Dispersion of natural arsenic in the Malcantone watershed, Southern Switzerland: field evidence for repeated sorption-desorption and oxidation-reduction processes

In recent years, elevated arsenic concentrations have been found in waters and soils of many, countries, often resulting in a health threat for the local population. Switzerland is not an exception and this paper deals with the release and subsequent fate of arsenic in a 200-km(2) mountainous watershed, characterized by crystalline silicate rocks (gneisses, schists, amphibolites) that contain abundant As-bearing sulfide ore deposits, some of which have been mined for iron and gold in the past. Using analytical methods common for mineralogical, ground water and soil studies (XRD, XRF, XAS-XANES and -EXAFS, electron microprobe, extraction, ICP, AAS with hydride generator, ion chromatography), seven different field situations and related dispersion processes of natural arsenic have been studied: (1) release by rock weathering, (2) transport and deposition by water and ice; (3) release of As to the ground and surface water due to increasing pH; (4) accumulation in humic soil horizons; (5) remobilization by reduction in water-saturated soils and stagnant ground waters; (6) remobilization by using P-rich fertilizers or dung and (7) oxidation, precipitation and dilution in surface waters. Comparison of the results with experimental adsorption studies and speciation diagrams from the literature allows us to reconstruct and identify the typical behavior of arsenic in a natural environment under temperate climatic conditions. The main parameters identified are: (a) once liberated from the primary minerals, sorption processes on Fe-oxy-hydroxides dominate over Al-phases, such as Al-hydroxides or clay minerals and limit the As concentrations in the spring and well waters between 20 and 300 mug/l. (b) Precipitation as secondary minerals is limited to the weathering domain, where the As concentrations are still high and not yet too diluted by rain and soils waters. (c) Although neutral and alkaline pH conditions clearly increase the mobility of As, the main factor to mobilize As is a low redox potential (Eh close or below 0 mV), which favors the dissolution of the Fe-oxy-hydroxides on which the As is sorbed. (d) X-ray absorption spectroscopy (XAS) of As in water-logged humic forest soils indicates that the reduction to As III only occurs at the solid-water interface and that the solid contains As as As V (e) A and Bh horizons of humic cambisols can effectively capture As when As-rich waters flow through them. Complex spatial and temporal variation of the various parameters in a watershed results in repeated mobilization and immobilization of As, which continuously transports As from the upper to the lower part of a watershed and ultimately to the ocean. (C) 2004 Elsevier B.V. All rights reserved.

Fitoplancton e condicoes oceanográficas em areas de ressurgencia do Perú (invierno de 1987 e 1988)

During winter periods in 1987 and 1988, corresponding to the Pós-Niño and "La Niña", respectively, 182 water samples were collected for phytoplankton qualitative and quantitative analysis. The samples were taken from perpendicular transects ot the coast of peru, between 4° and 12° S. The results were related to temperature, salinity, water density, inorganic nutrients (nitrate, silicate and phosphate), phytoplanskton biomass (Chl a) and peruvian anchovy (Engraulis ringens J.) date used to explain the results.

Chemical characterization and infrared spectroscopy of soil organic matter from two southern brazilian soils

Soil organic matter from the surface horizon of two Brazilian soils (a Latosol and a Chernosol), in bulk samples (in situ SOM) and in HF-treated samples (SOM), was characterized by elemental analyses, diffuse reflectance (DRIFT) and transmission Fourier transform infrared spectroscopy (T-FTIR). Humic acids (HA), fulvic acids (FA) and humin (HU) isolated from the SOM were characterized additionally by ultraviolet-visible spectroscopy (UV-VIS). After sample oxidation and alkaline treatment, the DRIFT technique proved to be more informative for the detection of "in situ SOM" and of residual organic matter than T-FTIR. The higher hydrophobicity index (HI) and H/C ratio obtained in the Chernosol samples indicate a stronger aliphatic character of the organic matter in this soil than the Latosol. In the latter, a pronounced HI decrease was observed after the removal of humic substances (HS). The weaker aliphatic character, the higher O/C ratio, and the T-FTIR spectrum obtained for the HU fraction in the Latosol suggest the occurrence of surface coordination of carboxylate ions. The Chernosol HU fraction was also oxygenated to a relatively high extent, but presented a stronger hydrophobic character in comparison with the Latosol HU. These differences in the chemical and functional group composition suggest a higher organic matter protection in the Latosol. After the HF treatment, decreases in the FA proportion and the A350/A550 ratio were observed. A possible loss of FA and condensation of organic molecules due to the highly acid medium should not be neglected.

Igneous garnet and amphibole fractionation in the roots of island arcs: experimental constraints on andesitic liquids

To evaluate the role of garnet and amphibole fractionation at conditions relevant for the crystallization of magmas in the roots of island arcs, a series of experiments were performed on a synthetic andesite at conditions ranging from 0.8 to 1.2 GPa, 800-1,000 degrees C and variable H2O contents. At water undersaturated conditions and fO(2) established around QFM, garnet has a wide stability field. At 1.2 GPa garnet ? amphibole are the high-temperature liquidus phases followed by plagioclase at lower temperature. Clinopyroxene reaches its maximal stability at H2O-contents <= 9 wt% at 950 degrees C and is replaced by amphibole at lower temperature. The slopes of the plagioclase-in boundaries are moderately negative in T-XH2O space. At 0.8 GPa, garnet is stable at magmatic H2O contents exceeding 8 wt% and is replaced by spinel at decreasing dissolved H2O. The liquids formed by crystallization evolve through continuous silica increase from andesite to dacite and rhyolite for the 1.2 GPa series, but show substantial enrichment in FeO/MgO for the 0.8 GPa series related to the contrasting roles of garnet and amphibole in fractionating Fe-Mg in derivative liquids. Our experiments indicate that the stability of igneous garnet increases with increasing dissolved H2O in silicate liquids and is thus likely to affect trace element compositions of H2O-rich derivative arc volcanic rocks by fractionation. Garnet-controlled trace element ratios cannot be used as a proxy

Advantages of using TEM when analysing asbestos in ambient air

Asbestos is an industrial term to describe some fibrous silicate minerals, which belong to the amphiboles or serpentines group. Six minerals are defined as asbestos including: chrysotile (white asbestos), amosite (grunerite, brown asbestos), crocidolite (riebeckite, blue asbestos), anthophyllite, tremolite and actonolite, but only in their fibrous form. In 1973, the IARC (International Agency for Research on Cancer) classified the asbestos minerals as carcinogenic substances (IARC,1973). The Swiss threshold limit (VME) is 0.01 fibre/ml (SUVA, 2007). Asbestos in Switzerland has been prohibited since 1990, but this doesn't mean we are over asbestos. Up to 20'000 tonnes/year of asbestos was imported between the end of WWII and 1990. Today, all this asbestos is still present in buildings renovated or built during that period of time. During restorations, asbestos fibres can be emitted into the air. The quantification of the emission has to be evaluated accurately. To define the exact risk on workers or on the population is quite hard, as many factors must be considered. The methods to detect asbestos in the air or in materials are still being discussed today. Even though the EPA 600 method (EPA, 1993) has proved itself for the analysis of bulk materials, the method for air analysis is more problematic. In Switzerland, the recommended method is VDI 3492 using a scanning electron microscopy (SEM), but we have encountered many identifications problems with this method. For instance, overloaded filters or long-term exposed filters cannot be analysed. This is why the Institute for Work and Health (IST) has adapted the ISO10312 method: ambient air - determination of asbestos fibres - direct-transfer transmission electron microscopy (TEM) method (ISO, 1995). Quality controls have already be done at a French institute (INRS), which validate our practical experiences. The direct-transfer from MEC's filters on TEM's supports (grids) is a delicate part of the preparation for analysis and requires a lot of trials in the laboratory. IST managed to do proper grid preparations after about two years of development. In addition to the preparation of samples, the micro-analysis (EDX), the micro-diffraction and the morphologic analysis (figure 1.a-c) are also to be mastered. Theses are the three elements, which prove the different features of asbestos identification. The SEM isn't able to associate those three analyses. The TEM is also able to make the difference between artificial and natural fibres that have very similar chemical compositions as well as differentiate types of asbestos. Finally the experiments concluded by IST show that TEM is the best method to quantify and identify asbestos in the air.

Metamorphism on Chromite Ores from the Dobromirtsi ultramafic massif, Rhodope Mountains (SE Bulgaria)

Podiform chromitite bodies occur in highly serpentinized peridotites at Dobromirtsi Ultramafic Massif (Rhodope Mountains, southeastern Bulgaria). The ultramafic body is believed to represent a fragment of Palaeozoic ophiolite mantle. The ophiolite sequence is associated with greenschist - lower-temperature amphibolite facies metamorphosed rocks (biotitic gneisses hosting amphibolite). This association suggests that peridotites, chromitites and metamorphic rocks underwent a common metamorphic evolution. Chromitites at Dobromirtsi have been strongly altered. Their degree of alteration depends on the chromite/silicate ratio and to a lesser extent, on the size of chromitite bodies. Alteration is recorded in individual chromite grains in the form of optical and chemical zoning. Core to rim chemical trends are expressed by MgO- and Al2O3- impoverishment, mainly compensated by FeO and/or Fe2O3 increases. Such chemical variations correspond with three main alteration events. The first one was associated with ocean-floor metamorphism and was characterized by a lizardite replacement of olivine and the absence of chromite alteration. The second event took place during greenchist facies metamorphism. During this event, MgO- and SiO2-rich fluids (derived from low temperature serpentinization of olivine and pyroxenes) reacted with chromite to form chlorite; as a consequence, chromite became altered to a FeO- and Cr2O3-rich, Al2O3-poor chromite. The third event, mainly developed during lower temperature amphibolite facies metamorphism, caused the replacement of the primary and previously altered chromite by Fe2O3-rich chromite (ferritchromite).

Ophiolite-related ultramafic rocks (Serpentinites) in the Caribbean region: a review of their occurrence, composition, origin, emplacements and Ni-Laterite soil formation

Ultramafic rocks, mainly serpentinized peridotites of mantle origin, are mostly associated with the ophiolites of Mesozoic age that occur in belts along three of the margins of the Caribbean plate. The most extensive exposures are in Cuba. The ultramafic-mafic association (ophiolites) were formed and emplaced in several different tectonic environments. Mineralogical studies of the ultramafic rocks and the chemistry of the associated mafic rocks indicate that most of the ultramafic-mafic associations in both the northern and southern margins of the plate were formed in arc-related environments. There is little mantle peridotite exposed in the ophiolitic associations of the west coast of Central America, in the south Caribbean in Curacao and in the Andean belts in Colombia. In these occurrences the chemistry and age of the mafic rocks indicates that this association is mainly part of the 89 Ma Caribbean plateau province. The age of the mantle peridotites and associated ophiolites is probably mainly late Jurassic or Early Cretaceous. Emplacement of the ophiolites possibly began in the Early Cretaceous in Hispaniola and Puerto Rico, but most emplacement took place in the Late Cretaceous to Eocene (e.g. Cuba). Along the northern South America plate margin, in the Caribbean mountain belt, emplacement was by major thrusting and probably was not completed until the Oligocene or even the early Miocene. Caribbean mantle peridotites, before serpentinization, were mainly harzburgites, but dunites and lherzolites are also present. In detail, the mineralogical and chemical composition varies even within one ultramafic body, reflecting melting processes and peridotite/melt interaction in the upper mantle. At least for the northern Caribbean, uplift (postemplacement tectonics) exposed the ultramafic massifs as a land surface to effective laterization in the beginning of the Miocene. Tectonic factors, determining the uplift, exposing the peridotites to weathering varied. In the northern Caribbean, in Guatemala, Jamaica, and Hispaniola, uplift occurred as a result of transpresional movement along pre-existing major faults. In Cuba, uplift occurred on a regional scale, determined by isostatic adjustment. In the south Caribbean, uplift of the Cordillera de la Costa and Serrania del Interior exposing the peridotites, also appears to be related to strike-slip movement along the El Pilar fault system. In the Caribbean, Ni-laterite deposits are currently being mined in the central Dominican Republic, eastern Cuba, northern Venezuela and northwest Colombia. Although apparently formed over ultramafic rocks of similar composition and under similar climatic conditions, the composition of the lateritic soils varies. Factors that probably determined these differences in laterite composition are geomorphology, topography, drainage and tectonics. According to the mineralogy of principal ore-bearing phases, Dominican Ni-laterite deposits are classified as the hydrous silicate-type. The main Ni-bearing minerals are hydrated Mg-Ni silicates (serpentine and ¿garnierite¿) occurring deeper in the profile (saprolite horizon). In contrast, in the deposits of eastern Cuba, the Ni and Cooccurs mainly in the limonite zone composed of Fe hydroxides and oxides as the dominant mineralogy in the upper part of the profile, and are classified as the oxide-type.

Genesis and classification of Oxisols in a highland toposequence of the upper Jequitinhonha Valley (MG)

The Brazilian System of Soil Classification (SiBCS) is a taxonomic system, open and in permanent construction, as new knowledge on Brazilian soils is obtained. The objective of this study was to characterize the chemical, physical, morphological, micro-morphological and mineralogical properties of four pedons of Oxisols in a highland toposequence in the upper Jequitinhonha Valley, emphasizing aspects of their genesis, classification and landscape development. The pedons occupy the following slope positions: summit - Red Oxisol (LV), mid slope (upper third) - Yellow-Red Oxisol (LVA), lower slope (middle third)- Yellow Oxisol (LA) and bottom of the valley (lowest third) - "Gray Oxisol" ("LAC"). These pedons were described and sampled for characterization in chemical and physical routine analyses. The total Fe, Al and Mn contents were determined by sulfuric attack and the Fe, Al and Mn oxides in dithionite-citrate-bicarbonate and oxalate extraction. The mineralogy of silicate clays was identified by X ray diffraction and the Fe oxides were detected by differential X ray diffraction. Total Ti, Ga and Zr contents were determined by X ray fluorescence spectrometry. The "LAC" is gray-colored and contains significant fragments of structure units in the form of a dense paste, characteristic of a gleysoil, in the horizons A and BA. All pedons are very clayey, dystrophic and have low contents of available P and a pH of around 5. The soil color was related to the Fe oxide content, which decreased along the slope. The decrease of crystalline and low- crystalline Fe along the slope confirmed the loss of Fe from the "LAC". Total Si increased along the slope and total Al remained constant. The clay fraction in all pedons was dominated by kaolinite and gibbsite. Hematite and goethite were identified in LV, low-intensity hematite and goethite in LVA, goethite in LA. In the "LAC", no hematite peaks and goethite were detected by differential X ray diffraction. The micro-morphology indicated prevalence of granular microstructure and porosity with complex stacking patterns.. The soil properties in the toposequence converged to a single soil class, the Oxisols, derived from the same source material. The landscape evolution and genesis of Oxisols of the highlands in the upper Jequitinhonha Valley are related to the evolution of the drainage system and the activity of excavating fauna.

Soil-applied silicon decreases severity of wheat spot blotch on silicon-deficient soils

Spot bloth caused by Bipolaris sorokiniana is an important wheat desease mainly in hot and humid regions. The aim of this study was to evaluate the response of wheat to different sources and modes of Si application, as related to the severity of wheat spot blotch and plant growth, in two Si-deficient Latosols (Oxisols). An greenhouse experiment was arranged in a 2 x 5 factorial completely randomized design, with eight replications. The treatments consisted of two soils (Yellow Latosol and Red Latosol) and five Si supply modes (no Si application; Si applied as calcium silicate and monosilicic acid to the soil; and Si applied as potassium silicate or monosilicic acid to wheat leaves). No significant differences were observed between the two soils. When Si was applied to the soil, regardless the Si source, the disease incubation period, the shoot dry matter yield and the Si content in leaves were greater. Additionally, the final spot blotch severity was lower and the area under the spot blotch disease progress curve and the leaf insertion angle in the plant were smaller. Results of Si foliar application were similar to those observed in the control plants.

The Lithium, Boron and Beryllium content of serpentinized peridotites from ODP Leg 209 (Sites 1272A and 1274A): Implications for lithium and boron budgets of oceanic lithosphere

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 mu g g(-1)) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 mu g g(-1)), depleted in Li (most values below I mu g g(-1)) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 mu g g(-1)), H2O and Cl contents and to lower Li contents (0.07-3.37 mu g g(-1)) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at I and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of I m x I m x thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li. (C) 2008 Elsevier Ltd. All rights reserved.

Comparison of digestion methods to determine heavy metals in fertilizers

The lack of a standard method to regulate heavy metal determination in Brazilian fertilizers and the subsequent use of several digestion methods have produced variations in the results, hampering interpretation. Thus, the aim of this study was to compare the effectiveness of three digestion methods for determination of metals such as Cd, Ni, Pb, and Cr in fertilizers. Samples of 45 fertilizers marketed in northeastern Brazil were used. A fertilizer sample with heavy metal contents certified by the US National Institute of Standards and Technology (NIST) was used as control. The following fertilizers were tested: rock phosphate; organo-mineral fertilizer with rock phosphate; single superphosphate; triple superphosphate; mixed N-P-K fertilizer; and fertilizer with micronutrients. The substances were digested according to the method recommended by the Ministry for Agriculture, Livestock and Supply of Brazil (MAPA) and by the two methods 3051A and 3052 of the United States Environmental Protection Agency (USEPA). By the USEPA method 3052, higher portions of the less soluble metals such as Ni and Pb were recovered, indicating that the conventional digestion methods for fertilizers underestimate the total amount of these elements. The results of the USEPA method 3051A were very similar to those of the method currently used in Brazil (Brasil, 2006). The latter is preferable, in view of the lower cost requirement for acids, a shorter digestion period and greater reproducibility.

EFFECT OF ALTERNATIVE MULTINUTRIENT SOURCES ON SOIL CHEMICAL PROPERTIES

The current high price of potassium chloride and the dependence of Brazil on imported materials to supply the domestic demand call for studies evaluating the efficiency of alternative sources of nutrients. The aim of this work was to evaluate the effect of silicate rock powder and a manganese mining by-product, and secondary materials originated from these two materials, on soil chemical properties and on brachiaria production. This greenhouse experiment was conducted in pots with 5 kg of soil (Latossolo Vermelho-Amarelo distrófico - Oxisol). The alternative nutrient sources were: verdete, verdete treated with NH4OH, phonolite, ultramafic rock, mining waste and the proportion of 75 % of these K fertilizers and 25 % lime. Mixtures containing 25 % of lime were heated at 800 ºC for 1 h. These sources were applied at rates of 0, 150, 300, 450 and 600 kg ha-1 K2O, and incubated for 45 days. The mixtures of heated silicate rocks with lime promoted higher increases in soil pH in decreasing order: ultramafic rock>verdete>phonolite>mining waste. Applying the mining waste-lime mixture increased soil exchangeable K, and available P when ultramafic rock was incorporated. When ultramafic rock was applied, the release of Ca2+ increased significantly. Mining subproduct released the highest amount of Zn2+ and Mn2+ to the soil. The application of alternative sources of K, with variable chemical composition, altered the nutrient availability and soil chemical properties, improving mainly plant development and K plant uptake, and are important nutrient sources.

Characterization of Ornamental Rock Residue and Potassium Liberation Via Organic Acid Application

ABSTRACT Organic acids present in organic matter and, or, exudates by microorganisms and plants can increase the liberation of potassium present in minerals. The objective of this study was to characterize the residue from ornamental rocks and evaluate the release of K from these residues after the application of organic acids. The experiment was conducted under laboratory conditions and followed a 2 × 3 × 5 factorial design with three replicates. The studied factors were: two organic acids (citric acid and malic acid), three ornamental rock residues (R1, R2 and R3) and five organic acid rates (0, 5, 10, 20 and 40 mmol L-1). After agitation, K concentrations were determined in the equilibrium solution. Successive extractions were performed (1, 5, 10, 15, 30 and 60 days after the start of the experiment). The organic acids used (citric and malic) promoted the release of up to 4.86 and 4.34 % of the total K contained in the residue, respectively, reinforcing the role of organic acids in the weathering of minerals and in providing K to the soil. The K quantities were, on average, 6.1 % higher when extracted with citric acid compared to malic acid.

Optimization of Soil Stabilization with Class C Fly Ash, January 1987

Previous Iowa DOT sponsored research has shown that some Class C fly ashes are ementitious (because calcium is combined as calcium aluminates) while other Class C ashes containing similar amounts of elemental calcium are not (1). Fly ashes from modern power plants in Iowa contain significant amounts of calcium in their glassy phases, regardless of their cementitious properties. The present research was based on these findings and on the hyphothesis that: attack of the amorphous phase of high calcium fly ash could be initiated with trace additives, thus making calcium available for formation of useful calcium-silicate cements. Phase I research was devoted to finding potential additives through a screening process; the likely chemicals were tested with fly ashes representative of the cementitious and non-cementitious ashes available in the state. Ammonium phosphate, a fertilizer, was found to produce 3,600 psi cement with cementitious Neal #4 fly ash; this strength is roughly equivalent to that of portland cement, but at about one-third the cost. Neal #2 fly ash, a slightly cementitious Class C, was found to respond best with ammonium nitrate; through the additive, a near-zero strength material was transformed into a 1,200 psi cement. The second research phase was directed to optimimizing trace additive concentrations, defining the behavior of the resulting cements, evaluating more comprehensively the fly ashes available in Iowa, and explaining the cement formation mechanisms of the most promising trace additives. X-ray diffraction data demonstrate that both amorphous and crystalline hydrates of chemically enhanced fly ash differ from those of unaltered fly ash hydrates. Calciumaluminum- silicate hydrates were formed, rather than the expected (and hypothesized) calcium-silicate hydrates. These new reaction products explain the observed strength enhancement. The final phase concentrated on laboratory application of the chemically-enhanced fly ash cements to road base stabilization. Emphasis was placed on use of marginal aggregates, such as limestone crusher fines and unprocessed blow sand. The nature of the chemically modified fly ash cements led to an evaluation of fine grained soil stabilization where a wide range of materials, defined by plasticity index, could be stabilized. Parameters used for evaluation included strength, compaction requirements, set time, and frost resistance.

Circum-Alpine marine circulation and paleoenvironmental conditions during the Miocene

Trace element and isotopic compositions of marine fossils and sediment were analyzed from several Miocene deposits in the circum-Alpine region in order to reconstruct the paleoceanographic and paleoclimatic changes related to sea level changes, basin evolution and Alpine orogeny. To the north and the east the Alps were border by an epicontinental sea, the Paratethys, while to the south the Mediterranean surrounded the uplifting mountains during the Miocene. The thesis mainly focused on sediments and fossils sampled from Miocene beds of these two oceanic provinces. The north Alpine Molasse, the Vienna and Pannonian Basins were located in the Western and Central Paratethys. O-isotope compositions of well-preserved phosphatic fossils in these sediments support deposition under sub-tropical to warm-temperate climate with water temperatures between 14 to 28 °C for the Miocene. δ18O values of fossil shark teeth from different horizons vary similarly to those of the global trend until the end of the Badenian, however the δ18O values show wider range, which indicates local effects iii the sub-basins. The trend of 87Sr/86Sr in the samples roughly agrees with an open ocean environment for the Miocene. Yet a number of samples deviate from typical open ocean compositions with higher ratios suggesting modification of seawater by local and old terrestrial sources. In contrast, two exceptional teeth from the locality of La Moliere have extremely low δ18O values and low 87Sr/86Sr. However, the REE patterns of their enameloid are similar to those of teeth having O and Sr isotopic compositions typical of a marine setting at this site. Collectively, this suggests that the two teeth formed while the sharks frequented a freshwater environment with very low 18O-content and 87Sr/86Sr controlled by Mesozoic calcareous rocks. This is consistent with a paleogeography of high-elevation (~2300m) Miocene Alps adjacent to a marginal sea. The local effects are also reflected in the εNd values of the Paratethyan fossils, which is compatible with input from ancient crystalline rocks and Mesozoic sediments, while other samples with elevated εNd values indicate an influence of Neogene volcanism on the water budget. Excluding samples whose isotopic compositions reflect a local influence on the water column, an average εNd value of -7.9 ± 0.5 may be inferred for the Paratethys seawater. This value is indistinguishable from the Miocene value of the Indian Ocean, supporting a dominant role of ludo-Pacific water masses in the Paratethys. Regarding the Mediterranean, stable C-and O-isotope compositions of benthic and planktonic foraminifera from the Umbria-Marche region (UMC) have an offset typical for their habitats and the changes in composition mimic global changes, suggesting that the regional conditions of climate and the carbon cycle were controlled by global changes. The radiogenic isotope compositions of the fossil assemblages allow for distinction of periods. From 25 to 19 Ma, high εNd values and low 87Sr/86Sr of sediments and fossils support intense tectonism and volcanism, related to the opening of the western Mediterranean. Between 19 and 13 Ma the Mediterranean has εNd values that are largely controlled by incursion of Indian Ocean water. Brief periods of local hinterland control on seawater compositions are indicated by spikes in the εNd record, coinciding with volcanic events and a short sea-level decrease at about 15.2 Ma. Lower 87Sr/86Sr compared to the open ocean is compatible with rapid uplift of the hinterland and intense influx of Sr from Mesozoic carbonates of the western Apennines, while higher 87Sr/86Sr for other sites indicates erosion of old crustal silicate rocks. Finally, from 13 to 7 Ma the fossils have 87Sr/86Sr similar to those of Miocene seawater and their εNd values indicates fluctuating influence of Atlantic, and Indian Ocean or Paratethys sources of seawater entering the Mediterranean, driven by global sealevel changes and local tectonism. RÉSUMÉ DE LA THÈSE Les compositions en éléments traces et isotopiques de fossiles marins et de sédiments on été analysées à partir de nombreux dépôts marins dans la région circum Alpine dans le but de reconstruire les changements paléocéanographiques et paléoclimatiques liés aux changements du niveau marin, à l'évolution en bassins et à l'orogénie alpine. Au nord et à l'est des Alpes, une mer épicontinentale appelée Paratéthys s'est ouverte, alors que plus au sud la mer Méditerranée bordait au Miocène les Alpes naissantes. Le but de cette recherche est de se concentrer sur les sédiments et les fossiles provenant des couches du Miocènes de ces deux provinces marines. Les bassins de la Molasse Alpine du nord, de Vienne et Pannonien étaient situés au niveau de la Paratéthys Occidentale et Centrale. Les compositions isotopiques de l'oxygène de fossiles phosphatés bien préservés dans ces sédiments étayent la théorie d'un dépôt sous un climat subtropical à tempéré chaud avec des températures entre 14 et 28°C pendant le Miocène. Les valeurs δ18O des fossiles sont similaires à la tendance globale jusqu'à la fin du Badénien. Cependant les larges fluctuations en δ18O indiquent des effets locaux au niveau des sous bassins. En outre, deux dents de requin exceptionnelles présentent des valeurs extrêmement basses de δ18O. Ces données suggèrent que ces deux dents se sont formées alors que les requins fréquentaient un environnement d'eau douce avec de faibles valeurs de 18O. Le calcul de la composition isotopique de l'oxygène de cette eau douce permet d'obtenir une estimation de la paléoélévatian moyenne des Alpes du Miocène (~2300m). La tendance 87Sr/86Sr pour ces échantillons concorde approximativement avec un environnement d'océan ouvert au cours du Miocène. Toutefois un nombre d'échantillons dévie des compositions d'océan ouvert typiques, avec des rapports élevés suggérant des modifications de l'eau de mer par des sources locales et terrestres. Les effets locaux sont aussi reflétés au niveau des valeurs en εNd des fossiles paratéthysiens. Ceci est cohérent avec un apport d'anciennes roches cristallines et de sédiments mésozoïques, tandis que d'autres échantillons avec des valeurs hautes de εNd indiquent une influence d'un volcanisme néogène dans le budget marin. En excluant les échantillons dont les compositions isotopiques confirment une influence locale, une valeur moyenne de εNd de 7.9 t 0.5 peut être déduite pour l'eau de la Parathétys. Cette valeur est semblable à la valeur correspondant à l'Océan Indien durant le Miocène, confirmant un rôle dominant de cet océan dans la Paratéthys. Au niveau de la Méditerranée, les compositions en isotopes stables du Carbone et de l'Oxygène de foraminifères planctoniques et benthique de la région Umbria-Marche présentent un offset typique à leurs habitats. De plus les changements dans leurs compositions suivent les changements globaux, suggérant ainsi que les conditions climatiques régionales et le cycle du carbone étaient contrôlés par des phénomènes globaux. La composition en isotopes radiogéniques d'assemblages fossiles permet une reconnaissance sur trois périodes distinctes. De 25 à 19 millions d'années (Ma), des valeurs élevées de εNd et un faible rapport 87Sr/86Sr dans les sédiments soutiennent l'idée d'une activité tectonique et volcanique intense, liée à l'ouverture de la Méditerranée occidentale. Entre 19 et 13 Ma, la Méditerranée montre des valeurs de εNd qui sont largement contrôlées par une incursion d'eau provenant de l'Océan Indien. En effet, aux alentours de 15,2 Ma, des pics dans l'enregistrement des valeurs de εNd, coïncidant avec des événements volcaniques et de brèves diminutions du niveau marin. Enfin, de 13 à 7 Ma, les fossiles ont des rapports ß7Sr/8fiSr similaires à ceux de l'eau de mer au Miocène. Leurs valeurs de εNd indiquent une influence changeante de l'océan Atlantique, et de l'océan Indien ou des sources d'eau de merde la Parathétys qui entrent dans les bassins méditerranéens. Ce changement est guidé par des modifications globales du niveau marin et par la tectonique locale. RÉSUMÉ DE LA THÈSE (POUR LE GRAND PUBLIC) Les analyses des compositions en éléments traces et isotopiques des fossiles marins sont un outil très utile pour reconstruire les conditions océaniques et climatiques anciennes. Ce travail de thèse se concentre sur les sédiments déposés dans un environnement marin proches des Alpes au cours du Miocène, entre 23 et 7 millions d'années (Ma). Cette période est caractérisée par une tectonique alpine active, ainsi que par des changements climatiques et océanographiques globaux importants. Dans le but de tracer ces changements, les compositions isotopiques du Strontium, du Néodyme, de l'Oxygène et du Carbone ont été analysées dans des fossiles bien préservés ainsi que les sédiments contemporains. Les échantillons proviennent de deux provinces océaniques distinctes, la première est la Mer Méditerranée, et l'autre est une mer épicontinentale appelée Parathétys, qui existait au nord et à l'est des Alpes durant le Miocène. Au niveau de la Parathétys Occidentale et Orientale, les compositions isotopiques d'oxygène de dents de requins confirment un dépôt sous un climat subtropical à tempéré chaud avec des températures d'eau entre 14 et 28°C au Miocène. En outre, deux dents de requins exceptionnelles ont enregistré des compositions isotopiques d'oxygène extrêmement basses. Cela suggère que ces deux dents se sont formées alors que les requins entraient dans un système d'eau douce. Le calcul de la composition isotopique de l'oxygène de cette eau douce permet d'obtenir une estimation de la paléoélévation des Alpes au Miocène qui est aussi élevée que celle d'aujourd'hui. La tendance isotopique du Strontium pour ces échantillons concorde approximativement avec un environnement d'océan ouvert. Cependant un certain nombre d'échantillons indique des modifications de l'eau de mer par des sources terrestres locales. Les effets locaux sont aussi visibles au niveau des compositions isotopiques du Néodyme, qui sont en accord avec un apport provenant de roches cristallines anciennes et de sédiments du Mésozoïque, alors que d'autres échantillons indiquent une influence volcanique néogène dans le budget marin. A l'exclusion des échantillons dont les compositions correspondent à une influence locale, les compositions isotopiques du Néodyme de la Parathétys sont très similaires aux valeurs de l'Océan Indien, montrant ainsi un rôle important des masses d'eau IndoPacifiques dans cette région. Au niveau de la Méditerranée, les compositions en isotopes stables du Carbone et de l'Oxygène de foraminifères planctoniques et benthique de la région Umbria-Marche présentent un offset typique à leurs habitats. De plus, les changements dans leurs compositions suivent les changements globaux, suggérant ainsi que les conditions climatiques régionales et le cycle du carbone étaient contrôlés par des phénomènes globaux. La composition en isotopes radiogéniques d'assemblages fossiles permet une reconnaissance sur trois périodes distinctes. De 25 à 19 Ma, des rapport isotopiques élevés pour le Néodyme et faibles pour le Strontium dans les sédiments et les fossiles soutiennent l'idée d'une activité tectonique et volcanique intense, liée à l'ouverture de la Méditerranée occidentale. Entre 19 et 13 Ma, la Méditerranée présente des rapports isotopiques du Néodyme qui sont largement contrôlés par une incursion d'eau provenant de l'Océan Indien. En effet, aux alentours de 15,2 Ma, des pics dans l'enregistrement des valeurs des isotopes du Néodyme coïncident avec des événements volcaniques et de brèves diminutions du niveau marin. Finalement, de 13 à 7 Ma, les fossiles ont des rapports isotope Strontium similaires à ceux de l'eau de mer au Miocène. Les rapports isotopiques du Néodyme indiquent une influence changeante de l'océan Atlantique, et de l'océan Indien ou des sources d'eau de mer de la Parathétys qui entrent dans les bassins méditerranéens. Ce changement est guidé par des modifications globales du niveau marin et par la tectonique locale.