The Upper Oligocene of Montgat (Catalan Coastal Ranges, Spain): new age constraints to the western Mediterranean Basin opening

The Oligocene deposits of Montgat are integrated in a small outcrop made up of Cenozoic and Mesozoic rocks located in the Garraf-Montnegre horst, close to the major Barcelona fault. The Oligocene of Montgat consists of detrital sediments of continental origin mainly deposited in alluvial fan environments; these deposits are folded and affected by thrusts and strike-slip faults. They can be divided in two lithostratigraphic units separated by a minor southwest-directed thrust: (i) the Turó de Montgat Unit composed of litharenites and lithorudites with high contents of quartz, feldspar, plutonic and limestone rock fragments; and (ii) the Pla de la Concòrdia Unit composed of calcilitharenites and calcilithorudites with high contents of dolosparite and dolomicrite rock fragments. The petrological composition of both units indicates that sediments were derived from the erosion of Triassic (Buntsandstein, Muschelkalk and Keuper facies), Jurassic and Lower Cretaceous rocks (Barremian to Aptian in age). Stratigraphic and petrological data suggest that these units correspond to two coalescent alluvial fans with a source area located northwestwards in the adjoining Collserola and Montnegre inner areas. Micromammal fossils (Archaeomys sp.) found in a mudstone layer of the Pla de la Concòrdia Unit assign a Chattian age (Late Oligocene) to the studied materials. Thus, the Montgat deposits are the youngest dated deposits affected by the contractional deformation that led to the development of the Catalan Intraplate Chain. Taking into account that the oldest syn-rift deposits in the Catalan Coastal Ranges are Aquitanian in age, this allows to precise that the change from a compressive to an extensional regime in this area took place during latest Oligocene-earliest Aquitanian times. This age indicates that the onset of crustal extension related to the opening of the western Mediterranean Basin started in southern France during latest Eocene-early Oligocene and propagated southwestward, affecting the Catalan Coastal Ranges and the northeastern part of the Valencia trough during the latest Chattian-earliest Aquitanian times.

Radiometric age constraints on mineral growth, metamorphism, and tectonism of the Gummfluh klippe, Brianconnais domain of the Prealpes, Switzerland

A combined Ar-40/Ar-39, K/Ar, Rb/Sr and stable isotope study has been made of white micas from the Gummfluh klippe (Brianconnais domain of the Prealpes), Switzerland. The klippe consists mainly of Mesozoic to early Tertiary carbonate rocks metamorphosed from anchizonal to epizonal conditions. At the base of the klippe is a 10-50 m thick, ductilely deformed marble mylonite containing deformed authigenic quartz segregations. Stable isotope measurements of the coexisting calcite (deltaO-18SMOW=24.5) and quartz (deltaO-18SMOW=28.4) from the mylonite indicate relatively low temperatures (< 300-degreesC) during mylonitization. Analyses of white mica separates of varying size fractions from the mylonitic rocks by K/Ar and Rb/Sr techniques yield ages between 57 and 103 Ma. This variation is correlated with two parameters, the size of the mineral fraction, and the proportion of 2M1 (more phengitic) to 1M (more muscovitic) polytype in the sample. The K/Ar and Rb/Sr ages are generally younger in the smaller size fractions, which also containless 2M1 phengite. High precision Ar-40/Ar-39 age spectra from different size fractions of these micas record three distinct components, a small Hercynian component (ca. 200-300 Ma), a significant Eoalpine component (64-80 Ma) forming Ar-40/Ar-39 age plateaus, and a very minor Tertiary component (ca. 20-40 Ma). Characterization of the samples by SEM indicates the presence of two white mica populations, a coarser grained, deformed, detrital mica that probably corresponds to the 2M1 phengite and a finer grained neoformed 1M mica. Collectively these observations suggest that the Gummfluh samples contain a mixture of detrital phengites of Hercynian age together with neocrystallized muscovites grown during the late Eoalpine metamorphic event followed by minor argon loss during the Tertiary. The main geologic episode recorded in the Ar-40/Ar-39 age spectra of white micas in the mylonite is of Late Cretaceous/Early Tertiary age (64-80 Ma), representing the first reliable Eoalpine ages ever to be reported from the Prealpes. Contrary to tectonic models, the marble mylonite at the base of the Gummfluh klippe appears to be a Cretaceous thrust plane and not the thrust surface formed during transport of the klippe into its present position from the Penninic Alps during the Tertiary. The late Cretaceous thrust developed during marine sedimentation at a depth of 800 m below the seafloor at temperatures of approximately 280-degrees-C, facilitated by warm fluids along the tectonic discontinuity.

Structure and kinematics of the Jungfrau syncline, Faflertal (Valais, Alps), and its regional significance

The formation and structural evolution of the jungrau syncline is described, based on excellent outcrops occurring in the lotschental, in the central alps of switzerland. the quality of the outcrops allows us to demonstrate that the external massifs of the swiss alps have developed due to internal folding. The jungfrau suncline, which separates the autochtonous gastern dome from the aar massif basement gneiss folds, is composed of slivers of basement rocks with their mesozoic sedimentary cover. in the inner faflertal, a side valley of the lotschental, the 200 m thick syncline cp, roses fpir imots, the gastern massif with a reduced mesozoic sedimentary cover in a normal stratigraphic succession, two units of overturned basement rocks with their mesozoic sedimentary cover, and the overturned lower limn of the tschingelhorn gneiss fold of the aar massif with lenses of its sedimentary cover. stratigraphy shows that the lower units, related to the gastern massis, are condensed and that the upper units, deposited farther away from a gastern paleo-high, form a more complete sequence, linked to the doldenhorn meso-cneozoic basin fill. the integration of these local observations with published regional data leads to the following model. on the northern margin of the doldenhorn hbasin, at the northern fringe of the alpine tethuys, the pre-triassic crystalline basement and its mesozoic sedimentary cover were folded by ductile deformation at temperatures above 300 degrees C and in the presence of high fluid pressures, as the helveti c and penninic nappes were overthrusted towards the northwest during the main alpine deformation phase, the visosity contrast between the basement gneisses and the sediments caused the formation of large basement anticlines and tight sedimentary sunclines (mullion-type structures). The edges of basement blocks bounded buy pre-cursor se-dipping normal faults at the northwestern border of the doldenhorn basin were deformed bu simple shear, creating overturned slices of crystalline rocks with their sedimentary cover in what now forms the hungfrau syncline. the localisation of ductile deformation in the vicinity of pre-existing se-dipping faults is thought to have been helped by the circulation of fluids along the faults; these fluids would have been released from the mesozoic sediments by metamorphic dehydration reactions accompanied by creep and dynamic recrystallisation of quartz at temperatures above 300 degrees C. Quantification of the deformation suggests an strain ellipsoid with a ratio (1 + e(1)/+ e(3)) of approximately 1000. The jungfrau suncline was deformed bu more brittle nw-directed shear creating well-developed shear band cleavages at a late stage, after cooling by uplift and erosion. It is suggested that the external massifs of the apls are basement gneiss folds created at temperatures of 300 degrees C by detachment through ductile deformation of the upper crust of the european plate as it was underthrusted below the adriatic plate.

The effects of arbuscular mycorrhizal fungi inoculation on Euterpe oleracea mart. (açaí) seedlings

With the objective of verifying the response of Euterpe oleracea seedlings to seven arbuscular mycorrhizal fungi species, an experimental trial was carried out under greenhouse conditions. Seeds of E. oleracea were sown in carbonized rice husk. Germinating seeds were initially transferred to plastic cups, containing fumigated Reddish Yellow Quartz Sand and inoculated with arbuscular mycorrhizal fungi. Two months later, seedlings were transferred to 2 kg black plastic bags, containing the same soil without fumigation. Plant growth and mineral nutrients were evaluated nine months after mycorrhizal inoculation. Differential effects were observed among the species tested, with Scutellispora gilmorei being the most effective ones in promoting growth and nutrient content of E. oleracea seedlings. The increment resulted from inoculation with S. gilmorei were 92% in total plant height, 116% in stem diameter, 361% in dry matter production, 191% in N, 664% in P, 46% in K, 562% in Ca, 363% in Mg and 350% in Zn contents, comparing to uninoculated controls. Infected root length was positively correlated to nutrient content and plant growth. It was concluded that growth and nutrient uptake of E. oleracea seedlings could be significantly improved by inoculation of effective arbuscular mycorrhizal fungi.

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.

Igneous layering, fractional crystallization and growth of granitic plutons: The Dolbel batholith in SW Niger

This study reassesses the development of compositional layering during the growth of granitic plutons, with emphasis on fractional crystallization and its interaction with both injection and inflation-related deformation. The Dolbel batholith (SW Niger) consists of 14, kilometre-sized plutons emplaced by pulsed magma inputs. Each pluton has a coarse-grained core and a peripheral layered series. Rocks consist of albite (An(<= 11)), K-feldspar (Or(96 99), Ab(1) (4)), quartz, edenite (X(Mg)=0337-0.55), augite (X(Mg)=0.65-0.72) and accessories (apatite, titanite and Fe-Ti-oxides). Whole-rock compositions are metaluminous, sodic (K(2)O/Na(2)O=0.49-0.62) and iron-rich [FeO(tot)/(FeO(tot)+MgO)=0.65-0.82]. The layering is present as size-graded and modally graded, sub-vertical, rhythmic units. Each unit is composed of three layers, which are, towards the interior: edenite +/- plagioclase (C(a/p)), edenite+plagioclase+augite+quartz (C(q)), and edenite+plagioclase+augite+quartz+K-feldspar (C(k)). All phases except quartz show zoned microstructures consisting of external intercumulus overgrowths, a central section showing oscillatory zoning and, in the case of amphibole and titanite, complexly zoned cores. Ba and Sr contents of feldspars decrease towards the rims. Plagioclase crystal size distributions are similar in all units, suggesting that each unit experienced a similar thermal history. Edenite, characteristic of the basal C(a/p) layer, is the earliest phase to crystallize. Microtextures and phase diagrams suggest that edenite cores may have been brought up with magma batches at the site of emplacement and mechanically segregated along the crystallized wall, whereas outer zones of the same crystals formed in situ. The subsequent C(q) layers correspond to cotectic compositions in the Qz-Ab-Or phase diagram at P(H2O)=5 kbar. Each rhythmic unit may therefore correspond to a magma batch and their repetition to crystallization of recurrent magma recharges. Microtextures and chemical variations in major phases allow four main crystallization stages to be distinguished: (1) open-system crystallization in a stirred magma during magma emplacement, involving dissolution and overgrowth (core of edenite and titanite crystals); (2) in situ fractional crystallization in boundary layers (C(a/p) and C(q) layers); (3) equilibrium `en masse' eutectic crystallization (C(k) layers); (4) compaction and crystallization of the interstitial liquid in a highly crystallized mush (e. g. feldspar intercumulus overgrowths). It is concluded that the formation of the layered series in the Dolbel plutons corresponds principally to in situ differentiation of successive magma batches. The variable thickness of the Ck layers and the microtextures show that crystallization of a rhythmic unit stops and it is compacted when a new magma batch is injected into the chamber. Therefore, assembly of pulsed magma injections and fractional crystallization are independent, but complementary, processes during pluton construction.

Calcareous plankton biostratigraphy and 40Ar /39Ar dating of miocene volcaniclastic layers from Monferrato (NW Italy)

The results of Ar-40/Ar-39 dating integrated with calcareous plankton biostratigraphical data performed on two volcaniclastic layers (VLs) interbedded in Burdigalian to Lower Langhian outer shelf carbonate sediments cropping out in Monferrato (NW Italy) are presented. The investigated VLs, named Villadeati and Varengo, are thick sedimentary bodies with scarce lateral continuity. They are composed of prevalent volcanogenic material (about 87 up to 90% by volume) consisting of glass shards and volcanic phenocrysts (plagioclase, biotite, quartz, amphibole, sanidine and magnetite) and minor extrabasinal and intrabasinal components. On the basis of their composition and sedimentological features, the VLs have been interpreted as distal shelf turbidites deposited below storm wave base. However, compositional characteristics evidence the rapid resedimentation of the volcanic detritus after its primary deposition and hence the VL sediments can be considered penecontemporaneous to the encasing deposits. Biostratigraphical analyses were carried out on the basis of a quantitative study of calcareous nannofossil and planktonic foraminifer associations, whilst Ar-40/Ar-39 dating were performed on biotite at Villadeati and on homeblende at Varengo. The data resulting from the Villadeati section have permitted to estimate an age of 18.7 +/- 0.1 Ma for the last common occurrence (LCO) of Sphenolithus belemnos whereas those from Varengo allowed to extrapolate an age of 16.4 Ma +/-0.1 Ma for the first occurrence (FO) of Praeorbulina sicana. This latter biovent is commonly used to approximate the base of the Langhian stage, that corresponds to the Early-Middle Miocene boundary.

Impact of controlled changes in grain size and pore space characteristics on the hydraulic conductivity and spectral induced polarization response of "proxies" of saturated alluvial sediments

Understanding the influence of pore space characteristics on the hydraulic conductivity and spectral induced polarization (SIP) response is critical for establishing relationships between the electrical and hydrological properties of surficial unconsolidated sedimentary deposits, which host the bulk of the world's readily accessible groundwater resources. Here, we present the results of laboratory SIP measurements on industrial-grade, saturated quartz samples with granulometric characteristics ranging from fine sand to fine gravel, which can be regarded as proxies for widespread alluvial deposits. We altered the pore space characteristics by changing (i) the grain size spectra, (ii) the degree of compaction, and (iii) the level of sorting. We then examined how these changes affect the SIP response, the hydraulic conductivity, and the specific surface area of the considered samples. In general, the results indicate a clear connection between the SIP response and the granulometric as well as pore space characteristics. In particular, we observe a systematic correlation between the hydraulic conductivity and the relaxation time of the Cole-Cole model describing the observed SIP effect for the entire range of considered grain sizes. The results do, however, also indicate that the detailed nature of these relations depends strongly on variations in the pore space characteristics, such as, for example, the degree of compaction. The results of this study underline the complexity of the origin of the SIP signal as well as the difficulty to relate it to a single structural factor of a studied sample, and hence raise some fundamental questions with regard to the practical use of SIP measurements as site- and/or sample-independent predictors of the hydraulic conductivity.

Low latitude Paleocene to early Eocene radiolarian systematics, biochronology and paleoenvironmental analysis

Highly diverse radiolarian faunas of latest Maastrichtian to early Eocene age have been recovered from the low latitude realm in order to contribute to the clarification of radiolarian taxonomy, construct a zonation based on a discrete sequence of co-existence intervals of species ranging from the late Paleocene to early Eocene and to describe a rich low latitude latest Cretaceous to late Paleocene fauna. 225 samples of late Paleocene to early Eocene age have been collected from ODP Leg 171 B-Hole 1051 A (Blake Nose), DSDP Leg 43-Site 384 (Northwest Atlantic) and DSDP Leg 10-Sites 86, 94, 95, 96. Sequences consist of mainly pelagic oozes and chalks, with some clay and ash layers. A new imaging technique is devised to perform (in particular on topotypic material) both transmitted light microscopy and SEM imaging on individual radiolarian specimens. SEM precedes transmitted light imaging. Radiolarians are adhered to a cover slip (using nail varnish) which is secured to a stub using conductive levers. Specimens are then photographed in low vacuum (40-50Pa; 0.5mbar), which enables charge neutralization by ionized molecules of the chamber atmosphere. Thus gold coating is avoided and subsequently this allows transmitted light imaging to follow. The conductive levers are unscrewed and the cover slip is simply overturned and mounted with Canada balsam. In an attempt towards a post-Haeckelian classification, the initial spicule (Entactinaria), micro- or macrosphere (Spumellaria) and initial spicule and cephalis (Nassellaria) have been studied by slicing Entactinaria and Spumellaria, and by tilting Nassellaria in the SEM chamber. A new genus of the family Coccodiscidae is erected and Spongatractus HAECKEL is re-located to the subfamily Axopruinae. The biochronology has been carried out using the Unitary Association Method (Guex 1977, 1991). A database recording the occurrences of 112 species has been used to establish a succession of 22 Unitary Associations. Each association is correlated to chronostratigraphy via calcareous microfossils that were previously studied by other authors. The 22 UAs have been united into seven Unitary Associations Zones (UAZones) (JP10- JE4). The established zones permit to distinguish supplementary subdivisions within the existing zonation. The low-latitude Paleocene radiolarian zonation established by Sanfilippo and Nigrini (1998a) is incomplete due to the lack of radiolarian-bearing early Paleocene sediments. In order to contribute to the study of sparsely known low latitude early Paleocene faunas, 80 samples were taken from the highly siliceous Guayaquil Formation (Ecuador). The sequence consists of black cherts, shales, siliceous limestones and volcanic ash layers. The carbonate content increases up section. Age control is supplied by sporadic occurrences of silicified planktonic foraminifera casts. One Cretaceous zone and seven Paleocene zones have been identified. The existing zonation for the South Pacific can be applied to the early-early late Paleocene sequence, although certain marker species have significantly shorter ranges (notably Buryella foremanae and B. granulata). Despite missing marker species in the late Paleocene, faunal distribution correlates reasonably to the Low-Latitude zonation. An assemblage highly abundant in Lithomelissa, Lophophaena and Cycladophora in the upper RP6 zone (correlated by the presence of Pterocodon poculum, Circodiscus circularis, Pterocodon? sp. aff. P. tenellus and Stylotrochus nitidus) shows a close affinity to contemporaneous faunas reported from Site 1121, Campbell Plateau. Coupled with a high diatom abundance (notably Aulacodiscus spp. and Arachnoidiscus spp.), these faunas are interpreted as reflecting a period of enhanced biosiliceous productivity during the late Paleocene. The youngest sample is void of radiolarians, diatoms and sponge spicules yet contains many pyritized infaunal benthic foraminifera which are akin to the midway-type fauna. The presence of this fauna suggests deposition in a neritic environment. This is in contrast to the inferred bathyal slope depositional environment of the older Paleocene sediments and suggests a shoaling of the depositional environment which may be related to a coeval major accretionary event. RESUME DE LA THESE Des faunes de radiolaires de basses latitudes très diversifiées d'âge Maastrichtien terminal à Eocène inférieur, ont été étudiées afin de contribuer à la clarification de leur taxonomie, de construire une biozonation basée sur une séquence discrète d'intervalles de coexistence des espèces d'age Paléocène supérieur à Eocène inférieur et de décrire une riche faune de basse latitude allant du Crétacé terminal au Paléocène supérieur. L'étude de cette faune contribue particulièrement à la connaissance des insaisissables radiolaires de basses latitudes du Paléocène inférieur. 225 échantillons d'âge Paléocène supérieur à Eocène inférieur provenant des ODP Leg 171B-Site 1051A (Blake Nose), Leg DSDP 43-Site 384 (Atlantique Nord -Ouest) et des DSDP Leg 10 -Sites 86, 94, 95, 96, ont été étudiés. Ces séquences sont constituées principalement de « ooze » et de « chalks »pélagiques ainsi que de quelques niveaux de cendres et d'argiles. Une nouvelle technique d'imagerie a été conçue afin de pouvoir prendre conjointement des images en lumière transmise et au Microscope Electronique à Balayage (MEB) de spécimens individuels. Ceci à été particulièrement appliqué à l'étude des topotypes. L'imagerie MEB précède l'imagerie en lumière transmise. Les radiolaires sont collés sur une lame pour micropaléontologie (au moyen de vernis à ongles) qui est ensuite fixée à un porte-objet à l'aide de bras métalliques conducteurs. Les spécimens sont ensuite photographiés en vide partiel (40-50Pa; 0.5mbar), ce qui permet la neutralisation des charges électrostatiques dues à la présence de molécules ionisées dans l'atmosphère de la chambre d'observation. Ainsi la métallisation de l'échantillon avec de l'or n'est plus nécessaire et ceci permet l'observation ultérieure en lumière transmise. Les bras conducteurs sont ensuite dévissés et la lame est simplement retournée et immergée dans du baume du Canada. Dans une approche de classification post Haeckelienne, le spicule initial (Entactinaires), la micro- ou macro -sphère (Spumellaires) et le spicule initial et cephalis (Nassellaires) ont été étudiés. Ceci a nécessité le sectionnement d'Entactinaires et de Spumellaires, et de pivoter les Nassellaires dans la chambre d'observation du MEB. Un nouveau genre de la Famille des Coccodiscidae a été érigé et Spongatractus HAECKEL à été réassigné à la sous-famille des Axopruninae. L'analyse biostratigraphique à été effectuée à l'aide de la méthode des Associations Unitaires {Guex 1977, 1991). Une base de données enregistrant les présences de 112 espèces à été utilisée poux établir une succession de 22 Associations Unitaires. Chaque association est corrélée à la chronostratigraphie au moyen de microfossiles calcaires précédemment étudiés par d'autres auteurs. Les 22 UAs ont été combinées en sept Zones d'Associations Unitaires (UAZones) (JP10- JE4). Ces Zones permettent d'insérer des subdivisions supplémentaires dans la zonation actuelle. La zonation de basses latitudes du Paléocène établie par Sanfilippo et Nigrini (1998a) est incomplète due au manque de sédiments du Paléocène inférieur contenant des radiolaires. Afin de contribuer à l'étude des faunes peu connues des basses latitudes du Paléocène inférieur, 80 échantillons ont été prélevés d'une section siliceuse de la Formation de Guayaquil (Equateur). La séquence est composée de cherts noirs, de shales, de calcaires siliceux et de couches de cendres volcaniques. La fraction carbonatée augmente vers le haut de la section. Des contraintes chronologiques sont fournies par la présence sporadique de moules de foraminifères planctoniques. Une zone d'intervalles du Crétacé et sept du Paléocène ont été mises en évidence. Bien que certaines espèces marqueur ont des distributions remarquablement plus courtes (notamment Buryella foremanae et B. granulata), la zonation existante pour le Pacifique Sud est applicable à la séquence d'age Paléocène inférieure à Paléocène supérieur basal étudiée. Malgré l'absence d'espèces marqueur du Paléocène supérieur, la succession faunistique se corrèle raisonnablement avec la zonation pour les basses latitudes. Un assemblage contenant d'abondants représentant du genre Lithomelissa, Lophophaena et Cycladophora dans la zone RP6 (correlée par la présence de Pterocodon poculum, Circodiscus circularis, Pterocodon? sp. aff. P. tenellus et Stylotrochus nitidus) montre une grande similitude avec certaines faunes issues des hauts latitudes et d'age semblable décrites par Hollis (2002, Site 1121, Campbell Plateau). Ceci, en plus d'une abondance importante en diatomés (notamment Aulacodiscus spp. et Arachnoidiscus spp.) nous mènent à interpréter cette faune comme témoin d'un épisode de productivité biosiliceuse accrue dans le Paléocène supérieur. L'échantillon le plus jeune, dépourvu de radiolaires, de diatomés et de spicules d'éponge contient de nombreux foraminifères benthiques infaunaux pyritisés. Les espèces identifiées sont caractéristiques d'une faune de type midway. La présence de ces foraminifères suggère un environnement de type néritique. Ceci est en contraste avec l'environnement de pente bathyale caractérisent les sédiments sous-jacent. Cette séquence de diminution de la tranche d'eau peut être associée à un événement d'accrétion majeure. RESUME DE LA THESE (POUR LE GRAND PUBLIC) Les radiolaires constituent le groupe de plancton marin le plus divers et le plus largement répandu de l'enregistrement fossile. Un taux d'évolution rapide et une variation géographique considérable des populations font des radiolaires un outil de recherche sans égal pour la biostratigraphie et la paléocéanographie. Néanmoins, avant de pouvoir les utiliser comme outils de travail, il est essentiel d'établir une solide base taxonomique. L'étude des Radiolaires peut impliquer plusieurs techniques d'extraction, d'observation et d'imagerie qui sont dépendantes du degré d'altération diagénétique des spécimens. Le squelette initial, qu'il s'agisse d'un spicule initial (Entactinaria), d'une micro- ou macro -sphère (Spumellaria) ou d'un spicule initial et d'un cephalis (Nassellaria), est l'élément le plus constant au cours de l'évolution et devrait représenter le fondement de la systématique. Des échantillons provenant de carottes de basses latitudes du Deep Sea Drilling Project et de l' Ocean Drilling ont été étudiés. De nouvelles techniques d'imagerie et de sectionnement ont été développées sur des topotypes de radiolaires préservés en opale, dans le but d'étudier les caractéristiques de leur squelette initial qui n'étaient pas visibles dans leur illustration originale. Ceci aide entre autre à comparer des spécimens recristallisés en quartz, provenant de terrains accrétés, avec les holotypes en opale de la littérature. La distribution des espèces étudiés a fourni des données biostratigraphiques qui ont été compilées à l'aide de la méthode des Associations Unitaires (Guez 1977, 1991). Il s'agit d'un modèle mathématique déterministe conçu pour exploiter la totalité de l'assemblage plutôt que de se confiner à l'utilisation de taxons marqueurs individuels. Une séquence de 22 Associations Unitaires a été établie pour la période allant du Paléocène supérieur à l'Éocène inférieur. Chaque Association Unitaire a été corrélée à l'échelle de temps absolue à l'aide de microfossiles calcaires. Les 22 UAs ont été combinées en sept Zones d'Associations Unitaires (JP10- JE4). Ces Zones permettent d'insérer des subdivisions supplémentaires dans la zonation actuelle. Les radiolaires du Paléocène inférieur à moyen des basses latitudes sont rares. Les meilleures sections connues se trouvent dans les hautes latitudes (Nouvelle Zélande). Quelques assemblages épars ont été mentionnés par le passé en Californie, en Équateur et en Russie. Une séquence siliceuse de 190 mètres dans la Formation de Guayaquil (Équateur), s'étendant du Maastrichtien supérieur au Paléocène supérieur, a fourni des faunes relativement bien préservées. L'étude de ces faunes a permis de mettre en évidence la première séquence complète de radiolaires de basses latitudes dans le Paléocène inférieure. Huit zones allant du Crétacé terminal au Paléocène supérieur ont pu être appliqués et la présence de foraminifères planctoniques a fournie plusieurs points d'attache chronologiques. Dans le Paléocène supérieur, un riche assemblage contenant d'abondants diatomés et radiolaires ayant des similitudes faunistiques marquantes avec des assemblages de hautes latitudes de Nouvelle Zélande, témoigne d'un épisode de productivité biosiliceuse accrue pendant cette période. Étant donné que la pointe du continent sud-américain et l'Antarctique étaient plus proches au cours du Paléocène, ce phénomène peut être expliqué par le transport, le long de la côte ouest de l'Amérique du Sud, d'eaux riches en nutriments en provenance de l'Océan Antarctique. Suite à cet épisode, l'enregistrement en radiolaires est interrompu. Ceci peut être associé à des événements tectoniques régionaux qui ont eu pour effet de diminuer la tranche d'eau relative, rendant l'environnement plus favorable aux foraminifères benthiques qui sont abondamment présents dans l'échantillon le plus jeune de la séquence.

The Role of Magnesium in Concrete Deterioration, HR-355, Appendix, 1994

In the main report concerning the role that magnesium may have in highway concrete aggregate, over 20,000 electron microprobe data were obtained, primarily from automated scans, or traverses, across dolomite aggregate grains and the adjacent cement paste. Representative traverses were shown in figures and averages of the data were presented in Table II. In this Appendix, detailed representative and selected analyses of carbonate aggregate only are presented. These analyses were not presented in the main report because they would be interesting to only a few specialists in dolomite· rocks. In this Appendix, individual point analyses of mineral compositions in the paste have been omitted along with dolomite compositions at grain boundaries and cracks. Clay minerals and quartz inclusions in the aggregate are also not included. In the analyses, the first three column headings from left to right show line number, x-axis, and y-axis (Line number is an artifact of the computer print-out for each new traverse. Consecutive line numbers indicate a continuous traverse with distances between each point of 1.5 to a few μ-m. X-axis and y-axis are coordinates on the electron microscope stage). The next columns present weight percent oxide content of FeO, K20, CaO, Si02, Al203, MgO, SrO, BaO, MnO, Na20, and C02 (calculated assuming the number of moles of C02 is equal to the sum of moles of oxides, chiefly CaO and MgO), TOTAL (the sum of all oxides), and total (sum of all oxides excluding COi). In many of the analyses total is omitted.

Deterioration of Iowa Highway Concrete Pavements: A Petrographic Study, HR-1065, 1999

Major highway concrete pavements in Iowa have exhibited premature deterioration attributed to effects of ettringite formation, alkali-silica expansive reactions, and to frost attack, or some combination of them. These pavements were constructed in the mid- 1980s as non-reinforced, dual-lane, roads ranging in thickness between 200 mm and 300 mm, with skewed joints reinforced with dowels. Deterioration was initially recognized with a darkening of joint regions, which occurred for some pavements as soon as four years after construction. Pavement condition ranges from severe damage to none, and there appeared to be no unequivocal materials or processing variables correlated with failure. Based upon visual examinations, petrographic evaluation, and application of materials models, the deterioration of concrete highway pavements in Iowa appear related to a freeze-thaw failure of the coarse aggregate and the mortar. Crack patterns sub-parallel to the concrete surface transecting the mortar fraction and the coarse aggregate are indicative of freeze-thaw damage of both the mortar and aggregate. The entrained air void system was marginal to substandard, and filling of some of the finer-sized voids by ettringite appears to have further degraded the air void system. The formation of secondary ettringite within the entrained air voids probably reflects a relatively high degree of concrete saturation causing the smaller voids to be filled with pore solution when the concrete freezes. Alkali-silica reaction (ASR) affects some quartz and shale in the fine aggregate, but is not considered to be a significant cause of the deterioration. Delayed ettringite formation was not deemed likely as no evidence of a uniform paste expansion was observed. The lack of field-observed expansion is also evidence against the ASR and DEF modes of deterioration. The utilization of fly ash does not appear to have affected the deterioration as all pavements with or without fly ash exhibiting substantial damage also exhibit significant filling of the entrained air void system, and specimens containing fly ash from sound pavements do not have significant filling. The influence of the mixture design, mixing, and placing must be evaluated with respect to development of an adequate entrained air void system, concrete homogeneity, longterm drying shrinkage, and microcracking. A high-sand mix may have contributed to the difficult mixture characteristics noted upon placement and exacerbate concrete heterogeneity problems, difficulty in developing an adequate entrained air void system, poor consolidation potential, and increased drying shrinkage and cracking. Finally, the availability of moisture must also be considered, as the secondary precipitation of ettringite in entrained air voids indicates they were at least partially filled with pore solution at times. Water availability at the base of the slabs, in joints, and cracks may have provided a means for absorbing water to a point of critical saturation.

Performance of Poly-Carb, Inc. Flexogrid Bridge Overlay System, MLR-86-04, 2001

Intrusion of deicing materials and surface water into concrete bridge decks is a main contributor in deck reinforcing steel corrosion and concrete delamination. Salt, spread on bridge decks to melt ice, dissolves in water and permeates voids in the concrete deck. When the chloride content of the concrete in contact with reinforcing steel reaches a high enough concentration, the steel oxidizes. In Iowa, the method used to reduce bridge deck chloride penetration is the application of a low slump dense concrete overlay after the completion of all Class A and Class B floor repairs. A possible alternative to the use of dense concrete overlays, developed by Poly-Carb, Inc., is the MARK-163 FLEXOGRID Overlay System. FLEXOGRID is a two component system of epoxy and urethane which is applied on a bridge deck to a minimum thickness of ¼ inch. An aggregate mixture of silica quartz and aluminum oxide is broadcast onto the epoxy at a prescribed rate to provide deck protection and superior friction properties. The material is mixed on site and applied to the deck in a series of lifts (usually two) until the desired overlay thickness has been attained.

Quantification of magmatic and hydrothermal processes in a peralkaline syenite-alkali granite complex based on textures, phase equilibria, and stable and radiogenic isotopes

The Puklen complex of the Mid-Proterozoic Gardar Province, South Greenland, consists of various silica-saturated to quartz-bearing syenites, which are intruded by a peralkaline granite. The primary mafic minerals in the syenites are augite +/- olivine + Fe-Ti oxide + amphibole. Ternary feldspar thermometry and phase equilibria among mafic silicates yield T = 950-750degreesC, a(SiO2) = 0.7-1 and an f(O2) of 1-3 log units below the fayalite-magnetite-quartz (FMQ) buffer at 1 kbar. In the granites, the primary mafic minerals are ilmenite and Li-bearing arfvedsonite, which crystallized at temperatures below 750degreesC and at f(O2) values around the FMQ buffer. In both rock types, a secondary post-magmatic assemblage overprints the primary magmatic phases. In syenites, primary Ca-bearing minerals are replaced by Na-rich minerals such as aegirine-augite and albite, resulting in the release of Ca. Accordingly, secondary minerals include ferro-actinolite, (calcite-siderite)(ss), titanite and andradite in equilibrium with the Na-rich minerals. Phase equilibria indicate that formation of these minerals took place over a long temperature interval from near-magmatic temperatures down to similar to300degreesC. In the course of this cooling, oxygen fugacity rose in most samples. For example, late-stage aegirine in granites formed at the expense of arfvedsonite at temperatures below 300degreesC and at an oxygen fugacity above the haematite-magnetite (HM) buffer. The calculated delta(18)O(melt) value for the syenites (+5.9 to +6.3parts per thousand) implies a mantle origin, whereas the inferred delta(18)O(melt) value of <+5.1parts per thousand for the granitic melts is significantly lower. Thus, the granites require an additional low-delta(18)O contaminant, which was not involved in the genesis of the syenites. Rb/Sr data for minerals of both rock types indicate open-system behaviour for Rb and Sr during post-magmatic metasomatism. Neodymium isotope compositions (epsilonNd(1170 Ma) = -3.8 to -6.4) of primary minerals in syenites are highly variable, and suggest that assimilation of crustal rocks occurred to variable extents. Homogeneous epsilon(Nd) values of -5.9 and -6.0 for magmatic amphibole in the granites lie within the range of the syenites. Because of the very similar neodymium isotopic compositions of magmatic and late- to post-magmatic minerals from the same syenite samples a principally closed-system behaviour during cooling is implied. In contrast, for the granites an externally derived fluid phase is required to explain the extremely low epsilon(Nd) values of about -10 and low delta(18)O between +2.0 and +0.5parts per thousand for late-stage aegirine, indicating an open system in the late-stage history. In this study we show that the combination of phase equilibria constraints with stable and radiogenic isotope data on mineral separates can provide much better constraints on magma evolution during emplacement and crystallization than conventional whole-rock studies.

Magmatic fluids in the Breccia-hosted epithermal Au-Ag deposit of Rosia Montana, Romania

The breccia-hosted epithermal Au-Ag deposit of Rosia Montana is located 7 kin northeast of Abrud, in the northern part of the South Apuseni Mountains, Romania. Estimated total reserves of 214.91 million metric toils (Mt) of ore at 1.46 g/t An and 6.9 g/t Ag (10.1 Moz of An and 47.6 Moz of Ag) make Rosia Montana one of the largest gold deposits in Europe. At this location, Miocene calc-alkaline magmatic and hydrothermal activity was associated with local extensional tectonics within a strike-slip regime related to the indentation of the Adriatic microplate into the European plate during the Carpathian orogenesis. The host rocks of the magmatic complex consist of pre-Mesozoic metamorphosed continental crust covered by Cretaceous turbiditic sediment (flysch). Magmatic activity at Rosia Montana and its surroundings occurred in several pulses and lasted about 7 m.y, Rosia Montana is a breccia-hosted epithermal system related to strong phreatomagmatic activity due to the shallow emplacement of the Montana dacite. The Montana dacite intruded Miocene volcaniclastic material (volcaniclastic breccias) and crops out at Cetate and Carnic Hills. Current mining is focused primarily on the Cetate open pit, which was mapped in detail, leading to the recognition of three distinct breccia bodies: the dacite breccia with a dominantly hydrothermal matrix, the gray polymict breccia with a greater proportion of sand-sized matrix support, and the black polymict breccia, which reached to the surface, contains carbonized tree trunks and has a dominantly barren elastic matrix. The hydrothermal alteration is pervasive. Adularia alteration with a phyllic overprint is ubiquitous; silicification and argillic alteration occur locally. Mineralization consists of quartz, adularia, carbonates (commonly Mn-rich), pyrite, Fe-poor sphalerite, galena, chalcopyrite, tetrahedrite, and native gold and occurs as disseminations, as well as in veins and filling vugs within the Montana dacite and the different breccias. The age of mineralization (12.85 +/- 0.07 Ma) was determined by Ar-40- Ar-39 dating on hydrothermal adularia crystals from vugs in the dacite breccia in the Cetate open pit. Microthermometric measurements of fluid inclusions in quartz phenocrysts from the Montana dacite revealed two fluid types that are absent from the hydrothermal breccia and must have been trapped at depth prior to dacite dome emplacement: brine inclusions (32-55 -wt % NaCl equiv, homogenizing at T-h > 460 degrees C) and intermediate density fluids (4.9-15.6 wt % NaCl equiv, T, between 345 degrees-430 degrees C). Secondary aqueous fluid inclusion assemblages in the phenocrysts have salinities of 0.2 to 2.2 wt percent NaCl equiv and T-h of 200 degrees to 280 degrees C. Fluid inclusion assemblages in hydrothermal quartz from breccias and veins have salinities of 0.2 to 3.4 wt percent NaCl equiv and T-h, from 200 degrees to 270 degrees C. The oxygen isotope composition of several zones of an ore-related epithermal quartz crystal indicate a very constant delta O-18 of 4.5 to 5.0 per mil for the mineralizing fluid, despite significant salinity and temperature variation over time. Following microthermometry, selected fluid inclusion assemblages were analyzed by laser ablation-inductively coupled-plasma mass spectrometry (LA-ICMS). Despite systematic differences in salinity between phenocryst-hosted fluids trapped at depth and fluids from quartz in the epithermal breccias, all fluids have overlapping major and trace cation ratios, including identical Na/K/Rb/Sr/Cs/Ba. Consistent with the constant near-magmatic oxygen isotope composition of the hydrothermal fluids, these data strongly indicate a common magmatic component of these chemically conservative solutes in all fluids. Cu, Pb, Zn, and Mn show variations in concentration relative to the relatively non-reactive alkalis, reflecting the precipitation of sulfide minerals together with An in the epithermal breccia, and possibly of Cu in an inferred subjacent porphyry environment. The magmatic-hydrothermal processes responsible for epithermal Au-Ag mineralization at Rosia Montana are, however, not directly related to the formation of the spatially associated porphyry Cu-Au deposit of Rosia Poieni, which occurred lout 3 m.y. later.

Fluid geochemistry of the Acqui Terme-Visone geothermal area (Piemonte, Italy)

The main geothermal reservoir of Acqui Terme-Visone hosts Na-Cl waters, which are in chemical equilibrium at 120-130 degrees C with typical hydrothermal minerals including quartz, albite, K-feldspar, illite, chlorite (or smectite), anhydrite, calcite and an unspecified Ca-Al-silicate. In the Acqui Terme-Visone area, these geothermal waters ascend along zones of high vertical permeability and discharge at the surface almost undiluted or mixed with cold, shallow waters. To the SW of Acqui Terme, other ascending geothermal waters, either undiluted or mixed with low-salinity waters, enter relatively shallow secondary reservoirs, where they reequilibrate at 65-70 degrees C. Both chemical and isotopic data indicate that bacterial SO4 reduction affects all these waters, especially those discharged by the secondary reservoirs. Therefore, geothermal waters must get in contact with oil, acquiring the relatively oxidized organic substances needed by SO4-reducing bacteria. This oil-water interaction process deserves further investigations, for potential economic implications. (C) 2000 Elsevier Science Ltd. All rights reserved.