Epidote in hydrous mafic magmas : near solidus phase relations in the lower crust

Crystallisation of hydrous mafic magmas at high pressure is a subject of numerous petrologic and experimental studies since the last century and is mainly related to the process of continental crust formation and the possible link between mantle derived melts and low pressure granitoids. Albeit the sequence of crystallization is well constrained by experimental studies, the origin of exposed lower crustal rocks exposed on the earth surface is controversial. Ones line of argument is favouring high pressure crystallization of dry or wet mafic magmas, whereas others invoke partial melting of pre-existing crust. Therefore studies involving field, textural and chemical observations of exposed lower crust such as in Kohistan (Pakistan) or Talkeetna (Alaska) are crucial to understand the continental crust formation processes via arc magmatism. Epidote-bearing gabbros are very sparse and always associated with the deep part of continental crust (>30 km) as in the Kohistan Arc Complex (Pakistan) or in the Chelan Complex (western U.S.). Magmatic epidote is restricted to a small temperature interval above the water-saturated solidus of MORB and represent the last crystallizing liquids in lower crustal regions. However, epidote and melt stability at lower crustal pressures are not clearly established.¦The Chelan complex (western U.S.) at the base of the Cascadian Arc is composed mainly by peraluminous tonalité associated with gabbroic and ultramafic rocks and was traditionally interpreted as a migmatitic terrain. However field, chemical and mineralogical observations rather suggest a magmatic origin and point to a protracted crystallization at intermediate to high pressure ~ 1.0 GPa dominated by amphibole fractionation and followed by isobaric cooling down to 650°C. Crystal fractionation modelling using whole rock composition and field constraints is able to generate peraluminous tonalité. The modelled crystallisation sequence and the volume proportions are in agreement with experimental studies performed at these pressures. The Chelan complex was thus not formed during a partial melting event, but represent the sequence of crystallisation occurring at the base of the crust. Massive fractionation of hornblende is able to generate peraluminous tonalité without significant assimilation of crustal rock.¦Similarly to the Chelan complex, the base of the Kohistan arc is composed of cumulates derived by high pressure crystallization of hydrous magma. In garnet gabbros, epidote occurs as magmatic phase, crystallising from hydrous interstitial melt trapped between grain boundaries at lower crustal pressures (Ρ ~ 1.2 GPa) for temperature of (650-700 °C). Trace and REE signature in epidote indicate that epidote was formed through peritectic reaction involving garnet, clinopyroxene and plagioclase. At the beginning of the crystallisation epidote signature is dominated by REE content in the melt, whereas at the end the signature is dominated by reacting phases. Melt in equilibrium with epidote inferred from the partition coefficients available is similar to intrusive tonalité up the section indicating that hydrous melt was extracted from the garnet gabbros. In some gabbros epidote shows single homogeneous compositions, while in others coexisting epidote have different compositions indicating the presence of solvi along the Al-Fe3+ join. The overgowths are only observed in presence of paragonite in the assemblage, suggesting high water content. At high water content, the hydrous solidus is shift to lower temperature and probably intersects the solvi observed along the Al-Fe3+ join. Therefore, several compositions of epidote is stable at high water content.¦-¦La composition chimique de la croûte continentale est considérée comme similaire à celle du magmatisme calco-alcalin de marge continentale active (enrichissement en éléments mobiles dans les fluides, anomalies négatives en Nb, Ta et éléments à haut potentiel électronique, etc...). Cependant la nature andésitique de la croûte continentale (Si02 > 60 wt%), résultant des nombreuses intrusions de granitoïdes dans la croûte supérieure, est sujette à polémique et le lien entre les magmas dérivés du manteau et les roches évoluées de faible profondeur n'est pas clairement établi (fusion partielle de croûte basaltique, cristallisation fractionnée à haute pression, etc...).¦Les affleurements de croûte profonde sont rares mais précieux, car ils permettent d'observer les phénomènes se passant à grande profondeur. Le complexe de Chelan (Washington Cascades) en est un exemple. Formé à environ 30 km de profondeur, il est composé de roches gabbroïques et ultramafiques, ainsi que de tonalités, qui furent souvent interprétés comme le produit de la fusion partielle de la croûte. Cependant, les relations de terrain, la chimie des éléments majeurs et des éléments traces sont cohérentes avec l'évolution d'un complexe magmatique mafique dans la croûte profonde ou moyenne ( 1.0 GPa), dominée par le fractionnement de l'amphibole. Après son emplacement, le complexe a subi un refroidissement isobare jusqu'à des températures de l'ordre de 650 °C, déduit de la composition chimique des minéraux. Un bilan de masse contraint pax les observations de terrain permet de calculer la séquence et les volumes de fractionnement. Les faciès évolués légèrement hyperalumineux observés sur le terrain peuvent être générés par la cristallisation de 3 % de websterite à olivine, 12 % d'hornblendite à pyroxène 33 % d'hornblendite, 19 % de gabbros, 15 % de diorite et 2 % de tonalité. Nous montrons ainsi qu'une série de fractionnement contrôlée par l'amphibole permet de générer des tonalités sans assimilation de matériel crustal et l'exemple de Chelan illustre la viabilité de ce processus dans la formation de croûte continentale.¦Les réactions proches du solidus saturé en H20 dans les systèmes basaltiques à des pressions élevées restent énigmatiques. Diverses expériences tendent à montrer que l'épidote est stable dans ces conditions, mais rarement observée (décrite ?) comme phase primaire dans les systèmes naturels. Les épidotes trouvées dans les gabbros de Jijal (nord-Pakistan) montrent des textures de type .magmatique telles qu'observées dans les roches évoluées. Le contenu en terres rares de ces épidotes est très variable allant de signatures enrichies en terres rares légères impliquant la présence de liquide interstitiel à des signatures complètement déprimées en ces mêmes éléments, évoquant une cristallisation en coexistence avec du grenat. Ces diverses signatures reflètent un chemin de cristallisation en présence de liquide interstitiel et enregistrent des réactions péritectiques impliquant grenat, clinopyroxene et plagioclase à des pressions de ~ 1.2 GPa pour des températures de 650-700 °C. Cependant dans quelques échantillons deux ou trois compositions d'épidotes coexistent démontrant la présence de lacunes d'immiscibilité le long de la solution solide épidote-clinozoïsite. La forte teneur en H20 du liquide magmatique est certainement à l'origine de la coexistence de deux compositions distinctes.

Accessory phases as a tool to investigate magmatic underplating in polymetamorphic metasediments : an example from a fossil lower crust : Ivrea Verbano zne, NW Italy

The Ivrea and the Strona-Ceneri zones, NW italy and S Switzerland, offer the possibility to study the continental crust of the Southern Alps. Because of its high metamorphic degree and the abundant Permo- Carboniferous mafic intrusions, the Ivrea Zone is classically interpreted an exposed section trough the Permian lower crust. The present work is focused here on metasedimentary slices (septa) intercalated within Permian gabbro (mafic complex). In particular I studied the evolution of accessory phases such as rutile and zircon and the chemistry of the metasediments. The septa build an irregular and discontinuous band that cut obliquely the mafic complex from its deepest part (N) to its roof (S). The chemistry of the metasediments evolves along the band and the chemical evolution can be compared with that observed in the country-rock surrounding the mafic intrusion to the NE and overprinted by a main regional metamorphic event. This suggests that the degree of chemical depletion of the septa was mainly established during the same regional metamorphic event. Moreover it suggests that incorporation of the septa within the gabbro did not modify their original stratigraphie distribution within the crust. It implies that the mafic complex has been emplaced following a dynamic substantially different from the classic model of « gabbro glacier » (Quick et al., 1992; Quick et al., 1994). It is more likely that it has been emplaced by repeated injections of sills at different depths during a protracted period of time. Zircon trace elements and U-Pb ages suggest that regional metamorphism occurred 330-320Ma, the first sills in the deepest part of the Mafic Complex are injected at ~300Ma, the mafic magmas reached higher levels in the crust at 285Ma and the magmatic activity continued locally until 275Ma. The ages of detrital cores in zircons fix the maximal sedimentation age at ~370Ma, this age corresponds therefore with the maximal age of the incorporation of the Ivrea zone within the lower crust. I propose that the Ivrea zone has been accreted to the lower crust during the Hercynian orogeny sensu lato. The analysis of detrital ages suggests that the source terrains for the Ivrea zone and those for the Strona-Ceneri zone have a completely different Palaeozoic history. The systematic analysis of rutile in partially molten metasediments of the Ivrea zone reveals the occurrence of two generations. The two generations are characterized by a different chemistry and textural distribution. A first generation is formed during pro-grade metamorphism in the restitic counterpart. The second generation is formed in the melts during cooling at the same time that part of the first generation re-equilibrate. Re-equilibration of the first generation seems to be spatially controlled by the presence of fluids. Locally the second generation forms overgrowths on the first generation. Considered the different diffusivity of U and Pb in rutile, U heterogeneities have important implication for U-Pb dating of rutile. ID-TIMS and LA-ICPMS dating coupled with a careful textural investigation (SEM) suggest that rutile grains are characterized by multiple path along which Pb diffusion can occur: volume diffusion is an important process, but intragrain and subgrain boundaries provide additional high diffusivity pathways for Pb escape and reduce drastically the effective diffusion length. -- La zone d'Ivrea et la zone de Strona-Ceneri, en Italie nord-occidentale et Suisse méridionale, offrent la possibilité d'étudier la croûte continentale des Alpes du Sud. En raison du haut degré métamorphique et l'abondance d'intrusions mafiques d'âge Permo-Carbonifère [complexe mafique), la zone d'Ivrea est interprétée classiquement comme de la croûte inférieure permienne. Ce travail ce concentre sur des bandes metasédimentaires (septa) incorporées dans les magmas mafiques lors de l'intrusion. Les septa forment une bande irrégulière qui coupe obliquement le complexe mafique du bas (N) vers le haut (S). La chimie des septa évolue du bas vers le haut et l'évolution chimique se rapproche de l'évolution observé dans la roche encaissante l'intrusion affecté par un événement métamorphique régionale. Cette relation suggère que le degré d'appauvrissement chimique des septa a été établit principalement lors de l'événement métamorphique régional. De plus l'incorporation dans les gabbros n'a pas perturbée la distribution stratigraphique originelle des septa. Ces deux observations impliquent que le métamorphisme dans la roche encaissante précède la mise en place du gabbro et que cette dernière ne se fait pas selon le modèle classique (« gabbro glacier » de Quick et al., 1992, 1994), mais se fait plutôt par injections répétées de sills a différentes profondeurs. Les âges U-Pb et les éléments traces des zircons suggèrent que le métamorphisme régionale a eu lieu 330-320Ma, alors que les premiers sills dans la partie profonde du Mafic Complex s'injectent à ~300Ma, le magmatisme mafique atteigne des niveaux supérieurs à 285Ma et continue localement jusqu'à 270Ma. Les âges des coeurs détritiques des zircons permettent de fixer l'âge maximale de sédimentation à ~370Ma ce qui correspond donc à l'âge maximale de l'incorporation de la zone d'Ivrea dans la croûte inférieur. L'analyse systématique des rutiles, nous a permit de montrer l'existence de plusieurs générations qui ont une répartition texturale et une chimie différente. Une génération se forme lors de l'événement UHT dans les restites, une autre génération se forme dans les liquides lors du refroidissement, au même temps qu'une partie de la première génération se rééquilibre au niveau du Zr. Localement la deuxième génération peut former des surcroissances autour de la première génération. Dans ces cas, des fortes différences en uranium entre les deux générations ont des importantes implications pour la datation U-Pb sur rutile. Classiquement les ratios Pb/U dans le rutile sont interprétés comme indiquant l'âges du refroidissement du minéral sous une température à la quelle la diffusion du Pb dans le minéral n'est plus détectable et la diffusion à plus hautes températures est assumée se faire par «volume diffusion» dans le grain (Mezger et al., 1989). Par des datations ID-TIMS (sur grain entier) et LA-ICPMS (in-situ) et une analyse texturale (MEB) approfondie nous montrons que cette supposition est trop simpliste et que le rutile est repartie en sous-domaines. Chacun de ces domaines a ça propre longueur ou chemin de diffusion spécifique. Nous proposons donc une nouvelle approche plus cohérente pour l'interprétation des âges U-Pb sur rutile.

Arcabouço geofísico, isostasia e causas do magmatismo cenozóico da província Borborema e de sua margem continental (Nordeste do Brasil)

The Borborema Province (BP) is a geologic domain located in Northeastern Brazil. The BP is limited at the south by the São Francisco craton, at the west by the Parnaíba basin, and both at the north and east by coastal sedimentary basins. Nonetheless the BP surface geology is well known, several key aspects of its evolution are still open, notably: i)its tectonic compartmentalization established after the Brasiliano orogenesis, ii) the architecture of its cretaceous continental margin, iii) the elastic properties of its lithosphere, and iv) the causes of magmatism and uplifting which occurred in the Cenozoic. In this thesis, a regional coverage of geophysical data (elevation, gravity, magnetic, geoid height, and surface wave global tomography) were integrated with surface geologic information aiming to attain a better understanding of the above questions. In the Riacho do Pontal belt and in the western sector of the Sergipano belt, the neoproterozoic suture of the collision of the Sul domain of the BP with the Sanfranciscana plate (SFP) is correlated with an expressive dipolar gravity anomaly. The positive lobule of this anomaly is due to the BP lower continental crust uplifting whilst the negative lobule is due to the supracrustal nappes overthrusting the SFP. In the eastern sector of the Sergipano belt, this dipolar gravity anomaly does not exist. However the suture still can be identified at the southern sector of the Marancó complex arc, alongside of the Porto da Folha shear zone, where the SFP N-S geophysical alignments are truncated. The boundary associated to the collision of the Ceará domain of the BP with the West African craton is also correlated with a dipolar gravity anomaly. The positive lobule of this anomaly coincides with the Sobral-Pedro II shear zone whilst the negative lobule is associated with the Santa Quitéria magmatic arc. Judging by their geophysical signatures, the major BP internal boundaries are: i)the western sector of the Pernambuco shear zone and the eastern continuation of this shear zone as the Congo shear zone, ii) the Patos shear zone, and iii) the Jaguaribe shear zone and its southwestern continuation as the Tatajuba shear zone. These boundaries divide the BP in five tectonic domains in the geophysical criteria: Sul, Transversal, Rio Grande do Norte, Ceará, and Médio Coreaú. The Sul domain is characterized by geophysical signatures associated with the BP and SFP collision. The fact that Congo shear zone is now proposed as part of the Transversal domain boundary implies an important change in the original definition of this domain. The Rio Grande do Norte domain presents a highly magnetized crust resulted from the superposition of precambrian and phanerozoic events. The Ceará domain is divided by the Senador Pompeu shear zone in two subdomains: the eastern one corresponds to the Orós-Jaguaribe belt and the western one to the Ceará-Central subdomain. The latter subdomain exhibits a positive ENE-W SW gravity anomaly which was associated to a crustal discontinuity. This discontinuity would have acted as a rampart against to the N-S Brasiliano orogenic nappes. The Médio Coreaú domain also presents a dipolar gravity anomaly. Its positive lobule is due to granulitic rocks whereas the negative one is caused by supracrustal rocks. The boundary between Médio Coreaú and Ceará domains can be traced below the Parnaíba basin sediments by its geophysical signature. The joint analysis of free air anomalies, free air admittances, and effective elastic thickness estimates (Te) revealed that the Brazilian East and Equatorial continental margins have quite different elastic properties. In the first one 10 km < Te < 20 km whereas in the second one Te ≤ 10 km. The weakness of the Equatorial margin lithosphere was caused by the cenozoic magmatism. The BP continental margin presents segmentations; some of them have inheritance from precambrian structures and domains. The segmentations conform markedly with some sedimentary basin features which are below described from south to north. The limit between Sergipe and Alagoas subbasins coincides with the suture between BP and SFP. Te estimates indicates concordantly that in Sergipe subbasin Te is around 20 km while Alagoas subbasin has Te around 10 km, thus revealing that the lithosphere in the Sergipe subbasin has a greater rigidity than the lithosphere in the Alagoas subbasin. Additionally inside the crust beneath Sergipe subbasin occurs a very dense body (underplating or crustal heritage?) which is not present in the crust beneath Alagoas subbasin. The continental margin of the Pernambuco basin (15 < Te < 25 km) presents a very distinct free air edge effect displaying two anomalies. This fact indicates the existence in the Pernambuco plateau of a relatively thick crust. In the Paraíba basin the free air edge effect is quite uniform, Te ≈ 15 km, and the lower crust is abnormally dense probably due to its alteration by a magmatic underplating in the Cenozoic. The Potiguar basin segmentation in three parts was corroborated by the Te estimates: in the Potiguar rift Te ≅ 5 km, in the Aracati platform Te ≅ 25 km, and in the Touros platform Te ≅ 10 km. The observed weakness of the lithosphere in the Potiguar rift segment is due to the high heat flux while the relatively high strength of the lithosphere in the Touros platform may be due to the existence of an archaean crust. The Ceará basin, in the region of Mundaú and Icaraí subbasins, presents a quite uniform free air edge effect and Te ranges from 10 to 15 km. The analysis of the Bouguer admittance revealed that isostasy in BP can be explained with an isostatic model where combined surface and buried loadings are present. The estimated ratio of the buried loading relative to the surface loading is equal to 15. In addition, the lower crust in BP is abnormally dense. These affirmations are particularly adequate to the northern portion of BP where adherence of the observed data to the isostatic model is quite good. Using the same above described isostatic model to calculate the coherence function, it was obtained that a single Te estimate for the entire BP must be lower than 60 km; in addition, the BP north portion has Te around 20 km. Using the conventional elastic flexural model to isostasy, an inversion of crust thickness was performed. It was identified two regions in BP where the crust is thickened: one below the Borborema plateau (associated to an uplifting in the Cenozoic) and the other one in the Ceará domain beneath the Santa Quitéria magmatic arc (a residue associated to the Brasiliano orogenesis). On the other hand, along the Cariri-Potiguar trend, the crust is thinned due to an aborted rifting in the Cretaceous. Based on the interpretation of free air anomalies, it was inferred the existence of a large magmatism in the oceanic crust surrounding the BP, in contrast with the incipient magmatism in the continent as shown by surface geology. In BP a quite important positive geoid anomaly exists. This anomaly is spatially correlated with the Borborema plateau and the Macaú-Queimadas volcanic lineament. The integrated interpretation of geoid height anomaly data, global shear velocity model, and geologic data allow to propose that and Edge Driven Convection (EDC) may have caused the Cenozoic magmatism. The EDC is an instability that presumably occurs at the boundary between thick stable lithosphere and oceanic thin lithosphere. In the BP lithosphere, the EDC mechanism would have dragged the cold lithospheric mantle into the hot asthenospheric mantle thus causing a positive density contrast that would have generated the main component of the geoid height anomaly. In addition, the compatibility of the gravity data with the isostatic model, where combined surface and buried loadings are present, together with the temporal correlation between the Cenozoic magmatism and the Borborema plateau uplifting allow to propose that this uplifting would have been caused by the buoyancy effect of a crustal root generated by a magmatic underplating in the Cenozoic

The 3.4-3.5 Ga Sao Jose do Campestre massif, NE Brazil: remnants of the oldest crust in South America

The oldest fragment of continental crust recognized in South America occurs as an isolated Archean enclave in northeastem Brazil's Borborema Province, ca. 600 Ma Brasiliano-Pan African orogenic belt. This Archean fragment, the Sao Jose do Campestre massif, is surrounded by large tracts of 2.2-2.0 Ga Paleoproterozoic gneisses and is located more than 600-1500 km from the much larger assemblages of Archean rocks found in the Sao Fransciso and Amazonian cratons, located to the south and west, respectively. Geochronological studies of the Sao Jose do Campestre massif show that its oldest rocks contain zircons with U-Pb ages up to 3.5 Ga and Sm-Nd T-DM model ages of more than 3.7 Ga, indicating that they represent reworked crust. This older nucleus is flanked by both reworked and juvenile 3.25 and 3.18 Ga rocks which arc intruded by both 3.00 and 2.69 Ga plutonic bodies. The protracted evolution the Sao Jose do Campestre massif is consistent with that of a larger continental mass as opposed to a small crustal fragment that grew in isolation. As such, the Sao Jose do Campestre massif is interpreted as representing a detached piece of an evolved craton that became entrained with younger rocks during a subsequent Paleoproterozoic accretionary-orogenic event. This hypothesis is bolstered by the presence of Paleoproterozoic gneisses that envelop the Sao Jose do Campestre massif, as well as the existence of ca. 2.0 Ga metamorphic zircon and monazite within its rocks. The occurrence of several different Archean cratonic basement inliers within the greater Paleoproterozoic crustal framework of the Borborema Province suggests that cratonic slices spalled off one or more larger Archean masses prior to the ca. 2.2-2.0 Ga Paleoproterozoic orogenic collage. A important challenge is to link these older fragments to their parent cratons. Although results are not unique, the pattern of ages and isotopic signatures observed in the Sao Jose do Campestre massif is similar to that seen in parts of the Sao Francisco Craton, and it is possible that the Sao Jose do Campestre massif is a fragment of an Archean continental fragment formed during an episode of continental breakup prior to 2200 Ma. (C) 2003 Elsevier B.V. All rights reserved.

Re-Os isotope and highly siderophile element systematics of the Parana continental flood basalts (Brazil)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Continental degassing of He-4 by surficial discharge of deep groundwater

Radiogenic He-4 is produced by the decay of uranium and thorium in the Earths mantle and crust. From here, it is degassed to the atmosphere(1-5) and eventually escapes to space(1,5,6). Assuming that all of the He-4 produced is degassed, about 70% of the total He-4 degassed from Earth comes from the continental crust(2,-5,7). However, the outgoing flux of crustal He-4 has not been directly measured at the Earths surface(2) and the migration pathways are poorly understood(2-4,7,8). Here we present measurements of helium isotopes and the long-lived cosmogenic radio-isotope Kr-81 in the deep, continental-scale Guarani aquifer in Brazil and show that crustal He-4 reaches the atmosphere primarily by the surficial discharge of deep groundwater. We estimate that He-4 in Guarani groundwater discharge accounts for about 20% of the assumed global flux from continental crust, and that other large aquifers may account for about 33%. Old groundwater ages suggest that He-4 in the Guarani aquifer accumulates over half- to one-million-year timescales. We conclude that He-4 degassing from the continents is regulated by groundwater discharge, rather than episodic tectonic events, and suggest that the assumed steady state between crustal production and degassing of He-4, and its resulting atmospheric residence time, should be re-examined.

Evolução tectônica e estratigráfica das bacias da margem continental do Uruguai

Pós-graduação em Geociências e Meio Ambiente - IGCE

Re-Os isotope and highly siderophile element systematics of the Parana continental flood basalts (Brazil)

Basalts of the Parana continental flood basalt (PCFB) province erupted through dominantly Proterozoic continental crust during the Cretaceous. In order to examine the mantle source(s) of this major flood basalt province, we studied Os, Sr, Nd, and Pb isotope systematics, and highly siderophile element (HSE) abundances in tholeiitic basalts that were carefully chosen to show the minimal effects of crustal contamination. These basalts define a precise Re-Os isochron with an age of 131.6 +/- 2.3 Ma and an initial Os-187/Os-188 of 0.1295 +/- 0.0018 (gamma Os-187 = +2.7 +/- 1.4). This initial Os isotopic composition is considerably more radiogenic than estimates of the contemporary Depleted Mantle (DM). The fact that the Re-Os data define a well constrained isochron with an age similar to Ar-40/Ar-39 age determinations, despite generally low Os concentrations, is consistent with closed-system behavior for the HSE. Neodymium, Sr, and Pb isotopic data suggest that the mantle source of the basalts had been variably hybridized by melts derived from enriched mantle components. To account for the combined Os, Nd, Sr, and Pb isotopic characteristics of these rocks, we propose that the primary melts formed from metasomatized asthenospheric mantle (represented by arc-mantle peridotite) that underwent mixing with two enriched components, EM-I and EM-II. The different enriched components are reflected in minor isotopic differences between basalts from southern and northern portions of the province. The Tristan da Cunha hotspot has been previously suggested to be the cause of the Parana continental flood basalt magmatism. However, present-day Tristan da Cunha lavas have much higher Os-187/Os-188 isotopic compositions than the source of the PCFB. These data, together with other isotopic and elemental data, preclude making a definitive linkage between the Tristan plume and the PCFB. (C) 2012 Elsevier B.V. All rights reserved.

Partial melting within the lower crust – Constraints from bulk rock geochemical data and trace element mineral analyses of granulites and migmatites from Central Finland

This PhD thesis concerns geochemical constraints on recycling and partial melting of Archean continental crust. A natural example of such processes was found in the Iisalmi area of Central Finland. The rocks from this area are Middle to Late Archean in age and experienced metamorphism and partial melting between 2.7-2.63 Ga. The work is based on extensive field work. It is furthermore founded on bulk rock geochemical data as well as in-situ analyses of minerals. All geochemical data were obtained at the Institute of Geosciences, University of Mainz using X-ray fluorescence, solution ICP-MS and laser ablation-ICP-MS for bulk rock geochemical analyses. Mineral analyses were accomplished by electron microprobe and laser ablation ICP-MS. Fluid inclusions were studied by microscope on a heating-freezing-stage at the Geoscience Center, University Göttingen. Part I focuses on the development of a new analytical method for bulk rock trace element determination by laser ablation-ICP-MS using homogeneous glasses fused from rock powder on an Iridium strip heater. This method is applicable for mafic rock samples whose melts have low viscosities and homogenize quickly at temperatures of ~1200°C. Highly viscous melts of felsic samples prevent melting and homogenization at comparable temperatures. Fusion of felsic samples can be enabled by addition of MgO to the rock powder and adjustment of melting temperature and melting duration to the rock composition. Advantages of the fusion method are low detection limits compared to XRF analyses and avoidance of wet-chemical processing and use of strong acids as in solution ICP-MS as well as smaller sample volumes compared to the other methods. Part II of the thesis uses bulk rock geochemical data and results from fluid inclusion studies for discrimination of melting processes observed in different rock types. Fluid inclusion studies demonstrate a major change in fluid composition from CO2-dominated fluids in granulites to aqueous fluids in TTG gneisses and amphibolites. Partial melts were generated in the dry, CO2-rich environment by dehydration melting reactions of amphibole which in addition to tonalitic melts produced the anhydrous mineral assemblages of granulites (grt + cpx + pl ± amph or opx + cpx + pl + amph). Trace element modeling showed that mafic granulites are residues of 10-30 % melt extraction from amphibolitic precursor rocks. The maximum degree of melting in intermediate granulites was ~10 % as inferred from modal abundances of amphibole, clinopyroxene and orthopyroxene. Carbonic inclusions are absent in upper-amphibolite facies migmatites whereas aqueous inclusion with up to 20 wt% NaCl are abundant. This suggests that melting within TTG gneisses and amphibolites took place in the presence of an aqueous fluid phase that enabled melting at the wet solidus at temperatures of 700-750°C. The strong disruption of pre-metamorphic structures in some outcrops suggests that the maximum amount of melt in TTG gneisses was ~25 vol%. The presence of leucosomes in all rock types is taken as the principle evidence for melt formation. However, mineralogical appearance as well as major and trace element composition of many leucosomes imply that leucosomes seldom represent frozen in-situ melts. They are better considered as remnants of the melt channel network, e.g. ways on which melts escaped from the system. Part III of the thesis describes how analyses of minerals from a specific rock type (granulite) can be used to determine partition coefficients between different minerals and between minerals and melt suitable for lower crustal conditions. The trace element analyses by laser ablation-ICP-MS show coherent distribution among the principal mineral phases independent of rock composition. REE contents in amphibole are about 3 times higher than REE contents in clinopyroxene from the same sample. This consistency has to be taken into consideration in models of lower crustal melting where amphibole is replaced by clinopyroxene in the course of melting. A lack of equilibrium is observed between matrix clinopyroxene / amphibole and garnet porphyroblasts which suggests a late stage growth of garnet and slow diffusion and equilibration of the REE during metamorphism. The data provide a first set of distribution coefficients of the transition metals (Sc, V, Cr, Ni) in the lower crust. In addition, analyses of ilmenite and apatite demonstrate the strong influence of accessory phases on trace element distribution. Apatite contains high amounts of REE and Sr while ilmenite incorporates about 20-30 times higher amounts of Nb and Ta than amphibole. Furthermore, trace element mineral analyses provide evidence for magmatic processes such as melt depletion, melt segregation, accumulation and fractionation as well as metasomatism having operated in this high-grade anatectic area.

Forward modelling of petrological crust-forming processes on the early Earth

Tonalite-trondhjemite-granodiorite (TTG) gneisses form up to two-thirds of the preserved Archean continental crust and there is considerable debate regarding the primary magmatic processes of the generation of these rocks. The popular theories indicate that these rocks were formed by partial melting of basaltic oceanic crust which was previously metamorphosed to garnet-amphibolite and/or eclogite facies conditions either at the base of thick oceanic crust or by subduction processes.rnThis study investigates a new aspect regarding the source rock for Archean continental crust which is inferred to have had a bulk compostion richer in magnesium (picrite) than present-day basaltic oceanic crust. This difference is supposed to originate from a higher geothermal gradient in the early Archean which may have induced higher degrees of partial melting in the mantle, which resulted in a thicker and more magnesian oceanic crust. rnThe methods used to investigate the role of a more MgO-rich source rock in the formation of TTG-like melts in the context of this new approach are mineral equilibria calculations with the software THERMOCALC and high-pressure experiments conducted from 10–20 kbar and 900–1100 °C, both combined in a forward modelling approach. Initially, P–T pseudosections for natural rock compositions with increasing MgO contents were calculated in the system NCFMASHTO (Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–TiO2) to ascertain the metamorphic products from rocks with increasing MgO contents from a MORB up to a komatiite. A small number of previous experiments on komatiites showed the development of pyroxenite instead of eclogite and garnet-amphibolite during metamorphism and established that melts of these pyroxenites are of basaltic composition, thus again building oceanic crust instead of continental crust.rnThe P–T pseudosections calculated represent a continuous development of their metamorphic products from amphibolites and eclogites towards pyroxenites. On the basis of these calculations and the changes within the range of compositions, three picritic Models of Archean Oceanic Crust (MAOC) were established with different MgO contents (11, 13 and 15 wt%) ranging between basalt and komatiite. The thermodynamic modelling for MAOC 11, 13 and 15 at supersolidus conditions is imprecise since no appropriate melt model for metabasic rocks is currently available and the melt model for metapelitic rocks resulted in unsatisfactory calculations. The partially molten region is therfore covered by high-pressure experiments. The results of the experiments show a transition from predominantly tonalitic melts in MAOC 11 to basaltic melts in MAOC 15 and a solidus moving towards higher temperatures with increasing magnesium in the bulk composition. Tonalitic melts were generated in MAOC 11 and 13 at pressures up to 12.5 kbar in the presence of garnet, clinopyroxene, plagioclase plus/minus quartz (plus/minus orthopyroxene in the presence of quartz and at lower pressures) in the absence of amphibole but it could not be explicitly indicated whether the tonalitic melts coexisting with an eclogitic residue and rutile at 20 kbar do belong to the Archean TTG suite. Basaltic melts were generated predominantly in the presence of granulite facies residues such as amphibole plus/minus garnet, plagioclase, orthopyroxene that lack quartz in all MAOC compositions at pressures up to 15 kbar. rnThe tonalitic melts generated in MAOC 11 and 13 indicate that thicker oceanic crust with more magnesium than that of a modern basalt is also a viable source for the generation of TTG-like melts and therefore continental crust in the Archean. The experimental results are related to different geologic settings as a function of pressure. The favoured setting for the generation of early TTG-like melts at 15 kbar is the base of an oceanic crust thicker than existing today or by melting of slabs in shallow subduction zones, both without interaction of tonalic melts with the mantle. Tonalitic melts at 20 kbar may have been generated below the plagioclase stability by slab melting in deeper subduction zones that have developed with time during the progressive cooling of the Earth, but it is unlikely that those melts reached lower pressure levels without further mantle interaction.rn

Continental degassing of 4He by surficial discharge of deep groundwater

Radiogenic He is produced by the decay of uranium and thorium in the Earth’s mantle and crust. From here, it is degassed to the atmosphere and eventually escapes to space. Assuming that all of the 4He produced is degassed, about 70% of the total He degassed from Earth comes from the continental crust. However, the outgoing flux of crustal He has not been directly measured at the Earth’s surface and the migration pathways are poorly understood. Here we present measurements of helium isotopes and the long-lived cosmogenic radio-isotope Kr in the deep, continental-scale Guarani aquifer in Brazil and show that crustal He reaches the atmosphere primarily by the surficial discharge of deep groundwater. We estimate that He in Guarani groundwater discharge accounts for about 20% of the assumed global flux from continental crust, and that other large aquifers may account for about 33%. Old groundwater ages suggest that He in the Guarani aquifer accumulates over half- to one-millionyear timescales. We conclude that He degassing from the continents is regulated by groundwater discharge, rather than episodic tectonic events, and suggest that the assumed steady state between crustal production and degassing of He, and its resulting atmospheric residence time, should be re-examined.

Trace element contents in zircons from oceanic crust

We present newly acquired trace element compositions for more than 300 zircon grains in 36 gabbros formed at the slow-spreading Mid-Atlantic and Southwest Indian Ridges. Rare earth element patterns for zircon from modern oceanic crust completely overlap with those for zircon crystallized in continental granitoids. However, plots of U versus Yb and U/Yb versus Hf or Y discriminate zircons crystallized in oceanic crust from continental zircon, and provide a relatively robust method for distinguishing zircons from these environments. Approximately 80% of the modern ocean crust zircons are distinct from the field defined by more than 1700 continental zircons from Archean and Phanerozoic samples. These discrimination diagrams provide a new tool for fingerprinting ocean crust zircons derived from reservoirs like that of modern mid-ocean ridge basalt (MORB) in both modern and ancient detrital zircon populations. Hadean detrital zircons previously reported from the Acasta Gneiss, Canada, and the Narryer Gneiss terrane, Western Australia, plot in the continental granitoid field, supporting hypotheses that at least some Hadean detrital zircons crystallized in continental crust forming magmas and not from a reservoir like modern MORB.

Composition of alkali picrites from the southwestern Greenland continental margin

The Labrador Sea is a basin with oceanic crust in its deep part. Bottom morphology of the Labrador Sea is rather complicated. Data of seismic profiling in this region indicate presence of numerous submarine mountains and hills, which are dominated by volcanic rocks. Some chemical and mineral characteristics of the rocks, in particular, high concentrations of alkalis and phosphorus, and presence of high-titanium augite, ilmenite, and devitrified glass enriched in K and Na, allow us to attribute them to K-Na subalkaline picrites typical for ocean islands, seamounts, and oceanic plateaus. Rocks of the K-Na subalkaline series usually form submarine basements and subaerial volcanoes of ocean islands, seamounts, and oceanic plateaus. Thus, the suggestion on formation of the highs on the continental crust is not confirmed by petrographic data, which require a refinement of the tectonic model of the northern part of the Labrador Sea.

Volcanic resurfacing and the early terrestrial crust: Zircon U-Pb and REE constraints from the Isua Greenstone Belt, southern West Greenland

The oldest known bona fide succession of elastic metasediments Occurs in the Isua Greenstone Belt. SW Greenland and consists of a variety of mica schists and rare metaconglomerates. The metasediments are in direct contact with a felsic metavolcanic lithology that has previously been dated to 3.71 Ga. Based on trace element geochemical data for 30 metasediments, we selected the six samples with highest Zr concentrations for zircon extraction. These samples all yielded very few or no zircon, Those extracted from mica schists yielded ion probe U/Pb ages between 3.70 and 3,71 Ga. One metaconglomerate sample yielded just a single zircon of 3.74 Ga age. The mica schist hosted zircons have U/Pb ages. Th/U ratios, REE patterns and Eu anomalies indistinguishable from zircon in the adjacent 3.71 Ga felsic metavolcanic unit. Trace element modelling requires the bulk of material in the metasediments to be derived from variably weathered mafic lithologies but some metasediments contain substantial contribution from more evolved source lithologies. The paucity of zircon in the mica schists is thus explained by incorporation of material from largely zircon-free volcanic lithologies. The absence of older zircon in the mica schists and the preponderance of mafic source material imply intense, mainly basaltic resurfacing of the early Earth. The implications of this process are discussed, Thermal considerations suggest that horizontal growth of Hadean crust by addition of mafic ultramafic lavas must have triggered self-reorganisation of the protocrust by remelting. Reworking oft Hadean crust may have been aided by burial of hydrated (weathered) metabasalt due to semi-continuous addition of new voluminous basalt Outpouring,;, This process Causes a bias towards eruption of Zr-saturated partial melts at the surface with O-isotope corn posit ion,, potentially different from the mantle. The oldest zircons hosted in sediments would have been buried to substantial depth or formed in plutons that crystallised at some depth from which it took hundreds of millions of years for them to be exhumed and incorporated into much younger sediments. (C) 2005 Elsevier B.V.All rights reserved.

Arc crust-magma interaction in the Andean Southern Volcanic Zone from thermobarometry, mineral composition, radiogenic isotope and rare earth element systematics of the Azufre-Planchon-Peteroa volcanic complex, Chile

The Andean Southern Volcanic Zone (SVZ) is a vast and complex continental arc that has been studied extensively to provide an understanding of arc-magma genesis, the origin and chemical evolution of the continental crust, and geochemical compositions of volcanic products. The present study focuses on distinguishing the magma/sub-arc crustal interaction of eruptive products from the Azufre-Planchon-Peteroa (APP 35°15'S) volcanic center and other major centers in the Central SVZ (CSVZ 37°S–42°S), Transitional SVZ (TSVZ 34.3–37.0°S), and Northern SVZ (NSVZ 33°S–34°30'S). New Hf and Nd isotopic and trace element data for SVZ centers are consistent with former studies that these magmas experienced variable depths of crystal fractionation, and that crustal assimilation is restricted to the lower crustal depths with an apparent role of garnet. Thermobarometric calculations applied to magma compositions constrain the depth of magma separation from mantle sources in all segments of the SVZ to(70-90 km). Magmatic separation at the APP complex occurs at an average depth of ~50 km which is confined to the mantle lithosphere and the base of the crust suggesting localized thermal abrasion both reservoirs. Thermobarometric calculations indicate that CSVZ primary magmas arise from a similar average depth of (~54 km) which confines magma separation to the asthenospheric mantle. The northwards along-arc Sr-Nd-Hf isotopic data and LREE enrichment accompanied with HREE depletion of SVZ mafic magmas correlates well with northward increasing crustal thickness and decreasing primary melt separation from mantle source regions indicating an increased involvement of lower crustal components in SVZ magma petrogenesis. ^ The study concludes that the development of mature subduction zones over millions of years of continuous magmatism requires that mafic arc derived melts stagnate at lower crustal levels due to density similarities and emplace at lower crustal depths. Basaltic underplating creates localized hot zone environments below major magmatic centers. These regions of high temperature/partial melting, and equilibration with underplated mafic rocks provides the mechanism that controls trace element and isotopic variability of primary magmas of the TSVZ and NSVZ from their baseline CSVZ-like precursors.^