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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.

The Miocene distal alluvial fan and palustrine deposits of the Madrid Basin (Paracuellos de Jarama area) were examined to establish the sequence of its pedogenic–diagenetic processes and the main factors controlling them. In this area the diagenetic processes operated not only on carbonates, as commonly studied, but also in high magnesium clays and opaline cherts. This paper provides a dynamic model for saline–alkaline lake margins that complements the existing freshwater palustrine model. Three sections (BER, PEL and UPC) containing limestones, sepiolite, dolostones and opaline cherts were examined; these represent the entire transition from alluvial fan deposit to lake environment. The alluvial fan deposits (PEL section) show the most complex sequence of processes. After a weak edaphic imprint, the primary mudstone and siltstones are affected by silicification (opaline levels formed mainly by selective replacement of sepiolites) and later dolomitization. Several types of dolomite are present, rounded crystals, spherules and globular bodies being the most characteristic. In the ponds situated at the foot of the alluvial fans or in interfan areas, sepiolite precipitated within free water bodies (BER section) and an intense pedogenesis led to the formation of palustrine sepiolite deposits. Later, the intense silicification of the sepiolite produced lenticular opaline levels that were locally transformed to quartz by aging. In the shallow lakes (UPC section), palustrine limestones and sepiolite were deposited. The carbonates are partially affected by silicification, the sepiolite becoming completely silicified. The opaline levels clearly preserve the structure of the limestones and sepiolite host rocks. All the opaline levels show local aging processes. The silicification processes were different in the three settings due to the interplay of groundwater with sedimentary environments and facies. In the distal alluvial fan sediments of the PEL section, the initial host rock affected by silicification is not preserved due to the later dolomitization that erased both it and its textures. The silicification environment was therefore not easy to determine. In the BER and UPC section, the main silicification took place in groundwater-influenced environments but evidence was seen of cements and silicifications in vadose environments. In all study settings, the overlapping of pedogenic, vadose and groundwater processes was controlled by changes in the position of the water table. Four stages were concluded to explain the transformation from the primary deposits to the later dolomitization process and the formation of vadose cements. The majority of the silicifications seen occurred as responses to changes in the water table position linked to the aggradation of this closed basin. In all the studied environments, the sepiolite deposits were preferentially silicified; their fibrous structure and high absorption capacity helping to retain interstitial fluids. Moreover sepiolite and opal are stable under relatively similar geochemical conditions in arid environments. The dissolution of the sepiolite caused an increase in silica in the interstitial fluids, favouring silicification and ruling out the need of a biogenic source. The replacement of limestones by silica is usually driven by variations in pH and salinity, which are very common in surface environments such as shallow lakes and soils.

El presente trabajo estudia los diferentes tipos de sílex que aparecen en la Formación Calizas de Oriñón (Aptiense superior-Albiense inferior), en un zona concreta de la costa oriental de Cantabria (Liendo-Castro Urdiales), debido a su gran abundancia y espectacularidad. Las rocas que los incluyen son principalmente biocalcarenitas (wackestones/packstones de pellets, fragmentos de equinodermos, ostreidos, foraminíferos y espículas calcáreas o silíceas calcificadas), siendo el ambiente de depósito marino de plataforma abierta, y existiendo un hardground regional, donde las silicificaciones son diferentes. La fuente de la sílice proviene de la calcitización o disolución de las espículas de esponjas silíceas. Se determina que la gran mayoría de sílex (mosaicos de cuarzo micro-microcriptalino y calcedonita principalmente), se forman por la silicificación selectiva de estructuras biogénicas, siendo las galerías de Thalassinoidespreferentemente silicificadas, debido a que en su relleno existe mayor proporción de materia orgánica y mayor porosidad y permeabilidad. En las calizas que soportan el hardground además de las silicificaciones selectivas sobre fósiles (rostros de belemnites, ostreidos y equínidos), la sílice se acumula de forma importante en huellas de alimentación y rellenos de perforaciones, dando lugar a su vez a costras sobre bioturbaciones y perforaciones que a pesar de su importancia no han podido ser clasificadas. La silicificación de todas las estructuras biogénicas, originó inicialmente fases opalinas y tuvo lugar durante la diagénesis temprana cuando la oxidación de la materia orgánica estaba todavía activa, conservándose en los Thalassinoides silicificados formas (filamentos y cocoides) que podrían ser consideradas microbianas. La transformación ópalo-cuarzo fue temprana, preservándose dichas formas. En las galerías silicificadas de Thalassinoides los procesos diagenéticos son diferentes a los de los sedimentos carbonáticos marinos que las incluyen, y al resto de estructuras biogénicas silicificadas, existiendo en estas galerías neoformación de dolomita y calcita, en un microambiente cerrado donde las condiciones cambian de oxidantes a reductoras.

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

In the eastern sector of the Betic Cordillera outcrops of the Internal Subbetic display chert lenses in the upper parts of oolitic limestones (Camarena Formation, Mid-Jurassic). The stratigraphy indicates a sedimentary record related to synsedimentary tectonics (tilting). The sediments were deposited in different tectonic blocks, at varying depths. The Camarena Formation is mainly made up of shallow platform oolitic limestones and was deposited on a `pelagic' swell, a shallow isolated platform that developed far from continental areas. The chert lenses appear in those stratigraphic units deposited in the lowermost sunken fault blocks which display biosiliceous facies overlying the Camarena Formation. The chert mainly consists of megaquartz, formed by replacement of the oolitic host rocks without an opaline precursor. The part of the host that has been most affected by the silicification is the carbonate cement. The petrological features indicate a slow replacement from solutions which were poor in silica and cations. Comparing the textures and fabric of the cherts and their host rocks, it is deduced that the silicification took place after compaction, cementation, fracturing and local dissolution of the oolitic limestones. The stable isotopic data (δ18O, δ13C) obtained from the chert, oolitic host rock and overlain biosiliceous rocks display significant differences. The host rocks (Camarena Formation) and overlying biosiliceous rocks have isotopic signatures that are typical of marine environments or shallow-marine diagenesis. However, the chert isotopic values are interpreted to suggest meteoric water participation in the silicification process. The timing of the chertification is suggested to have been between the Bathonian (beginning of the deposition of the biosiliceous source facies) and the Aptian (first appearance of this chert as clasts in breccia beds). In palaeogeographic terms the optimum timing would have been during emergence (i.e. between the Bathonian and Tithonian). The exposed areas could have acted as recharge areas of meteoric water into the regional aquifer system. The involvement of meteoric water in the silicification processes gives new support to the hypothesis that pelagic swells were subjected to episodic exposure.

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.

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.

The volcanic caves of Algar do Carvão (a pit with a complex genesis) and of Branca Opala (a lava-tube cave), differ from other caves on the island of Terceira by having speleothems composed only by opal. This kind of speleothems, in volcanic caves, suggests that the silica origin can be related to hydrothermal activity. The objective of this study is to determine the speleothem isotopic composition in δ¹⁸OSMOW and δDSMOW to determine their geochemical signature and conditions of formation. The studied samples from Algar do Carvão pit are stalactites and flowstones/gours that have been formed in subaerial conditions, while those from the Branca Opala lava tube have been defined as underwater silica stromatolites. dD data of speleothems from both caves are relatively similar (−102.0 ± 10.5‰ in Branca Opala and −103.7 ± 11.1‰ in Algar do Carvão) and it can be assumed that the fluids involved in the silica deposition may be similar. Moreover the δ¹⁸OSMOW data show that the Algar do Carvão speleothems have higher values (δ¹⁸OSMOW 39,4 ± 0,3‰), relatively to the Branca Opala stromatolites (δ¹⁸OSMOW 35,2 ± 0,8‰). The diagenesis that affected the opal A may explain, in part, the observed differences. However, other genetic factors are also influencing such as the fact that Algar do Carvão stalactites are formed in sub aerial conditions, under the influence of evaporation processes, while Branca Opala speleothems were formed in underwater conditions. However, it is also possible, that the water that originated the Branca Opala speleothems was 10,7 °C warmer than the water that formed the Algar do Carvão stalactites.Las cuevas de Algar do Carvão (una sima volcánica de génesis compleja) y Branca Opala (un tubo volcánico) se diferencian de otras cuevas de la isla de Terceira por tener espeleotemas formados sólo por ópalo. Esta composición, y el hecho de ser cuevas volcánicas, hacen pensar que el origen de la sílice pueda estar ligado a la actividad hidrotermal. El objetivo de este estudio es determinar la composición isotópica en δ¹⁸OSMOW, y en δDSMOW de los espeleotemas de sílice, para determinar su impronta geoquímica y las condiciones de formación. Las muestras estudiadas de la sima de Algar do Carvão son estalactitas y revestimientos de paredes, que se han formado en ambiente subaéreo, mientras que, las estudiadas en el tubo volcánico de Branca Opala, han sido definidas como estromatolitos silíceos subacuáticos. Los datos de δD de los espeleotemas de ambas cuevas son relativamente parecidos (−102,0 ± 10,5‰ en Branca Opala y −103,7 ± 11,1‰ en Algar do Carvão) y se puede asumir que los fluidos involucrados en su formación puedan ser similares. Por otra parte, los datos del δ¹⁸OSMOW revelan que los espeleotemas de Algar do Carvão presentan valores relativamente más altos (δ¹⁸OSMOW 39,4 ± 0,3‰) que los estromatolitos opalinos de Branca Opala (δ¹⁸OSMOW 35,2 ± 0,8‰). La diagénesis que sufre el ópalo A puede explicar, en parte, las diferencias observadas, pero, otros factores genéticos también están influyendo, como pueda ser el hecho de que las estalactitas de Algar do Carvão se formaran en condiciones subaéreas, con la influencia de la evaporación, mientras que los espeleotemas de Branca Opala fueran subacuáticos, o bien, que las aguas de precipitación de los espeleotemas de Branca Opala fueran hasta 10,7 °C más calientes que las de Algar do Carvão.

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.

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.