Enhancing Arsenic Solidification/Stabilisation Efficiency of Metallurgical Slag-Based Green Mining Fill and Its Structure Analysis

To dispose of arsenic-containing tailings with low carbon and high efficiency, sodium sulphate (Na2SO4), sodium hydroxide (NaOH), calcium nitrate Ca(NO3)2 and calcium hydroxide Ca(OH)2 were independently added to metallurgical slag-based binder (MSB) solidification/stabilisation (S/S)-treated tailings (MSTs) to enhance the MST arsenic S/S performance. Results showed that only Ca(OH)2 could increase the unconfined compressive strength of MST from 16.3 to 20.49 MPa and decrease the leachate As concentration from 31 μg/L to below 10 μg/L. Na3AsO4·12H2O and NaAsO2 were used to prepare pure MSB paste for mechanism analysis. The results of microstructure analyses showed the high specific surface area and amorphous properties of calcium–sodium aluminosilicate hydrate facilitated the adsorption or solid-solution formation of As(V) and As(III). As(V) formed an inner-sphere complex in ettringite, whereas As(III) formed an outer-sphere complex, and the relatively larger size and charge of As(V) compared with SO42− restrict substitution inside channels without affecting the ettringite structure under high loading of As(V). The added Ca(OH)2 promoted the hydration reaction of MSBs and facilitated the formation of a Ca–As(V) precipitate with low solubility, from Ca4(OH)2(AsO4)2·4H2O (Ksp = 10−27.49) to Ca5(AsO4)3(OH) (Ksp = 10−40.12). This work is beneficial for the application of cement-free MSB in the S/S process.

Resolving the kinetics of individual aqueous reaction steps of actinyl (AnO2+ and AnO22+; An=U, Np, and Pu) tricarbonate complexes with ferrous iron and hydrogen sulfide from first principles

The solubility and mobility of actinides (An), like uranium, neptunium, and plutonium, in the environment largely depends on their oxidation states. Actinyls (AnV,VIO2+/2+(aq)) form strong complexes with available ligands, like carbonate (CO32−), which may inhibit reduction to relatively insoluble AnIVO2(s). Here we use quantum-mechanical calculations to explore the kinetics of aqueous homogeneous reaction paths of actinyl tricarbonate complexes ([AnO2(CO3)3]5−/4−) with two different reductants, [Fe(OH)2(H2O)4]0 and [H2S(H2O)6]0. Energetically-favorable outer-sphere complexes (OSC) are found to form rapidly, on the order of milliseconds to seconds over a wide actinyl concentration range (pM to mM). The systems then encounter energy barriers (Ea), some of which are prohibitively high (>100 kJ/mol for some neptunyl and plutonyl reactions with Fe2+ and H2S), that define the transition from outer- to inner-sphere complex (ISC; for example, calculated Ea of ISC formation between UO2+ and UO22+ with Fe2+ are 35 and 74 kJ/mol, respectively). In some reactions, multiple OSCs are observed that represent different hydrogen bonding networks between solvent molecules and carbonate. Even when forming ISCs, electron transfer to reduce An6+ and An5+ is not observed (no change in atomic spin values or lengthening of An–Oax bond distances). Proton transfer from bicarbonate and water to actinyl O was tested as a mechanism for electron transfer from Fe2+ to U6+ and Pu6+. Not all proton transfer reactions yielded reduction of An6+ to An5+ and only a few pathways were energetically-favorable (e. g. H+ transfer from H2O to drive Pu6+ reduction to Pu5+ with ΔE = −5 kJ/mol). The results suggest that the tricarbonate complex serves as an effective shield against actinide reduction in the tested reactions and will maintain actinyl solubility at elevated pH conditions. The results highlight reaction steps, such as inner-sphere complex formation and electron transfer, which may be rate-limiting. Thus, this study may serve as the basis for future research on how they can be catalyzed by a mineral surface in a heterogeneous process.

Silica Pillared Montmorillonites as Possible Adsorbents of Antibiotics from Water Media

In this work, three silica pillared clays (Si-PILC) were synthetized, characterized, and evaluated as possible adsorbents of ciprofloxacin (CPX) and tetracycline (TC) form alkaline aqueous media. The pillared clays obtained showed significant increases in their specific surface areas (SBET) and micropore volumes (Vμp) regarding the raw material, resulting in microporosity percentages higher than 57% in all materials. The studies of CPX and TC removal using pillared clays were compared with the natural clay and showed that the Si-PILC adsorption capacities have a strong relationship with their porous structures. The highest adsorption capacities were obtained for CPX on Si-PILC due to the lower molecular size of CPX respect to the TC molecule, favoring the interaction between the CPX− and the pillars adsorption sites. Tetracycline adsorption on silica pillared clays evidenced that for this molecule the porous structure limits the interaction between the TCH− and the pillars, decreasing their adsorption capacities. However, the results obtained for both antibiotics suggested that their negative species interact with adsorption sites on the pillared structure by adsorption mechanisms that involve inner-sphere complex formation as well as van der Waals interactions. The adsorption mechanism proposed for the anionic species on Si-PILC could be considered mainly as negative cooperative phenomena where firstly there is a hydrophobic effect followed by other interactions, such as der Waals or inner-sphere complex formation.

The hyperbolicity of the sphere complex via surgery paths

In [We give a shorter alternative proof of this theorem, using surgery paths in Hatcher’s sphere complex (another model for the free splitting complex), instead of Handel and Mosher’s fold paths. As a byproduct, we get that surgery paths are unparameterized quasi-geodesics in the sphere complex.We explain how to deduce from our proof the hyperbolicity of the free factor complex and the arc complex of a surface with boundary.

Exploring ion induced folding of a single-stranded DNA oligomer from molecular simulation studies

Formation of Na+ ion-induced inner-sphere complex folds the DNA strand by bringing two non-sequential residues in close contact with a net free energy change of −4.1 kcal mol−1.

Quantum chemical study of inner-sphere complexes of trivalent lanthanide and actinide ions on the corundum (110) surface

Summary Sorption plays a major role in the safety assessment of nuclear waste disposal. In the present theoretical study we focused on understanding the interaction of trivalent lanthanides and actinides (La3+, Eu3+ and Cm3+) with the corundum (110) surface. Optimization of the structures were carried out using density functional theory with different basis sets. Additionally, Møller-Plesset perturbation theory of second order was used for single point energy calculations. We studied the structure of different inner-sphere complexes depending on the surface deprotonation and the number of water molecules in the first coordination shell. The most likely structure of the inner-sphere complex (tri- or tetradentate) was predicted. For the calculations we used a cluster model for the surface. By deprotonating the cluster a chemical environment at elevated pH values was mimicked. Our calculations predict the highest stability for a tetradentate inner-sphere surface complexes with five water molecules remaining in the first coordination sphere of the metal ions. The formation of the inner-sphere complexes is favored when a coordination takes place with at most one deprotonated surface aluminol group located beneath the inner-sphere complex. The mutual interaction between sorbing metal ions at the surface is studied as well. The minimal possible distance between two inner-sphere sorbed metal ions at the surface was determined to be 530 pm.