Direct Observations of Ordered Nanoporosity in Deprotonated 2-(Acetoacetoxy)ethyl Methacrylate (AAEMA-) Polymer: Preliminary Results.

Polymers based on 2-(acetoacetoxy)ethyl methacrylate, charged with iron or sodium, were thermally heated at 150 °C. Both polymers were studied and characterized by SEM, TEM, STEM microscopy and SAEDF techniques. The morphological investigation revealed that, upon heating, both polymers were endowed with microholes, sometimes perfectly ordered, whose dimensions varied from 4-5 nm to approximately 500 nm. In the case of an Fe-containing copolymer, unexpectedly, iron did not fill in the cavities, thus implying that it was "dispersed" in the polymeric matrix. Electronic microdiffraction documented that both polymers exhibited a proto-crystallinity, likely induced by thermal heating.

Shifts in bentonite bacterial community and mineralogy in response to uranium and glycerol-2-phosphate exposure.

The multi-barrier deep geological repository system is currently considered as one of the safest option for the disposal of high-level radioactive wastes. Indigenous microorganisms of bentonites may affect the structure and stability of these clays through Fe-containing minerals biotransformation and radionuclides mobilization. The present work aimed to investigate the behavior of bentonite and its bacterial community in the case of a uranium leakage from the waste containers. Hence, bentonite microcosms were amended with uranyl nitrate (U) and glycerol-2-phosphate (G2P) and incubated aerobically for 6 months. Next generation 16S rRNA gene sequencing revealed that the bacterial populations of all treated microcosms were dominated by Actinobacteria and Proteobacteria, accounting for >50% of the community. Additionally, G2P and nitrate had a remarkable effect on the bacterial diversity of bentonites by the enrichment of bacteria involved in the nitrogen and carbon biogeochemical cycles (e.g. Azotobacter). A significant presence of sulfate-reducing bacteria such as Desulfonauticus and Desulfomicrobium were detected in the U-treated microcosms. The actinobacteria Amycolatopsis was enriched in G2P­uranium amended bentonites. High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy analyses showed the capacity of Amycolatopsis and a bentonite consortium formed by Bradyrhizobium-Rhizobium and Pseudomonas to precipitate U as U phosphate mineral phases, probably due to the phosphatase activity. The different amendments did not affect the mineralogy of the bentonite pointing to a high structural stability. These results would help to predict the impact of microbial processes on the biogeochemical cycles of elements (N and U) within the bentonite barrier under repository relevant conditions and to determine the changes in the microbial community induced by a uranium release.

A DFT study of the adsorption of glycine in the interlayer space of montmorillonite.

The adsorption properties of clay minerals have been widely studied in several technological areas, due to their versatility, absorption capacity and catalytic properties. The interaction of amino acids with clay surfaces can be interesting due to their role in prebiotic scenarios. Different degrees of hydration and the adsorption of the glycine molecule and glycinium cation in the interlayer space of montmorillonite were investigated by means of calculations based on density functional theory (DFT). Our calculations show that the cation exchange of K+ by glycinium in the interlayer of hydrated K-montmorillonite is highly possible and exothermic. This supports previous experimental results by explaining the possible adsorption of glycine as a molecule and cation. Glycine is adsorbed in a zwitterionic form in the interlayer without being solvated with water. Besides, glycine and glycinium are highly exothermically adsorbed in the interlayer. The interlayer spacings under different conditions were in agreement with the experimental values. Hydrogen bonds and electrostatic interactions between molecules and surface atoms are responsible for this exothermicity. The IR spectra were calculated and compared with the experimental results showing interesting frequency shifts depending on the intermolecular interactions in the interlayer space of montmorillonite.

Modeling the Adsorption of Oxalate onto Montmorillonite.

In this work, a multiscale modeling of the interaction of oxalate with clay mineral surfaces from macroscale thermodynamic equilibria simulations to atomistic calculations is presented. Previous results from macroscopic adsorption data of oxalate on montmorillonite in 0.01 M KNO3 media at 25 °C within the pH range from 2.5 to 9 have been used to develop a surface complexation model. The experimental adsorption edge data were fitted using the triple-layer model (TLM) with the aid of the FITEQL 4.0 computer program. Surface complexation of oxalate is described by two reactions: >AlOH + Ox(2-) + 2H(+) = >AlOxH + H2O (log K = 14.39) and >AlOH + Ox(2-) + H(+) = >AlOx(-) + H2O (log K = 10.39). The monodentate complex >AlOxH dominated adsorption below pH 4, and the bidentate complex >AlOx(-) was predominant at higher pH values. Both of the proposed inner-sphere oxalate species are qualitatively consistent with previously published diffuse reflectance FTIR spectroscopic results for oxalate on montmorillonite edge surface (Chem. Geol. 2014, 363, 283-292). Atomistic computational studies have been performed to understand the interactions at the molecular level between adsorbates and mineral surface, showing the atomic structures and IR frequency shifts of the adsorption complexes of oxalate with the edge surface of a periodic montmorillonite model.

In situ observation of biotite (001) surface dissolution at pH 1 and 9.5 by advanced optical microscopy.

Laser confocal differential interference contrast microscopy (LCM-DIM) allows for the study of the reactivity of surface minerals with slow dissolution rates (e.g., phyllosilicates). With this technique, it is possible to carry out in situ inspection of the reacting surface in a broad range of pH, ionic strength and temperature providing useful information to help unravel the dissolution mechanisms of phyllosilicates. In this work, LCM-DIM was used to study the mechanisms controlling the biotite (001) surface dissolution at pH 1 (11 and 25 °C) and pH 9.5 (50 °C). Step edges are the preferential sites of dissolution and lead to step retreat, regardless of the solution pH. At pH 1, layer swelling and peeling takes place, whereas at pH 9.5 fibrous structures (streaks) form at the step edges. Confocal Raman spectroscopy characterization of the reacted surface could not confirm if the formation of a secondary phase was responsible for the presence of these structures.

Surface chemistry of K-montmorillonite: ionic strength, temperature dependence and dissolution kinetics.

The surface chemistry of K-montmorillonite was investigated by potentiometric titrations conducted at 25, 50 and 70 degrees C and at ionic strengths of 0.001, 0.01 and 0.1 M KNO(3). Proton adsorption decreases with electrolyte concentration at all pHs. The pH of zero net proton charge (PZNPC) decreases from 8.1 to 7.6 when the ionic strength increases from 0.001 to 0.1 M. Temperature has a very small effect on surface charge. A constant capacitance model that accounts for protonation/deprotonation of aluminol and silanol edge sites and basal plane H(+)/K(+) exchange is used to fit the experimental data. H(+) and OH(-) adsorption to specific surface sites appear to account for the pH-dependence of the K-montmorillonite dissolution.

Halobacillus alkaliphilus sp. nov., a halophilic bacterium isolated from a salt lake in Fuente de Piedra, southern Spain.

A Gram-positive, spore-forming, halophilic bacterial strain, FP5T, was isolated from a salt lake in southern Spain and subjected to a polyphasic taxonomic study. Strain FP5T was strictly aerobic. Cells were coccoidal, occurring singly or in clusters. The cell-wall peptidoglycan type of strain FP5T was A4 beta based on l-Orn-d-Asp. Strain FP5T was characterized chemotaxonomically by having MK-7 as the major menaquinone and anteiso-C15 : 0, anteiso-C17 : 0, iso-C15 : 0 and iso-C16 : 0 as the main fatty acids. The isolate grew optimally at 37 degrees C and in presence of 10 % NaCl; no growth was observed in the absence of NaCl. The DNA G+C content was 43.5 mol%. Phylogenetic analyses based on 16S rRNA gene sequences showed that strain FP5T falls within the evolutionary radiation of species of the genus Halobacillus. Levels of 16S rRNA gene sequence similarity between strain FP5T and the type strains of nine recognized Halobacillus species were in the range 97.0-99.0 %. Levels of DNA-DNA relatedness indicated that strain FP5T represents a genomic species that is distinct from recognized Halobacillus species. Strain FP5T could be differentiated from recognized Halobacillus species based on several phenotypic characteristics. On the basis of phenotypic, phylogenetic and genomic data, strain FP5T is considered to represent a novel species of the genus Halobacillus, for which the name Halobacillus alkaliphilus sp. nov. is proposed. The type strain is FP5T (=DSM 18525T =ATCC BAA-1361T).

Haloterrigena hispanica sp. nov., an extremely halophilic archaeon from Fuente de Piedra, southern Spain.

An extremely halophilic archaeon belonging to the order Halobacteriales was isolated from Fuente de Piedra salt lake, Spain. This strain, designated FP1(T), was a pleomorphic coccoid, neutrophilic and required at least 15 % (w/v) NaCl for growth. Strain FP1(T) grew at 37-60 degrees C, with optimal growth at 50 degrees C. Mg(2+) was not required, but growth was observed with up to 10 % (w/v) MgSO(4). Polar lipid analysis revealed the presence of mannose-6-sulfate(1-2)-glucose glycerol diether as a major glycolipid. Both C(20)C(20) and C(20)C(25) core lipids were present. The genomic DNA G+C content was 62.0 mol%. Phylogenetic analysis based on comparison of 16S rRNA gene sequences demonstrated that the isolate was most closely related to species of the genus Haloterrigena. DNA-DNA reassociation values between strain FP1(T) and the most closely related species of the genus Haloterrigena (Haloterrigena thermotolerans, Haloterrigena saccharevitans and Haloterrigena limicola) were lower than 29 %. It is therefore considered that strain FP1(T) represents a novel species of the genus Haloterrigena, for which the name Haloterrigena hispanica sp. nov. is proposed. The type strain is FP1(T) (=DSM 18328(T)=ATCC BAA-1310(T)).

An Experimental Study on the Ion-Exchange Behavior of the Smectite of Cabo de Gata (Almería, Spain): FEBEX Bentonite.

Binary cation-exchange processes (Na-K, Na-Mg, and Na-Ca) have been investigated at 25 degrees C in samples of bentonite from Cabo de Gata (Almería, SE Spain). Exchange isotherms and Vanselow selectivity coefficients indicate that the preference of this bentonite for K(+), Ca(2+), and Mg(2+) ions is greater than that for the Na(+) ion. The change in (i)(j)K(V) as a function of the equivalent fraction of cation M, E(M), is interpreted on the basis of the presence of different types of adsorption/exchange sites (tetrahedral, octahedral, and edge sites). For the Na/K exchange, (K)(Na)K(V) exhibits a steep decrease for E(K)<0.25-0.3. This is interpreted as due to preferential exchange at the tetrahedral sites. However, the opposite behavior is observed in the case of Ca and Mg, with a noticeable increase of (i)(Na)K(V) for E(Ca)(E(M(g)))>0.6-0.8. The compared selectivities of Ca and Mg for this smectite are nearly equal. As far as the exchanger is concerned, the Na-Ca and Na-Mg exchange is nearly ideal, in the raoultian sense. Thermodynamic exchange constants and the corresponding Gibbs free energies of reaction have been computed from (i)(j)K(V) coefficients. This allow us to quantify the exchanger's affinity sequence, which appears to be Na(+)