Kinetic Modeling and Mechanisms of Manganese Removal from Alkaline Mine Water Using a Pilot Scale Column Reactor

Manganese (Mn) is a major element in various aqueous and soil environments that is sometimes highly concentrated in mine water and other mineral processing wastewater. In this study, we investigated Mn removal from alkaline mine water (pH > 9) with an Mn-coated silica sand packed into a pilot-scale column reactor and examined the specific reaction mechanism using X-ray absorption near-edge structure (XANES) analysis and geochemical kinetic modeling. The kinetic effect of dissolved Mn(II) removal by birnessite (δ-Mn(IV)O2) at pH 6 and 8 was evaluated at different Mn(II)/Mn(IV) molar ratios of 0.1–10. Our results confirmed the positive effect of the presence of δ-MnO2 on the short-term removal (60 min) of dissolved Mn. XANES analysis results revealed that δ-MnO2 was more abundant than Mn(III)OOH in the reactor, which may have accumulated during a long-term reaction (4 months) after the reactor was turned on. A gradual decrease in dissolved Mn(II) concentration with depth was observed in the reactor, and comparison with the kinetic modeling result confirmed that δ-MnO2 interaction was the dominant Mn removal mechanism. Our results show that δ-MnO2 contents could play a significant role in controlling Mn removability from mine water in the reactor.

The Leading-Edge Structure Based on Geometric Bionics Affects the Transient Cavitating Flow and Vortex Evolution of Hydrofoils

A hydrofoil is a fundamental structure in fluid machinery, and it is widely applied to the fields of propellers, blades of axial flow pumps and underwater machinery. To reveal that the geometric structure of the leading-edge of a hydrofoil is the mechanism that affects the transient cavitating flow, we regard the three fish-type leading-edge structures of mackerel, sturgeon and small yellow croaker as the research objects and use high-precision non-contact 3D scanners to establish three bionic hydrofoils (Mac./Stu./Cro.). We use large eddy simulation to simulate the transient cavitating flow of hydrofoils numerically and compare and analyze their lift–drag characteristics, the transient behavior of unsteady cavitation and the vortex evolution. The numerical simulation results are in good agreement with the experimental results. The warping of leading-edge structure will cause a change in lift–drag characteristics, and the Cro. hydrofoil has a good lift-to-drag ratio. When the leading-edge structure is tilted upward (Cro. hydrofoil), the position of the attached cavity will move forward, which will accelerate the cavitation evolution and improve the velocity fluctuation of the trailing edge. When the leading-edge structure is tilted downward (Stu. hydrofoil), the change in the vortex stretching and dilatation terms will be complex, and the influence area of the vortex will widen.

Chromium (VI) Inhibition of Low pH Bioleaching of Limonitic Nickel-Cobalt Ore

Limonitic layers of the regolith, which are often stockpiled as waste materials at laterite mines, commonly contain significant concentrations of valuable base metals, such as nickel, cobalt, and manganese. There is currently considerable demand for these transition metals, and this is projected to continue to increase (alongside their commodity values) during the next few decades, due in the most part to their use in battery and renewable technologies. Limonite bioprocessing is an emerging technology that often uses acidophilic prokaryotes to catalyse the oxidation of zero-valent sulphur coupled to the reduction of Fe (III) and Mn (IV) minerals, resulting in the release of target metals. Chromium-bearing minerals, such as chromite, where the metal is present as Cr (III), are widespread in laterite deposits. However, there are also reports that the more oxidised and more biotoxic form of this metal [Cr (VI)] may be present in some limonites, formed by the oxidation of Cr (III) by manganese (IV) oxides. Bioleaching experiments carried out in laboratory-scale reactors using limonites from a laterite mine in New Caledonia found that solid densities of ∼10% w/v resulted in complete inhibition of iron reduction by acidophiles, which is a critical reaction in the reductive dissolution process. Further investigations found this to be due to the release of Cr (VI) in the acidic liquors. X-ray absorption near edge structure (XANES) spectroscopy analysis of the limonites used found that between 3.1 and 8.0% of the total chromium in the three limonite samples used in experiments was present in the raw materials as Cr (VI). Microbial inhibition due to Cr (VI) could be eliminated either by adding limonite incrementally or by the addition of ferrous iron, which reduces Cr (VI) to less toxic Cr (III), resulting in rates of extraction of cobalt (the main target metal in the experiments) of >90%.

Enhanced hydrogen generation by reverse spillover effects over bicomponent catalysts

The contribution of the reverse spillover effect to hydrogen generation reactions is still controversial. Herein, the promotion functions for reverse spillover in the ammonia borane hydrolysis reaction are proven by constructing a spatially separated NiO/Al2O3/Pt bicomponent catalyst via atomic layer deposition and performing in situ quick X-ray absorption near-edge structure (XANES) characterization. For the NiO/Al2O3/Pt catalyst, NiO and Pt nanoparticles are attached to the outer and inner surfaces of Al2O3 nanotubes, respectively. In situ XANES results reveal that for ammonia borane hydrolysis, the H species generated at NiO sites spill across the support to the Pt sites reversely. The reverse spillover effects account for enhanced H2 generation rates for NiO/Al2O3/Pt. For the CoOx/Al2O3/Pt and NiO/TiO2/Pt catalysts, reverse spillover effects are also confirmed. We believe that an in-depth understanding of the reverse effects will be helpful to clarify the catalytic mechanisms and provide a guide for designing highly efficient catalysts for hydrogen generation reactions.

Implementation of cryogenic tender X-ray HR-XANES spectroscopy at the ACT station of the CAT-ACT beamline at the KIT Light Source

The ACT experimental station of the CAT-ACT wiggler beamline at the Karlsruhe Institute of Technology (KIT) Light Source is dedicated to the investigation of radionuclide materials with radioactivities up to 1000000 times the exemption limit by various speciation techniques applying monochromatic X-rays. In this article, the latest technological developments at the ACT station that enable high-resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy for low radionuclide loading samples are highlighted – encompassing the investigation of actinide elements down to 1 p.p.m. concentration – combined with a cryogenic sample environment reducing beam-induced sample alterations. One important part of this development is a versatile gas tight plexiglass encasement ensuring that all beam paths in the five-analyzer-crystal Johann-type X-ray emission spectrometer run within He atmosphere. The setup enables the easy exchange between different experiments (conventional X-ray absorption fine structure, HR-XANES, high-energy or wide-angle X-ray scattering, tender to hard X-ray spectroscopy) and opens up the possibility for the investigation of environmental samples, such as specimens containing transuranium elements from contaminated land sites or samples from sorption and diffusion experiments to mimic the far field of a breached nuclear waste repository.

Opportunities and challenges of applying advanced X-ray spectroscopy to actinide and lanthanide N-donor ligand systems

N-donor ligands such as n-Pr-BTP [2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine] preferentially bind trivalent actinides (An3+) over trivalent lanthanides (Ln3+) in liquid–liquid separation. However, the chemical and physical processes responsible for this selectivity are not yet well understood. Here, an explorative comparative X-ray spectroscopy and computational (L 3-edge) study for the An/Ln L 3-edge and the N K-edge of [An/Ln(n-Pr-BTP)3](NO3)3, [Ln(n-Pr-BTP)3](CF3SO3)3 and [Ln(n-Pr-BTP)3](ClO4)3 complexes is presented. High-resolution X-ray absorption near-edge structure (HR-XANES) L 3-edge data reveal additional features in the pre- and post-edge range of the spectra that are investigated using the quantum chemical codes FEFF and FDMNES. X-ray Raman spectroscopy studies demonstrate the applicability of this novel technique for investigations of liquid samples of partitioning systems at the N K-edge.

Numerical Analysis of the Primary Gas Boundary Layer Flow Structure in Laser Fusion Cutting in Context to the Striation Characteristics of Cut Edges

In cutting metals with solid-state lasers, a characteristic cutting edge structure is generated whose formation mechanisms still elude a consistent explanation. Several studies suggest a major contribution of the pressurized gas flow. Particular emphasis must be devoted to the gas boundary layer and its developing flow characteristics, since they determine the heat and momentum exchange between the cutting gas and the highly heated melt surface and thus the expulsion of the molten material from the kerf. The present study applies a CFD simulation model to analyze the gas flow during laser cutting with appropriate boundary conditions. Specifically, the gas boundary layer development is considered with a high spatial discretization of this zone in combination with a transition turbulence model. The results of the calculation reveal for the first time that the boundary layer is characterized by a quasi-stationary vortex structure composed of nearly horizontal geometry- and shock-induced separation zones and vertical vortices, which contribute to the transition to turbulent flow. Comparison of the results with the striation structure of experimental cut edges reveals a high agreement of the location, orientation, and size of the characteristic vortices with particular features of the striation structure of cut edges.

Structural Phase Transition and In-Situ Energy Storage Pathway in Nonpolar Materials: A Review

Benefitting from exceptional energy storage performance, dielectric-based capacitors are playing increasingly important roles in advanced electronics and high-power electrical systems. Nevertheless, a series of unresolved structural puzzles represent obstacles to further improving the energy storage performance. Compared with ferroelectrics and linear dielectrics, antiferroelectric materials have unique advantages in unlocking these puzzles due to the inherent coupling of structural transitions with the energy storage process. In this review, we summarize the most recent studies about in-situ structural phase transitions in PbZrO3-based and NaNbO3-based systems. In the context of the ultrahigh energy storage density of SrTiO3-based capacitors, we highlight the necessity of extending the concept of antiferroelectric-to-ferroelectric (AFE-to-FE) transition to broader antiferrodistortive-to-ferrodistortive (AFD-to-FD) transition for materials that are simultaneously ferroelastic. Combining discussion of the factors driving ferroelectricity, electric-field-driven metal-to-insulator transition in a (La1−xSrx)MnO3 electrode is emphasized to determine the role of ionic migration in improving the storage performance. We believe that this review, aiming at depicting a clearer structure–property relationship, will be of benefit for researchers who wish to carry out cutting-edge structure and energy storage exploration.