Characteristics and origin of agates in sedimentary rocks from the Dryhead area, Montana, USA

Agates from the Bighorn district in Montana (USA), the so-called Dryhead area, and their adjacent host rocks have been examined in the present study. Analyses by XRD, polarizing microscopy, LA-ICP-MS, cathodoluminescence (CL), SEM and of oxygen isotopes were performed to obtain information surrounding the genesis of this agate type. Investigations of the agate microstructure by polarizing microscopy and CL showed that chalcedony layers and macrocrystalline quartz crystals may have formed by crystallization from the same silica source by a process of self-organization. High defect densities and internal structures (e. g. sector zoning) of quartz indicate that crystallization went rapidly under non-equilibrium conditions. Most trace-element contents in macrocrystalline quartz are less than in chalcedony due to a process of `self-purification', which also caused the formation of Fe oxide inclusions and spherules. Although the agates formed in sedimentary host rocks, analytical data indicate participation of hydrothermal fluids during agate formation. Trace elements (REE distribution patterns, U contents up to 70 ppm) and CL features of agate (transient blue CL), as well as associated minerals (fluorite, REE carbonates) point to the influence of hydrothermal processes on the genesis of the Dryhead agates. However, formation temperatures <120 degrees C were calculated from O-isotope compositions between 28.9 parts per thousand (quartz) and 32.2 parts per thousand (chalcedony).

Origin of cadmium enrichments in carbonate rocks deposited in the Alpine Tethys area during the Middle-Late Jurassic

ABSTRACTThe pollution of air, soil and water by heavy metals through anthropogenic activities is an object of numerous environmental studies since long times. A number of natural processes, such as volcanic activity, hydrothermal fluid circulation and weathering of metal-rich deposits may lead to an additional and potentially important input and accumulation of heavy metals in the environment. In the Swiss and French Jura Mountains, anomalous high cadmium (Cd) concentrations (up to 16 ppm) in certain soils are related to the presence of underlying Cd-enriched (up to 21 ppm) carbonate rocks of Middle to Late Jurassic age. The aim of this study is to understand the processes controlling Cd incorporation into carbonate rocks of Middle and Late Jurassic age and to reconstruct the sedimentary and environmental conditions, which have led to Cd enrichments in these sedimentary rocks.Cd concentrations in studied hemipelagic sections in France vary between 0.1 and 0.5 ppm (mean 0.15 ppm). Trace-element behavior and high Mn concentrations suggest that sediment accumulation occurred in a well-oxygenated environment. Increases in Cd contents in the bulk-rock carbonate sediments may be related to increases in surface-water productivity under oxic conditions and important remineralization of organic matter within the water column. In platform settings preserved in the Swiss Jura Mountains, no correlation is observed between Cd contents and evolution of environmental conditions. Cd concentrations in these platform sections are often below the detection limit, with isolated peaks of up to 21 ppm. These important Cd enrichments are associated with peaks in Zn concentrations and are present in carbonate rocks independently of facies and age. The high Cd contents in these shallow-water carbonate rocks are partly related to the presence of disseminated, Cd-rich (up to 1.8%), sphalerite (ZnS) mineralization. The basement rocks are considered to be the source of metals for sulfide mineralization in the overlying Jurassic strata, as the sphalerite Pb isotope pattern is comparable to that of granite rocks from the nearby southern Black Forest crystalline massif. The Rb-Sr ages of sphalerite samples indicate that a main phase of sphalerite formation occurred near the boundary between the late Middle and early Late Jurassic, at around 162 Ma, as a result of enhanced tectonic and hydrothermal activity in Europe, related to the opening of the Central Atlantic and to the tectonic/thermal subsidence during spreading of the Alpine Tethys. I therefore propose to use unusually high Cd concentrations in carbonates as a tracer of tectonic activity in the Jura Mountains area, especially in the case when important enrichments in Zn co-occur. Paleoproductivity reconstructions based on records of authigenic Cd may be compromised not only by post-depositional redistribution, but also by incorporation of additional Cd from hydrothermal solutions circulating in the rock.The circulation of metal-rich hydrothermal fluids through the sediment sequence, in addition to specific environmental conditions during sedimentation, contributes to the incorporation of Cd into the carbonate rocks. However, only hydrothermal activity has led to the unusually high concentrations of Cd in carbonate rocks of Bajocian-Oxfordian age, through the formation of sphalerite mineralization.

Permian-polysulphide-siderite-barite-haematite deposit Rude in Samoborska Gora Mts., Zagorje-Mid-Transdanubian zone of the Inner Dinarides

Samoborska Gora Mts. is situated within the westernmost part of the Zagorje-Mid-Transdanubian zone of the Internal Dinarides. The Samoborska Gora Mts. predominantly consists of Permian unmetamorphosed siliciclastic sediments and evaporites, overlain by Lower Triassic sediments. Rude mineralisation is hosted by Permian siliciclastic sediments, below gypsum and anhydrite strata. The central part of the deposit consists of a 1.5 km long stratabound mineralisation, grading laterally into ferruginous sandstone and protruding vertically into a gypsum-anhydrite layer. Siderite-polysulphide-barite-quartz veins are located below the stratabound mineralisation. The stratiform part of the deposit is situated above the stratabound and consists of haematite layer with barite concretions and veinlets. Late stage galena-barite veins overprint earlier types of mineralisation. The Rude ore deposit was generated by predominantly NaCl +/- CaCl(2)-H(2)O solutions. Detrital quartz from stratiform mineralisation contains fluid inclusions with salinities between 7 and 11 wt. % NaCl equ., homogenizing between 150 degrees C to 230 degrees C. Stratabound/siderite-polysulphide-barite-quartz vein type mineralisation was derived from solutions with salinities between 5 and 19 wt. % NaCl equ., homogenizing between 60 degrees C and 160 degrees C, while late stage galenabarite veins were precipitated from solutions with salinities between 11 and 16 wt. % NaCl equ., homogenizing between 100 degrees C to 140 degrees C. Fluid inclusion bulk leachate chemistry recorded Na(+)> Mg(2+)>K(+)>Ca(2+)>Li(+) and Cl-> SO(4)(2-) ions. Sulphur isotope composition of barites and overlying gypsum stems from Permian seawater sulphate, supported by increased Br(-) content, which follows successively the seawater evaporation line. The sulphur isotopic composition of sulphides varies between -0.2 and + 12.5 parts per thousand , as a result of thermal reduction of Permian marine sulphate. Ore-forming fluids were produced by hydrothermal convective cells (reflux brine model), and were derived primarily from Permian seawater, modified by evaporation and interaction with Permian sedimentary rocks. Rude deposits in Samoborska Gora Mts. may be declared as a prototype of the Permian siderite-polysulphide-barite deposits (products of rifting along the passive Gondwana margin), in the Inner Dinarides, and their equivalents extending northeastward into the Zagorje-Mid-Transdanubian Zone and the Gemerides, and southeastward to the Hellenide-Albanides.

Sr, C and O isotope systematics in the Pucara Basin, central Peru - Comparison between Mississippi Valley-type deposits and barren areas

A combined Sr, O and C isotope study has been carried out in the Pucara basin, central Peru, to compare local isotopic trends of the San Vicente and Shalipayco Zn-Pb Mississippi Valley-type (MVT) deposits with regional geochemical patterns of the sedimentary host basin. Gypsum, limestone and regional replacement dolomite yield Sr-87/Sr-86 ratios that fall within or slightly below the published range of seawater Sr-87/Sr-86 values for the Lower Jurassic and the Upper Triassic. Our data indicate that the Sr isotopic composition of seawater between the Hettangian and the Toarcian may extend to lower Sr-87/Sr-86 ratios than previously published values. An Sr-87-enrichment is noted in (1) carbonate rocks from the lowermost part of the Pucara basin, and (2) different carbonate generations at the MVT deposits. This indicates that host rocks at MVT deposits and in the lowermost part of the carbonate sequence interacted with Sr-87-enriched fluids. The fluids acquired their radiogenic nature by interaction with lithologies underlying the carbonate rocks of the Pucara basin. The San Ramon granite, similar Permo-Triassic intrusions and their elastic derivatives in the Mitu Group are likely sources of radiogenic Sr-87. The Brazilian shield and its erosion products are an additional potential source of radiogenic Sr-87. Volcanic rocks of the Mitu Group are not a significant source for radiogenic Sr-87; however, molasse-type sedimentary rocks and volcaniclastic rocks cannot be ruled out as a possible source of radiogenic Sr-87. The marked enrichment in Sr-87 of carbonates toward the lower part of the Pucara Group is accompanied by only a slight decrease in delta(18)O values and essentially no change in delta(13)C values, whereas replacement dolomite and sparry carbonates at the MVT deposits display a coherent trend of progressive Sr-87-enrichment, and O-18- and C-13-depletion. The depletion in O-18 in carbonates from the MVT deposits are likely related to a temperature increase, possibly coupled with a O-18-enrichment of the ore-forming fluids. Progressively lower delta(13)C values throughout the paragenetic sequence at the MVT deposits are interpreted as a gradually more important contribution from organically derived carbon. Quantitative calculations show that a single fluid-rock interaction model satisfactorily reproduces the marked Sr-87-enrichment and the slight decrease in delta(18)O values in carbonate rocks from the lower part of the Pucara Group. By contrast, the isotopic covariation trends of the MVT deposits are better reproduced by a model combining fluid mixing and fluid-rock interaction. The modelled ore-bearing fluids have a range of compositions between a hot, saline, radiogenic brine that had interacted with lithologies underlying the Pucara sequence and cooler, dilute brines possibly representing local fluids within the Pucara sequence. The composition of the local fluids varies according to the nature of the lithologies present in the neighborhood of the different MVT deposits. The proportion of the radiogenic fluid in the modelled fluid mixtures interacting with the carbonate host rocks at the MVT deposits decreases as one moves up in the stratigraphic sequence of the Pucara Group.

A search for the origin of cadmium in the soil of the Swiss Jura

The top soil of a 14.5 km(2) region at la Chaux-de-Fonds in the Swiss Jura is exceptionally rich in cadmium. It contains an average of 1.3 mg per kg of soil. The spatial distribution of the metal has no simple pattern that could be explained by atmospheric deposition or agricultural practices. Thin soil contained most of its Cd at the surface; in thicker soil Cd is mainly concentrated between 60 and 80 cm depth. No specific minerals or soil fractions could account for these accumulation, and the vertical distribution of Cd is best explained by leaching from the topsoil and further adsorption within layers of nearly neutral pH. The local Jurassic sedimentary rocks contained too little Cd to account for the Cd concentrations in the soil. Alpine gravels from glacial till were too sparse in soils to explain such a spreading of Cd. Moreover this origin is contradictory with the fact that Cd is concentrated in the sand fraction of soils. The respective distributions of Fe and Cd in soils, and soil fractions, suggested that the spreading of iron nodules accumulated during the siderolithic period (Eocene) was not the main source of Cd. Atmospheric deposition, and spreading of fertiliser or waste from septic tanks seem the only plausible explanation for the Cd concentrations, but at present few factors allow us to differentiate between them.

Textural, chemical, and isotopic effects of late-magmatic carbonatitic fluids in the carbonatite-syenite Tamazeght complex, High Atlas Mountains, Morocco

Carbonatites of the Eocene Tamazeght complex, High Atlas Mountains, Morocco, consist of calciocarbonatites (alvikite and sovite dykes) and magnesiocarbonatites (diatreme breccias and dykes rocks). These are associated with ultramafic, shonkinitic, gabbroic to monzonitic and various foid syenitic silicate units. Stable and radiogenic isotope compositions for carbonatites and silicate rocks indicate that they share a common source in the mantle, although for some carbonatitic samples contamination with sedimentary rocks seems important. The observed isotopic heterogeneity is mainly attributed to source characteristics, fractional crystallization (accompanied by various degrees of assimilation), and late- to post-magmatic fluid-rock interaction. During the late fluid-rock interaction, Sr, Mn, and possibly also Fe were mobilized and redistributed to form secondary carbonate minerals in carbonatites. These fluids also penetrated into the adjacent syenitic rocks, causing enrichment in the same elements.

Constraints on palaeodrainage evolution induced by uplift and exhumation on the southern flank of the Zagros-Iranian Plateau

Foreland sedimentary rocks from the northern Fars region of Iran contain a record of deformation associated with the Cenozoic collision between Arabia and Eurasia that resulted in formation of the Zagros orogen. The timing of the deformation associated with this event is poorly known. To address this we conducted a study of Miocene foreland sedimentary rocks (19.7-14.8 Ma) of the Chahar-Makan syncline using clast composition, clay mineralogy and low-temperature fission-track dating. The results showed that most of the sedimentary rocks were sourced from ophiolitic rocks. Detrital apatite fission-track (AFT) age signatures of Miocene sedimentary rocks record exhumation in the hanging wall of the Main Zagros Thrust and confirm that the change from underthrusting of the stretched Arabian margin to widespread crustal thickening and deformation in the Zagros region is no younger than 19.7 Ma. A transition from Late Oligocene to Mesozoic-Eocene AFT detrital age signatures between 19.7-16.6 Ma and 16.6-13.8 Ma is interpreted to reflect a possible rearrangement of palaeodrainage distribution that resulted from folding and expansion-uplift of the Zagros-Iranian Plateau region.

Synorogenic extension: Quantitative constraints on the age and displacement of the Zanskar shear zone (northwest Himalaya)

subsequent extension-induced exhumation. Geochronological dating of various Structural, thermobarometric, and geochronological data place limits on the age and tectonic displacement along the Zanskar shear zone, a major north-dipping synorogenic extensional structure separating the high-grade metamorphic sequence of the High Himalayan Crystalline Sequence from the overlying low-grade sedimentary rocks of the Tethyan Himalaya, A complete Barrovian metamorphic succession, from kyanite to biotite zone mineral assemblages, occurs within the I-km-thick Zanskar shear zone. Thermobarometric data indicate a difference In equilibration depths of 12 +/- 3 km between the lower kyanite zone and the garnet zone, which is Interpreted as a minimum estimate for the finite vertical displacement accommodated by the Zanskar shear zone. For the present-day dip of the structure (20 degrees), a simple geometrical model shows that a net slip of 35 +/- 9 km is required to regroup these samples to the same structural level. Because the kyanite to garnet zone rocks represent only part of the Zanskar shear zone, and because its original dip may have been less than the present-day dip, these estimates fur the finite displacement represent minimum values. Field relations and petrographic data suggest that migmatization and associated leucogranite intrusion in the footwall of the Zanskar shear zone occurred as a continuous profess starting at the Barrovian metamorphic peak and lasting throughout the subsequent extension-induced exhumation. Geochronological dataing of various leucogranitic plutons and dikes in the Zanskar shear zone footwall indicates that the main ductile shearing along the structure ended by 19.8 Ma and that extension most likely initiated shortly before 22.2 Ma.

Late Jurassic continental flood basalt doleritic dykes in northwestern Cuba: remnants of the Gulf of Mexico opening

Accreted terranes, comprising a wide variety of Late Jurassic and Early Cretaceous igneous and sedimentary rocks are an important feature of Cuban geology. Their characterization is helpful for understanding Caribbean paleogeography. The Guaniguanico terrane (western Cuba) is formed by upper Jurassic platform sediments intruded by microgranular dolerite dykes. The geochemical characteristics of the dolerite whole rock samples and their minerals (augitic clinopyroxene, labradorite and andesine) are consistent with a tholeiitic affinity. Major and trace element concentrations as well as Nd, Sr and Pb isotopes show that these rocks also have a continental affinity. Sample chemistry indicates that these lavas are similar to a low Ti-P2O5 (LTi) variety of continental flood basalts (CFB) similar to the dolerites of Ferrar (Tasmania). They derived from mixing of a lithospheric mantle Source and an asthenopheric component similar to E-MORB with minor markers of crustal contamination and sediment assimilation. However, the small quantity of Cuban magmatic rocks, similarly to Tasmania, Antarctica and Siberia differs from other volumetrically important CFB occurrences Such as Parana and Deccan. These dolerites are dated as 165-150 Ma and were emplaced during the separation of the Yucatan block from South America. They could in fact be part of the Yucatan-South America margin through which the intrusive system was emplaced and which was later accreted to the Cretaceous arc of central Cuba and to the Palaeogene arc of eastern Cuba. These samples could therefore reflect the pre-rift stage between North and South America and the opening of the gulf of Mexico.

Origin of siderite mineralisation in Petrova and Trgovska Gora Mts., NW Dinarides

The Petrova and Trgovska Gora Mts. (Gora=Mountain) are Variscan basement units incorporated into the northwestern Dinarides during the Alpine orogeny. They host numerous siderite-quartz-polysulphide, siderite-chalcopyrite, siderite-galena and barite veins, as well as stratabound hydrothermal-replacement ankerite bodies within carbonates in non-metamorphosed, flysch-like Permo-Carboniferous sequences. The deposits have been mined for Cu, Pb, Ag and Fe ores since Medieval times. Fluid inclusion studies of quartz from siderite-polysulphide-quartz and barite veins of both regions have shown the presence of primary aqueous NaCl-CaCl(2)+/- MgCl(2)-H(2)O +/- CO(2) inclusions. The quartz-sulphide stage of both regions show variable salinities; 2.7-26.2 wt% NaCl eq. for the Trgovska Gora region and 3.4-23.4 wt% NaCl eq. for the Petrova gora region, and similar homogenisation temperatures (100-230A degrees C). Finally, barite is precipitated from low salinity-low temperature solutions (3.7-15.8 wt % NaCl equ. and 115-145A degrees C). P-t conditions estimated via isochore construction yield formation temperatures between 180-250A degrees C for the quartz-sulphide stage and 160-180A degrees C for the barite stage, using a maximum lithostatic pressure of 1 kbar (cc. 3 km of overburden). The sulphur isotope composition of barite from both deposits indicates the involvement of Permian seawater in ore fluids. This is supported by the elevated bromium content of the fluid inclusion leachates (120-660 ppm in quartz, 420-960 ppm in barite) with respect to the seawater, indicating evaporated seawater as the major portion of the ore-forming fluids. Variable sulphur isotope compositions of galena, pyrite and chalcopyrite, between -3.2 and +2.7aEuro degrees, are interpreted as a product of incomplete thermal reduction of the Permian marine sulphate mixed with organically- and pyrite-bound sulphur from the host sedimentary rocks. Ore-forming fluids are interpreted as deep-circulating fluids derived primarily from evaporated Permian seawater and later modified by interaction with the Variscan basement rocks. (40)Ar/(39)Ar data of the detrital mica from the host rocks yielded the Variscan age overprinted by an Early Permian tectonothermal event dated at 266-274 Ma. These ages are interpreted as those reflecting hydrothermal activity correlated with an incipient intracontinental rifting in the Tethyan domain. Nevertheless, 75 Ma recorded at a fine-grained sericite sample from the alteration zone is interpreted as a result of later resetting of white mica during Campanian opening/closure of the Sava back arc in the neighbouring Sava suture zone (Ustaszewski et al. 2008).

Influence of bedrock structures on the spatial pattern of erosional landforms in small alpine catchments

Structural settings and lithological characteristics are traditionally assumed to influence the development of erosional landforms, such as gully networks and rock couloirs, in steep mountain rock basins. The structural control of erosion of two small alpine catchments of distinctive rock types is evaluated by comparing the correspondences between the orientations of their gullies and rock couloirs with (1) the sliding orientations of potential slope failures mechanisms, and (2) the orientation of the maximum joint frequency, this latter being considered as the direction exploited primarily by erosion and mass wasting processes. These characteristic orientations can be interpreted as structural weaknesses contributing to the initiation and propagation of erosion. The morphostructural analysis was performed using digital elevation models and field observations. The catchment comprised of magmatic intrusive rocks shows a clear structural control, mostly expressed through potential wedges failure. Such joint configurations have a particular geometry that encourages the development of gullies in hard rock, e.g. through enhanced gravitational and hydrological erosional processes. In the catchment underlain by sedimentary rocks, penetrative joints that act as structural weaknesses seem to be exploited by gullies and rock couloirs. However, the lithological setting and bedding configuration prominently control the development of erosional landforms, and influence not only the local pattern of geomorphic features, but the general morphology of the catchment. The orientations of the maximum joint frequency are clearly associated with the gully network, suggesting that its development is governed by anisotropy in rock strength. These two catchments are typical of bedrock-dominated basins prone to intense processes of debris supply. This study suggests a quantitative approach for describing the relationship between bedrock jointing and geomorphic features geometry. Incorporation of bedrock structure can be relevant when studying processes governing the transfer of clastic material, for the assessment of sediment yields and in landforms evolution models.

Predictive analysis and mapping of indoor radon concentrations in Switzerland

It is estimated that around 230 people die each year due to radon (222Rn) exposure in Switzerland. 222Rn occurs mainly in closed environments like buildings and originates primarily from the subjacent ground. Therefore it depends strongly on geology and shows substantial regional variations. Correct identification of these regional variations would lead to substantial reduction of 222Rn exposure of the population based on appropriate construction of new and mitigation of already existing buildings. Prediction of indoor 222Rn concentrations (IRC) and identification of 222Rn prone areas is however difficult since IRC depend on a variety of different variables like building characteristics, meteorology, geology and anthropogenic factors. The present work aims at the development of predictive models and the understanding of IRC in Switzerland, taking into account a maximum of information in order to minimize the prediction uncertainty. The predictive maps will be used as a decision-support tool for 222Rn risk management. The construction of these models is based on different data-driven statistical methods, in combination with geographical information systems (GIS). In a first phase we performed univariate analysis of IRC for different variables, namely the detector type, building category, foundation, year of construction, the average outdoor temperature during measurement, altitude and lithology. All variables showed significant associations to IRC. Buildings constructed after 1900 showed significantly lower IRC compared to earlier constructions. We observed a further drop of IRC after 1970. In addition to that, we found an association of IRC with altitude. With regard to lithology, we observed the lowest IRC in sedimentary rocks (excluding carbonates) and sediments and the highest IRC in the Jura carbonates and igneous rock. The IRC data was systematically analyzed for potential bias due to spatially unbalanced sampling of measurements. In order to facilitate the modeling and the interpretation of the influence of geology on IRC, we developed an algorithm based on k-medoids clustering which permits to define coherent geological classes in terms of IRC. We performed a soil gas 222Rn concentration (SRC) measurement campaign in order to determine the predictive power of SRC with respect to IRC. We found that the use of SRC is limited for IRC prediction. The second part of the project was dedicated to predictive mapping of IRC using models which take into account the multidimensionality of the process of 222Rn entry into buildings. We used kernel regression and ensemble regression tree for this purpose. We could explain up to 33% of the variance of the log transformed IRC all over Switzerland. This is a good performance compared to former attempts of IRC modeling in Switzerland. As predictor variables we considered geographical coordinates, altitude, outdoor temperature, building type, foundation, year of construction and detector type. Ensemble regression trees like random forests allow to determine the role of each IRC predictor in a multidimensional setting. We found spatial information like geology, altitude and coordinates to have stronger influences on IRC than building related variables like foundation type, building type and year of construction. Based on kernel estimation we developed an approach to determine the local probability of IRC to exceed 300 Bq/m3. In addition to that we developed a confidence index in order to provide an estimate of uncertainty of the map. All methods allow an easy creation of tailor-made maps for different building characteristics. Our work is an essential step towards a 222Rn risk assessment which accounts at the same time for different architectural situations as well as geological and geographical conditions. For the communication of 222Rn hazard to the population we recommend to make use of the probability map based on kernel estimation. The communication of 222Rn hazard could for example be implemented via a web interface where the users specify the characteristics and coordinates of their home in order to obtain the probability to be above a given IRC with a corresponding index of confidence. Taking into account the health effects of 222Rn, our results have the potential to substantially improve the estimation of the effective dose from 222Rn delivered to the Swiss population.

Environmental changes in the aftermath of Neoproterozoic glaciations: a biogeochemical study of sediments from SW-Gondwana

Abstract The late Neoproterozoic or Ediacaran period, (635 to -543 Ma) is a primordial time in the Earth history corresponding to the beginning of animal life and the most extreme ice ages on Earth. In this dissertation, palaeoenvironmental conditions were reconstructed for Ediacaran, post-Gaskiers shelf deposits in SW- Gondwana and their changes were evaluated according to the diversity of organisms. The present study addresses the question of interactions between biodiversity and environmental change by using the elemental and isotopic geochemistry of sedimentary rocks and associated organic matter, as well as the distribution of hydrocarbon biomarkers. The studied sedimentary sequences are from a large basin extended from the Paraguay belt to the Rio de la Plata craton, including the Corumbâ Group in SW-Brazil (Paraguay belt), the Arroyo del Soldado Group in Uruguay and the Sierras Bayas Group in Argentina (both in the Rio de la Plata craton). Several geochemical signatures of the sediments from Corumbâ and Sierras Bayas groups provides evidence for an euxinic setting in the Ediacaran Ocean: 1) The occurrence of syngenetic pyrite in the Corumbâ Group together with hydrocarbon biomarkers of an anoxic microbial consortium including traces of gammacerane, a distribution of hopanes with maxima at C29 as well as a low pristane/phytane (Pr/Ph) ratio; 2) the occurrence of 34S enrichments within sulfides of the Sierras Bayas Group exceeding the sulfur isotopic composition of coeval carbonate-associated sulfate. In the Arroyo del Soldado Group, an event of reducing conditions was revealed by higher concentrations of redox-sensitive trace elements and negative 513Ccar shifts in all sections. This event is extended to the whole unit in the deepest section and is restricted to tempestites in the two other shallow sections. The persistent negative. ôl3Ccar values recorded at the basinal setting implies strong isotopic gradient between shallow and deep water environments and therefore, a locus of deposition below the redox chemocline. In all studied sections, the excursions, the strong enrichment of authigenic trace-elements, the occurrence of longer chain «-alkanes, gammacerane and low Pr/Ph and Ph/>;-C]a ratios, combined with the previous sedimentological and paleontological observations indicate that the chemistry of the ocean was strongly controlled by the oxygen availability; waters being moderately oxic at the surface and anoxic at depth for much of the Neoproterozoic. This water column stratification was favourable to the storage of large amounts of nutrients in the deep ocean. During upwelling periods, the export of these nutrient-rich waters may have triggered an important bioproductivity in surface waters. Drops in Al3Cc,,.](Cr and positive ôl3Ccllr excursions highlight the increase in primary productivity. Preservation of organic carbon was ensured by reducing conditions at the bottom. The Al3ccar.kcr excursions could also reflect changes in the composition of the primary biomass. New geochemical evidence from SW-Gondwana sections supports a stratified Ediacaran ocean, outside restricted or hypersaline environments, in the aftermath of glaciations. The association of ocean stratification and the appearance of metazoans support the model that the evolution of eukaryotic life was related to the increase of oxygen levels in surface environments due to an efficient recycling of nutrients in the anoxic deep ocean. Résumé Le Néoprotérozoïque terminal, ou Édiacarien (635 à -543 Ma), est un période de première importance dans l'histoire de la Terre, car elle correspond a l'apparition des métazoaires pendant un intervalle de glaciations extrêmes. Le présent mémoire se propose de reconstituer les conditions paléoenvironnementales des dépôts de plateforme mis en place durant l'Édiacarien, au sud-ouest du Gondwana. Les interactions entre changements environnementaux et biodiversité sont évaluées en s'appuyant d'une part sur la composition élémentaire et isotopique des roches sédimentaires et de leur matière organique, et d'autre part sur la distribution moléculaire de biomarqueurs hydrocarbonés. Les séquences sédimentaires étudiées proviennent d'un grand bassin qui s'étend de la chaîne du Paraguay jusqu'au craton du Rio de la Plata. La séquence du Groupe Corumbâ au Sud Ouest du Brésil se situe dans la chaîne du Paraguay, tandis que le Groupe Arroyo del Soldado en Uruguay et le Groupe Sierras Bayas en Argentine sont situés sur le craton du Rio de la Plata. L'étude géochimique des sédiments des groupes Corumbâ et Sierras Bayas révèle de façon claire des conditions euxiniques dans l'océan édiacarien. On trouve ainsi, dans le Groupe Corumbâ, les biomarqueurs d'un cortège microbien anoxique et sulfurique comprenant des bactéries sulfato-réductrices, et dans les sulfures du Groupe Sierras Bayas, des enrichissements en Î4S excédant les rapports isotopiques du soufre dans le sulfate cogénétique associé aux carbonates. Dans la séquence de l'Arroyo del Soldado, un événement réducteur est mis en évidence par des teneurs plus élevées en éléments traces sensibles aux conditions redox et par des excursions négatives du 613Ccardans toutes les coupes. Cet événement affecte la totalité de la section la plus profonde et n'apparaît que dans les tempestites dans les sections les moins profondes. La persistance de valeurs négatives du ô13Ccarau large implique un gradient isotopique prononcé entre les environnements superficiels et profonds, et donc, ta présence d'une chémocline redox. Les excursions du. ôBCcar, l'enrichissement authigène en éléments traces, la présence de gammacérane et de rt-alcanes à longue chaîne, ainsi que de faibles rapports Pr/Ph et Ph/«-Cl8, viennent s'ajouter aux observations préliminaires sur la sédimentologie et la paléontologie pour indiquer que la chimie de l'océan était fortement contrôlée par la disponibilité d'oxygène, les eaux étant modérément oxiques à la surface et anoxiques en profondeur pendant la plus grande partie du Néoprotérozoïque. La stratification de la colonne d'eau était favorable au stockage de grandes quantités de nutriments dans l'océan profond. Dans les zones d'upwelling, la migration d'eaux profondes riches en nutriment vers la surface a pu provoquer une bioproductivité prononcée dans les eaux de surface. La conservation du carbone organique était assurée par les conditions anoxiques prévalant au fond. Les excursions du A13Ccar.kt.r pourraient aussi refléter des changements dans la biomasse primaire. Le présent travail apporte donc de nouvelles preuves qu'un océan stratifié s'est maintenu à la suite des glaciations néoprotérozoïques dans le Sud Ouest du Gondwana. L'association d'un océan stratifié et de l'apparition de la vie animale est en accord avec le modèle stipulant que l'évolution de la vie est associée à une meilleure oxygénation des environnements de surface. Résumé pour le grand public La période Ediacarienne (635 à -543 Ma) à la fin du Précambrien est l'une de plus énigmatiques dans l'histoire de la Terre, car elle est caractérisée par la diversification de la vie multicellulaire (eucaryote) pendant un intervalle de glaciations extrêmes. Dans ce travail de thèse, nous cherchons à déceler l'existence éventuelle d'un lien entre ces changements environnementaux et l'évolution de la vie eucaryote à travers une étude biogéochimique. La biogéochimie est l'étude des activités biologiques dans la géosphère, telles que celles intervenant dans les cycles des éléments chimiques (y compris les isotopes stables) et celles de production de composés carbonés caractérisant certains groups d'organismes ou taxons. La recherche des signatures paléoenvironnementales dans les roches précambriennes a été fortement facilitée par l'utilisation des biomarqueurs ou fossiles moléculaires. Ces composés, provenant des lipides biologiques (molécules avec des fonctions spécifiques dans les organismes), peuvent être reliés à des taxons spécifiques ou à des voies métaboliques. La transformation d'un biolipide en fossile moléculaire intervient lorsque des restes organiques déposés dans un substrat subissent un enfouissement et une augmentation de la pression (diagenèse). Ce processus mène à la formation de kérogène, un grand agrégat chimique de matière organique insoluble dans des solvants organiques, et de bitume ou fraction soluble (extractible) de la matière organique. L'analyse intégrée du kérogène et du bitume fournit des indications précieuses pour les reconstitutions paléoenvironnementales. Des conditions paléoenvironnementales ont ainsi été déterminées pour une plateforme marine Ediacarienne située dans la partie sud-américaine du bloc occidental du paléocontinent Gondwana. Les séquences sédimentaires étudiées appartiennent au même bassin qui s'étend de la ceinture du Paraguay (Groupe Corumbâ, Brésil) au craton du Rio de la Plata (Groupes Arroyo del Soldado, Uruguay et Sierras Bayas, Argentina). Nous nous sommes intéressés aux isotopes stables de carbonates et de la matière organique associée (kérogène et bitume), aux éléments majeurs et traces, ainsi qu'aux biomarqueurs caractérisant ces roches. Les résultats de cette dissertation suggèrent qu'au cours de l'Édiacarien, suite aux glaciations néoprotérozoïques dans le bloc occidental du Gondwana, l'océan était stratifié en zones spécifiques d'eaux riches en sulfures et dépourvues d'oxygène (euxiniques). L'association d'un océan stratifié et de l'apparition de la vie animale est en accord avec le modèle stipulant que l'évolution de la vie est associée à une meilleure oxygénation des environnements de surface. Les excursions isotopiques (tendance à des valeurs positives ou négatives) en constante fluctuation pour le carbone et très positives pour le soufre des sulfures, l'enrichissement en éléments trace et la présence de certains composés (e.g. gammacerane; Pr/Ph et Ph/«-Ci8 en basse proportion) conjugués aux observations sédimentologiques et paléontologiques des différents profils étudiés indiquent que la chimie de l'océan était fortement contrôlée par la disponibilité d'oxygène, avec des eaux modérément oxygénées en surface et euxiniques en profondeur pour la plupart du Néoprotérozoïque.

Geological structure, recharge processes and underground drainage of a glacierised karst aquifer system, Tsanfleuron-Sanetsch, Swiss Alps

The relationships between stratigraphic and tectonic setting, recharge processes and underground drainage of the glacierised karst aquifer system `Tsanfleuron-Sanetsch' in the Swiss Alps have been studied by means of various methods, particularly tracer tests (19 injections). The area belongs to the Helvetic nappes and consists of Jurassic to Palaeogene sedimentary rocks. Strata are folded and form a regional anticlinorium. Cretaceous Urgonian limestone constitutes the main karst aquifer, overlain by a retreating glacier in its upper part. Polished limestone surfaces are exposed between the glacier front and the end moraine of 1855/1860 (Little Ice Age); typical alpine karrenfields can be observed further below. Results show that (1) large parts of the area are drained by the Glarey spring, which is used as a drinking water source, while marginal parts belong to the catchments of other springs; (2) groundwater flow towards the Glarey spring occurs in the main aquifer, parallel to stratification, while flow towards another spring crosses the entire stratigraphic sequence, consisting of about 800 m of marl and limestone, along deep faults that were probably enlarged by mass movements; (3) the variability of glacial meltwater production influences the shape of the tracer breakthrough curves and, consequently, flow and transport in the aquifer.

Fluid migration through thrust faults in the Helvetic nappes (Western Swiss Alps)

The delta(18)O, delta(13)C and Sr-87/Sr-86 values of calcite and organic matter were measured for carbonate mylonites from numerous thrusts in the Helvetic Alps. Carbonate mylonites in most of the thrusts retain essentially unaltered protolith delta(18)O and delta(13)C values, consistent with there having been little to no advection of isotopically distinct fluid through these faults. Only carbonate mylonites from the basal thrusts of the largest nappes have delta(18)O and/or delta(13)C values that differ from those of their protoliths. The zone of isotopic alteration/exchange is confined to c. 10 to 20 meters of these fault contacts. We propose the fluids that migrated through these faults contained variable amounts of organically derived carbon and radiogenic strontium, and were probably derived from dewatering of the sedimentary rocks and prograde metamorphic reactions in the nappes' root zones. Apart from the basal thrusts of the largest nappes that behaved as narrow, laterally extensive conduits for fluids, there is little isotopic evidence that large quantities of fluids passed through most of the carbonate-hosted thrusts in the Helvetic Alps.