Effect of acid treatment on the structure of sepiolite.

An ab initio determination of the structure of sepiolite after acid treatment (HCl 0.5 N for 24 h) was carried out using X-ray powder diffraction data. After acid treatment, the sections normal to the a and c axes presented discontinuities, ~2.25 Å wide, parallel to the (010) plane, with no electronic density maxima, thus suggesting that adjacent planes are joined by van der Waals-like residual links. Partial dissolution was detected on both octahedral and tetrahedral sheets, beginning by breaking the ribbons not along the edges, but in the centre, thus creating a 5.20x6.79 Å tunnel along the a axis. By interrupting the tetrahedral sheet, this mechanism changes the phyllosilicate-like nature of the sepiolite to an inosilicate-like structure.Peer reviewe

Sharp-based, mixed carbonate–siliciclastic shallow-marine deposits (upper Miocene, Betic Cordillera, Spain): The record of ancient transgressive shelf ridges?

Isolated sharp-based sedimentary bodies in shelf settings can develop via the reworking of regressive deposits during transgressions. An example of these are shelf ridges, formed under a wide range of processes, and widely studied due to their high reservoir potential. However, there is still a lack of examples in mixed (carbonate–siliciclastic) successions. This study presents an outcrop example from the Upper Miocene of the Betic Cordillera (Spain), with the aim to propose a model for the development of transgressive sharp-based mixed carbonate–siliciclastic deposits, and to provide criteria to differentiate these from their regressive counterparts. The studied succession is ca. 300 m-thick, and shows a cyclic alternation of coarse and fine-grained mixed deposits. Depositional cycles start with siliciclastic-dominated offshore to offshore transition deposits, progressively replaced by lower shoreface deposits. These are abruptly truncated by sharp erosive contacts bioturbated by passively-infilled large burrows; their ichnological features allow assignation to the Glossifungites ichnofacies. These contacts are interpreted as ravinement surfaces. They are overlain by mixed carbonate–siliciclastic barforms, rich in skeletal fragments and extraclasts, and displaying large-scale cross bedding. These form several m-thick and hundreds of m-long depositional elements interpreted as mixed shelf ridges. These ridges formed in a fine-grained, shallow-water shelf, which occasionally received coarse siliciclastic sediment supply via gravity flows, but had a coeval offshore carbonate factory, which provided the skeletal fragments. The sharp-based, coarser-grained nature and lithological break at the base of these mixed carbonate–clastic deposits could lead to their misinterpretation as forced-regressive wedges. However, the nature of their lower contact, combined with the reworked offshore skeletal fragments, and their stacking pattern are consistent with these mixed units forming during transgression. Other studies in relatively time-equivalent deposits have demonstrated the existence of coeval regressive, coarser siliciclastic-dominated shoreline systems in relatively close localities. These evidence a complex basin configuration in the area during the upper Miocene, with the development of local depocentres and relatively narrow corridors or seaways in the Mediterranean–Atlantic connection, which could have favoured shelf reworking processes, but also promoted the development of diverse stacking patterns, reflecting the differential interaction between active tectonics and sedimentation across the region.FEDER AndalucíaSecretaría de Estado de I+D+IAker BPUniversitetet i OsloUniversidad de Granada PID2019-104625RB-100, PID2020-114381GB-100European Regional Development Fund CGL2017-89618-RJunta de Andalucía B-RNM-072-UGR18, P18-RT-4074Agencia Estatal de Investigació

Spatial distribution of prokaryotic communities in hypersaline soils

Increasing salinization in wetland systems is a major threat to ecosystem services carried out by microbial communities. Thus, it is paramount to understand how salinity drives both microbial community structures and their diversity. Here we evaluated the structure and diversity of the prokaryotic communities from a range of highly saline soils (EC1:5 from 5.96 to 61.02 dS/m) from the Odiel Saltmarshes and determined their association with salinity and other soil physicochemical features by analyzing 16S rRNA gene amplicon data through minimum entropy decomposition (MED). We found that these soils harbored unique communities mainly composed of halophilic and halotolerant taxa from the phyla Euryarchaeota, Proteobacteria, Balneolaeota, Bacteroidetes and Rhodothermaeota. In the studied soils, several site-specific properties were correlated with community structure and individual abundances of particular sequence variants. Salinity had a secondary role in shaping prokaryotic communities in these highly saline samples since the dominant organisms residing in them were already well-adapted to a wide range of salinities. We also compared ESV-based results with OTU-clustering derived ones, showing that, in this dataset, no major differences in ecological outcomes were obtained by the employment of one or the other method.España, Ministerio de Economía, Industria y Competitividad CGL2013-46941-P and CGL2017-83385-PJunta de Andalucía BIO-21

Nanocomposite gels of poloxamine and Laponite for β-Lapachone release in anticancer therapy

Nano-hybrid systems have been shown to be an attractive platform for drug delivery. Laponite® RD (LAP), a biocompatible synthetic clay, has been exploited for its ability to establish of strong secondary interactions with guest compounds and hybridization with polymers or small molecules that improves, for instance, cell adhesion, proliferation, and differentiation or facilitates drug attachment to their surfaces through charge interaction. In this work, LAP was combined with Tetronics, X-shaped amphiphilic PPO-PEO (poly (propylene oxide)–poly (ethylene oxide) block copolymers. β-Lapachone (BLPC) was selected for its anticancer activity and its limited bioavailability due to very low aqueous solubility, with the aim to improve this by using LAP/Tetronic nano-hybrid systems. The nanocarriers were prepared over a range of Tetronic 1304 concentrations (1 to 20% w/w) and LAP (0 to 3% w/w). A combination of physicochemical methods was employed to characterize the hybrid systems, including rheology, particle size and shape (DLS, TEM), thermal analysis (TG and DSC), FTIR, solubility studies and drug release experiments. In vitro cytotoxicity assays were performed with BALB/3T3 and MCF-7 cell lines. In hybrid systems, a sol-gel transition can occur below physiological temperature. BLPC exhibits the most significant increase in solubility in formulations with a high concentration of T1304 (over 10% w/w) and 1.5% w/w LAP, or systems with only LAP (1.5%), with a 50 and 100-fold increase in solubilisation, respectively. TEM images showed spherical micelles of T1304, which elongated into wormlike micelles with concentration (20%) and in the presence of LAP, a finding that has not been reported before. A sustained release of BLPC over 140 hours was achieved in one of the formulations (10% T1304 with 1.5% laponite), which also showed the best selectivity index towards cancer cells (MCF-7) over BALB/3T3 cell lines. In conclusion, BLPC-loaded T1304/LAP nano-hybrid systems proved safe and highly effective and are thus a promising formulation for anticancer therapy.Financial support for this research was provided by the Coordination of Improvement of Higher-Level Personnel - Brazil (CAPES) - 1575/2015. We also acknowledge the collaboration of Prof. Dr. Daniele Ribeiro de Araujo from Federal University of ABC for the rheological experiments. Dr. Raquel de Melo Barbosa acknowledges the grant for mobility to Brazilian professors from Fundación Carolina (Spain), the Spanish research group CTS-946, to the Centre for Scientific Instrumentation (Centro de Instrumentación Científica or CIC) for transmission microscopy analysis and the Andalusian Earth Sciences Institute (IACT) for support during her mobility period in Spain

Does Sedimentology have a role in the energy transition? A proposal

El proyecto SOSGAS tiene por objeto calibrar el impacto de la heterogeneidad sedimentaria inherente a formaciones fluviales y deltaicas en el geo-almacenamiento sostenible de CO2 y H2 verde. Se han seleccionado 6 ejemplos mesozoicos y cenozoicos en la Meseta Ibérica, la Cuenca del Ebro y la Cuenca de Graus-Tremp a los que se aplica el flujo de trabajo OBO. Con esta base de datos de afloramiento y subsuelo se construyen modelos estáticos 3D de distribución de facies reservorio y sello y de propiedades petrofísicas, y finalmente se simula la inyección de los fluidos. Diferentes hipótesis de conectividad entre litofacies porosas y de distribución de los sellos conducen a diferentes escenarios de dinámica de fluidos y de entrampamiento. Con este proyecto iniciamos una línea de investigación que permitirá evaluar la validez de la sedimentología para contribuir al reto social de la transición energética.The SOSGAS project aims to gauge the impact of sedimentary heterogeneity inherent to fluvial and deltaic formations on the sustainability of a possible geo-storage of CO2 and green H2. 6 Mesozoic and Cenozoic examples have been selected in the Iberian Meseta, the Ebro Basin and the Graus-Tremp Basin to which the OBO workflow is applied. Using this outcrop and subsurface database, 3D static models are constructed to reproduce the distribution of reservoir and seal facies and petrophysical properties, and finally fluid injection is simulated. Different hypotheses of connectivity of porous lithofacies and seal distribution lead to different scenarios of fluid flow dynamics and trapping. With this project, we are initiating a line of research that will make it possible to assess the validity of sedimentology in contributing to the social challenge of the energy transition.Grants PID2022-140850OB-C21 and PID2022-140850OB-C22 funded by MCIN/AEI/10.13039/501100011033/ and by “ERDF A way of making Europe”. REPSOL EP, CEPSA EP, ENAGAS, SLB, AGGEP, the MS2022-17 contract -NextGenerationEU- and the groups RNM369 (PAI) and 2021SGR00076 (GC) are also grateful

How phyllosilicate mineral structure affects fault strength in Mg-rich fault systems

The clay mineralogy of fault gouges has important implications for the frictional properties of faults, often identified as a major factor contributing to profound fault weakness. This work compares the frictional strength of a group of Mg‐rich minerals common in the Mg‐Al‐Si‐O compositional space (talc, saponite, sepiolite, and palygorskite) by conducting triaxial frictional tests with water or argon as pore fluid. The studied minerals are chemically similar but differ in their crystallographic structure. Results show that fibrous Mg‐rich phyllosilicates are stronger than their planar equivalents. Frictional strength in this group of minerals is highly influenced by strength of the atomic bonds, continuity of water layers within the crystals, and interactions of mineral surfaces with water molecules, all of which are dictated by crystal structure. The formation and stability of the minerals studied are mainly controlled by small changes in pore fluid chemistry, which can lead to significant differences in fault strength

Drilling Predation on Serpulid Polychaetes (Ditrupa arietina) from the Pliocene of the Cope Basin, Murcia Region, Southeastern Spain

We report quantitative analyses of drilling predation on the free-living, tube-dwelling serpulid polychaete Ditrupa arietina from the Cope Cabo marine succession (Pliocene, Spain). Tubes of D. arietina are abundant in the sampled units: 9 bulk samples from 5 horizons yielded ∼5925 specimens of D. arietina. Except for fragmentation, tubes were well preserved. Complete specimens ranged from 3.1 to 13.4 mm in length and displayed allometric growth patterns, with larger specimens being relatively slimmer. Drilled Ditrupa tubes were observed in all samples. Drillholes, identified as Oichnus paraboloides, were characterized by circular to elliptical outline (drillhole eccentricity increased with its diameter), parabolic vertical profile, outer diameter larger than inner diameter, penetration of one tube wall only, narrow range of drill-hole sizes, and non-random (anterior) distribution of drillholes. A total of 233 drilled specimens were identified, with drilling frequencies varying across horizons from 2.7% to 21% (3.9% for pooled data). Many tube fragments were broken across a drillhole suggesting that the reported frequencies are conservative and that biologically-facilitated (drill-hole induced) fragmentation hampers fossil preservation of complete serpulid tubes. No failed or repaired holes were observed. Multiple complete drillholes were present (3.9%). Drilled specimens were significantly smaller than undrilled specimens and tube length and drill-hole diameter were weakly correlated. The results suggest that drillholes were produced by a size-selective, site-stereotypic predatory organism of unknown affinity. The qualitative and quantitative patterns reported here are mostly consistent with previous reports on recent and fossil Ditrupa and reveal parallels with drilling patterns documented for scaphopod mollusks, a group that is ecologically and morphologically similar to Ditrupa. Consistent with previous studies, the results suggest that free-dwelling serpulid polychaetes are preyed upon by drilling predators and may provide a viable source of data on biotic interactions in the fossil record