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En el presente trabajo se estudian los procesos de carbonatación de frústulas de diatomeas y la consecuente formación de calizas/dolomías diagenéticas, en estratos de diatomitas marinas (Messiniense, sección de Níjar) y lacustres (Turoliense, sección de Tresjuncos). Se realiza un estudio mineralógico y petrológico para conocer el reemplazo de ópalo A por calcita o dolomita, considerando los factores que favorecen este reemplazo en ambos ambientes. Los datos obtenidos son relevantes para la investigación del uso de diatomitas en la captura y alma­cenamiento de dióxido de carbono a través de su carbonatación. Los procesos pseudomórficos de carbonatación de las valvas se llevaron a cabo mediante el reemplazo directo del ópalo A por calcita o dolomita y la cementación de la microporosidad. La perfecta reproducción de las valvas indica un mecanismo de reacción con acoplamiento de disolución-precipitación en la interfase de reacción. Se interpreta que la organización de las microesferas de ópalo A, dentro de las valvas, condicionaría la organización de complejos amor­fos de varios iones o nanopartículas de carbonatos amorfos, que posteriormente recristalizarían a calcita o dolomita. En las diatomitas lacustres, el proceso de carbonatación de las valvas fue favorecido por la materia orgánica proveniente de la gran cantidad de biota (anfibios, crustáceos, insectos, plantas... etc.) que incorporan. En este ambiente, los procesos de sulfato-reducción durante la degradación de la materia orgánica, generaron CO2, que junto con cambios de pH y salinidad facilitaron los reemplazos. Es posible que las carbonataciones de las valvas fueran coetáneas a la precipitación de calcita y dolomita que fosiliza la biota y por lo tanto, diagenéticas tempra­nas. En las diatomitas marinas, el proceso desencadenante del reemplazo de las valvas fue la formación de capas lenticulares y nódulos opalinos, ya que al disolverse los microfósiles calcáreos que las diatomitas incluían, se liberó CO2 y Ca. Pequeñas variaciones de pH en un entorno alrededor de 9, y la presencia de sulfatos facilitarían el reemplazado durante la diagénesis por enterramiento.

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from −9·02 to −5·83‰ δ13CPDB and −7·10 to 1·22‰ δ18OPDB; for the dolomite, these values vary from −8·93 to −3·96‰ δ13CPDB and −5·53 to 2·4‰ δ18OPDB. Quartz from the cherts has δ18OSMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ18OSMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar., This research was funded by the Spanish Ministry of Economy and Competitiveness, projects CGL2011‐27826‐CO2‐02 and CGL2014‐54818‐P.

Unusual mineralized and silicified carbonate-rich geodes were found hosted in Lower Triassic red mudstones in Central Spain. From their borders to their centres, the geodes display (a) a millimetric carbonate crust, (b) a quartz rim, (c) massive dolomite, (d) gold-bearing iron-rich infills (hematite laths and goethite with up to 7000 ppm of gold) and (e) calcite cements that sometimes seal the central hollow. Textural evidence indicates that the geodes were originally anhydrite, which was subsequently replaced by quartz and dolomite. The resultant porosity from this replacement, or by later dissolution, has been filled by epithermal gold-bearing iron-oxide hydroxides, romanechite and calcite.δ13C values indicate the participation of meteoric waters in an environment which was characterized by both a sub-desert climate and a temperate–tropical climate. Oxygen signatures reflect very variable temperatures for all minerals, with the exception of calcite, which appears to have precipitated at

This paper reports a detailed study of the calcrete and silcrete profiles in the Miocene detrital deposits in the western area of Madrid, at the boundary of two main sedimentary units. The aims of this work were to better understand the pedogenic and diagenetic environments in which these profiles formed and to determine the cause(s) of their enrichment in uranium. Calcrete and silcrete duricrusts are characteristic features of closed continental basins in semiarid climates; this paper discusses the significance of duricrusts as indicators of important change in such basins. The detailed macromorphological, micromorphological, and geochemical study of three duricrust profiles revealed the sequence of pedogenic, vadose, and groundwater processes responsible for their formation. During the first stage of their development, carbonate laminae formed a white ¿grill-like¿ structure within the detrital parent materials. The microstructure and macrostructure of the carbonate, which includes alveolar septal structures and needle-fiber calcite, indicates the important role of roots and their associated microorganisms in calcrete formation. Early silicification occurred in the pedogenic-vadose environment affecting the detrital parent material, roots, and calcretes, forming an early silcrete defined by opaline glaebules and silica rhizoliths. The detailed preservation of the cells in the silicified roots denotes the early replacement of root organic matter. The green or green-yellowish fluorescence of the silicified root structures under short-wavelength UV shows their preferential enrichment in uranium. Calcitization and silicification coexisted in the pedogenic vadose environment, leading to several reversible replacements of calcite and silica. Later, the rise of the water table promoted silicification under phreatic conditions, as indicated by the good preservation of the texture of the detrital host rocks and calcretes. Other silcrete textures, such as ovoidal opaline accumulations, intraclasts produced by autobrecchification, and vadose silica cements, indicate later vadose environments, and consequently variations in the water table. The geochemical features of the calcretes and silcretes (major, minor, and rare earth elements) were inherited from their parent materials. The rare-earth-element patterns of some silcretes show them to have a positive Ce anomaly, suggesting that oxidizing conditions reigned during their formation. The good correlation between silica and uranium suggests that the silica phases acquired uranium through the direct silicification of roots that had fixed uranium from organic matter. This study shows that calcrete-silcrete duricrusts provide detailed information regarding the processes occurring in semiarid continental basins. In the studied basin, roots played a key role in both the development of the duricrust profiles and their enrichment in uranium. These duricrusts provide important information for understanding the overall stratigraphy of the studied basin and its large-scale sequential evolution., This work was funded by Projects CGL2011-27826-CO2-01 and CGL2011-27826-CO2-02 from the Spanish Ministry of Science and Innovation.

7 páginas, 3 figuras, 3 tablas., Green opals have been identified in veins and vugs in hydrothermalized basalts from the area of Taganana (Tenerife). The aim of this paper is to document the petrology and geochemistry of these opals and to describe the formation process from amorphous components. Green opals were studied using optical microscopy, powder X-ray diffraction, electron microprobe, atomic absorption spectroscopy and induced coupled plasma mass spectrometer. Our textural and X-ray powder diffraction analyses indicate that green opals are composed of a major groundmass fraction of crystalline (opal CT and celadonite) and amorphous components (opal A and Fe-(hydro)oxides), which host minor siderite and dolomite crystals. The results indicate green opals were formed during the hydrothermal process from a Fe-rich silica amorphous phase (pseudoglass) which aging and alteration transformed into a groundmass of celadonite and opaline mixture rich in Fe-(hydro)oxides. The opaline–celadonite groundmass, or its amorphous precursor, served as a substrate for the growth of siderite and dolomite crystals., The research was supported by the project PB-98-0668-CO2-01 and the project about the research of terrestrial models for the exploration of Mars of the Centro de Astrobiologia (CSICINTA, Associated to the NASA Astrobiology Institute).

Repetitive sequences of carbonate deposits, occurrence include in the lower part of the Paleogene Carbonate Unit (northeast border of the Madrid Basin), have been studied, defining regressive lacustrine sequences and early diagenetic processes. Binocular microscopic examination, scanning electron microscopic/energy dispersive X-ray observations, and X-ray diffraction analyses joint to isotopic studies (d18O and d13C) have been used to characterise the facies and environments. The sequences consist of a lower uncemented carbonate mud unit, calcitic or dolomitic in composition, and an upper carbonate unit (arenites, bioclastic limestones, and microbial laminated limestones with cherts). Visual features (vertical prismatic structures, fissures, massive nodulization, rhizoliths, brecciation) and microscopic features (micrite micronodules, vug porosity, circumgranular cementation, gypsum lenticular crystals) outline pedogenic processes. These features, found locally in bioclastic and microbial laminated limestones or in dolomite uncemented muds, define, respectively, palustrine limestones or dolocretes. Facies analysis allows us to define several lacustrine sub-environments (basinal, littoral, eulittoral and supralittoral) and characterises different types of shallowing upward lacustrine sequences, either with or without subaerial exposure. The isotopic values of the bioclastic and microbial laminated limestone (from 5.77xto 6.78xfor d13C, and from 5.25xto 5.53xfor d18O) and those of uncemented calcitic muds (from 5.80xto 7.01xfor d13C, and from 4.98xto 5.58xfor d18O) establish that both types of carbonates precipitated in equilibrium with meteoric waters. In the palustrine carbonate deposits, the d13C values suggest a strong organic contribution. The dolomitization that only affected the uncemented carbonate muds is early interpreted because of the structural and compositional characteristics of the dolomite (micro-rhombic dolomicrite, nearly stoichiometric and poorly ordered), and because the calculated average D18O dol–cal for calcitic and dolomitic uncemented muds is about 6x. The d18O isotopic values indicate that the dolomite precipitated from water that was slightly more enriched in heavy isotopes than the calcite, because of an increase in evaporation rates. Nodules and nodular levels of cherts occur in the upper units of littoral and eulittoral sequences, probably as a consequence of the existence of microbial mats that could include the silica source. According to their mineralogy (Opal CT and quartz/moganite) and structures (double nodules, lamination and bioturbation), three types of chert are described (TB, MB and WO). These types define three general stages of silicification during the early diagenesis, from the recently buried to the postcompactation of carbonate deposits. The d18O values of quartz show that the silicification and ageing of opaline phases occurred from meteoric waters, which were lighter than the calcite or dolomite precipitating waters. The cherts included in palustrine limestones show d18O values of quartz that record more evaporated waters than those of the general stages of silicification.

In Upper Jurassic carbonate turbidites of the Betic mountains (southern Spain), chert occurs in three morphologies: bedded chert, nodular chert and mottled chert. The last refers to a weak dispersed and selective silification which gives a speckled appearance to the rock. The three types of chert are formed by replacement of limestones and are associated with different calcareous facies. Turbidite packstones of Saccocoma and peloids, and turbidite lime mudstones of pelagic material contain bedded and nodular cherts. The silicification textures are mainly micro- and cryptocrystalline quartz, with local chalcedonic quartz (both length-fast and length-slow) which is more common in the packstones. Only mottled chert is produced where calcareous breccia beds are silicified. Mottled chert consists of micro- and cryptocrystalline quartz, length-slow chalcedonic quartz and mosaics or individual crystals of euhedral megaquartz. Beds and nodules are the result of early diagenetic silicification, with silica derived from the calcitization and dissolution of radiolarians and, subordinately, sponge spicules, whereas mottled chert is the consequence of later silicification in a probably Mg-rich environment. Early silicification is mainly confined to turbidite beds and only rarely occurs in the interbedded pelagic limestones. Turbidite sedimentation favours silicification because rapid burial of the transported siliceous tests prevents silica from the dissolution of tests passing into overlying sea water. A silica-rich interstitial fluid develops in the turbidite layer and this migrates to more permeable zones giving rise to bedded and nodular chert.

The radiolarite sequence of the middle Subbetic (Betic cordillera, southern Spain) is composed of three main lithologies: radiolarite, siliceous mudstone and marl, and pelagic limestone with radio larians. Virtually all transitional lithologies among the three listed exist. Clay minerals, calcite, and hematite make up the radiolarite impurities. Smectite, illite, and locally kaolinite are the clay minerals present, smectite always being most abundant. No radiolarite bed with more than 85% silica has been found; the total SiO2 content ranges from 61 to 85%. Frequently the compact appearance of the radiolarite results from a high carbonate content. The ratios Si/Si + Al + Fe + Ca, Si/Si + Al + Fe, and Al/Al + Fe + Mn are calculated and used to compare the beds of couplets in rhythmic sequences and to obtain the relative distance of sections from their terrigenous source. These three chemical indices do not give consistent results. Fe enrichment of radiolarite relative to siliceous mudstone is probably related to the low mean sedimentation rate of these sequences from the Subbetic (3.5 mm/1,000 y). Pelagic settling in a basin with irregular bottom topography and with areas topographically protected from sediment input is proposed for deposition of these deposits. Productivity cycles and terrigenous dilution gave rise locally to rhythmically bedded sequences, usually composed of radiolarite mudstone alternations. Locally, contour and distal dilute turbidity currents reworked and deposited the sediment, and gave rise to thin sequences of layered sedimentary rocks and to laminated beds. Deposition above a relatively shallow CCD is deduced, and a water depth shallower than previously thought is suggested for these deposits, which are considered as the deepest water deposits of the Betic External Zones.

15 páginas, 1 figura, 3 láminas., [ES] El análisis sedimentológico y petrológico del conjunto de los sedimentos calcáreos y las rocas silíceas continentales del Mioceno medio, al sur de Villaluenga, da nuevas perspectivas a la interpretación y génesis de estas rocas. Las principales facies calcáreas encontradas han sido: 1) micritas complejas con laminación difusa (¿criptoalgar ?), pseudomorfos de cristales lenticulares de yesos e indicios de posibles diatomeas; 2) biomicritas con alta proporción de charáceas, moluscos y ostrácodos que se disponen con estructura laminada por acumulación de los componentes esqueléticos en niveles; 3) biomicritas con los mismos componentes anteriores, pero desorganizados, existiendo además en algún caso diatomeas; 4) pseudoesparitas y microesparitas con pseudomorfos calcáreos de cristales lenticulares de yeso; 5) margas sepiolíticas, El ambiente de sedimentación es, en general, muy superficial, de baja salinidad, calcáreo, altamente productivo, con abundante vegetación (a veces diatomeas) y ocasionalmente llegan a existir períodos de exposición subaérea. Todos los tipos de facies, desde las lacustres; poco profundas a las que manifiestan subaerismo, presentan fenómenos de silicificación, aunque éstos pueden ser diferentes. Se determina que hay una silicificación penecontemporánea, discontinua que origina sólo minerales de la sílice y que puede estar relacionada con la disolución de las frústulas de diatomeas incluidas en la caliza. Muy tempranamente en la diagénesis, pero posterior a la anterior, tiene lugar una nuevas silicificación más compleja que ha originado los niveles continuos ópalo-arcillosos, homogéneos o con estructuras Liesegang, y en los que, además de los minerales exclusivamente silíceos, se ha producido Sepiolita. Se piensa que esta segunda silicificación se origina en la interfase agua-sedimento, cuando en las pequeñas depresiones, en las que se origina la sedimentación lacustre-palustre, el espesor de la lámina de agua es muy pequeña, llegando, a veces , a la desecación. Las cementaciones silíceas sobre diferentes porosidades de la roca (fenestral, pequeños huecos kársticos, etc.) indican que aunque las dos silicificaciones son muy tempranas, posteriormente hay removilizaciones que originan cementaciones y posiblemente silicificaciones tardías de cuarzo que hacen muy compleja la historia diagenética de la roca calco-silícea., [EN] The petrological and sedimentological analysis Middle Miocene carbonate sediments and siliceous rocks, outcropping North Toledo, provides new ideas on the interpretation of these lacustrine and paludine sedimentation. The main lithofacies found are: 1) micrite with crytalgal (?) laminite, calcite gypsum pseudomorphs, and trace of diatoms; 2) biomicrite with varying amount of lacustrine mollusks, ostracodes and charophytes, which form laminar structure; 3) biomicrite with the same skeletal components (charopytes, ostracodes, etc.) and sometimes diatoms but disorganized, 4) pseudospar and microspar calcite with lenticular gypsum pseudomorphs; 5) sepiolitic marls.