Fluid-rock-strain feedbacks in extensional shear zones

La présence de fluide météorique synchrone à l'activité du détachement (Farmin, 2003 ; Mulch et al., 2007 ; Gébelin et al., 2011), implique que les zones de cisaillement sont des systèmes ouverts avec des cellules de convections à l'échelle crustale et un intense gradient géothermique au sein du détachement (Morrison et Anderson, 1998, Gottardi et al., 2011). De plus, les réactions métamorphiques liées à des infiltrations fluides dans les zones de cisaillement extensionnel peuvent influencer les paramètres rhéologiques du système (White and Knipe, 1978), et impliquer la localisation de la déformation dans la croûte. Dans ce manuscrit, deux zones de cisaillement infiltrées par des fluides météoriques sont étudiées, l'une étant largement quartzitique, et l'autre de nature granitique ; les relations entre déformation, fluides, et roches s'appuient sur des approches structurales, microstructurales, chimiques et isotopiques. L'étude du détachement du Columbia river (WA, USA) met en évidence que la déformation mylonitique se développe en un million d'années. La phase de cisaillement principal s'effectue à 365± 30°C d'après les compositions isotopiques en oxygène du quartz et de la muscovite. Ces minéraux atteignent l'équilibre isotopique lors de leur recristallisation dynamique contemporaine à la déformation. La zone de cisaillement enregistre une baisse de température, remplaçant le mécanisme de glissement par dislocation par celui de dissolution- précipitation dans les derniers stades de l'activité du détachement. La dynamique de circulation fluide bascule d'une circulation pervasive à chenalisée, ce qui engendre localement la rupture des équilibres d'échange isotopiques. La zone de cisaillement de Bitterroot (MT, USA) présente une zone mylonitique de 600m d'épaisseur, progressant des protomylonites aux ultramylonites. L'intensité de la localisation de la déformation se reflète directement sur l'hydratation des feldspaths, réaction métamorphique majeure dite de « rock softening ». Une étude sur roche totale indique des transferts de masse latéraux au sein des mylonites, et d'importantes pertes de volume dans les ultramylonites. La composition isotopique en hydrogène des phyllosilicates met en évidence la présence (1) d'une source magmatique/métamorphique originelle, caractérisée par les granodiorites ayant conservé leur foliation magmatique, jusqu'aux protomylonites, et (2) une source météorique qui tamponne les valeurs des phyllosilicates des fabriques mylonitiques jusqu'aux veines de quartz non-déformées. Les compositions isotopiques en oxygène des minéraux illustrent le tamponnement de la composition du fluide météorique par l'encaissant. Ce phénomène cesse lors du processus de chloritisation de la biotite, puisque les valeurs des chlorites sont extrêmement négatives (-10 per mil). La thermométrie isotopique indique une température d'équilibre isotopique de la granodiorite entre 600-500°C, entre 500-300°C dans les mylonites, et entre 300 et 200°C dans les fabriques cassantes (cataclasites et veines de quartz). Basé sur les résultats issus de ce travail, nous proposons un modèle général d'interactions fluide-roches-déformation dans les zones de détachements infiltrées par des fluides météoriques. Les zones de détachements évoluent rapidement (en quelques millions d'années) au travers de la transition fragile-ductile ; celle-ci étant partiellement contrôlée par l'effet thermique des circulations de fluide météoriques. Les systèmes de détachements sont des lieux où la déformation et les circulations fluides sont couplées ; évoluant rapidement vers une localisation de la déformation, et de ce fait, une exhumation efficace. - The presence of meteoric fluids synchronous with the activity of extensional detachment zones (Famin, 2004; Mulch et al., 2007; Gébelin et al., 2011) implies that extensional systems involve fluid convection at a crustal scale, which results in high geothermal gradients within active detachment zones (Morrison and Anderson, 1998, Gottardi et al., 2011). In addition, the metamorphic reactions related to fluid infiltration in extensional shear zones can influence the rheology of the system (White and Knipe, 1978) and ultimately how strain localizes in the crust. In this thesis, two shear zones that were permeated by meteoric fluids are studied, one quartzite-dominated, and the other of granitic composition; the relations between strain, fluid, and evolving rock composition are addressed using structural, microstructural, and chemical/isotopic measurements. The study of the Columbia River detachment that bounds the Kettle core complex (Washington, USA) demonstrates that the mylonitic fabrics in the 100 m thick quartzite- dominated detachment footwall developed within one million years. The main shearing stage occurred at 365 ± 30°C when oxygen isotopes of quartz and muscovite equilibrated owing to coeval deformation and dynamic recrystallization of these minerals. The detachment shear zone records a decrease in temperature, and dislocation creep during detachment shearing gave way to dissolution-precipitation and fracturing in the later stages of detachment activity. Fluid flow switched from pervasive to channelized, leading to isotopic disequilibrium between different minerals. The Bitterroot shear zone detachment (Montana, USA) developed a 600 m thick mylonite zone, with well-developed transitions from protomylonite to ultramylonite. The localization of deformation relates directly to the intensity of feldspar hydration, a major rock- softening metamorphic reaction. Bulk-rock analyses of the mylonitic series indicate lateral mass transfer in the mylonite (no volume change), and significant volume loss in ultramylonite. The hydrogen isotope composition of phyllosilicates shows (1) the presence of an initial magmatic/metamorphic source characterized by the granodiorite in which a magmatic, and gneissic (protomylonite) foliation developed, and (2) a meteoric source that buffers the values of phyllosilicates in mylonite, ultramylonite, cataclasite, and deformed and undeformed quartz veins. The mineral oxygen isotope compositions were buffered by the host-rock compositions until chloritization of biotite started; the chlorite oxygen isotope values are negative (-10 per mil). Isotope thermometry indicates a temperature of isotopic equilibrium of the granodiorite between 600-500°C, between 500-300°C in the mylonite, and between 300 and 200°C for brittle fabrics (cataclasite and quartz veins). Results from this work suggest a general model for fluid-rock-strain feedbacks in detachment systems that are permeated by meteoric fluids. Phyllosilicates have preserved in their hydrogen isotope values evidence for the interaction between rock and meteoric fluids during mylonite development. Fluid flow generates mass transfer along the tectonic anisotropy, and mylonites do not undergo significant volume change, except locally in ultramylonite zones. Hydration of detachment shear zones attends mechanical grain size reduction and enhances strain softening and localization. Self-exhuming detachment shear zones evolve rapidly (a few million years) through the transition from ductile to brittle, which is partly controlled by the thermal effect of circulating surface fluids. Detachment systems are zones in the crust where strain and fluid flow are coupled; these systems. evolve rapidly toward strain localization and therefore efficient exhumation.

Événements et déformations tardi-métamorphiques dans le segment Ossola-Ticino (Val Vigezzo-Centovalli, Italie-Suisse)

RESUME: Une zone tectonique large et complexe, connue sous le nom de ligne des Centovalli, traverse le secteur des Alpes Centrales compris entre Domodossola et Locarno. Cette région, formée par le Val Vigezzo et la vallée des Centovalli, constitue la terminaison méridionale du dôme Lepontin et représente une portion de la zone des racines des nappes alpines. Elle fait partie d’une grande et complexe zone de cisaillement, en partie associée à des phénomènes hydrothermaux d’âge alpin (<20 Ma), qui comprend le système tectonique Insubrien et celui du Simplon. Le Val Vigezzo et les Centovalli constituent un vrai carrefour entre les principaux accidents tectoniques des Alpes ainsi qu'une zone de juxtaposition du socle Sudalpin avec la zone des racines de l’Austroalpin et du Pennique. Les phases de déformation et les structures géologiques qui peuvent être étudiées s'étalent sur une période comprise entre environ 35 Ma et l'actuel. L’étude détaillée de terrain a mis en évidence la présence de nombreuses roches et structures de déformation de type ductile et cassant tels que des mylonites, des cataclasites, des pseudotachylites, des kakirites, des failles minéralisées, des gouges de faille et des plis. Sur le terrain on a pu distinguer au moins quatre générations de plis liés aux différentes phases de déformation. Le nombre et la complexité de ces structures indiquent une histoire très compliquée, selon plusieurs étapes distinctes, parfois liées, voire même superposées. Une partie de ces structures de déformation affectent aussi les dépôts sédimentaires d’âge quaternaire, notamment des limons et des sables lacustres. Ces sédiments constituent les restes d'un bassin lacustre attribué à l'époque interglaciaire Riss/Würm (éemien, 67.000-120.000 ans) et ils affleurent dans la partie centrale de la zone étudiée, à l'Est de la plaine de Santa Maria Maggiore. Ces sédiments montrent en leur sein toute une série de structures de déformation tels que des plans de faille inverses, des structures conjuguées de raccourcissement et des véritables plis. Ces failles et ces plis représenteraient les évidences de surface d’une déformation probablement active en époque quaternaire. Une autre formation rocheuse a retenu tout notre attention; il s'agit d'un corps de brèches péridotitiques monogéniques qui affleure en discontinuité le long du versant méridional et le long du fond de la vallée Vigezzo sur environ 20 km. Ces brèches se posent indifféremment sur le socle (unités Finero, Orselina) ou sur les sédiments lacustres. Elles sont traversées par des plans de failles qui développent des véritables stries de faille et des gouges de faille; l’orientation de ces plans est la même que celle affectant les failles à gouges du socle. La genèse de cette brèche est liée à l'altération et au modelage glacier (rock-glaciers) d'une brèche tectonique originelle qui borde la partie externe du Corps de Finero. Les structures de déformation de cette brèche, pareillement à celles des sédiments lacustres, ont été considérées comme les évidences de surface d'une tectonique quaternaire active dans la région. La dernière phase de déformation cassante qui affecte cette région peut donc être considérée comme active en époque quaternaire. Une vue d’ensemble de la région étudiée nous permet de reconnaître à l’échelle régionale une zone de cisaillement complexe orientée E-W, parallèlement à l’axe de la vallée Centovalli-Val Vigezzo. Les données de terrain, indiquent que cette zone de cisaillement débute sous conditions ductiles et évolue en plusieurs étapes jusqu’à des conditions de failles cassantes de surface. La reconstruction de l'évolution géodynamique de la région a permis de définir trois étapes distinctes qui marquent le passage, de ce secteur de socle cristallin, de conditions P-T profondes à des conditions de surface. Dans ce contexte, on a reconnu trois phases principales de déformation à l’échelle régionale qui caractérisent ces trois étapes. La phase la plus ancienne est constituée par des mylonites en faciès amphibolite, associées à des mouvements de cisaillement dextre, qui sont ensuite remplacés par des mylonites en faciès schistes verts et des plis rétrovergentes liés au rétrocharriage des nappes alpines. Une deuxième étape est identifiée par le développement d’une phase hydrothermale liée à un système de failles extensives et décrochantes dextres à direction principale E-W, NE-SW et NW-SE. Leur caractérisation minéralogique a permis la mise en évidence des phases cristallines de néoformation liées à cet événement constituées par : K-feldspath (microcline), chlorites (Fe+Mg), épidotes, prehnite, zéolites (laumontite), sphène, calcite. Dans ce contexte, pour obtenir une meilleure caractérisation de cet événement hydrothermal on a utilisé des géothermomètres sur chlorites, sensible aussi à la pression et a la a(H2O), qui ont donné des valeurs descendantes comprises entre 450-200°C. Les derniers mouvements sont mis en évidence par le développement d’une série de plans majeurs de failles à gouge, qui forment une structure en sigmoïdes d’épaisseur kilométrique reconnaissable à l’échelle de la vallée et caractérisée par des mouvements transpressifs avec une composante décrochante dextre toujours importante. Cette phase de déformation forme un système conjugué de failles avec direction moyenne E-W qui coupent la zone des racines des nappes alpines, la zone du Canavese et le corps ultramafique de Finero. Ce système se déroule de manière subparallèle à l'axe de la vallée le long de plusieurs dizaines de kilomètres. Une analyse complète et détaillée des gouges de faille par XRD a montré que la fraction argileuse (<2 µm) de ces gouges contient une partie de néoformation très importante constituée par, des illites, des chlorites et des interstratifiés de type illite/smectite ou chlorite/smectite. Des datations avec méthode K-Ar sur ces illites ont donné des valeurs comprises entre 12 et 4 Ma qui représentent l'âge de cette dernière déformation cassante. L'application de la méthode de la cristallinité de l'illite (C.I.) a permis d'évaluer les conditions thermiques qui caractérisent le déroulement de cette dernière phase tectonique qui se produit sous conditions de température caractéristiques de l'anchizone et de la diagenèse. L'ensemble des structures de déformation qu'on vient de décrire s'insère parfaitement dans le contexte de convergence oblique entre la plaque adriatique et celle européenne qui à produit l'orogène alpin. On peut considérer les structures tectoniques du Val Vigezzo-Centovalli comme l'expression d'une zone majeure de cisaillement "Simplo-Insubrienne". L'empilement structural et les structures tectoniques affleurantes dans la région sont le résultat de l'interaction entre un régime tectonique transpressif et un régime transtensif. Ces deux champs de tension sont antagonistes entre eux mais sont reliés, de toute façon, à une seule phase décrochante dextre principale, due à une convergence oblique entre deux plaques. À l'échelle de l'évolution géodynamique on peut distinguer différentes étapes au cours desquelles les structures de ces deux régimes tectoniques interagissent en manière différente. En accord avec les données géophysiques et les reconstructions paléodynamiques prises dans la littérature on considère que la ligne Rhône-Simplon-Centovalli représente l'évidence de surface de la suture majeure profonde entre la plaque Adriatique et celle Européenne. Les vitesses de soulèvement qui ont été calculées dans cette étude pour cette région des Alpes donnent une valeur moyenne de 0.8 mm/a qui est tout à fait comparable avec les données proposées par la littérature sur cette zone. La zone Val Vigezzo-Centovalli peut être donc considérée comme un carrefour géologique où se croisent différentes phases tectoniques qui représentent les évidences de surface d'une suture profonde majeure entre deux plaques dans un contexte de collision continentale. ABSTRACT: A wide and complex tectonic zone known as Centovalli line, crosses the Central Alps sector between Domodossola and Locarno. This area, formed by the Vigezzo Valley and Centovalli valley, constitutes the southernmost termination of the Lepontin dome and represents a portion of the alpine nappes root zone. It belongs to a large and complex shear-zone, partly associated with hydrothermal phenomena of alpine age (<20 My), which includes the Insubric Line and the Simplon fault zone. Vigezzo Valley and Centovalli constitute a real crossroads between the mains alpines tectonics lines as well as a zone of juxtaposition of the Southalpine basement with the Austroalpin and Pennique root zone. The deformation phases and the geological structures that can be studied between approximately 35 My and the present. The detailed field study showed the presence of many brittle and ductile deformation structures and fault rocks such as mylonites, cataclasites, pseudotachylites, kakirites, mineralized faults, fault gouges and folds. In the field we could distinguish at least four folds generations related to the various deformation phases. The number and the complexity of these structures indicate a very complicated history, comprising several different stages, that sometimes are related and even superimposed. Part of these deformation structures affect also the sedimentary deposits of quaternary age, in particular the silts and sands lake deposit. These sediments constitute the remainders of a lake basin ascribed to the interglacial Riss/Würm (Eemien, 67.000-120.000 years) and outcroping in the central part of the studied area, in the Eastern part of Santa Maria Maggiore plain. These sediments show a whole series of deformation structures such as inverse fault planes, combined shortening structures and true folds. These faults and folds would represent the surface evidence of a probably active tectonic deformation in quaternary time. Another rock formation attracted all our attention. It is a body of monogenic peridotite breccia which outcrops in discontinuity along the southernmost slope and the bottom of the Vigezzo valley on approximately 20 km. This breccia lies indifferently on the basement (Finero and Orselina units) or on the lake sediments. They are crossed by fault planes which developed slikenside and fault gouges whose orientation is the same of the faults gouges in the alpine basement. This breccia results from the weathering and the surface modelling of an original tectonic breccia which borders the external part of Finero peridotite body. This breccia deformation structures, like those of the lake sediments, were regarded as the surface interaction of active quaternary tectonics in the area. So the last brittle deformation phases which affects this area seems to be actives in quaternary time. Theoverall picture of the studied area on a regional scale enables us to point out a complex shear-zone directed E-W, parallel to the axis of the Centovalli and Vigezzo Valley. The field analysis indicates that this shear-zone began under ductile conditions and evolved in several stages to brittle faulting under surface conditions. The analysis of the geodynamic evolution of the area allows to define three different stages which mark the transition of this alpine basement root zone, from deep P-T conditions to P-T surface conditions. In this context on regional scale three principal deformation phases, which characterize these three stages can be distinguished. The oldest phase consisted of the amphibolitie facies mylonites, associated to dextral strikeslip movements. They are then replaced by green-schists facies mylonites and backfolds related to the backthrusting of the alpines nappes. A second episode is caracterized by the development of an hydrothermal phase bound to an extensive fault and dextral strike-slip fault system, with E-W, NW-SE and SE-NW principal directionsThe principal neoformed mineral phases related to this event are: K-feldspar (microcline), chlorites (Fe+Mg), epidotes prehnite, zéolites (laumontite), sphene and calcite. In this context, to obtain a better characterization of this hydrothermal event, we have used an chlorite geothermometer, sensitive also to the pressure and has the a(H2O), which gave downward values ranging between 450-200°C. The last movements are caracterized by the development of important gouge fault plans, which form a sigmoid structure of kilometric thickness which is recognizable at the valley scale, and is characterized by transpressive movements always with a significant dextral strike-slip component. This deformation phase forms a combined faults system with an average E-W direction, which cuts trough the alpine root zone, the Canavese zone and the Finero ultramafic body. This fault system takes place subparallel to the axis of the valley over several tens of kilometers. A complete and detailed XRD analysis of the gouges fault showed that the clay fraction (<2µm) contains a very significant neo-formation of illite, chlorites and mixed layered clays such as illite/smectite or chlorite/smectite. The K-Ar datings of the illite fraction <2µm gave values ranging between 12 and 4 My and the illite fraction <0.2µm gave more recents values until to 2,4-0 My.This values represent the age of this last brittle deformation. The application of the illite crystallinity method (C.I.) allowed evaluating the thermal conditions which characterize this tectonic phase that occured under temperature conditions of the anchizone and diagenesis. The whole set of deformation structures which we just described, perfectly fit the context of oblique convergence between the Adriatic and the European plate that produced the alpine orogen. We can regard the Vigezzo valley and Centovalli tectonic structures as the expression of a major "Simplo-Insubric" shear-zone. Structural stacking and tectonic structures that outcrop in the studied area, are the result of the interaction between a transpressive and a transtensve tectonic phases. These two tension fields are antagonistic but they are also connected, in any event, with only one principal dextral strike-slip movement, caused by an oblique convergence between two plates. On the geodynamic evolution scale we can distinguish various stages during which these two tectonic structures fields interact in various ways. In agreement with the geophysical data and the paleodynamic recostructions taken in the literature we considers that the Rhone-Simplon-Centovalli line are the surface feature of the major collision between the Adriatique and the European plate at depth. The uplift speeds we calculated in this study for this Alpine area give an average value of 0.8 mm/a, which is in good agreement with the data suggested by the literature on this zone. TheVigezzo Valley and Centovalli zone can therefore be regarded as a geological crossroad where various tectonic phases are superimposed. They represent the evidences of a major and deeper suture between two plates in a continental collision context.

Sanitizer residues in the milk of cows which had passed through footbaths

Copper sulfate and sodium hypochlorite are used in footbath solutions for the prevention and treatment of bovine digital diseases; however, data on the residues of such elements in milk are sparse in Brazil. This study evaluated the cost of applying the footbath treatment and the total amount of copper and chlorite residues in the milk of healthy cows after they had passed through these footbath solutions. Two groups of 7 cows each (GI and GII) were studied. In the case of GI, 1% sodium hypochlorite was used and for GII 5% copper sulfate was employed in the footbath. The milk samples were collected before the 7-day footbath treatment period (M0) and 24 h (M1), 48 h (M2), 72 h (M3) and 15 days (M15) after the last footbath. Statistical analysis to compare the different samples within each group was carried out by applying Friedman's test, followed by Dunn's test (p<0.05). It was concluded that the amount of total chlorites and copper in the milk of healthy cattle after routine daily footbaths for a period of 7 days presented some variations. However, the concentrations observed were considered insufficient to represent a risk to human health. The cost of the footbath solutions was found to be reasonable.

Application of reactive fluid transport modeling to hydrothermal systems

A one-dimensional multi-component reactive fluid transport algorithm, 1DREACT (Steefel, 1993) was used to investigate different fluid-rock interaction systems. A major short coming of mass transport calculations which include mineral reactions is that solid solutions occurring in many minerals are not treated adequately. Since many thermodynamic models of solid solutions are highly non-linear, this can seriously impact on the stability and efficiency of the solution algorithms used. Phase petrology community saw itself faced with a similar predicament 10 years ago. To improve performance and reliability, phase equilibrium calculations have been using pseudo compounds. The same approach is used here in the first, using the complex plagioclase solid solution as an example. Thermodynamic properties of a varying number of intermediate plagioclase phases were calculated using ideal molecular, Al-avoidance, and non-ideal mixing models. These different mixing models can easily be incorporated into the simulations without modification of the transport code. Simulation results show that as few as nine intermediate compositions are sufficient to characterize the diffusional profile between albite and anorthite. Hence this approach is very efficient, and can be used with little effort. A subsequent chapter reports the results of reactive fluid transport modeling designed to constrain the hydrothermal alteration of Paleoproterozoic sediments of the Southern Lake Superior region. Field observations reveal that quartz-pyrophyllite (or kaolinite) bearing assemblages have been transformed into muscovite-pyrophyllite-diaspore bearing assemblages due to action of fluids migrating along permeable flow channels. Fluid-rock interaction modeling with an initial qtz-prl assemblage and a K-rich fluid simulates the formation of observed mineralogical transformation. The bulk composition of the system evolves from an SiO2-rich one to an Al2O3+K2O-rich one. Simulations show that the fluid flow was up-temperature (e.g. recharge) and that fluid was K-rich. Pseudo compound approach to include solid solutions in reactive transport models was tested in modeling hydrothermal alteration of Icelandic basalts. Solid solutions of chlorites, amphiboles and plagioclase were included as the secondary mineral phases. Saline and fresh water compositions of geothermal fluids were used to investigate the effect of salinity on alteration. Fluid-rock interaction simulations produce the observed mineral transformations. They show that roughly the same alteration minerals are formed due to reactions with both types of fluid which is in agreement with the field observations. A final application is directed towards the remediation of nitrate rich groundwaters. Removal of excess nitrate from groundwater by pyrite oxidation was modeled using the reactive fluid transport algorithm. Model results show that, when a pyrite-bearing, permeable zone is placed in the flow path, nitrate concentration in infiltrating water can be significantly lowered, in agreement with proposals from the literature. This is due to nitrogen reduction. Several simulations investigate the efficiency of systems with different mineral reactive surface areas, reactive barrier zone widths, and flow rates to identify the optimum setup.

Prediction of water–rock interaction and porosity evolution in a granitoid-hosted enhanced geothermal system, using constraints from the 5 km Basel-1 well

Numerical simulations based on plans for a deep geothermal system in Basel, Switzerland are used here to understand chemical processes that occur in an initially dry granitoid reservoir during hydraulic stimulation and long-term water circulation to extract heat. An important question regarding the sustainability of such enhanced geothermal systems (EGS), is whether water–rock reactions will eventually lead to clogging of flow paths in the reservoir and thereby reduce or even completely block fluid throughput. A reactive transport model allows the main chemical reactions to be predicted and the resulting evolution of porosity to be tracked over the expected 30-year operational lifetime of the system. The simulations show that injection of surface water to stimulate fracture permeability in the monzogranite reservoir at 190 °C and 5000 m depth induces redox reactions between the oxidised surface water and the reduced wall rock. Although new calcite, chlorite, hematite and other minerals precipitate near the injection well, their volumes are low and more than compensated by those of the dissolving wall-rock minerals. Thus, during stimulation, reduction of injectivity by mineral precipitation is unlikely. During the simulated long-term operation of the system, the main mineral reactions are the hydration and albitization of plagioclase, the alteration of hornblende to an assemblage of smectites and chlorites and of primary K-feldspar to muscovite and microcline. Within a closed-system doublet, the composition of the circulated fluid changes only slightly during its repeated passage through the reservoir, as the wall rock essentially undergoes isochemical recrystallization. Even after 30 years of circulation, the calculations show that porosity is reduced by only ∼0.2%, well below the expected fracture porosity induced by stimulation. This result suggests that permeability reduction owing to water–rock interaction is unlikely to jeopardize the long-term operation of deep, granitoid-hosted EGS systems. A peculiarity at Basel is the presence of anhydrite as fracture coatings at ∼5000 m depth. Simulated exposure of the circulating fluid to anhydrite induces a stronger redox disequilibrium in the reservoir, driving dissolution of ferrous minerals and precipitation of ferric smectites, hematite and pyrite. However, even in this scenario the porosity reduction is at most 0.5%, a value which is unproblematic for sustainable fluid circulation through the reservoir.

(Table 1) Oxygen isotopes in minerals at DSDP Hole 83-504B basalts

The D/H, 18O/16O and 87Sr/86Sr ratios of the basaltic basement from the Leg 83 section of DSDP Hole 504B show that in that area the oceanic crust has experienced intensive but not pervasive alteration. Isotope ratios of the basalts are very heterogeneous because of an input of oxygen, hydrogen, and strontium from seawater. The hydrogen isotopic composition of many samples displays the complete thermal history of the water-rock interactions. High-temperature mineral formations (actinolites, epidotes, and chlorites) were overgrown by a mineralization at lower temperatures (mixedlayer smectites, iddingsites, and smectites) during successive stages of cooling of the oceanic crust by cold seawater. From 87Sr/86Sr data bulk water/rock ratios up to 5:1 have been calculated. There is evidence that some primary minerals like high-An plagioclases contain oxygen from altered basalts. We have discussed the probability that there existed a seawater/crust interface, now at a depth of 620 m sub-basement, during the high-temperature water/rock interactions. This interface was covered during later magmatism by thick flows, pillow lavas, and intrusives.

Messinian and pre-Messinian sediments of ODP Holes 107-652A and 107-654A

Sedimentology, mineralogy, and petrology of the pre-Pliocene sediments drilled at ODP Sites 652 and 654 in the Tyrrhenian Sea (Leg 107) have been studied with emphasis on the lower Messinian to pre-Messinian intervals. Messinian at Site 652 is essentially turbiditic and basinal in character; it was deposited during the syn-rift phase in a strongly subsiding half-graben and is correlatable with emerged coeval sequences; in part with the Laga Formation of the foredeep of Apennines, and in part with the filling of grabens dissecting that chain in the Tyrrhenian portion of Tuscany. The sequence found in Site 654 indicates an upper Tortonian to Messinian transgression accompanying crustal stretching in the western Tyrrhenian Sea and is perfectly correlatable with the so-called "Sahelian cycle" and with "postorogenic" cycles recognized in peninsular Italy and in Sicily.

Mineralogy and geochemistry of weathered serpentinites in DSDP Leg 84 sediments

At Sites 566, 567, and 570 of Leg 84, ophiolitic serpentinite basement was covered by a sequence of serpentinitic mud that was formed by weathering of the serpentinites under sea- or pore-water conditions. Several mineralogical processes were observed: (1) The serpentinitic mud that consists mainly of chrysotile was formed from the lizardite component of the serpentinites by alteration. (2) Slightly trioctahedral smectites containing nonexpandable mica layers, trioctahedral smectites containing nonexpandable chlorite layers, and swelling chlorites were presumably formed from detrital chlorite and/or serpentine. (3) The occurrence of tremolite, chlorite, analcime, and talc can be attributed to reworking of gabbroic ophiolite rocks. (4) Dolomite, aragonite, and Mg-calcite, all authigenic, occur in the serpentinitic mud.