Ammonium-bearing micas in very low-grade metapelites: micro- and nano-texture and composition

The present study examines the micro- and nano-texture and composition of an ammonium-bearing and potassium micas in very-low grade metamorphic black Silurian shales from the SE Iberian Range (NE Spain). Two organic-rich shales were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), analytical electron microscopy (AEM) and electron energy loss spectroscopy (EELS). The XRD showed the presence of two populations of micas: pure K micas with d(001) = 9.98 angstrom and ammonium-bearing micas with larger d(001) values (10.08 angstrom and 10.05 angstrom). The latter values indicate NH4 contents between 13 and 29% in the interlayer, which was confirmed by IR. Interstratifications of smectite and mica layers in the mica packets were not detected by XRD and TEM. Mica packets with sizes ranging from 100 to 250 angstrom show disordered polytypes and (001) lattice fringes that reflect the presence of K- and NH4-bearing layers (9.9-10.2 angstrom). The combination of AEM and EELS analyses on powdered and lamellar samples indicates that micas have typical dioctahedral compositions with highly variable K contents. This variation in K is consistent with the presence of K and NH4 in the interlayers, even though the NH4 and K are not distributed homogeneously; rather they are segregated in nm-sized domains in the mica interlayer

Origin and geochemical evolution from ferrallitized clays to karst bauxite: An example from the Lower Cretaceous of NE Spain

Four outcrops of Lower Cretaceous (Barremian) karst bauxites located in Teruel (NE Spain) were analysed. The deposits show a heterogeneous-chaotic lithostructure consisting of pisolitic bauxite blocks embedded in lateritic red clays filling karst cavities. The research has focused on the geochemical study of major, minor, and trace elements (including some critical to industry) of both the bauxites and clays. The objective was to investigate the bauxite precursor material and to characterize the system's geochemical evolution. Geochemical analyses were carried out by inductively-coupled plasma optical emission and mass spectroscopy. An absolute weathering index has been calculated to estimate element mobility, assuming Ti as an immobile element and the Upper Continental Crust (UCC) as parent material. Further, selected samples were observed by field emission scanning electron microscopy. The data indicate that both the bauxites and red clays originated by intense chemical weathering from more mafic argillaceous sediments than the UCC. Ongoing weathering caused the bauxitization of the upper parts of the original profile, preventing the lower parts from being bauxitized, thus producing the ferrallitized clays underlying the pisolitic bauxites. Subsequent karst reactivation gave rise to the current lithostructure. Ferrallitization is related to Fe, Sc, and V enrichment. On the other hand, although bauxites are relatively enriched in some elements compared to clays, the more intense chemical weathering associated with bauxitization led to chemical homogenization and widespread element depletion. During the bauxitization, Al, Ti, Zr, Cr, and probably Hf and the critical element Nb behaved as more immobile elements in the system. Bauxitization also enhanced homogenization and depletion of the REE, which is more pronounced for the LREE. HREE trends seem to be partly related to the concentration of Ti oxides in the bauxites, whereas P-bearing phases, more frequent in the clays, control the LREE. Subsequent to bauxitization, partial kaolinization of the bauxite took place related to the circulation of acid solutions that also caused the karst reactivation. These late processes caused some Al depletion in the bauxites and enhanced Fe loss together with V and, to a lesser extent, Ge

Weathering events recorded in uppermost Hauterivian-lower Barremian clay-dominated continental successions from the NW Iberian Range: climatic vs. tectonic controls

The facies and clay mineral study of clay/marl-rich levels from the Torrelapaja Formation (latest Hauterivian-early Barremian, NW Iberian Range, NE Spain) allowed to establish the palaeoclimatic and palaeoenvironmental conditions under they were generated. The muddy levels and pisoids contained therein of two logs were sampled and studied by X-ray diffraction and optical and electron microscopy. A similar mineralogical upwards trend is recorded in both logs, with a decrease in calcite coupled with an increase in quartz and orthoclase content and constant proportions in goethite, hematite, diaspore, anatase, rutile, ilmenite, and clay mineral content. The lower muddy levels have higher kaolinite content than the upper levels, where illitic phases are the dominant clay minerals. Smectite and intergrowths of illitic phases and kaolinite are also detected upwards. The kaolinite and smectite textures indicate an authigenic origin, whereas the illitic phases are former phases acting as a substrate for kaolinite crystallization. Pisoids mineralogy and texture show an in-situ origin, but some are fractured, indicating reworking processes. The mineral association found in the muddy levels is characteristic of oxisols formed under warm and humid conditions. The upward decrease in kaolinite content is coeval with an increase in the illitic phases and quartz content, related to siliciclastic input, but is also coeval with the presence of authigenic smectite. This indicates a decrease in chemical weathering, not fully registered due to the siliciclastic contribution, which was possibly associated with a change to colder, drier conditions during the latest Hauterivian-early Barremian in the studied area

Protocol for the reconstruction of micromammals from fossils. Two case studies: The skulls of Beremendia fissidens and Dolinasorex glyphodon

We have developed a protocol for reconstructing 3D models of the skulls of extinct species of small mammals. For the first time, the reconstruction uses fragments of fossils from a mixture of different specimens and from related extant species. We use free software and commercial computers to make the process reproducible and usable for the scientific community. We present a semi-quantitative protocol to face the problem of making 3D reconstructions of fossil species that are incomplete in the fossil record and/or represented by a mixture of different individuals, as usually occurs with small vertebrates. Therefore this approach is useful when no complete skull is available. The protocol combines the use of microCT scan technology with a subsequent computer treatment using different software tools for 3D reconstruction from microCT and 3D design and printing (e.g. Fiji, SPIERS, Meshlab, Meshmixer) in a defined order. This kind of free and relatively simple software, plus the detailed description, makes this protocol practicable for researchers who do not necessarily have great deal of experience in working with 3D. As an example, we have performed virtual reconstructions of the skulls of two species of insectivore small mammals (Eulipotyphla): Beremendia fissidens and Dolinasorex glyphodon. The resulting skulls, plus models of the extant shrews Blarina brevicauda, Neomys fodiens, Crocidura russula and Sorex coronatus, make it possible to compare characteristics that can only be observed by means of microCT 3D reconstructions, and given the characteristics of the material, using this protocol. Among the characters we can compare are the position of the mandibles, the spatial relations among all the teeth, the shape of the snout and, in general, all parameters related with the anatomy of the rostrum. Moreover, these reconstructions can be used in different types of context: for anatomical purposes, especially to see internal features or characteristics at whole-skull scale, for bioengineering, animation, or other techniques that need a digital model

Mineral and textural transformations in mixtures of Al-rich and Al–K-rich clays with firing: Refractory potential of the fired products

The present work analyses a set of cylinders manufactured by pressing and fired from 1000 °C to 1270 °C, which are composed of pure Al-rich rocks (bauxite) and mixtures of bauxite with Al–K-rich clays. The aim of the study is to determine the mineral and textural transformations that take place in the mixtures with firing and their influence on the physical properties of the final products in order to evaluate their refractory potential by comparing them with various fired commercial bauxites. To this end, raw and fired samples were analysed by X-ray diffraction, X-ray fluorescence, and optical and field emission scanning electron microscopy, and significant physical properties (e.g. density, linear shrinkage, porosity, colour, water absorption, thermal conductivity and point load resistance) were determined in the fired cylinders. The raw bauxite was mainly formed by boehmite, kaolinite and hematite whereas the illite- and kaolinite-rich clay was formed by quartz, illite and kaolinite. Kaolinite, illite and boehmite are not detected at 1000 °C and, from this temperature upwards, mullite, corundum, ¿-Al2O3, hercynite, ilmenite, cristobalite and vitreous phase are formed. Changes in physical properties with rising temperature are associated with the mineralogical changes. The increases in density and linear shrinkage are related to the formation of vitreous phase and the crystallization of mullite, and correlate with the decrease in porosity, water absorption and thermal conductivity. The changes in the colour of the samples are related to the hematite content at each temperature, whereas the point load resistance is greater with higher corundum content. Both the firing temperature and the clay content play an important role in the refractory potential of the mixtures, since samples mixed with illite- and kaolinite-rich clay present similar properties at lower temperatures to those of the fired commercial bauxites

SEM and TEM evidence of mixed-layer illite-smectite formed by dissolutioncrystallization processes in continental Paleogene sequences in northwestern Argentina

In the northernmost Calchaquí Valley (Salta, Argentina), the Paleogene continental sediments show a transition from smectite, at the top, to R3 I-S (>90% illite) through R1 I-S (65–80% illite), in contrast to the remaining sectors, containing smectite up to the bottom. Samples at the base of the succession were characterized by high-quality step-scan X-ray diffraction (XRD), scanning electron microscopy (SEM) and analytical high-resolution transmission electron microscopy (HRTEM). Analysis by SEM demonstrated dissolution of primary phases (feldspars, micas and quartz) and crystallization of illite, I-S and kaolinite. As this alteration is not pervasive, an intermediate fluid/rock ratio could be inferred. The lattice-fringe images of the samples from upper parts of the sequence show abundant I1-rich areas, whereas in the lower parts of the sequence, illite packets and I3 I-S coexist and compositions evolve towards muscovite (tetrahedral-charge increase, principally compensated by Mgby-Al substitution in octahedral sites and by a slight decrease in Ca in interlayer sites). As burial temperatures were probably similar in all the samples, depth was not responsible for the illite formation at the bottom. The TEM textures suggest that illitization proceeded mainly by dissolution-crystallization. The active faults close to the northern Calchaquí Valley probably promoted the circulation of hot, deep fluids, favouring illitization

Evidence of cyclic climatic changes recorded in clay mineral assemblages from a continental Paleocene-Eocene sequence, northwestern Argentina

The continental Paleocene-Eocene sequence investigated in this study belongs to the Salta Group, deposited in an intracontinental rift, the Salta Basin (NW Argentina), that evolved from the lower Cretaceous to the middle Paleogene, and is subdivided into the Pirgua, the Balbuena and the Santa Barbara Subgroups. The Maíz Gordo Formation (200 m thick) is the middle unit of the Santa Bárbara Subgroup, deposited during late post-rift sedimentation. We studied the mineralogy of fine-grained horizons of this formation by X-ray diffraction and Scanning Electron Microscopy (SEM) in order to examine the connection between vertical changes in clay mineralogy in alluvial sediments and paleosols, and global paleoclimatic changes registered during the Paleogene. Paleosols vary from calcic vertisols in the lowermost levels, to inseptisols and gleysols in intermediate positions, to gleyed oxisols in the upper section, indicating increased chemical weathering through time. Clay mineral relative abundances vary with a general increase in kaolinite content from bottom to top. However, at one site there are significant variations in kaolinite/muscovite (Kln/Ms) that define five cycles of kaolinite abundance and Kln/Ms. that indicate cyclic patterns of paleoprecipitation and paleotemperature. These are interpreted as several short-lived hyperthermals during the Paleocene-early Eocene in the Southern Hemisphere, which correlate with well-established episodes of warmth documented from the Northern Hemisphere

Evaluación de la fisibilidad y durabilidad de pizarras de techar mediante microscopía óptica y SEM

The fissility and durability of representative samples of commercial roofing slates from ten deposits in the NW of Spain have been evaluated using transmitted and reflectedlight optical microscopy, scanning electron microscopy, chemical testing and geomechanical procedures. The dominant sulphides in the different slate samples are pyrite and pyrrhotite, the weathering potential of which can be highly variable. The dominant carbonate mineral is ankerite, which explains the low reactivity of these slates in acidic media. The minimum commercial plate thickness varies between 3.5 and 5 mm, depending on the microtexture of the rock. The methodology used in this paper is proposed in order to eliminate the subjectivity of input data that are used in current methods of evaluation and modelling of slate deposits, thus producing an improvement in the profitability of mining operations and a reduction in waste materials.Para evaluar la fisibilidad y la durabilidad de pizarras de techar comerciales, muestras representativas de diez yacimientos del NO de España han sido estudiadas mediante microscopía óptica de luz transmitida y reflejada, microscopía electrónica de barrido y ensayos tecnológicos. Los sulfuros dominantes en las diferentes pizarras estudiadas son pirita o pirrotina, por lo que la alterabilidad de estas es muy variable. La especie carbonatada dominante es ankerita, lo que explica la baja reactividad de estas pizarras en medios ácidos. El espesor comercial mínimo varía en función de la microtextura de la roca, oscilando entre 3,5 y 5 mm. Se propone el uso de la metodología desarrollada en este trabajo, con objeto de eliminar la subjetividad de los inputs de entrada utilizados en las metodologías actuales de evaluación y modelización de yacimientos, lo que incidiría en la mejora de los rendimientos de las explotaciones y en la minimización de la producción de estériles

A multi-ootaxic assemblage from the Lower Cretaceous of the Cameros Basin (La Rioja; Northern Spain)

Here we describe the new fossil site of El Horcajo in the vicinity of Trevijano (La Rioja, Spain). It is located in the palustrine facies of the Enciso Group (Cameros Basin). This new locality has provided dozens of eggshell fragments, together with other vertebrate remains and charophyte fructifications, which allow dating of the locality as Valanginian-Hauterivian. Five ootaxa have being recognized: 1) the Spheroolithidae Guegoolithus turolensis; 2) a surprisingly thick Prismatoolithidae indet., with certain affinities to the oogenus Sankofa, that may represent a new oogenus and oospecies for this oofamily; 3) the Krokolithida