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Naisten ääniä ja periferian politiikkaa: feministisiä tulkintoja 1990-luvun murroskauden Irlannista

Abstract: Women's voices and peripheral politics : feminist interpretations of the transition of stage in the Ireland of the 1990's

Remediation of a marine shore tailings deposit and the importance of water-rock interaction on element cycling in the coastal aquifer

We present the study of the geochemical processes associated with the first successful remediation of a marine shore tailings deposit in a coastal desert environment (Bahia de Ite, in the Atacama Desert of Peru). The remediation approach implemented a wetland on top of the oxidized tailings. The site is characterized by a high hydrauliz gradient produced by agricultural irrigation on upstream gravel terraces that pushed river water (similar to 500 mg/L SO(4)) toward the sea and through the tailings deposit. The geochemical and isotopic (delta(2)H(water) and delta(18)O(water), delta(34)S(sulfate) , delta(18)O(sulfate)) approach applied here revealed that evaporite horizons (anhydrite and halite) in the gravel terraces are the source of increased concentrations of SO(4), Cl, and Na up to similar to 1500 mg/L in the springs at the base of the gravel terraces. Deeper groundwater interacting with underlying marine sequences increased the concentrations of SO(4), Cl, and Na up to 6000 mg/L and increased the alkalinity up to 923 mg/L CaCO(3) eq. in the coastal aquifer. These waters infiltrated into the tailings deposit at the shelf-tailings interface. Nonremediated tailings had a low-pH oxidation zone (pH 1-4) with significant accumulations of efflorescent salts (10-20 cm thick) at the surface because of upward capillary transport of metal cations in the arid climate. Remediated tailings were characterized by neutral pH and reducing conditions (pH similar to 7, Eh similar to 100 mV). As a result, most bivalent metals such as Cu, Zn, and Ni had very low concentrations (around 0.01 mg/L or below detection limit) because of reduction and sorption processes. In contrast, these reducing conditions increased the mobility of iron from two sources in this system: (1) The originally Fe(III)-rich oxidation zone, where Fe(II) was reduced during the remediation process and formed an Fe(II) plume, and (2) reductive dissolution of Fe(III) oxides present in the original shelf lithology formed an Fe-Mn plume at 10-m depth. These two Fe-rich plumes were pushed toward the shoreline where more oxidizing and higher pH conditions triggered the precipitation of Fe(HI)hydroxide coatings on silicates. These coatings acted as a filter for the arsenic, which naturally infiltrated with the river water (similar to 500 mu g/L As natural background) into the tailings deposit.

Fluid-rock interaction during late stages of the Alpine exhumation

Résumé de la thèseLa fracturation des roches au cours de phases compressives ou extensives est un souvent évoquée pour expliquer la circulation de fluide au sein des roches cristallines. Dans le cadre de cette thèse, la circulation des fluides lors de l'exhumation tardive des Alpes a été étudiée en utilisant deux approches différentes: analyses structurales de la déformation fragile d'une part et analyses géochimiques des roches et des minéraux (isotopes stables, datations U/Pb, thermochronologie (U-Th)/He) d'autre part. Cette approche combinée a permis de mieux comprendre l'interaction existante entre les fluides métamorphiques et les fluides météoriques, ainsi que leur interaction avec les roches encaissantes. Le travail a été effectué dans la zone Pennique du Valais suisse.La première partie était focalisée sur la déformation fragile, le but étant de définir les différents types de déformations existantes et de déterminer l'âge relatif des différentes familles de failles. Dans la région d'étude, quatre domaines ont été distingués. Chacun d'eux comportent deux types de structures fragiles, certaines sont minéralisées alors que d'autre non. Au sein de chaque domaine, la direction principale des structures minéralisées correspond à l'orientation des accidents tectoniques majeurs de la région (Aosta- Ranzola Line au Sud, Rhône Line au Nord et Simplon Fault Zone à l'Est), alors que les structures non- minéralisées montrent des orientations plus variables. Ainsi, le premier type de structure est interprété comme résultant d'une dislocation tectonique alors que le deuxième type de structure résulterait d'une dislocation gravitaire locale. Il n'est néanmoins pas possible de classer chronologiquement la formation de ces deux types de structure ni d'attribuer un âge relatif aux changements d'orientation des contraintes majeures.La deuxième étude a été effectuée dans la région de la zone de faille du Simplon. Dans cette zone, la composition isotopique des minéraux ayant cristallisé à l'intérieur des fractures tardives permet de distinguer différents types de circulation de fluide. Les valeurs δ180 du quartz de la roche encaissante ainsi que ceux des veines tardives du bloque inférieur de la faille sont comparables. Ces valeurs indiquent un rééquilibrage et un tamponnage isotopique des fluides tardifs au contact de la roche encaissante lors de la fracturation de cette dernière et de la cristallisation des veines tardives. La même situation est observée dans la partie nord du bloque supérieur ainsi que dans sa partie sud. Ceci n'est néanmoins pas le cas pour la partie centrale du bloque supérieur où les valeurs isotopiques des minéraux dans les veines tardives sont approximativement 3 %o plus basses (avec des valeurs extrêmes négatifs), indiquant une contribution d'eau météorique aux fluides circulant dans les veines. Ces données suggèrent qu'une infiltration d'eau météorique a pu avoir lieu dans le bloque supérieur, où la fracturation des roches est plus intensive car le déplacement relatif le long de la faille y fut plus important, et la température maximale du métamorphisme plus basse. La troisième contribution traite de la géo-thermochronologie de la zone de contact entre la klippe de la Dent Blanche et la nappe de Tsaté. De petits zircons euhédraux ont été trouvés dans un plan de faille minéralisé (parallèle à la Faille du Rhône, voir première partie de l'étude), riche en hématite et quartz, de la zone d'étude. Les analyses U/Pb donnent des âges radiométriques autour de 270 - 280 Ma aux zircons extraits de la minéralisation ainsi que ceux extraits de la roche encaissante, ce qui correspond à l'âge de la nappe de la Dent Blanche et non celui de la nappe du Tsaté qui est elle-même classiquement interprétée comme une ophiolite Jurassique de l'Océan Liguro-Piémontais. Ces données suggèrent que les zircons contenus dans la veine ont été hérités de la roche encaissante. Les résultats (U-Th)/He indiquent un âge de refroidissement différent pour la roche encaissante (25.5 ± 2.0 Ma) que celui de la minéralisation (17.7 ±1.4 Ma). Le thermomètre isotopique quartz-hématite indique une température d'équilibre, et donc de mise en place de la minéralisation, d'environ 170 °C, température très proche de la température de -180 °C de fermeture du zircon pour le système (U-Th)/He. Ceci suggère que l'âge de refroidissement des zircons de la minéralisation correspond aussi à l'âge de formation de la faille.Thesis abstractFluid circulation in fractured rocks is a common process in geology, and it is generally the consequence of faulting and fracturing during both tectonic compression and extension. This thesis is focused on fluid circulation during late stages of the Alpine exhumation. After a structural analysis of the late brittle deformation of the studied samples, several analytical methods (stable isotope investigations, U/Pb radiometric dating, (U-Th)/He thermochronology) have been applied to understand the interaction of metamorphic and meteoric fluids with one another as well as with the host rock. This thesis is articulated around three study directions. All studies were conducted in the Penninic Zone of the Valais, Switzerland. The first study deals with late, brittle deformation and focuses on the different deformation styles and on the relative age of the different families of fractures. In order to do this, late brittle structures observed in four different domains have been subdivided as a function of the existence (or not) and type of mineralization. Comparisons between mineralized and non-mineralized strike directions for all four domains show that mineralized structures follow the strike orientation of major tectonic movements indicated in the Penninic Zone of the Valais (Aosta-Ranzola Line to the S, Rhône Line to the Ν and Simplon Fault Zone to the E), whereas non-mineralized fractures have a more variable strike orientation. This difference could be interpreted as indicative of tectonic-related faulting (mineralized structures) vs. local, collapse-related faulting (non-mineralized fractures), but it is not strong enough to indicate a relative age of the late brittle structures, and/or a change in the orientation of the strain field in post-Miocene times. The second studied area is focused on the Simplon Fault Zone (SFZ). Stable isotope analyses of minerals filling these late fractures indicate that there are two different fluid circulation systems in the footwall and hanging wall of the SFZ. In the footwall, δ180 values of quartz from both the host rock and the late veins range from +10 %o to +12 %o. This is consistent with buffering of circulating fluids by the host rock during fracturing and vein precipitation. In the hanging wall, δΙ80 values for quartz crystals from the host rock and the late veins are similar in both the northern and southern parts of the detachment that are both affected by the same degree of metamorphism (greenschist to the Ν and amphibolite to the S). This is not the case in the central part of the SFZ, where there is a jump from amphibolite facies in the footwall to greenschist facies in the hanging wall. δ,80 values for quartz from the hanging wall late veins are approximately 3.0 %o lower (down to negative values in some cases) than the values observed in the footwall These data suggest that infiltration of meteoric water may have occurred in the most fractured parts of the hanging wall, where relative displacement on the SFZ was the greatest and the peak temperature lower. In the less fractured footwall the δ180 values reflect a host rock-buffered system.The third study is focused on geo-thermochronology at the contact between the Dent Blanche nappe and the Tsaté nappe where small, euhedral zircons were found in a hematite- and quartz-rich mineralization on a late normal fault plane parallel to the Rhône Line (see first part of the study). U/Pb analysis indicates that the zircons - both in the late mineralization and in the host rock - have absolute radiometric ages clustering around 270 - 280 Ma, which is the accepted age for intrusive rocks from the Austroalpine Dent Blanche units but not for the Tsaté nappe. The latter is classically interpreted as an ophiolitic remnant of the Jurassic Liguro-Piemontais Ocean. U/Pb analyses suggest that zircons in late mineralization are all inherited from the host rock; however, results of (U-Th)/He analyses indicate that cooling ages for the host rocks are different to the cooling ages for the zircons in late mineralization. Indeed, the calculated cooling age for the Arolla gneiss is 25.5 ± 2.0 Ma, whilst the cooling age for the associated mineralized fault plane is 17.7 ±1.4 Ma. Oxygen stable isotope fractionation between quartz and hematite in the same late mineralization corresponds to temperatures of about 170 °C. The proximity of the calculated emplacement temperature for the mineralization and the lower accepted closure temperature for zircon in the (U-Th)/He system (-180 °C) imply that the age of 17.7 ± 1.4 Ma can also be interpreted as the formation age of this late brittle fault.Résumé grand publicLa circulation des fluides dans les roches fracturées est typique de nombreux processus géologiques, et très souvent est la conséquence de la fracturation des roches. Cette thèse aborde la question de la circulation des fluides pendant les dernières phases du soulèvement des Alpes. Après une analyse structurale de la fracturation directement sur le terrain, plusieurs méthodes géochimiques ont été appliquées pour comprendre l'interaction entre les différents fluides circulants, et avec leur propre roche mère. L'étude, concentrée sur trois directions principales, a été conduite dans la zone Pennique du Valais suisse. La première partie traite de la déformation cassante dans le secteur cité. L'analyse détaillée des fractures a permis de les subdiviser en structures minéralisées et non-minéralisées, sur quatre domaines différents. La comparaison entre les directions des structures minéralisées et non-minéralisées a permis de montrer que les premières suivent l'orientation des accidents tectoniques majeurs de la région, alors que les structures non- minéralisées ont une orientation plus variable. Cette différence pourrait être interprétée comme indication d'une dislocation tectonique (structures minéralisées) contre une dislocation gravitaire locale (structures non-minéralisées), mais elle n'est pas assez forte pour indiquer un âge relatif des structures tardives et/ou un changement de l'orientation des contraintes après -20 Ma vers le présent.A partir de ces observations, la deuxième étude est concentrée dans la région de la faille du Simplon. Les analyses géochimiques sur les minéraux remplissant les structures tardives indiquent qu'il y a deux différents systèmes de circulation des fluides dans les deux parties (toit et mur) de la faille. Dans le mur, les valeurs isotopiques des minéraux cristallisés à partir d'un fluide tardif sont les mêmes de ceux de la roche mère, donc il y a eu rééquilibration chimique entre fluide et roche pendant la fracturation de cette dernière et la précipitation des minéraux. Dans le toit, les valeurs isotopiques dans la roche mère et dans les minéraux des veines tardives sont comparables dans les parties Ν et S de la faille, où les roches du toit et du mur ont atteint une température maximale - pendant phase prograde de la formation des Alpes - comparable. Au contraire, dans la partie centrale, où le mur a atteint des températures maximales plus élevées par rapport au toit, les valeurs géochimiques des minéralisations tardives du toit sont parfois plus basses que les valeurs observées dans le mur. Ces données suggèrent que l'infiltration de l'eau de surface aurait pu se produire dans la partie plus fracturée du toit, où le déplacement relatif le long de la faille était majeur et les températures maximales mineures. Au contraire, les données géochimiques du mur de la partie centrale indiquent un système isotopique équilibré par la roche mère.La troisième partie de ce travail se base sur l'étude géochimique intégrée des isotopes stables d'Oxygène et radioactifs du Plomb, Uranium, Thorium et Hélium, auprès d'une faille normale minéralisée et des roches de la région à cheval entre deux nappes, la nappe de la Dent Blanche et la nappe de Tsaté. Ici, des petits zircons ont été trouvés dans la minéralisation citée, riche en hématite et quartz. L'analyse radiométrique Uranium/Plomb a montré que les zircons dans la minéralisation et dans les roches autour ont des âges comparables (autour 280 Ma). Cela signifie que les zircons dans la minéralisation tardive ont été hérités de la roche mère pendant la fracturation et la circulation des fluides tardives. De l'autre coté, les résultats des analyses Uranium-Thorium/Hélium indiquent que les âges de refroidissement pour les roches mères sont différents comparés aux âges de refroidissement pour les zircons dans la minéralisation tardive: ces derniers sont plus jeunes d'environ 8 Ma (autour 25 Ma et autour 17 Ma respectivement). Les analyses des isotopes de l'oxygène sur quartz et hématite dans la même minéralisation donnent une température de mise en place de cette dernière d'environ 170° C. La température de fermeture du système chimique des zircons dans le système (Uranium-Thorium)/Hélium est d'environ 180 °C: la proximité de ces deux températures implique que l'âge de refroidissement de la minéralisation tardive peut également être interprété comme âge de formation de la faille.

Treatment of NI-containing acidic mine waters with calcite side-stones

Acid mine drainage (AMD) presents a serious problem for the environment for the massive formation of acidic leachates containing heavy metals. The present work deals with the AMD treatment using neutralizing limestone side-products. The conventional methods for prevention, mitigating and control of AMD formation are described. The experimental testing of Nordkalk Oy calcite-containing side-stones for acid neutralizing and removal of nickel from solutions presents the research objective. The batch experiments in acid neutralizing with subsequent metal content analysis were carried out. The results showed the dependence of pH on the dose of neutralizing material and the exposure time. The nickel removal, unlike iron, within the pH range from 1.2 to 6.0 appeared to be inadequate. The further research on nickel co-precipitation with iron and aluminium may appear to be necessary together with testing of alkalinity strengthening materials.

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.

Petrography, microprobe analyses and isotope composition of ultramafic rock from the northern Haskard Highlands, Shackleton Range, East Antarctica

In the Shackleton Range of East Antarctica, garnet-bearing ultramafic rocks occur as lenses in supracrustal high-grade gneisses. In the presence of olivine, garnet is an unmistakable indicator of eclogite facies metamorphic conditions. The eclogite facies assemblages are only present in ultramafic rocks, particularly in pyroxenites, whereas other lithologies - including metabasites - lack such assemblages. We conclude that under high-temperature conditions, pyroxenites preserve high-pressure assemblages better than isofacial metabasites, provided the pressure is high enough to stabilize garnet-olivine assemblages (i.e. >=18-20 kbar). The Shackleton Range ultramafic rocks experienced a clockwise P-T path and peak conditions of 800-850 °C and 23-25 kbar. These conditions correspond to ~70 km depth of burial and a metamorphic gradient of 11-12 °C/km that is typical of a convergent plate-margin setting. The age of metamorphism is defined by two garnet-whole-rock Sm-Nd isochrons that give ages of 525 ± 5 and 520 ± 14 Ma corresponding to the time of the Pan-African orogeny. These results are evidence of a Pan-African suture zone within the northern Shackleton Range. This suture marks the site of a palaeo-subduction zone that likely continues to the Herbert Mountains, where ophiolitic rocks of Neoproterozoic age testify to an ocean basin that was closed during Pan-African collision. The garnet-bearing ultramafic rocks in the Shackleton Range are the first known example of eclogite facies metamorphism in Antarctica that is related to the collision of East and West Gondwana and the first example of Pan-African eclogite facies ultramafic rocks worldwide. Eclogites in the Lanterman Range of the Transantarctic Mountains formed during subduction of the palaeo-Pacific beneath the East Antarctic craton.

Geochemistry of igneous rock samples of ODP Site 125-786

A morphologically complex igneous basement was penetrated at Leg 125 Site 786 beneath approximately 100 m of Eocene-Pleistocene sediments at 31°52.45 'N, 141°13.59'E in a 3082-m water depth. The site is located on the forearc basement high (FBH) of the Izu-Bonin (Ogasawara) Arc. In the broadest terms, the sequence in Hole 786B consists of a basal sheeted dike complex, heavily mineralized in places, with overlying pillow lavas giving way to a complex and repeated sequence of interlayered volcanic breccias and lava flows with some thin sedimentary intervals. The sequence has been further cut by dikes or sills, particularly of high-Ca and intermediate-Ca boninite, and is locally strongly sheared by faulting. The whole basement has been covered with middle Eocene-early Pleistocene sediments. A monomict breccia forms the shallowest portion of Hole 786B and a polymict breccia having Mn-oxide-rich clast coatings and matrix forms the deepest part of Hole 786A (-100-160 mbsf). The basement is tectonized in some places, and a mineralized stockwork is present in the deepest part of Hole 786B. A wide variety of rock types form this basement, ranging from mafic to silicic in character and including high-, intermediate-, and low-Ca boninites, intermediate- and low-Ca bronzite andesites, andesite, dacite, and rhyolite groups. Intragroup and intergroup relationships are complicated in detail, and several different upper mantle source(s) probably were involved. A significant role for orthopyroxene-clinopyroxene-plagioclase fractionation is indicated in the mafic-intermediate groups, and the most probable complementary cumulates should be noritic gabbros. Many overall similarities but some subtle differences are noted between the igneous basement at Site 786 and the subaerial outcrops of the FBH to the south in the type boninite locality of Chichijima. Both suites were derived by hydrous melting of a relatively shallow, refractory (harzburgitic) upper mantle source. These Bonin forearc basement rocks are similar in many respects to those of Eocene-Oligocene age now forming the forearc of the Marianas at Leg 60 Site 458 and on Guam. In sharp distinction, the geochemistry of the Eocene-Pleistocene ash sequences overlying the Bonin FBH must have been derived from a very different upper mantle source, implying considerable across-strike differences in sub-arc mantle composition.

Elements and isotopic measurements of magmatic rock samples from ODP Hole 104-642E

Trace element and isotopic signatures of magmatic rock samples from ODP Hole 642E at the Vøring Plateau provide insight into the interaction processes of mantle melt with crust during the initial magma extrusion phases at the onset of the continental breakup. The intermediate (basaltic-andesitic) to felsic (dacitic and rhyolitic) Lower Series magmas at ODP Hole 642E appear to be produced by large amounts of melting of upper crustal material. This study not only makes use of the traditional geochemical tools to investigate crust-mantle interaction, but also explores the value of Cs geochemistry as an additional tool. The element Cs forms the largest lithophile cation, and shows the largest contrast in concentration between (depleted) mantle and continental crust. As such it is a very sensitive indicator of involvement of crustal material. The Cs data reinforce the conclusion drawn from isotopic signatures that the felsic magmas are largely anatectic crustal melts. The down-hole geochemical variation within ODP Hole 642E defines a decreasing continental crustal influence from the Lower Series into the Upper Series. This is essential information to distinguish intrinsic geochemical properties of the mantle melts from signatures imposed by crustal contamination. A comparison with data from the SE Greenland margin highlights the compositional asymmetry of the crust-mantle interactions at both sides of the paleo-Iapetus suture. While Lower Series and Middle Series rocks from the SE Greenland margin have isotopic signatures reflecting interactions with lower and middle crust, such signatures have not been observed at the mid-Norwegian margin. The geochemical data either point to a dissimilar Caledonian crustal composition and/or to different geodynamic pre-breakup rifting history at the two NE Atlantic margin segments.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Whole-rock and mineral geochemistry of ODP Hole 176-735B gabbros

We report mineral chemistry, whole-rock major element compositions, and trace element analyses on Hole 735B samples drilled and selected during Leg 176. We discuss these data, together with Leg 176 shipboard data and Leg 118 sample data from the literature, in terms of primary igneous petrogenesis. Despite mineral compositional variation in a given sample, major constituent minerals in Hole 735B gabbroic rocks display good chemical equilibrium as shown by significant correlations among Mg# (= Mg/[Mg + Fe2+]) of olivine, clinopyroxene, and orthopyroxene and An (=Ca/[Ca + Na]) of plagioclase. This indicates that the mineral assemblages olivine + plagioclase in troctolite, plagioclase + clinopyroxene in gabbro, plagioclases + clinopyroxene + olivine in olivine gabbro, and plagioclase + clinopyroxene + olivine + orthopyroxene in gabbronorite, and so on, have all coprecipitated from their respective parental melts. Fe-Ti oxides (ilmenite and titanomagnetite), which are ubiquitous in most of these rocks, are not in chemical equilibrium with olivine, clinopyroxene, and plagioclase, but precipitated later at lower temperatures. Disseminated oxides in some samples may have precipitated from trapped Fe-Ti-rich melts. Oxides that concentrate along shear bands/zones may mark zones of melt coalescence/transport expelled from the cumulate sequence as a result of compaction or filter pressing. Bulk Hole 735B is of cumulate composition. The most primitive olivine, with Fo = 0.842, in Hole 735B suggests that the most primitive melt parental to Hole 735B lithologies must have Mg# 0.637, which is significantly less than Mg# = 0.714 of bulk Hole 735B. This suggests that a significant mass fraction of more evolved products is needed to balance the high Mg# of the bulk hole. Calculations show that 25%-45% of average Eastern Atlantis II Fracture Zone basalt is needed to combine with 55%-75% of bulk Hole 735B rocks to give a melt of Mg# 0.637, parental to the most primitive Hole 735B cumulate. On the other hand, the parental melt with Mg# 0.637 is far too evolved to be in equilibrium with residual mantle olivine of Fo > 0.89. Therefore, a significant mass fraction of more primitive cumulate (e.g., high Mg# dunite and troctolite) is yet to be sampled. This hidden cumulate could well be deep in the lower crust or simply in the mantle section. We favor the latter because of the thickened cold thermal boundary layer atop the mantle beneath slow-spreading ridges, where cooling and crystallization of ascending mantle melts is inevitable. These observations and data interpretation require reconsideration of the popular concept of primary mantle melts and relationships among the extent of mantle melting, melt production, and the composition and thickness of igneous crust.

Whole-rock geochemistry of amphibolites and metagabbros from ODP Holes 173-1067A and 173-1068A

The Leg 173 Site 1067 and 1068 amphibolites and metagabbros from the west Iberia margin exhibit variable whole-rock compositions from primitive to more evolved (Mg numbers = 49-71) that are generally incompatible trace and rare earth element enriched (light rare earth element [LREE] = 11-89 x chondrite). The Site 1067 amphibolites are compositionally similar to the basalts reported at Site 899 from this same region, based on trace and rare earth element contents. The Site 1068 amphibolites and metagabbros are similar to the Site 899 diabases but are more LREE enriched. However, the Sites 1067 and 1068 amphibolites and metagabbros are not compositionally similar to the Site 900 metagabbros, which are from the same structural high as the Leg 173 samples. The Leg 173 protoliths may be represented by basalts, diabases, and/or fine-grained gabbros that formed from incompatible trace element-enriched liquids.