122 resultados para isotope zoning

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Oxygen isotope measurements using SIMS and laser-fluorination methods confirm the presence of concentric and sector zoning in low-temperature (200 degrees C to < 400 degrees C) hydrothermal quartz from Alpine veins. While concentric zoning is most readily explained by changes in the chemical composition of the fluid or temperature of crystallization, the reasons for sector zoning are more difficult to explain. Relative enrichment in (18)O for crystallographically different sectors of quartz corresponds to m > r > z. Sector zoning is, however, largely limited to the exterior zones of crystals and/or to crystals with large Al (> 1000 ppm) and trace element contents, probably formed at temperatures < 250 degrees C. Differences in delta(18)O between the prismatic (m) relative to the rhombohedral (r and z) growth sectors of up to 2 parts per thousand can be explained by a combination of a face-related crystallographic and/or a growth rate control. In contrast, isotopic sector zoning of up to about 1.5 parts per thousand amongst the different rhombohedral faces increases in parallel with the trace element content and is likely to represent disequilibrium growth. This is indicated by non-systematic, up to 2 parts per thousand, differences within single growth zones and the irregular, larger or smaller, delta(18)O values (of several permil) of the exterior compared to the inner zones of the same crystals. Disequilibrium growth may be related to the large trace element content incorporated into the growing quartz at lower temperatures (< 250 degrees C) and/or be related to fluid-vapour separation, allowing crystal growth from both a vapour as well as a liquid phase.

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THESIS ABSTRACT : Stable isotope geochemistry is used to help resolve a large number of geological questions. In order to do this, it is essential to understand the different mechanisms that govern isotopic fractionation processes between different phases and to identify the conditions required to reach equilibrium fractionation. However, at low temperatures, these processes are poorly constrained and many factors can induce differential partitioning of the isotopes between sectors of a mineral species and the fluid during mineral growth. This can result in so-called 'sector zoning' of a mineral species. The aim of this thesis is to evaluate the occurrence of sector zoning of the oxygen isotopes and trace elements in natural α-quartz crystals and to identify the reasons for such zoning. The implications for the fluid-mineral interactions are studied in the context of the Alpine metamorphism. The approach chosen has focused on examining the crystal structure, cathodoluminescence appearance (CL), and on relating elemental (e.g. Li, Na, Al, P, K, Ca, Ge, Ti, Fe) to stable oxygen isotope compositions between and along different growth sectors. Low temperature quartz samples were selected from Alpine veins in different localities, where growth conditions have already been well constrained. The mineralogy as well as the isotopic compositions of the host rocks were also investigated, in order to interpret the variations obtained between the different growth stages in the framework of fluid-rock interaction during Alpine metamorphism. Depending on the growth conditions, most of the studied quartz is strongly zoned in CL, and it reveals corresponding zonations in the trace element content (e.g. growth zoning). Aluminium, substituting for Si in the lattice, was found in concentrations up to 1000's ppma, and its distribution is strongly related to Li and H and to a lesser extent, to Ge. Elemental sector zoning is evident from the distribution of these three elements since they exhibit differences in their respective concentrations between faces for distinct growth zones, with prismatic faces having the lowest Al contents. Quartz from veins in magmatic rocks, for example, tend to have lower Al concentrations and similar concentrations of Li and Ti suggesting also a contribution of these elements from the host rock. The relationship between Al and Li is still correlated. Only Alpine crystals grown at higher temperatures (~400°C) without any CL zoning feature are free of these impurities and do not show such zoning characteristics. Differences in the δ18O values were measured between different faces principally in the AIenriched growth zones or stages. These results were confirmed by the means of two different methods (in situ/non in situ). However, it was determined that the Al concentrations do not affect significantly oxygen isotope fractionations at 300°C. The results altogether suggest that the presence of sector zoning in quartz crystals is real, but not universal, and henceforth should be taken into consideration for any use of these systems. The occurrence of disequilibrium partitioning has been enhanced and is possibly related to kinetic processes as well as structural effects that do not affect similarly trace element incorporation and isotopic fractionation. In situ measurements also revealed fine scale δ18O zonations along growth paths that are useful to constrain fluid-rock interactions during Alpine metamorphism. Variations in the δ18O values present along growth vectors indicate changes in the fluid composition and origin. Association with oxygen isotope composition of the host rock allows for the deduction of interactions between rocks, veins and consequently fluids, as well as fluid regimes. RESUME DE LA THESE : A basses températures, (i.e. <400°C) les différents mécanismes qui régissent le fractionnement isotopique ainsi que les conditions nécessaires pour établir un état d'équilibre sont peu connus et nombre de paramètres peuvent entraîner un partitionnement chimique différentiel entre différents secteurs d'un minéral et le fluide en contact. Ainsi, ce travail de thèse a pour but d'évaluer la possible présence de zonages sectoriels en isotopes de l'oxygène mais aussi en éléments traces dans des cristaux naturels de quartz-α de basses températures, ainsi que les raisons d'un tel phénomène et enfin ses implications sur les interactions fluide-roche, principalement dans le cadre du métamorphisme Alpin. La structure et l'apparence en cathodoluminescence (CL) des échantillons ont été caractérisées avant de retracer en détail les compositions en élément traces (Li, Na, Al, P, K, Ca, Ge, Ti, Fe) et en isotopes de l'oxygène, le long et entre différents secteurs. Les échantillons de quartz sélectionnés proviennent majoritairement de veines Alpine de différentes localités, où les conditions de croissance ont été déjà bien caractérisées. Les compositions minéralogiques et isotopiques de la roche encaissante ont aussi été examinées, pour contraindre les variations obtenues dans un contexte Alpin. Selon leurs conditions de croissance, la plupart des cristaux étudiés sont fortement zonés, ce qui est souligné par un zonage des concentrations en éléments traces (e.g. zonage de croissance). L'Aluminium, qui peut se substituer à la Silice dans le réseau cristallin, a été retrouvé jusqu'en très grandes concentrations dans certaines zones (plusieurs milliers de ppma). De plus, la distribution en Al est fortement liée à celles de Li et H, ainsi que dans une moindre mesure à Ge. La présence de zonage sectoriel est évidente au niveau de ces éléments qui montrent de larges différences de concentrations entre différentes faces pour une même zone de croissance, avec les concentrations les plus basses retrouvées dans les faces prismatiques. Les quartz de veines situées dans des roches magmatiques par exemple possèdent des concentrations en Li et Ti de même ordre de grandeur, confirmant le rôle de la composition de la roche encaissante. La relation Li/Al est toujours fortement présente, mais ce rapport est fonction de la face mesurée. Seuls les cristaux Alpins de plus hautes températures (400°C) ne possédant pas de zones en CL ne présentent aucune de ces caractéristiques. Des différences dans les valeurs de δ18O de zones identiques enrichies en Al ont clairement été mesurées entre les différentes faces r, z, et m, mais aussi au sein d'une même seule zone, indiquant que le fractionnement a probablement eu lieu en déséquilibre. Il a été déterminé que la présence d'Al dans ces teneurs n'avait qu'un faible effet sur le fractionnement isotopique de l'oxygène. L'utilisation de deux méthodes différentes a permis d'obtenir des résultats in situ et non in situ concordants. La comparaison des résultats obtenus permet de démontrer que le zonage sectoriel est bien présent dans certains cristaux de quartz, et dépend des conditions de formation. La présence d'un partitionnement différentiel des éléments traces peut être due à des effets cinétiques aussi bien que structuraux, alors que le zonage sectoriel des isotopes de l'oxygène aurait d'autres origines. Il est alors évident que la possibilité de zonage sectoriel doit être désormais pris en considération avant toute interprétations de données isotopiques de cristaux zonés. Les mesures in situ ont de plus permis de distinguer de fines variations des valeurs δ18O au cours de la croissance, qui peuvent aider à retracer la circulations des fluides dans les Alpes durant cette période. En association avec les compositions des roches encaissantes, ii est possible de déduire les interactions entre roches, veines, et par conséquent fluides, au cours de différentes étapes. RESUME GRAND PUBLIC : La géochimie des isotopes stables a pris beaucoup d'importance depuis ces dernières années pour aider à résoudre nombre de questions géologiques, en se basant sur les caractéristiques du fractionnement isotopiques pour différents systèmes. Il est donc nécessaire d'avoir une connaissance approfondie des mécanismes qui s'appliquent au fractionnement isotopique entre les minéraux et les fluides à partir desquels ils se forment. Ces mécanismes ont été bien approchés par différents types de calibrations pour des systèmes à hautes températures, cependant cela n'est pas aussi évident pour les systèmes à des températures inférieures à 400-500°C. Ce travail de thèse a pour but d'aider à la description et la compréhension des phénomènes qui peuvent affecter le fractionnement isotopique à basses températures, ainsi que leurs implications, à partir de l'étude de cristaux de quartz. Le choix des échantillons s'est porté sur des cristaux naturels formés à des températures inférieures ou égales à 400°C, provenant majoritairement de fissures hydrothermales Alpines dont les conditions de formation ont déjà été déterminées. L'étude des cristaux Alpin permet de plus de replacer les résultats obtenus dans le contexte du métamorphisme Alpin au cours du Miocène (21-13 Ma). Après examen de la structure et de la morphologie des cristaux, et leur caractérisation par cathodoluminescence (CL), des analyses chimiques détaillées sur les éléments en traces pouvant entrer dans le réseau cristallin du quartz comme impuretés (i.e. Li, Na, Al, P, K, Ca, Ge, Ti), et des isotopes stables de l'oxygène, ont été menées. En fonction des conditions de croissance, la plupart des cristaux présentent des zonations, qui peuvent être facilement reliées à la distribution des éléments traces analysés par microsonde électronique, sonde ionique (SIMS) et LA-ICPMS. De fortes concentrations d'Aluminium (plusieurs milliers de parties par million atomique) ont pu être observées dans les zones les plus externes des cristaux. De plus, les concentrations en Al et en Li sont toujours corrélées; la présence d'Hydrogène déduite à partir d'analyses par FTIR suit cette même tendance. Les différentes faces des cristaux présentent des concentrations distinctes d'Al, Li et H pour des mêmes zones de croissance, avec par exemple les concentrations les plus faibles dans les zones des faces prismatiques. Cela implique la présence d'un zonage sectoriel, qui a déjà été observé principalement dans des carbonates mais jamais décrit auparavant pour des quartz. Seuls les cristaux alpins homogènes en CL dont la croissance s'est faite à plus haute température (400°C) ne présentent aucune de ces caractéristiques. Par analogie avec le zonage sectoriel en Al, élément qui se substitue au Si dans le réseau cristallin du quartz, il est possible de penser qu'un zonage sectoriel pourrait aussi s'appliquer aux isotopes de l'oxygène. Des précédentes études avaient en effet émis cette hypothèse. Nos résultats ont été obtenus à partir d'analyses à la fois in- situ par SIMS, et par extraction assistée par laser-CO2 sur des parties de quartz soigneusement séparées, et sont en accord entre les deux méthodes. Un zonage sectoriel est en effet bien présent pour les cristaux alpins, mais principalement au niveau des zones très riches en Aluminium. Cependant, il a été déterminé que la présence d'Al dans ces teneurs avait un effet plus que minimal sur le fractionnement isotopique de l'oxygène. Des différences importantes ont été observées entre les faces r & z mais aussi au sein d'une même et seule zone, indiquant que le fractionnement a pu avoir lieu en déséquilibre, ce qui est aussi visible au niveau des valeurs totalement opposées entre faces pour la dernière phase de croissance de certains cristaux. Ainsi l'association de ces résultats laisse suggérer que la présence d'un zonage sectoriel peut être liée à différents paramètres tels que le taux de croissance ou la structure de surface du cristal, mais qui n'affectent pas de la même façon l'incorporation des éléments traces et le fractionnement isotopique. La possibilité d'un zonage sectoriel est importante à prendre en compte lors de toute interprétation de données isotopiques. Les analyses des isotopes de l'oxygène effectuées par SIMS ont aussi permis de distinguer des variations importantes à petite échelle au cours de la croissance. Des mesures faites par laser CO2 sur certaines roches encaissantes, ont permis distinguer plusieurs étapes dans la croissance des minéraux et de déduire le rôle de l'encaissant et le type de fluide. En association avec de précédentes études, il a été ainsi possible de mieux contraindre la formation de ces cristaux dans le contexte alpin et la circulation de fluide au cours du métamorphisme alpin durant le Miocène.

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The large Cerro de Pasco Cordilleran base metal deposit in central Peru is located on the eastern margin of a middle Miocene diatreme-dome complex and comprises two mineralization stages. The first stage consists of a large pyrite-quartz body replacing Lower Mesozoic Pucara carbonate rocks and, to a lesser extent, diatreme breccia. This body is composed of pyrite with pyrrhotite inclusions, quartz, and black and red chalcedony (containing hypogene hematite). At the contact with the pyrite-quartz body, the diatreme breccia is altered to pyrite-quartz-sericite-pyrite. This body was, in part, replaced by pipelike pyrrhotite bodies zoned outward to carbonate-replacement Zn-Pb ores hearing Fe-rich sphalerite (up to 24 mol % Fes). The second mineralization stage is partly superimposed on the first and consists of zoned east-west-trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins hosted in the diatreme breccia in the western part of the deposit and well-zoned Zn-Pb-(Bi-Ag-Cu) carbonate-replacement orebodies; in both cases, sphalerite is Fe poor and the inner parts of the orebodies show typically advanced argillic alteration assemblages, including aluminum phosphate Sulfate (APS) minerals. The zoned enargite-pyrite veins display mineral zoning, from a core of enargite-pyrite +/- alunite with traces of Au, through an intermediate zone of tennantite, chalcopyrite, and Bi minerals to a poorly developed Outer zone hearing sphalerite-galena +/- kaolinite. The carbonate-hosted replacement ores are controlled along N 35 degrees E, N 90 degrees E, N 120 degrees E, and N 170 degrees E faults. They form well-zoned upward-flaring pipelike orebodies with a core of famatinite-pyrite and alunite, an intermediate zone with tetrahedrite-pyrite, chalcopyrite, matildite, cuprobismutite, emplectite, and other Bi minerals accompanied by APS minerals, kaolinite, and dickite, and an outer zone composed of Fe-poor sphalerite (in the range of 0.05-3.5 mol % Fes) and galena. The outermost zone consists of hematite, magnetite, and Fe-Mn-Zn-Ca-Mg carbonates. Most of the second-stage carbonate-replacement orebodies plunge between 25 degrees and 60 degrees to the west, suggesting that the hydrothermal fluids ascended from deeper levels and that no lateral feeding from the veins to the carbonate-replacement orebodies took place. In the Venencocha and Santa Rosa areas, located 2.5 km northwest of the Cerro de Pasco open pit and in the southern part of the deposit, respectively, advanced argillic altered dacitic domes and oxidized veins with advanced argillic alteration halos occur. The latter veins are possibly the oxidized equivalent of the second-stage enargite-pyrite veins located in the western part of the deposit. The alteration assemblage quartz-muscovite-pyrite associated with the pyrite-quartz body suggests that the first stage precipitated at slightly, acidic fin. The sulfide mineral assemblages define an evolutionary path close to the pyrite-pyrrhotite boundary and are characteristic of low-sulfidation states; they suggest that the oxidizing slightly acidic hydrothermal fluid was buffered by phyllite, shale, and carbonate host rock. However, the presence in the pyrite-quartz body of hematite within quartz suggests that, locally, the fluids were less buffered by the host rock. The mineral assemblages of the second mineralization stage are characteristic of high- to intermediate-sulfidation states. High-sulfidation states and oxidizing conditions were achieved and maintained in the cores of the second-stage orebodies, even in those replacing carbonate rocks. The observation that, in places, second-stage mineral assemblages are found in the inner and outer zones is explained in terms of the hydrothermal fluid advancing and waning. Microthermometric data from fluid inclusions in quartz indicate that the different ores of the first mineralization stage formed at similar temperatures and moderate salinities (200 degrees-275 degrees C and 0.2-6.8 wt % NaCl equiv in the pyrite-quartz body; 192 degrees-250 degrees C and 1.1-4.3 wt % NaCl equiv in the pyrrhotite bodies; and 183 degrees-212 degrees C and 3.2-4.0 wt % NaCl equiv in the Zn-Pb ores). These values are similar to those obtained for fluid inclusions in quartz and sphalerite from the second-stage ores (187 degrees-293 degrees C and 0.2-5.2 wt % NaCl equiv in the enargite-pyrite veins: 178 degrees-265 degrees C and 0.2-7.5 wt % NaCl equiv in quartz of carbonate-replacement orebodies; 168 degrees-999 degrees C and 3-11.8 wt % NaCl equiv in sphalerite of carbonate-replacement orebodies; and 245 degrees-261 degrees C and 3.2-7.7 wt % NaCl equiv in quartz from Venencocha). Oxygen and hydrogen isotope compositions oil kaolinite from carbonate-replacement orebodies (delta(18)O = 5.3-11.5%o, delta D = -82 to -114%o) and on alunite from the Venencocha and Santa Rosa areas (delta(18)O = 1.9-6.9%o, delta D = -56 to -73%o). Oxygen isotope compositions of quartz from the first and second stages have 6180 values from 9.1 to 1.7.8 per mil. Calculated fluids in equilibrium with kaolinite have delta(18)O values of 2.0 to 8.2 and delta D values of -69 to -97 per mil; values in equilibrium with alunite are -1.4 to -6.4 and -62 to -79 per mil. Sulfur isotope compositions of sulfides from both stages have a narrow range of delta(34)S values, between -3.7 and +4.2 per mil; values for sulfates from the second stage are between 4.2 and 31.2 per mil. These results define two mixing trends for the ore-forming fluids. The first trend reflects mixing between a moderately saline (similar to 10 wt % NaCl equiv) magmatic end member that had degassed (as indicated by the low delta D values) and meteoric water. The second mixing indicates condensation of magmatic vapor with HCl and SO(2) into meteoric water, which formed alunite. The hydrothermal system at Cerro de Pasco was emplaced at a shallow depth (similar to 500 m) in the epithermal and upper part of a porphyry environment. The similar temperatures and salinities obtained for the first stage and second stages, together with the stable isotope data, indicate that both stages are linked and represent successive stages of epithermal polymetallic mineralization in the upper part of a porphyry system.

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White micas in carbonate-rich tectonites and a few other rock types of large thrusts in the Swiss Helvetic fold-and-thrust belt have been analyzed by Ar-40/Ar-39 and Rb/Sr techniques to better constrain the timing of Alpine deformation for this region. Incremental Ar-40/Ar-39 heating experiments of 25 weakly metamorphosed (anchizone to low greenschist) samples yield plateau and staircase spectra. We interpret most of the staircase release spectra result from variable mixtures of syntectonic (neoformed) and detrital micas. The range in dates obtained within individual spectra depends primarily on the duration of mica nucleation and growth, and relative proportions of neoformed and detrital mica. Rb/Sr analyses of 12 samples yield dates of ca. 10-39 Ma (excluding one anomalously young sample). These dates are slightly younger than the Ar-40/Ar-39 total gas dates obtained for the same samples. The Rb/ Sr dates were calculated using initial Sr-87/Sr-86 ratios obtained from the carbonate-dominated host rocks, which are higher than normal Mesozoic carbonate values due to exchange with fluids of higher Sr-87/Sr-86 ratios (and lower O-18/O-16 ratios). Model dates calculated using Sr-87/Sr-86 values typical of Mesozoic marine carbonates more closely approximate the Ar-40/Ar-39 total gas dates for most of the samples. The similarities of Rb/Sr and Ar-40/Ar-39 total gas dates are consistent with limited amounts of detrital mica in the samples. The delta(18)O values range from 24-15%. (VSMOW) for 2-6 mum micas and 27-16parts per thousand for the carbonate host rocks. The carbonate values are significantly lower than their protolith values due to localized fluid-rock interaction and fluid flow along most thrust surfaces. Although most calcite-mica pairs are not in oxygen isotope equilibrium at temperatures of ca. 200-400 degreesC, their isotopic fractionations are indicative of either 1) partial exchange between the minerals and a common external fluid, or 2) growth or isotopic exchange of the mica with the carbonate after the carbonate had isotopically exchanged with an external fluid. The geological significance of these results is not easily or uniquely determined, and exemplifies the difficulties inherent in dating very fine-grained micas of highly deformed tectonites in low-grade metamorphic terranes. Two generalizations can be made regarding the dates obtained from the Helvetic thrusts: 1) samples from the two highest thrusts (Mt. Gond and Sublage) have all of their Ar-40/Ar-39 steps above 20 Ma, and 2) most samples from the deepest Helvetic thrusts have steps (often accounting for more than 80% of Ar-39 release) between 15 and 25 Ma. These dates are consistent with the order of thrusting in the foreland-imbricating system and increase proportions of neoformed to detrital mica in the more metamorphosed hinterland and deeply buried portions of the nappe pile. Individual thrusts accommodated the majority of their displacement during their initial incorporation into the foreland-imbricating system, and some thrusts remained active or were reactivated down to 15 Ma.

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Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960degreesC (average 710degreesC). The highest temperature is obtained from pyroxene-calcite pairs. The above range is in agreement with other carbonatite thermometric Studies. This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite-carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar-Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite-carbonatite magmas.

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BACKGROUND AND OBJECTIVES: The determination of the carbon isotope ratio in androgen metabolites has been previously shown to be a reliable, direct method to detect testosterone misuse in the context of antidoping testing. Here, the variability in the 13C/12C ratios in urinary steroids in a widely heterogeneous cohort of professional soccer players residing in different countries (Argentina, Italy, Japan, South Africa, Switzerland and Uganda) is examined. METHODS: Carbon isotope ratios of selected androgens in urine specimens were determined using gas chromatography/combustion/isotope ratio mass spectrometry (GC-C-IRMS). RESULTS: Urinary steroids in Italian and Swiss populations were found to be enriched in 13C relative to other groups, reflecting higher consumption of C3 plants in these two countries. Importantly, detection criteria based on the difference in the carbon isotope ratio of androsterone and pregnanediol for each population were found to be well below the established threshold value for positive cases. CONCLUSIONS: The results obtained with the tested diet groups highlight the importance of adapting the criteria if one wishes to increase the sensitivity of exogenous testosterone detection. In addition, confirmatory tests might be rendered more efficient by combining isotope ratio mass spectrometry with refined interpretation criteria for positivity and subject-based profiling of steroids.

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The stable isotope composition of waters (delta H-2, delta O-18) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the delta H-2 and delta O-18 values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Caren at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher delta O-18 values (by similar to +2% delta O-18 relative to delta H-2) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of H-2 and O-18 in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in H-2 and O-18. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. In temperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II.

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The 24-km diameter Ries crater, Germany, exhibits well-preserved crater filling and surficial melt-rich breccia deposits that are believed to have been altered by post-impact hydrothermal fluids. The alteration mineralogy of the crater filling breccias is characterized by clay (smectite, chlorite) and a zeolite assemblage, and secondary clay phases (smectite, minor halloysite) in surficial melt-bearing breccia deposits. Using stable isotope analysis of secondary smectitic clay fractions, evidence of significant hydrous alteration of impactites at large water/rock ratios was found. The estimated fluid temperatures, using data derived by delta(18)O and delta D fractionation, suggest smectite precipitation in surficial breccias in equilibrium with meteoric fluids at temperatures 16 +/- 5 degrees C in agreement with the long-term variation of modern precipitation in the area. The stable isotope composition of smectite in crater-fill breccia, however, suggests a trend of monotonously increasing temperatures from 43 to 112 degrees C. with increasing depth through the breccia sequence. This demonstrates a different origin of alteration and temperature distribution for the surficial and crater filling melt-bearing impact breccias in the Ries crater. Our results suggest that the inverted structure of hydrothermal systems observed in some terrestrial impact craters, including the Ries crater, could indicate the initial configuration of a thermal anomaly in the crater filling sequence, but which is replaced with a normal hydrothermal convection in crater proper, during the course of post-impact cooling. (C) 2010 Elsevier B.V. All rights reserved.

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A novel approach to measure carbon dioxide (CO2) in gaseous samples, based on a precise and accurate quantification by (13)CO2 internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable in the routine determination of CO2. The main drawback of the GC methods discussed in the literature for CO2 measurement is the lack of a specific internal standard necessary to perform quantification. CO2 measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ((13)CO2) on the basis of the stoichiometric formation of CO2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH(13)CO3). This method allows a precise measurement of CO2 concentration and was validated on various human postmortem gas samples in order to study its efficiency.

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The hydrogen and oxygen isotopes of water and the carbon isotope composition of dissolved inorganic carbon (DIC) from different aquifers at an industrial site, highly contaminated by organic pollutants representing residues of the former gas production, have been used as natural tracers to characterize the hydrologic system. On the basis of their stable isotope compositions as well as the seasonal variations, different groups of waters (precipitation, surface waters, groundwaters and mineral waters) as well as seasonably variable processes of mixing between these waters can clearly be distinguished. In addition, reservoir effects and infiltration rates can be estimated. In the northern part of the site an influence of uprising mineral waters within the Quaternary aquifers, presumably along a fault zone, can be recognized. Marginal infiltration from the Neckar River in the cast and surface water infiltration adjacent to a steep hill on the western edge of the site with an infiltration rate of about one month can also be resolved through the seasonal variation. Quaternary aquifers closer to the centre of the site show no seasonal variations, except for one borehole close to a former mill channel and another borehole adjacent to a rain water channel. Distinct carbon isotope compositions and concentrations of DIC for these different groups of waters reflect variable influence of different components of the natural carbon cycle: dissolution of marine carbonates in the mineral waters, biogenic, soil-derived CO2 in ground- and surface waters, as well as additional influence of atmospheric CO2 for the surface waters. Many Quaternary aquifer waters have, however, distinctly lower delta(13)C(DIC) values and higher DIC concentrations compared to those expected for natural waters. Given the location of contaminated groundwaters at this site but also in the industrially well-developed valley outside of this site, the most likely source for the low C-13(DIC) values is a biodegradation of anthropogenic organic substances, in particular the tar oils at the site.

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Stable isotope and Ar-40/Ar-39 measurements,were made on samples associated with a major tectonic discontinuity in the Helvetic Alps, the basal thrust of the Diablerets nappe (external zone of the Alpine Belt) in order to determine both the importance of fluids in this thrust zone and the timing of thrusting. A systematic decrease in the delta(18)O values (up to 6 parts per thousand) of calcite, quartz, and white mica exists within a 10- to 70-m-wide zone over a distance of 37 km along the thrust, and they become more pronounced toward the root of the nappe. A similar decrease in the delta(13)C values of calcite is observed only in the deepest sections (up to 3 parts per thousand). The delta D-SMOW (SMOW = standard mean ocean water) values of white mica are -54 parts per thousand +/- 8 parts per thousand (n = 22) and are independent of the distance from the thrust. These variations are interpreted to reflect syntectonic solution reprecipitation during fluid passage along the thrust. The calculated delta(18)O and delta D values (versus SMOW) for the fluid in equilibrium with the analyzed minerals is 12 parts per thousand to 16 parts per thousand and -30 parts per thousand to +5 parts per thousand, respectively, for assumed temperatures of 250 to 450 degrees C. The isotopic and structural data are consistent with fluids derived from the deep-seated roots of the Helvetic nappes where large volumes of Mesozoic sediments were metamorphosed to the amphibolite facies, It is suggested that connate and metamorphic waters, overpressured by rapid tectonic burial in a subductive system escaped by upward infiltration along moderately dipping pathways until they reached the main shear zone at the base of the moving pile, where they were channeled toward the surface, This model also explains the mechanism by which large amounts of fluid were removed from the Mesozoic sediments during Alpine metamorphism. White mica Ar-49/Ar-39 ages vary from 27 Ma far from the Diablerets thrust to 15 Ma along the thrust. An older component is observed in micas far from the thrust, interpreted as a detrital signature, and indicates that regional metamorphic temperatures were less than about 350 degrees C. The;plateau and near plateau ages nearest the thrust are consistent with either neocrystallization of white mica or argon loss by recrystallization during thrusting, which may have been enhanced in the zones of highest fluid flow. The 15 Ma Ar-40/Ar-39 age plateau measured on white mica sampled exactly on the thrust surface dates the end of both fluid flow and tectonic transport.

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Several quartz crystals from three different Alpine vein localities and of known petrologic setting and evolution have been examined for possible elemental sector zoning in order to help to constrain the mechanisms of such trace element incorporation. Using different in situ techniques (EMPA, LA-ICPMS, SIMS, FTIR-spectroscopy), it was established that Al and Li concentrations can exceed several hundreds of ppma for distinct growth zones within crystals formed at temperatures of about 300 degrees C or less and that also display patterns of cyclic growth when examined with cathodoluminescence. In contrast, crystals formed at temperatures closer to 400 degrees C and without visible cyclic growth have low concentrations of Al and Li as well as other trace elements. Al and Li contents are correlated along profiles measured within the crystals and in general their proportion does not change along the profiles. No relationships were found between Al, Na, and K, and germanium has a qualitative relationship with Al. FTIR spectra also show OH(-) absorption bands within the quartz, with higher amplitudes in zones rich in Al and Li. Sector zoning is present. It is most pronounced between prismatic and rhombohedral faces of the same growth zone, but also between the rhombohedral faces of r and z, which contain different amounts of trace elements. The sector zoning is also expressed by changes in the Li/Al ratio, with higher ratios in 17 compared to r faces. It is concluded that the incorporation of trace elements into hydrothermal quartz from Alpine veins is influenced by growth mechanisms and surface-structures of the growing quartz crystals, the influence of which may change as a function of temperature, pH, as well as the chemical composition of the fluid.

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Quartz veins ranging in size from less than 50 cm length and 5 cm width to greater than 10 m in length and 5 m in width are found throughout the Central Swiss Alps. In some cases, the veins are completely filled with milky quartz, while in others, sometimes spectacular void-filling quartz crystals are found. The style of vein filling and size is controlled by host rock composition and deformation history. Temperatures of vein formation, estimated using stable isotope thermometry and mineral equilibria, cover a range of 450 degrees C down to 150 degrees C. Vein formation started at 18 to 20 Ma and continued for over 10 My. The oxygen isotope values of quartz veins range from 10 to 20 permil, and in almost all cases are equal to those of the hosting lithology. The strongly rock-buffered veins imply a low fluid/rock ratio and minimal fluid flow. In order to explain massive, nearly morromineralic quartz formation without exceptionally large fluid fluxes, a mechanism of differential pressure and silica diffusion, combined with pressure solution, is proposed for early vein formation. Fluid inclusions and hydrous minerals in late-formed veins have extremely low delta D values, consistent with meteoric water infiltration. The change from rock-buffered, static fluid to infiltration from above can be explained in terms of changes in the large-scale deformation style occurring between 20 and 15 Ma. The rapid cooling of the Central Alps identified in previous studies may be explained in part, by infiltration of cold meteoric waters along fracture systems down to depths of 10 km or more. An average water flux of 0.15 cm 3 cm(-2)yr(-1) entering the rock and reemerging heated by 40 degrees C is sufficient to cool rock at 10 km depth by 100 degrees C in 5 million years. The very negative delta D values of < -130 permil for the late stage fluids are well below the annual average values measured in meteoric water in the region today. The low fossil delta D values indicate that the Central Alps were at a higher elevation in the Neogene. Such a conclusion is supported by an earlier work, where a paleoaltitude of 5000 meters was proposed on the basis of large erratic boulders found at low elevations far from their origin.

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The hydrogen isotope ratio (HIR) of body water and, therefore, of all endogenously synthesized compounds in humans, is mainly affected by the HIR of ingested drinking water. As a consequence, the entire organism and all of its synthesized substrates will reflect alterations in the isotope ratio of drinking water, which depends on the duration of exposure. To investigate the effect of this change on endogenous urinary steroids relevant to doping-control analysis the hydrogen isotope composition of potable water was suddenly enriched from -50 to 200 0/00 and maintained at this level for two weeks for two individuals. The steroids under investigation were 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 5α-androstane-3α,17β-diol, and 5β-androstane-3α,17β-diol (excreted as glucuronides) and ETIO, ANDRO and 3β-hydroxyandrost-5-en-17-one (excreted as sulfates). The HIR of body water was estimated by determination of the HIR of total native urine, to trace the induced changes. The hydrogen in steroids is partly derived from the total amount of body water and cholesterol-enrichment could be calculated by use of these data. Although the sum of changes in the isotopic composition of body water was 150 0/00, shifts of approximately 30 0/00 were observed for urinary steroids. Parallel enrichment in their HIR was observed for most of the steroids, and none of the differences between the HIR of individual steroids was elevated beyond recently established thresholds. This finding is important to sports drug testing because it supports the intended use of this novel and complementary methodology even in cases where athletes have drunk water of different HIR, a plausible and, presumably, inevitable scenario while traveling.