reservoirs. The latter are formed by several sills, which are in a mushy state and may interact and differentiate during a short time.The mineralogical, chemical and isotopic data presented in this study suggest a signature intermediate be¬tween E-MORB- and arc-like for the SJDD mafic sills and feeder dykes. The mantle source involved produced hydrated magmas and may be astenosphere modified by "arc-type" components, probably related to a sub¬ducting slab. Combined fluid mobile/immobile trace elements and Sr-Nd isotopes suggest that such subduc¬tion components are mainly fluids derived from altered oceanic crust with minor effect from the subducted sediments. Close match between the SJDD compositions and BABB may point to a continental back-arc setting with little crustal contamination. If so, the SjDD intrusion is a major witness of an extensional tectonic regime during the Early-Carboniferous, linked to the subduction of the Rheno-Hercynian Ocean beneath the Variscan terranes. Also of interest is the unusual association of cogenetic (same isotopic compositions) K-feldspar A- type granite and albite-granite. A-type granites may form by magma mixing between the mafic magma and crustal melts. Alternatively, they might derive from the melting of a biotite-bearing quartz-feldspathic crustal protolith triggered by early mafic injections at low crustal levels. Albite-granite may form by plagioclase cu¬mulate remelting issued from A-type magma differentiation.

Isotope geochemical and geochronologic studies of basement units in the Central Western Carpathians (Slovakia)

In dieser Arbeit werden geochronologische und isotopen-geochemische Daten zur Entwicklung der Zentralen Westlichen Karpathen präsentiert. Die Karpathen bilden die östliche Fortsetzung der Alpen und können in drei Alpine Grundgebirgsdecken unterteilt werden, von denen zwei, die Veporische und die Gemerische, bearbeitet wurden. In der Veporischen Einheit wurden polymetamorphe Grundgebirgseinheiten untersucht, um deren genaue Altersstellung zu definieren und sie isotopengeochemisch zu klassifizieren. Dagegen wurde in der der Gemerischen Einheit, welche die Veporische Einheit überlagert, ein spezialisierter S-Typ Granit im Detail untersucht, um die petrogenetischen Prozesse, die zur magmatischen Entwicklung dieses Granits geführt haben, zu identifizieren. U-Pb Datierungen an Zirkonen der Veporischen Grundgebirgseinheiten zeigen für die gesamte Veporische Einheit ordovizische Entsehungsalter an (440-470 Ma). Diese Datierungen revidieren publizierte kambrische Entstehungsalter dieses Grundgebirges. Die Isotopensignatur (epsilon Nd und 87Sr/86Sr) der ordovizischen Grundgebirgseinheiten, bestehend aus stark überprägten Amphiboliten und Gneissen, ist von der Signatur der sich im Norden anschliessenden Tatrischen Einheit gut unterscheidbar. Die Bleiisotopenzusammensetzung dieser Gesteine ist stark krustal geprägt und überschneidet sich mit der der Tatrischen Einheit. Zusammen mit den T-DM Altern sind diese Einheiten vergleichbar mit prävariskischen Einheiten der Alpen. Somit kann das ordovizische Grundgebirge zu den peri-Gondwana Terranen gezählt werden, die an einem aktiven Kontinentalrand im Norden von Gondwana gebildet wurden. In den Gesteinen der Veporischen Einheit wurde im Weiteren eine starke metamorphe überprägung und intensiver felsischer Magmatismus karbonischen Alters erkannt (320-350 Ma). Dieses Ereignis ist zeitgleich mit dem Magmatismus, welcher hauptsächlich in der sich im Norden anschliessenden Tatrischen Einheit beobachtet wird. Dieser gehört der variskischen Orogenese an. Intensive alpine Deformation und Metamorphose konnte in der südlichen Veporischen Einheit anhand der Einzelzirkondatierungen und der Isotopendaten der ordovizischen Einheiten nachgewiesen werden. Am Dlha Dolina Granit in der Gemerischen Einheit können starke Fraktionierungs- und Auto-Metasomatose-Effekte beobachtet werden. Durch die magmatische Fraktionierung wird eine Anreicherung der SEE erzeugt, wogegen die Metasomatose die SEE stark verarmt. Es kommt sogar zur Ausbildung eines Tetraden Effektes im SEE Muster, welche den starken Einfluss von Fluiden während der spät-magmatischen Phase belegt. Gesamtgesteins Pb-Pb Daten beschränken das minimale Intrusionsalter dieses Granites auf 240 Ma. Dieses Alter ist in guter übereinstimmung mit den Sr-Isotopendaten der magmatisch dominierten Gesteine, wohingegen die stark metasomatisch geprägten Gesteine ein zu radiogenes 87Sr/86Sri aufweisen. Während dieser Arbeit wurde intensiv mit der Blei-Isotopenzusammensetzung von Gesamtgesteinsproben gearbeitet. Um die Auswertung dieser Daten optimieren zu können wurde ein Computerscript für das GPL Programm Octave erstellt. Die Hauptaufgabe dieses Scripts besteht darin, Regressionen für geochronologische Anwendungen gemäss York (1969) zu berechnen. Ausserdem können mu und kappa-Werte für diese Regressionen berechnet und eine Hauptkomponentenanalyse, welche hilfreich für den Vergleich von zwei Datensätzen ist, durchgeführt werden. Am Ende der vorliegenden Arbeit wird die analytische Methode für einen Mikrowellen beschleunigten Säureaufschluss von granitoidem Material zur Bestimmung der Sr- und Nd-Isotopenzusammensetzung und der Elementkonzentrationen vorgestellt. Diese kombinierte Methode nutzt ein TIMS für die Sr und Nd Isotopenmessungen und eine Einzelkollektor-ICPMS zur Bestimmung der SEE, Rb und Sr Konzentrationen, welche mithilfe von relativen Sensitivitätsfaktoren gegenüber einem internen Standard quantifiziert werden. Diese Methode wird durch Messungen von internationalen Referenzmaterialien bewertet. Die Ergebnisse zeigen eine Reproduzierbarkeit von <10% für die Elementkonzentrationen und von <5% für Elementverhältnisse.

Petrology and geochemistry of Lipari Island (Aeolian archipelago): constraints on magma genesis and evolution

A full set of geochemical and Sr, Nd and Pb isotope data both on bulk-rock and mineral samples is provided for volcanic rocks representative of the whole stratigraphic succession of Lipari Island in the Aeolian archipelago. These data, together with petrographic observations and melt/fluid inclusion investigations from the literature, give outlines on the petrogenesis and evolution of magmas through the magmatic and eruptive history of Lipari. This is the result of nine successive Eruptive Epochs developing between 271 ka and historical times, as derived from recentmost volcanological and stratigraphic studies, combined with available radiometric ages and correlation of tephra layers and marine terrace deposits. These Eruptive Epochs are characterized by distinctive vents partly overlapping in space and time, mostly under control of the main regional tectonic trends (NNW-SSE, N-S and minor E-W). A large variety of lava flows, scoriaceous deposits, lava domes, coulees and pyroclastics are emplaced, ranging in composition through time from calcalkaline (CA) and high-K (HKCA) basaltic andesites to rhyolites. CA and HKCA basaltic andesitic to dacitic magmas were erupted between 271 and 81 ka (Eruptive Epochs 1-6) from volcanic edifices located along the western coast of the island (and subordinately the eastern Monterosa) and the M.Chirica and M.S.Angelo stratocones. These mafic to intermediate magmas mainly evolved through AFC and RAFC processes, involving fractionation of mafic phases, assimilation of wall rocks and mixing with newly injected mafic magmas. Following a 40 ka-long period of volcanic quiescence, the rhyolitic magmas were lately erupted from eruptive vents located in the southern and north-eastern sectors of Lipari between 40 ka and historical times (Eruptive Epochs 7-9). They are suggested to derive from the previous mafic to intermediate melts through AFC processes. During the early phases of rhyolitic magmatism (Eruptive Epochs 7-8), enclaves-rich rocks and banded pumices, ranging in composition from HKCA dacites to low-SiO2 rhyolites were erupted, representing the products of magma mixing between fresh mafic magmas and the fractionated rhyolitic melts. The interaction of mantle-derived magmas with the crust represents an essential process during the whole magmatic hystory of Lipari, and is responsible for the wide range of observed geochemical and isotopic variations. The crustal contribution was particularly important during the intermediate phases of activity of Lipari when the cordierite-bearing lavas were erupted from the M. S.Angelo volcano (Eruptive Epoch 5, 105 ka). These lavas are interpreted as the result of mixing and subsequent hybridization of mantle-derived magmas, akin to the ones characterizing the older phases of activity of Lipari (Eruptive Epochs 1-4), and crustal anatectic melts derived from dehydration-melting reactions of metapelites in the lower crust. A comparison between the adjacent islands of Lipari and Vulcano outlines that their mafic to intermediate magmas seem to be genetically connected and derive from a similar mantle source affected by different degrees of partial melting (and variable extent of crustal assimilation) producing either the CA magmas of Lipari (higher degrees) or the HKCA to SHO magmas of Vulcano (lower degrees). On a regional scale, the most primitive rocks (SiO2<56%, MgO>3.5%) of Lipari, Vulcano, Salina and Filicudi are suggested to derive from a similar MORB-like source, variably metasomatized by aqueous fluids coming from the slab and subordinately by the additions of sediments.

UHP metamorphic rocks of the Eastern Rhodope Massif, NE Greece: new constraints from petrology, geochemistry and zircon ages

In this PhD thesis, a multidisciplinary study has been carried out on metagranitoids and paragneisses from the Eastern Rhodope Massif, northern Greece, to decipher the pre-Alpine magmatic and geodynamic evolution of the Rhodope Massif and to correlate the eastern part with the western/central parts of the orogen. The Rhodope Massif, which occupies the major part of NE Greece and S Bulgaria, represents the easternmost part of the Internal Hellenides. It is regarded as a nappe stack of high-grade units, which is classically subdivided into an upper unit and a lower unit, separated by a SSE-NNW trending thrust plane, the Nestos thrust. Recent research in the central Greek Rhodope Massif revealed that the two units correspond to two distinct terranes of different age, the Permo-Carboniferous Thracia Terrane, which was overthrusted by the Late Jurassic/Early Cretaceous Rhodope Terrane. These terranes are separated by the Nestos suture, a composite zone comprising metapelites, metabasites, metagranitoids and marbles, which record high-pressure and even ultrahigh-pressure metamorphism in places. Similar characteristic rock associations were investigated during this study along several well-constrained cross sections in vincity to the Ada, Sidiro and Kimi villages in the Greek Eastern Rhodope Massif. Field evidence revealed that the contact zone of the two terranes in the Eastern Rhodope Massif is characterized by a mélange of metapelites, migmatitic amphibolites/eclogites, strongly sheared orthogneisses and marbles. The systematical occurrence of this characteristic rock association between the terranes implies that the Nestos suture is a continuous belt throughout the Greek Rhodope Massif. In this study, a new UHP locality could be established and for the first time in the Greek Rhodope, metamorphic microdiamonds were identified in situ in their host zircons using Laser-Raman spectroscopy. The presence of the diamonds as well as element distribution patterns of the zircons, obtained by TOF-SIMS, indicate metamorphic conditions of T > 1000 °C and P > 4 GPa. The high-pressure and ultrahigh-pressure rocks of the mélange zone are considered to have formed during the subduction of the Nestos Ocean in Jurassic times at ~150 Ma. Melting of metapelitic rocks at UHP conditions facilitated the exhumation to lower crustal levels. To identify major crust forming events, basement granitoids were dated by LA-SF-ICPMS and SHRIMP-II U-Pb analyses of zircons. The geochronological results revealed that the Eastern Rhodope Massif consists of two crustal units, a structurally lower Permo-Carboniferous unit corresponding to the Thracia Terrane and a structurally upper Late Jurassic/Early Cretaceous unit corresponding to the Rhodope Terrane, like it was documented for the Central Rhodope Massif. Inherited zircons in the orthogneisses from the Thracia Terrane of the Eastern Rhodope Massif indicate the presence of a pre-existing Neoproterozoic and Ordovician-Silurian basement in this region. Triassic magmatism is witnessed by the zircons of few orthogneisses from the easternmost Rhodope Massif and is interpreted to be related to rifting processes. Whole-rock major and trace element analyses indicate that the metagranitoids from both terranes originated in a subduction-related magmatic-arc environment. The Sr-Nd isotope data for both terranes of the Eastern and Central Rhodope Massif suggest a mixed crust-mantle source with variable contributions of older crustal material as already indicated by the presence of inherited zircons. Geochemical and isotopic similarity of the basement of the Thracia Terrane and the Pelagonian Zone implies that the Thracia Terrane is a fragment of a formerly unique Permo-Carboniferous basement, separated by rifting and opening of the Meliata-Maliac ocean system in Triassic times. A branch of the Meliata-Maliac ocean system, the Nestos Ocean, subducted northwards in Late Jurassic times leading to the formation of the Late Jurassic/Early Cretaceous Rhodope magmatic arc on remnants of the Thracia Terrane as suggested by inherited Permo-Carboniferous zircons. The ~150 Ma zircon ages of the orthogneisses from the Rhodope Terrane indicate that subduction-related magmatism and HP/UHP metamorphism occurred during the same subduction phase. Subduction ceased due to the closure of the Nestos Ocean in the Late Jurassic/Early Cretaceous. The post-Jurassic evolution of the Rhodope Massif is characterized by the exhumation of the Rhodope core complex in the course of extensional tectonics associated with late granite intrusions in Eocene to Miocene times.

Appendix A. Whole-rock major, trace and rare earth element analyses of the Ulubey volcanics, Appendix B. Analytical standards and detection limits for analyses

Collisional and post-collisional volcanic rocks in the Ulubey (Ordu) area at the western edge of the Eastern Pontide Tertiary Volcanic Province (EPTVP) in NE Turkey are divided into four suites; Middle Eocene (49.4-44.6 Ma) aged Andesite-Trachyandesite (AT), Trachyandesite-Trachydacite-Rhyolite (TTR), Trachydacite-Dacite (TD) suites, and Middle Miocene (15.1 Ma) aged Trachybasalt (TB) suite. Local stratigraphy in the Ulubey area starts with shallow marine environment sediments of the Paleocene-Eocene time and then continues extensively with sub-aerial andesitic to rhyolitic and rare basaltic volcanism during Eocene and Miocene time, respectively. Petrographically, the volcanic rocks are composed primarily of andesites/trachyandesites, with minor trachydacites/rhyolites, basalts/trachybasalts and pyroclastics, and show porphyric, hyalo-microlitic porphyric and rarely glomeroporphyric, intersertal, intergranular, fluidal and sieve textures. The Ulubey (Ordu) volcanic rocks indicate magma evolution from tholeiitic-alkaline to calc-alkaline with medium-K contents. Primitive mantle normalized trace element and chondrite normalized rare earth element (REE) patterns show that the volcanic rocks have moderate light rare earth element (LREE)/heavy rare earth element (HREE) ratios relative to E-Type MORB and depletion in Nb, Ta and Ti. High Th/Yb ratios indicate parental magma(s) derived from an enriched source formed by mixing of slab and asthenospheric melts previously modified by fluids and sediments from a subduction zone. All of the volcanic rocks share similar incompatible element ratios (e.g., La/Sm, Zr/Nb, La/Nb) and chondrite-normalized REE patterns, indicating that the basic to acidic rocks originated from the same source. The volcanic rocks were produced by the slab dehydration-induced melting of an existing metasomatized mantle source, and the fluids from the slab dehydration introduced significant large ion lithophile element (LILE) and LREE to the source, masking its inherent HFSE-enriched characteristics. The initial 87Sr/86Sr (0.7044-0.7050) and eNd (-0.3 to +3.4) ratios of the volcanics suggest that they originated from an enriched lithospheric mantle source with low Sm/Nd ratios. Integration of the geochemical, petrological and isotopical with regional and local geological data suggest that the Tertiary volcanic rocks from the Ulubey (Ordu) area were derived from an enriched mantle, which had been previously metasomatized by fluids derived from subducted slab during Eocene to Miocene in collisional and post-collisional extension-related geodynamic setting following Late Mesozoic continental collision between the Eurasian plate and the Tauride-Anatolide platform.

Chemistry of igneous rocks from, the Celebes Sea basement

Major and trace elements, mineral chemistry, and Sr-Nd isotope ratios are reported for representative igneous rocks of Ocean Drilling Program Sites 767 and 770. The basaltic basement underlying middle Eocene radiolarianbearing red clays was reached at 786.7 mbsf and about 421 mbsf at Sites 767 and 770, respectively. At Site 770 the basement was drilled for about 106 m. Eight basaltic units were identified on the basis of mineralogical, petrographical, and geochemical data. They mainly consist of pillow lavas and pillow breccias (Units A, B, D, and H), intercalated with massive amygdaloidal lavas (Units Cl and C2) or relatively thin massive flows (Unit E). Two dolerite sills were also recognized (Units F and G). All the rocks studied show the effect of low-temperature seafloor alteration, causing almost total replacement of olivine and glass. Calcite, clays, and Fe-hydroxides are the most abundant secondary phases. Chemical mobilization due to the alteration processes has been evaluated by comparing elements that are widely considered mobile during halmyrolysis (such as low-field strength elements) with those insensitive to seafloor alteration (such as Nb). In general, MgO is removed and P2O5 occasionally enriched during the alteration of pillow lavas. Ti, Cs, Li, Rb, and K, which are the most sensitive indicators of rock/seawater interaction, are generally enriched. The most crystalline samples appear the least affected by chemical changes. Plagioclase and olivine are continuously present as phenocrysts, and clinopyroxene is confined in the groundmass. Textural and mineralogical features as well as crystallization sequences of Site 770 rocks are, in all, analogous to typical mid-ocean-ridge basalts (MORBs). Relatively high content of compatible trace elements, such as Ni and Cr, indicate that these rocks represent nearly primitive or weakly fractionated MORBs. All the studied rocks are geochemically within the spectrum of normal MORB compositional variation. Their Sr/Nd isotopic ratios plot on the mantle array (87Sr/87Sr 0.70324-0.70348 with 143Nd/144Nd 0.51298-0.51291) outside the field of Atlantic and Pacific MORBs. However, Sr and Nd isotopes are typical of both Indian Ocean MORBs and of some back-arc basalts, such as those of Lau Basin. The mantle source of Celebes basement basalts does not show a detectable influence of a subduction-related component. The geochemical and isotopic data so far obtained on the Celebes basement rocks do not allow a clear discrimination between mid-ocean ridge and back-arc settings.

Geochemistry and petrology of ODP Site 136-843 basalts

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.

Geochemistry of Kerguelen-Heard Plateau basalts

During Leg 120 basalts were recovered at four drill holes on the Kerguelen-Heard Plateau. This paper reports the trace element and Sr, Nd, Hf, and Pb isotopic characteristics of these basalts and compares these basalts with Indian Ocean basalts and Kerguelen and Heard island volcanics. Kerguelen-Heard Plateau basalts are extremely heterogeneous in character. Intersite variations are larger than intrasite variations. Part of the chemical variations of the plateau volcanics overlap with those characteristics of Kerguelen Island volcanics, which indicates tapping of the same mantle source during the two different periods of activity. The estimates of the degree of melting for the plateau basalts (smaller degree of melting than for mid-ocean ridge basalts) and the heterogeneous character of the plateau exclude an origin that requires large degrees of melting or more rigorous convection than at ocean ridges. However, all characteristics indicate an oceanic origin for the Kerguelen-Heard Plateau.