Caracterização geológica do perfil laterítico no município de Rondon do Pará, bloco sul do projeto Alumina Rondon

This completion of course work has as its object of study the Bauxite Province of Paragominas regarded as the richest Amazon bauxite province and whose genesis is related to laterization processes responsible for the formation of mineral deposits of the Rondon Alumina Project, designed to assess areas in the southeast of Pará State, for mineral resources exploration of bauxite, which is the main source of aluminum in the country. Located in the region of Rondon do Pará - PA, the study area is geologically inserted in Lithostratigraphic Unit called Cobertura Laterítica Matura (Mature Lateritic Cover), formed by alteration of paleotropics Cretaceous siliciclastic rocks, and its geomorphology corresponds to a broad plateau with displays of representative profiles of the processes that acted in the region. In this context, the present research aims to characterize the geological evolution of the laterite profile, with detailed studies in the area, geological description of the formations from the bauxite surfaces, and mineralogical composition litochemical of different horizons that were correlated and deployed in an evolutionary model compatible with its traits. The data collected during the analysis subsidized metalogenetic understanding of the processes that acted in the enrichment of aluminum and iron as well as the redistribution of the latter modified profile. The results and information were embodied in the form of geological characterization of the different constituents of mineral associations of bauxite horizons, similarities or differences in both textural and structural aspects, in order to propose a evolutionary model with retaken of gibbsitization processes

Caracterização estrutural da mineralização da mina de Fazenda Nova - GO

The study area is includes in the geological context of Arenópolis Magmatic Arc, a region where there are neoproterozoic associations of granodioritic and tonalitic composiotion. (Ortogneisses of the western Goiás) and sequences metavolcanic-sedimentary (Jaupaci Metavolcanic-sedimentary Sequence ). In the mapped area, both units are covered by a cover-laterite. The Ortogneisses from Goiás West consist of a source granodioritic gneisses, corresponding to the Biotite granodiorite gneisse, and also by tonalitic gneiss composition corresponding to Metatonalit. The Jaupaci Metavolcanic-sedimentary Sequence is formed by Chlorite Schist (Metabasalt), Biotite Schist (Metadacite) and Sericite Schist (Metarhyolite), and even intrusions Sin/Tardi e Post Tectonic, granite to diorite composition (Diorites), and alson tonalitic (Bacilandia Tonalite). Post tectonic intrusions are observed, wich were Hornblend Diorite Porphyry and Lamprophyres, Structural analysis allowed the identification of three deformational events, Dn-1, Dn and Post-Dn. The first event is associated with a bygone foliation, lineation which generates an intersectional event, generating the foliation Sn, this being the most important structure in the study area, generating even the type mineral lineation and stretch. The last deformational event is characterized by folds on different scales, affecting the Sn foliation. The rocks of the region have features s active hydrothermal and regional metamorphism, and are composed os assembly indicative of mineralogical facies metamorphism Green Schist, in chlotite zone, with evidence of retro metamorphism. Locally there are sulfides as pyrite, arsenopyrit and pyrhotite, and te mineralization is associated with the arsenopyrite

Erosion rates and landscape evolution of the lowlands of the Upper Paraguay river basin (Brazil) from cosmogenic Be-10

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ultramafic complexes and associated mineral deposits in the Precambrian of eastern Minas Gerais, Brazil

Based on field work, prospection and petrographic studies ultramafic complexes and their mineral deposits from eastern Minas Gerais in southeastern Brazil are generally outlined to form a basis for future investigations in this region. The bodies dealt with occur at Ipanema, Córrego Novo, Bela Vista de Minas, Rio Pomba and Liberdade. These ultramafic bodies are generally enclosed in high-grade gneisses and consist of serpentinized peridotites and harzburgites which were metamorphosed together with their country rocks in upper amphibolite to granulite facies. Weathering of these rocks gives rise to nickeliferous laterite, while metamorphism has resulted in anthophyllite asbestos and talc deposits. © 1985 Springer-Verlag.

Anwendung der CE-ICP-MS und RIMS sowie Entwicklung und Anwendung der CE-RIMS auf Umweltproben

Die vorliegende Arbeit wurde im Rahmen des Verbundprojektes „Wechselwirkung und Transport von Actiniden im natürlichen Tongestein unter Berücksichtigung von Huminstoffen und Tonorganika – Wechselwirkung von Neptunium und Plutonium mit natürlichem Tongestein“ durchgeführt. Diese Untersuchungen sollen die thermodynamische Datenbasis für Actiniden erweitern sowie Informationen zur Ableitung von Bewertungskriterien für die Endlagerung radioaktiver Abfälle in Ton als Wirtsgestein, insbesondere über das Rückhaltevermögen von Tongestein gegenüber Radionukliden, liefern. Dabei stand die Anwendung verschiedener Speziationstechniken wie CE-ICP-MS, UV/VIS und die apparative Entwicklung der CE-RIMS im Vordergrund. Es sollte das Verhalten von Plutonium in umweltrelevanten Medien und Konzentrationen, im Ultraspurenbereich, untersucht werden. Unabhängig davon sollten Uranproben aus dem 2. Weltkrieg und Umweltproben des Landesamts für Umwelt und Forsten Rheinland-Pfalz auf ihren Plutoniumgehalt analysiert werden. Dazu wurde zunächst ein neues ICP-MS-Gerät Agilent 7500ce in Betrieb genommen und auf die Verwendung in Kombination mit der Kapillarelektrophorese optimiert. Die erreichte Nachweisgrenze für die vier Oxidationsstufen des Pu beträgt 0,05 ppb des gesamten Plutoniums in Lösung. Mit Hilfe der CE-ICP-MS wurde die Redoxstabilität einer Mischung aus verschiedenen Oxidationszuständen des Plutoniums in Opalinus-Ton-Porenwasser und Vergleichsmedien unter aeroben und anaeroben Bedingungen mit der CE untersucht. Die Untersuchungen zeigen das Pu(III) bis zu 40 min im verwendeten Elektrolytsystem stabil ist und dann oxidiert wird. In Porenwasser wurde als vorherrschende Spezies Pu(V) bestimmt. Die Redoxstabilität von Pu(VI) wurde untersucht, dabei wurde festgestellt, dass sich Pu(VI) bereits durch einfaches Verdünnen reduzieren lässt. Weiterhin wurden die Kd-Werte für die Sorption von Plutonium an Opalinuston unter aeroben und anaeroben Bedingungen für Pu(III) und Pu(IV) im System Porenwasser/Opalinuston von Kd(aerob) Pu(III) ≈ 53 m3/kg, Kd(aerob) Pu(IV) ≈ 14 m3/kg, Kd(anaerob) Pu(III) ≈ 114 m3/kg, Kd(anaerob) Pu(IV) ≈ 178 m3/kg bestimmt. Ein weiterer Schwerpunkt der Arbeit war die Entwicklung, Optimierung und Anwendung der Kopplung CE-RIMS zur Speziation des Plutoniums im Ultraspurenbereich. Dies konnte erfolgreich in mehreren Schritten durchgeführt und an den Proben aus den Batchversuchen zur Kd-Wert Bestimmung angewandt werden. Der Memory-Effekt des an den Kapillarwänden sorbierenden Pu(IV) konnte mit der empfindlichen Kopplung CE-RIMS ebenfalls nachgewiesen werden.

Migration von Technetium in natürlichem Tongestein

Die vorliegende Arbeit wurde im Rahmen des Verbundprojektes „Rückhaltung endlagerrelevanter Radionuklide im natürlichen Tongestein und salinaren Systemen“ (Förderkennzeichen: 02E10981), welches durch das Bundesministerium für Wirtschaft und Energie (BMWi) gefördert wurde, angefertigt. Ziel war es, erstmals Erkenntnisse zur Wechselwirkung zwischen dem Spaltprodukt Technetium und einem natürlichen Tongestein im Hinblick auf ein Endlager für wärmeentwickelnde radioaktive Abfälle zu erlangen. Hierfür wurde der in der Nordschweiz vorkommende Opalinuston aus Mont Terri als Referenzmaterial verwendet. Das Nuklid Technetium-99 liefert auf Grund seiner langen Halbwertszeit einen signifikanten Beitrag zur Radiotoxizität abgebrannter Brennelemente für mehr als tausend Jahre. Im Falle einer Freisetzung aus den Lagerbehältern wird die Geochemie des Technetiums von seiner Oxidationsstufe bestimmt, wobei lediglich die Oxidationsstufen +IV und +VII von Relevanz sind. Auf Grund seiner hohen Löslichkeit und geringen Affinität zur Sorption an Oberflächen von Mineralien ist Tc(VII) die mobilste und somit auch gefährlichste Spezies. Entsprechend lag der Fokus dieser Arbeit auf Diffusionsexperimenten dieser mobilen Spezies sowie auf dem Einfluss von Eisen(II) auf die Mobilität und die Speziation des Technetiums.rnDie Wechselwirkung zwischen Technetium und Opalinuston wurde in Sorptions- und Diffusionsexperimenten unter Variation verschiedener Parameter (pH-Wert, Zusatz verschiedener Reduktionsmittel, Einfluss von Sauerstoff, Diffusionsweg) untersucht. Im Zuge dieser Arbeit wurden erstmals ortsaufgelöste Untersuchungen zur Speziation des Technetiums an Dünnschliffen und Bohrkernen durchgeführt. Dabei konnten ergänzend zur Speziation auch Informationen über die Elementverteilung und die kristallinen Mineralphasen nahe lokaler Anreicherungen des Radionuklides gewonnen werden. Zusätzlich erlaubten Untersuchungen an Pulverproben die Bestimmung der molekularen Struktur des Technetiums an der Tonoberfläche.rnSowohl die Kombination der oben aufgeführten Sorptionsexperimente mit spektroskopischen Untersuchungen als auch die Diffusionsexperimente zeigten unter Sauerstoffausschluss eine Reduktion von Tc(VII) zu immobilen Tc(IV)-Spezies. Weiterhin konnte die Bildung eines Tc(IV)-Sorptionskomplexes an der Tonoberfläche gezeigt werden. Im Hinblick auf ein Endlager in Tongestein sind diese Ergebnisse positiv zu bewerten.

Distribution of metals in several vineyards of North Italy: from soil to wine

Nowadays we live in densely populated regions and this leads to many environmental issues. Among all pollutants that human activities originate, metals are relevant because they can be potentially toxic for most of living beings. We studied the fate of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in a vineyard environment analysing samples of plant, wine and soil. Sites were chosen considering the type of wine produced, the type of cultivation (both organic and conventional agriculture) and the geographic location. We took vineyards that cultivate the same grape variety, the Trebbiano). We investigated 5 vineyards located in the Ravenna district (Italy): two on the Lamone Valley slopes, one in the area of river-bank deposits near Ravenna city, then a farm near Lugo and one near Bagnacavallo in interfluve regions. We carried out a very detailed characterization of soils in the sites, including the analysis of: pH, electric conductivity, texture, total carbonate and extimated content of dolomite, active carbonate, iron from ammonium oxalate, Iron Deficiency Chlorosis Index (IDCI), total nitrogen and organic carbon, available phosphorous, available potassium and Cation Exchange Capacity (CEC). Then we made the analysis of the bulk chemical composition and a DTPA extraction to determine the available fraction of elements in soils. All the sites have proper ground to cultivate, with already a good amount of nutrients, such as not needing strong fertilisations, but a vineyard on hills suffers from iron deficiency chlorosis due to the high level of active carbonate. We found some soils with much silica and little calcium oxide that confirm the marly sandstone substratum, while other soils have more calcium oxide and more aluminium oxide that confirm the argillaceous marlstone substratum. We found some critical situations, such as high concentrations of Chromium, especially in the farm near Lugo, and we noticed differences between organic vineyards and conventional ones: the conventional ones have a higher enrichment in soils of some metals (Copper and Zinc). Each metal accumulates differently in every single part of grapevines. We found differences between hill plants and lowland ones: behaviors of plants in metal accumulations seems to have patterns. Metals are more abundant in barks, then in leaves or sometimes in roots. Plants seem trying to remove excesses of metal storing them in bark. Two wines have excess of acetic acid and one conventional farm produces wine with content of Zinc over the Italian law limit. We already found evidence of high values relating them with uncontaminated environments, but more investigations are suggested to link those values to their anthropogenic supplies.

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Diffusion of HTO, Br-, I-, Cs+, Sr-85(2+) and Co-60(2+) in a clay formation: Results and modelling from an in situ experiment in Opalinus Clay

The migration of radioactive and chemical contaminants in clay materials and argillaceous host rocks is characterised by diffusion and retention processes. Valuable information on such processes can be gained by combining diffusion studies at laboratory scale with field migration tests. In this work, the outcome of a multi-tracer in situ migration test performed in the Opalinus Clay formation in the Mont Terri underground rock laboratory (Switzerland) is presented. Thus, 1.16 x 10(5) Bq/L of HTO, 3.96 x 10(3) Bq/L of Sr-85, 6.29 x 10(2) Bq/L of Co-60, 2.01 x 10(-3) mol/L Cs, 9.10 x 10(-4) mol/L I and 1.04 x 10(-3) mol/L Br were injected into the borehole. The decrease of the radioisotope concentrations in the borehole was monitored using in situ gamma-spectrometry. The other tracers were analyzed with state-of-the-art laboratory procedures after sampling of small water aliquots from the reservoir. The diffusion experiment was carried out over a period of one year after which the interval section was overcored and analyzed. Based on the experimental data from the tracer evolution in the borehole and the tracer profiles in the rock, the diffusion of tracers was modelled with the numerical code CRUNCH. The results obtained for HTO (H-3), I- and Br- confirm previous lab and in situ diffusion data. Anionic fluxes into the formation were smaller compared to HTO because of anion exclusion effects. The migration of the cations Sr-85(2+), Cs+ and Co-60(2+) was found to be governed by both diffusion and sorption processes. For Sr-85(2+), the slightly higher diffusivity relative to HTO and the low sorption value are consistent with laboratory diffusion measurements on small-scale samples. In the case of Cs+, the numerically deduced high diffusivity and the Freundlich-type sorption behaviour is also supported by ongoing laboratory data. For Co, no laboratory diffusion data were yet available for comparison; however, the modelled data suggests that Co-60(2+) sorption was weaker than would be expected from available batch sorption data. Overall, the results demonstrate the feasibility of the experimental setup for obtaining high-quality diffusion data for conservative and sorbing tracers. (C) 2007 Elsevier Ltd. All rights reserved.

Long-term diffusion experiment at Mont Terri: first results from field and laboratory data

The diffusion of radionuclides is an important safety aspect for nuclear waste disposal in argillaceous host rocks. A long-term diffusion experiment, termed DI-A, is being carried out at the Mont Terri Rock Laboratory in the Opalinus Clay formation. The aim of this experiment is the understanding of the migration and sorption behaviour of cationic and anionic species in consolidated clays. This study reports on the experimental layout and the first results obtained from the DI-A experiment, which include the investigation of HTO, Na-22(+), Cs+, and I- migration during a period of 1 year by analysing these tracers in the water circulating in the borehole. In addition, results obtained from through-diffusion experiments on small-sized samples with HTO, I-, and Cl-36(-) are presented. The decrease of tracer concentrations in the borehole is fastest for Cs+, followed by Na-22(+), HTO, and finally I-. The chemical composition of the artificial pore water in the borehole shows very little variation with time, thus indicating almost no chemical disturbance around the borehole. Through-diffusion experiments in the laboratory that were performed parallel to the bedding plane with two different methods yielded effective diffusion coefficients for HTO of 4-5 X 10(-11) m(2) s(-1) and significantly lower ones for anions Cl- and I- (0.7-1.6 X 10(-11) m(2) s(-1)). The results indicate the importance of anion exclusion effects arising from the negatively charged clay surfaces. Furthermore, they demonstrate the anisotropic diffusion properties of the clay formation with significantly increased diffusion rates parallel to bedding relative to the perpendicular direction. The tracer data of the in situ experiment were successfully described with 2D diffusion models using diffusion and sorption parameters obtained from the above mentioned and other laboratory studies. The modelling results indicate that HTO and I- diffused with no retardation. The retardation of Na+ and Cs+ could be described by empirical sorption expressions from previously derived batch sorption (Cs+) or diffusion (Na+) experiments. Overall, the obtained results demonstrate the feasibility of the technical concept to study the diffusion of nonsorbing and sorbing tracers in consolidated clays. (C) 2004 Elsevier B.V. All rights reserved.

In-situ X-ray micro-diffraction studies of heterogeneous interfaces between cementitious materials and geological formations

In the present study the challenge of analyzing complex micro X-ray diffraction (microXRD) patterns from cement–clay interfaces has been addressed. In order to extract the maximum information concerning both the spatial distribution and the crystal structure type associated with each of the many diffracting grains in heterogeneous, polycrystalline samples, an approach has been developed in which microXRD was applied to thin sections which were rotated in the X-ray beam. The data analysis, performed on microXRD patterns collected from a filled vein of a cement–clay interface from the natural analogue in Maqarin (Jordan), and a sample from a two-year-old altered interface between cement and argillaceous rock, demonstrate the potential of this method.

The isotopic composition of pore-water from Tournemire argillite (France): An inter-comparison study.

The determination of stable isotope contents of pore-water from consolidated argillaceous rocks remains a critical issue. In order to understand the processes involved in techniques developed for acquiring stable isotope compositions of pore-water, a comparative study between different methods was based on core samples of the Tournemire argillite. It concerns two water extraction techniques based on vacuum distillation and two pore-water equilibration techniques (radial diffusion in liquid phase and diffusive exchange in vapor phase). The water-content values obtained from vacuum distillation at 50 °C are always the lowest, on average 8% lower than the values obtained by heating at 105 °C and 17% lower than the values obtained by heating at 150 °C. The amounts of pore-water estimated from vacuum distillation at 105 °C and 150 °C and from radial diffusion method are in good agreement with those determined by heating. On the contrary, the vapor exchange method provides the highest values of water contents. Concerning stable isotope data, a good agreement was found between those obtained by equilibration techniques and those of fracture water, especially for 2H. Vacuum distillation at high temperature (particularly at 150 °C) also provided results consistent with data of fracture fluids. On the other hand, distillation at 50 °C provides a systematic depletion in heavy isotopes (about –20‰ for 2H and –2.7‰ for 18O) that can be modelled by an incomplete Rayleigh-type distillation process.

Late Quaternary history of the Vakinankaratra volcanic field (central Madagascar): insights from luminescence dating of phreatomagmatic eruption deposits

The Quaternary Vakinankaratra volcanic field in the central Madagascar highlands consists of scoria cones, lava flows, tuff rings, and maars. These volcanic landforms are the result of processes triggered by intracontinental rifting and overlie Precambrian basement or Neogene volcanic rocks. Infrared-stimulated luminescence (IRSL) dating was applied to 13 samples taken from phreatomagmatic eruption deposits in the Antsirabe–Betafo region with the aim of constraining the chronology of the volcanic activity. Establishing such a chronology is important for evaluating volcanic hazards in this densely populated area. Stratigraphic correlations of eruption deposits and IRSL ages suggest at least five phreatomagmatic eruption events in Late Pleistocene times. In the Lake Andraikiba region, two such eruption layers can be clearly distinguished. The older one yields ages between 109 ± 15 and 90 ± 11 ka and is possibly related to an eruption at the Amboniloha volcanic complex to the north. The younger one gives ages between 58 ± 4 and 47 ± 7 ka and is clearly related to the phreatomagmatic eruption that formed Lake Andraikiba. IRSL ages of a similar eruption deposit directly overlying basement laterite in the vicinity of the Fizinana and Ampasamihaiky volcanic complexes yield coherent ages of 68 ± 7 and 65 ± 8 ka. These ages provide the upper age limit for the subsequently developed Iavoko, Antsifotra, and Fizinana scoria cones and their associated lava flows. Two phreatomagmatic deposits, identified near Lake Tritrivakely, yield the youngest IRSL ages in the region, with respective ages of 32 ± 3 and 19 ± 2 ka. The reported K-feldspar IRSL ages are the first recorded numerical ages of phreatomagmatic eruption deposits in Madagascar, and our results confirm the huge potential of this dating approach for reconstructing the volcanic activity of Late Pleistocene to Holocene volcanic provinces.

Mineralogical and isotopic record of diagenesis from the Opalinus Clay formation at Benken, Switzerland: Implications for the modeling of pore-water chemistry in a clay formation

Argillaceous rocks are considered to be a suitable geological barrier for the long-term containment of wastes. Their efficiency at retarding contaminant migration is assessed using reactive-transport experiments and modeling, the latter requiring a sound understanding of pore-water chemistry. The building of a pore-water model, which is mandatory for laboratory experiments mimicking in situ conditions, requires a detailed knowledge of the rock mineralogy and of minerals at equilibrium with present-day pore waters. Using a combination of petrological, mineralogical, and isotopic studies, the present study focused on the reduced Opalinus Clay formation (Fm) of the Benken borehole (30 km north of Zurich) which is intended for nuclear-waste disposal in Switzerland. A diagenetic sequence is proposed, which serves as a basis for determining the minerals stable in the formation and their textural relationships. Early cementation of dominant calcite, rare dolomite, and pyrite formed by bacterial sulfate reduction, was followed by formation of iron-rich calcite, ankerite, siderite, glauconite, (Ba, Sr) sulfates, and traces of sphalerite and galena. The distribution and abundance of siderite depends heavily on the depositional environment (and consequently on the water column). Benken sediment deposition during Aalenian times corresponds to an offshore environment with the early formation of siderite concretions at the water/sediment interface at the fluctuating boundary between the suboxic iron reduction and the sulfate reduction zones. Diagenetic minerals (carbonates except dolomite, sulfates, silicates) remained stable from their formation to the present. Based on these mineralogical and geochemical data, the mineral assemblage previously used for the geochemical model of the pore waters at Mont Terri may be applied to Benken without significant changes. These further investigations demonstrate the need for detailed mineralogical and geochemical study to refine the model of pore-water chemistry in a clay formation.

The supergene thorium and rare-earth element deposit at Morro do Ferro, Poços de Caldas, Minas Gerais, Brazil

The thorium and rare-earth element (Th-REE) deposit at Morro do Ferro formed under supergene lateritic weathering conditions. The ore body consists of shallow NW-SE elongated argillaceous lenses that extend from the top of the hill downwards along its south-eastern slope. The deposit is capped by a network of magnetite layers which protected the underlying highly weathered, argillaceous host rock from excessive erosion. The surrounding country rocks comprise a sequence of subvolcanic phonolite intrusions that have been strongly altered by hydrothermal and supergene processes. From petrological, mineralogical and geochemical studies, and mass balance calculations, it is inferred that the highly weathered host rock was originally carbonatitic in composition, initially enriched in Th and REEs compared to the surrounding silicate rocks. The intrusion of the carbonatite caused fenitic alteration in the surrounding phonolites, consisting of early potassic alteration followed by a vein-type Th-REE mineralization with associated fluorite, carbonate, pyrite and zircon. Subsequent weathering has completely decomposed the carbonatite forming a residual supergene enrichment of Th and REEs. Initial weathering of the carbonatite has created a chemical environment that might have been conductive to carbonate and phosphate complexing of the REEs in groundwaters. This may have appreciably restricted the dissolution of primary REE phases. Strongly oxidic weathering has resulted in a fractionation between Ce and the other light rare earth elements (LREEs). Ce3+ is oxidized to Ce4+ and retained together with Th by secondary mineral formation (cerianite, thorianite), and by adsorption on poorly crystalline iron- and aluminium-hydroxides. In contrast, the trivalent LREEs are retained to a lesser degree and are thus more available for secondary mineral formation (Nd-lanthanite) and adsorption at greater depths down the weathering column. Seasonally controlled fluctuations of recharge waters into the weathering column may help to explain the observed repetition of Th-Ce enriched zones underlain by trivalent LREE enriched zones.