Evaluation of Microcracking and Chemical Deterioration in Concrete Pavements Final Report, October 31, 1995

The major objective of this research project was to investigate the chemistry and morphology of portland cement concrete pavements in Iowa. The integrity of the various pavements was evaluated qualitatively, based on the presence or absence of microcracks, the presence or absence of sulfate minerals, and the presence or absence of alkali-silica gel(s). Major equipment delays and subsequent equipment replacements resulted in significant delays over the course of this research project. However, all these details were resolved and the equipment is currently in place and fully operational. The equipment that was purchased for this project included: ( I ) a LECO VP 50, 12-inch diameter, variable speed grinder/polisher: (2) a Hitachi S-2460N variable pressure scanning electron microscope; and (3) a OXFORD Instruments Link ISIS microanalysis system with a GEM (high-purity germanium) X-ray detector. This study has indicated that many of the concrete pavements contained evidence of multiple deterioration mechanisms: and hence, the identification of a single reason for the distress that was observed in any given pavement typically had to be based on opinion rather than empirical evidence.

Stable O and H isotopic composition of hydrous minerals as proxies for paleoclimate and -topography : application to the European Alps

The isotopie composition of clay minerals can be used to gain information on paleoaltitude, -topography and -climate during the time of their formation, as they form in isotopie equilibrium with ambient water, which has an isotopie composition that is determined by previous rain-out. In this thesis, the usability of this approach is evaluated for sample material from both the North Alpine Foreland Basin and internal parts of the European Alps. The isotopie composition of precipitation is determined by the air temperature and the extent of previous rain-out, which in turn is affected by the distance to the point of origin of the water vapor and the condensation conditions. An orographic barrier leads to uplift and adiabatic cooling of air masses and thereby enhances rainfall with a characteristic depletion in heavy 0 and H isotopes. Processes such as evaporation and mixing of water with different origin affect the isotopie composition further on the surface. Clay minerals are hydrous phyllosilicates that can form during weathering or pedogenesis in isotopie equilibrium with the present water and inherit its isotopie composition with a characteristic fractionation. If their isotopie composition was preserved after formation and the necessary parameters are known, it is possible to calculate the isotopie composition of the ambient water and thereby reconstruct climatic and topographic conditions during their formation. Due to the hygroscopic behavior of the sample material, analytical procedures needed to be modified to allow an analysis of the oxygen and hydrogen isotopie composition of the hydroxyl water built into their crystal structure and not the one of recently adsorbed water. In order to determine typical 5lsO and 8D values of meteoric water and minerals in the weathering environment in high Alpine regions, samples of surface water and soils from the valley of Visp in the Swiss Alps were studied that were collected along a transect with varying altitudes and host rock lithologies. The actual aim to attempt the reconstruction of Alpine paleoelevations was addressed by the analysis of sediments deposited under marine and terrestrial conditions during the Miocene and Oligocene, which were sampled from different locations in Switzerland, Germany and Austria. Further bentonite and fault gouge clay samples were used as reference material from low and high elevations. Results show that the isotopie composition of clay minerals can be influenced by several factors, such as the mode and site of their formation, possible isotope exchange (which is evident for 8D values), the samples' mineral composition (such as the presence of detrital material) and the deposition environment. With a consideration of these parameters and limitation to certain sample material, conclusions are drawn on the isotopie composition of the water from which the clay minerals formed. Most of the obtained values lie in the same range as has been reported in literature for foreland precipitation. The reconstruction of paleoelevation might be possible for selected sites with a geographical setting close to the Alpine chain or for intramontane basins. - La composition isotopique des argiles, qui se forment typiquement en contact avec des eaux superficielles, peut être utilisée pour obtenir des informations sur la paléoaltitude, la paléotopographie et le paléoclimat pendant leur création. La composition en isotopes stable (oxygène et hydrogène) des eaux de pluie est déterminée par l'altitude, la température, la distance depuis le lieu d'évaporation et par le taux de précipitation. Certains processus comme l'évaporation, l'interaction avec des minéraux et le mélange d'eaux d'origines variées peuvent aussi changer la composition des eaux de surface. Les argiles sont des pliyllosilicates hydratés qui sont crées par l'altération des roches au contact de ces eaux de surface et ils acquièrent une composition isotopique qui est soumise à un certain fractionnement. L'objectif de cette thèse est d'évaluer si l'effet de l'altitude des Alpes, est détectable dans la composition isotopique des sédiments du bassin d'avant-pavs pendant le Miocène. Après avoir établi la procédure analytique, des compositions isotopiques typiques de régions de hautes altitudes ont été determine sur les eaux de surfaces (rivières) et sur des échantillons de sols, le long d'une coupe dans la valée de Visp, dans les Alpes Suisses. Une reconstruction des paléoaltitudes Miocènes Alpines a ensuite été mené par l'analyse de sédiments marins et terrestres en utilisant des échantillons d'âges variés et provenant de Suisse, d'Allemagne et d'Autriche. Les résultats montrent que la composition isotopique des échantillons est impactée par de multiples facteurs, tels que le mode de et le lieu de formation. un possible échange isotopique tardif (surtout pour 5D). leur composition minéralogique et l'environnement de leur sédimentation. Après un examen prudent de ces paramètres, et en se limitant à un certain assortiment d'échatillons, on peut tirer des conclusions sur la composition isotopique des eaux originelles pour en déduire l'effet du climat et de la topographie.

Photonic characteristics of Langmuir-Blodgett self-assembled monolayers of colloidal silica particles

Monodispersed colloidal crystals based on silica sub-micrometric particles were synthesized using the Stöber-Fink-Bohn process. The control of nucleation and coalescence result in improved characteristics such as high sphericity and very low size dispersion. The resulting silica particles show characteristics suitable for self-assembling across large areas of closely-packed 2D crystal monolayers by an accurate Langmuir-Blodgett deposition process on glass, fused silica and silicon substrates. Due to their special optical properties, colloidal films have potential applications in fields including photonics, electronics, electro-optics, medicine (detectors and sensors), membrane filters and surface devices. The deposited monolayers of silica particles were characterized by means of FESEM, AFM and optical transmittance measurements in order to analyze their specific properties and characteristics. We propose a theoretical calculation for the photonic band gaps in 2D systems using an extrapolation of the photonic behavior of the crystal from 3D to 2D. In this work we show that the methodology used and the conditions in self-assembly processes are decisive for producing high-quality two-dimensional colloidal crystals by the Langmuir-Blodgett technique.

Quantification of magmatic and hydrothermal processes in a peralkaline syenite-alkali granite complex based on textures, phase equilibria, and stable and radiogenic isotopes

The Puklen complex of the Mid-Proterozoic Gardar Province, South Greenland, consists of various silica-saturated to quartz-bearing syenites, which are intruded by a peralkaline granite. The primary mafic minerals in the syenites are augite +/- olivine + Fe-Ti oxide + amphibole. Ternary feldspar thermometry and phase equilibria among mafic silicates yield T = 950-750degreesC, a(SiO2) = 0.7-1 and an f(O2) of 1-3 log units below the fayalite-magnetite-quartz (FMQ) buffer at 1 kbar. In the granites, the primary mafic minerals are ilmenite and Li-bearing arfvedsonite, which crystallized at temperatures below 750degreesC and at f(O2) values around the FMQ buffer. In both rock types, a secondary post-magmatic assemblage overprints the primary magmatic phases. In syenites, primary Ca-bearing minerals are replaced by Na-rich minerals such as aegirine-augite and albite, resulting in the release of Ca. Accordingly, secondary minerals include ferro-actinolite, (calcite-siderite)(ss), titanite and andradite in equilibrium with the Na-rich minerals. Phase equilibria indicate that formation of these minerals took place over a long temperature interval from near-magmatic temperatures down to similar to300degreesC. In the course of this cooling, oxygen fugacity rose in most samples. For example, late-stage aegirine in granites formed at the expense of arfvedsonite at temperatures below 300degreesC and at an oxygen fugacity above the haematite-magnetite (HM) buffer. The calculated delta(18)O(melt) value for the syenites (+5.9 to +6.3parts per thousand) implies a mantle origin, whereas the inferred delta(18)O(melt) value of <+5.1parts per thousand for the granitic melts is significantly lower. Thus, the granites require an additional low-delta(18)O contaminant, which was not involved in the genesis of the syenites. Rb/Sr data for minerals of both rock types indicate open-system behaviour for Rb and Sr during post-magmatic metasomatism. Neodymium isotope compositions (epsilonNd(1170 Ma) = -3.8 to -6.4) of primary minerals in syenites are highly variable, and suggest that assimilation of crustal rocks occurred to variable extents. Homogeneous epsilon(Nd) values of -5.9 and -6.0 for magmatic amphibole in the granites lie within the range of the syenites. Because of the very similar neodymium isotopic compositions of magmatic and late- to post-magmatic minerals from the same syenite samples a principally closed-system behaviour during cooling is implied. In contrast, for the granites an externally derived fluid phase is required to explain the extremely low epsilon(Nd) values of about -10 and low delta(18)O between +2.0 and +0.5parts per thousand for late-stage aegirine, indicating an open system in the late-stage history. In this study we show that the combination of phase equilibria constraints with stable and radiogenic isotope data on mineral separates can provide much better constraints on magma evolution during emplacement and crystallization than conventional whole-rock studies.

Trace element distribution among rock-forming minerals from metamorphosed to partially molten basic igneous rocks in a contact aureole (Fuerteventura, Canaries)

Low pressure partial melting of basanitic and ankaramitic dykes gave rise to unusual, zebra-like migmatites, in the contact aureole of a layered pyroxenite-gabbro intrusion, in the root zone of an ocean island (Basal Complex, Fuerteventura, Canary Islands). These migmatites are characterised by a dense network of closely spaced, millimetre-wide leucocratic segregations. Their mineralogy consists of plagioclase (An(32-36)), diopside, biotite, oxides (magnetite, ilmenite), +/-amphibole, dominated by plagioclase in the leucosome and diopside in the melanosome. The melanosome is almost completely recrystallised, with the preservation of large, relict igneous diopside phenocrysts in dyke centres. Comparison of whole-rock and mineral major- and trace-element data allowed us to assess the redistribution of elements between different mineral phases and generations during contact metamorphism and partial melting. Dykes within and outside the thermal aureole behaved like closed chemical systems. Nevertheless, Zr, Hf, Y and REEs were internally redistributed, as deduced by comparing the trace element contents of the various diopside generations. Neocrystallised diopside - in the melanosome, leucosome and as epitaxial phenocryst rims - from the migmatite zone, are all enriched in Zr, Hf, Y and REEs compared to relict phenocrysts. This has been assigned to the liberation of trace elements on the breakdown of enriched primary minerals, kaersutite and sphene, on entering the thermal aureole. Major and trace element compositions of minerals in migmatite melanosomes and leucosomes are almost identical, pointing to a syn- or post-solidus reequilibration on the cooling of the migmatite terrain i.e. mineral-melt equilibria were reset to mineral-mineral equilibria. (C) 2007 Elsevier B.V. All rights reserved.

Geology of the Cerro-Quema Au-Cu deposit (Azuero Peninsula, Panama)

The Cerro Quema district, located on the Azuero Peninsula, Panama, is part of a large regional hydrothermal system controlled by regional faults striking broadly E-W, developed within the Río Quema Formation. This formation is composed of volcanic, sedimentary and volcano-sedimentary rocks indicating a submarine depositional environment, corresponding to the fore-arc basin of a CretaceousPaleogene volcanic arc. The structures observed in the area and their tectono-stratigraphic relationship with the surrounding formations suggest a compressive and/or transpressive tectonic regime, at least during Late CretaceousOligocene times. The igneous rocks of the Río Quema Formation plot within the calc-alkaline field with trace and rare earth element (REE) patterns of volcanic arc affinity. This volcanic arc developed on the Caribbean large igneous province during subduction of the Farallon Plate. Mineralization consists of disseminations of pyrite and enargite as well as a stockwork of pyrite and barite with minor sphalerite, galena and chalcopyrite, hosted by a subaqueous dacitic lava dome of the Río Quema Formation. Gold is present as submicroscopic grains and associated with pyrite as invisible gold. A hydrothermal alteration pattern with a core of advanced argillic alteration (vuggy silica with alunite, dickite, pyrite and enargite) and an outer zone of argillic alteration (kaolinite, smectite and illite) has been observed. Supergene oxidation overprinted the hydrothermal alteration resulting in a thick cap of residual silica and iron oxides. The ore minerals, the alteration pattern and the tectono-volcanic environment of Cerro Quema are consistent with a high sulfidation epithermal system developed in the Azuero peninsula during pre-Oligocene times.

Effect of anionic salts on some blood and urine minerals, acid-base balance and udder oedema of dry pregnant cows

Selostus: Anionisten suolojen vaikutus ummessa olevien lehmien veren ja virtsan kivennäisiin, happo-emästasapainoon sekä utarepöhöön

Niobium and rare earth minerals from the Virulundo carbonatite, Namibe, Angola

The Virulundo carbonatite in Angola, one of the biggest in the world, contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias, trachytoids). The composition of the primary pyrochlore crystals is very close to fluornatrocalciopyrochlore in all these units. High-temperature hydrothermal processes caused the pseudomorphic replacement of the above crystals by a second generation of pyrochlore, characterized by lower F and Na contents. Low-temperature hydrothermal replacement of the above pyrochlores, associated with production of quartz-carbonates-fluorite veins, controled the development of a third generation of pyrochlore, characterized by high Sr contents. Finally, supergene processes produced the development of a secondary paragenesis in the carbonatite, consisting in late carbonates, goethite, hollandite and REE minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Separation of Ce from the other REE was allowed by oxidizing conditions. Therefore, Ce4+ was also incorporated into a late generation of pyrochlore, which is also strongly enriched in Ba and strongly depleted in Ca and Na

Evaluation of Microcracking and Chemical Deterioration in Concrete Pavements: Phase II, HR-358, Progress Report, 1995

The major objective of this research project is to investigate the chemistry and morphology of Portland cement concrete pavements in Iowa. The integrity of the various pavements is being ascertained based on the presence or absence of microcracks, the presence or absence of sulfate minerals, and the presence or absence of alkali-silica gel(s). Work is also being done on quantifying the air content of the concrete using image analysis techniques since this often appears to be directly related to the sulfate minerals that are commonly observed in the pavement cores.

Obtención de vidrio a partir de residuos de la minería del estaño en Bolivia

Manufacturing of glass from tin mining tailings in Bolivia Tailings from mining activities in Bolivia represent an environmental problem. In the vicinity of the tin mines of Llallagua,Potosí department, there are large dumps and tailings. We present a study of the use of these wastes as raw materials for the manufacture of glass. This procedure aims to contribute to environmental remediation of mining areas through the vitrification, a process which offers an alternative for stabilization of hazardous waste. In addition, the marketing of the obtained product would provide an additional income to the mining areas. For this study three samples of mining waste, with grain size between sand and silt, were used. The chemical composition of these raw materials, determined by X-ray fluorescence, is granitic, with high contents of heavy metals. On the basis of its composition, glass were made from silica glass by adding CaCO3 and Na2CO3. The thermal cycle has been determined from TDA. Tg values of glass range from 626º to 709 °C. Leaching tests of the obtained glasses confirm their capacity to retain heavy metals.

Sugars, organic acids, minerals and lipids in jabuticaba

The aim of this work was to determine the sugar, organic acid and mineral compositions of the whole fruit and fractions (skin, pulp and seed) of the Paulista (Plinia cauliflora) and Sabará (Plinia jaboticaba) jabuticaba tree genotypes, as well as the oil compositions of their skin and seeds. High levels of sugar, especially fructose, followed by glucose and sucrose, were encountered in the fruit. In the Paulista genotype, higher levels of total and reducing sugars were found in the pulp and skin, which was not observed when comparing the whole fruit of both genotypes. Five organic acids were found in the whole fruit and in the fractions of the two jabuticaba genotypes in quantitative order: citric acid > succinic acid > malic acid > oxalic acid > acetic acid. Potassium was the most abundant mineral found. This fruit was also shown to be rich in magnesium, phosphorus, calcium and copper. The seed oil had nearly the same constitution as the oil extracted from the skin in both genotypes and the major compounds were an unidentified phytosterol, palmitic, linoleic and oleic acids, and squalene.

Bulk silica-based luminescent materials by sol-gel processing of non-conventional precursors

The sol-gel synthesis of bulk silica-based luminescent materials using innocuous hexaethoxydisilane and hexamethoxydisilane monomers, followed by one hour thermal annealing in an inert atmosphere at 950oC-1150oC, is reported. As-synthesized hexamethoxydisilane-derived samples exhibit an intense blue photoluminescence band, whereas thermally treated ones emit stronger photoluminescence radiation peaking below 600 nm. For hexaethoxydisilane-based material, annealed at or above 1000oC, a less intense photoluminescence band, peaking between 780 nm and 850 nm that is attributed to nanocrystalline silicon is observed. Mixtures of both precursors lead to composed spectra, thus envisaging the possibility of obtaining pre-designed spectral behaviors by varying the mixture composition.

Obtención de vidrio a partir de residuos de la minería del estaño en Bolivia

Manufacturing of glass from tin mining tailings in Bolivia Tailings from mining activities in Bolivia represent an environmental problem. In the vicinity of the tin mines of Llallagua,Potosí department, there are large dumps and tailings. We present a study of the use of these wastes as raw materials for the manufacture of glass. This procedure aims to contribute to environmental remediation of mining areas through the vitrification, a process which offers an alternative for stabilization of hazardous waste. In addition, the marketing of the obtained product would provide an additional income to the mining areas. For this study three samples of mining waste, with grain size between sand and silt, were used. The chemical composition of these raw materials, determined by X-ray fluorescence, is granitic, with high contents of heavy metals. On the basis of its composition, glass were made from silica glass by adding CaCO3 and Na2CO3. The thermal cycle has been determined from TDA. Tg values of glass range from 626º to 709 °C. Leaching tests of the obtained glasses confirm their capacity to retain heavy metals.

Geology of the Cerro-Quema Au-Cu deposit (Azuero Peninsula, Panama)

The Cerro Quema district, located on the Azuero Peninsula, Panama, is part of a large regional hydrothermal system controlled by regional faults striking broadly E-W, developed within the Río Quema Formation. This formation is composed of volcanic, sedimentary and volcano-sedimentary rocks indicating a submarine depositional environment, corresponding to the fore-arc basin of a Cretaceous-Paleogene volcanic arc. The structures observed in the area and their tectono-stratigraphic relationship with the surrounding formations suggest a compressive and/or transpressive tectonic regime, at least during Late Cretaceous-Oligocene times. The igneous rocks of the Río Quema Formation plot within the calc-alkaline field with trace and rare earth element (REE) patterns of volcanic arc affinity. This volcanic arc developed on the Caribbean large igneous province during subduction of the Farallon Plate. Mineralization consists of disseminations of pyrite and enargite as well as a stockwork of pyrite and barite with minor sphalerite, galena and chalcopyrite, hosted by a subaqueous dacitic lava dome of the Río Quema Formation. Gold is present as submicroscopic grains and associated with pyrite as invisible gold. A hydrothermal alteration pattern with a core of advanced argillic alteration (vuggy silica with alunite, dickite, pyrite and enargite) and an outer zone of argillic alteration (kaolinite, smectite and illite) has been observed. Supergene oxidation overprinted the hydrothermal alteration resulting in a thick cap of residual silica and iron oxides. The ore minerals, the alteration pattern and the tectono-volcanic environment of Cerro Quema are consistent with a high sulfidation epithermal system developed in the Azuero peninsula during pre-Oligocene times.