The Effect of High Selenite and Selenate Concentrations on Ferric Oxyhydroxides Transformation under Alkaline Conditions.

Iron-based nanomaterials have high technological impacts on various pro-environmental applications, including wastewater treatment using the co-precipitation method. The purpose of this research was to identify the changes of iron nanomaterial's structure caused by the presence of selenium, a typical water contaminant, which might affect the removal when the iron co-precipitation method is used. Therefore, we have investigated the maturation of co-precipitated nanosized ferric oxyhydroxides under alkaline conditions and their thermal transformation into hematite in the presence of selenite and selenate with high concentrations. Since the association of selenium with precipitates surfaces has been proven to be weak, the mineralogy of the system was affected insignificantly, and the goethite was identified as an only ferric phase in all treatments. However, the morphology and the crystallinity of ferric oxyhydroxides was slightly altered. Selenium affected the structural order of precipitates, especially at the initial phase of co-precipitation. Still, the crystal integrity and homogeneity increased with time almost constantly, regardless of the treatment. The thermal transformation into well crystalized hematite was more pronounced in the presence of selenite, while selenate-treated and selenium-free samples indicated the presence of highly disordered fraction. This highlights that the aftermath of selenium release does not result in destabilization of ferric phases; however, since weak interactions of selenium are dominant at alkaline conditions with goethite's surfaces, it still poses a high risk for the environment. The findings of this study should be applicable in waters affected by mining and metallurgical operations.

Mobilisation of hazardous elements from arsenic-rich mine drainage ochres by three Aspergillus species.

Natural ferric ochres that precipitate in streambeds at abandoned mining sites are natural scavengers of various metals and metalloids. Thus, their chemical and structural modification via microbial activity should be considered in evaluation of the risks emerging from probable spread of contamination at mining sites. Our results highlight the role of various aspergilli strains in this process via production of acidic metabolites that affect mobility and bioavailability of coprecipitated contaminants. The Mössbauer analysis revealed subtle structural changes of iron in ochres, while the elemental analysis of non-dissolved residues of ochres that were exposed to filamentous fungi suggest coinciding bioextraction of arsenic and antimony with extensive iron mobilisation. However, the zinc bioextraction by filamentous fungi is less likely dependent on iron leaching from ferric ochres. The strain specific bioextraction efficiency and subsequent bioaccumulation of mobilised metals resulted in distinct tolerance responses among the studied soil fungal strains. However, regardless the burden of bioextracted metal(loid)s on its activity, the Aspergillus niger strain has shown remarkable capability to decrease pH of its environment and, thus, bioextract significant and environmentally relevant amounts of potentially toxic elements from the natural ochres.

Fungal-induced modification of spontaneously precipitated ochreous sediments from drainage of abandoned antimony mine.

Iron-containing spontaneously precipitated ochreous sediments serve as natural scavengers of various migrating elements and in this way contribute to removal and immobilization of potentially hazardous elements especially from mine drainage outflows. On the other hand, presence of filamentous fungi in their surroundings triggers biotransformation and contributes to the mobility of these elements. Three groups of samples of spontaneously precipitated ochreous sediments from an abandoned antimony mine in Poproc, Slovakia were studied: as-collected, sterilized at 95 °C for 30 min, and exposed to incubation with filamentous fungus Aspergillus niger which is frequently found in soils. Employing chemical analyses have determined the content of Fe, As, Sb, and Zn in the samples as well as their mobilization among the non-dissolved residue, culture medium of the fungus and/or its biomass. Significant degree of biovolatilization of antimony was unveiled. Speciation of iron was performed by 57Fe Mössbauer spectroscopy performed in a wide temperature range 300-4.2 K and external magnetic field of 6 T. Hyperfine interactions between 57Fe nuclei and their electronic shells have revealed superparamagnetic behavior characteristic for small particles. Their blocking temperatures of 46, 53, and 40 K, respectively, indicate a dependence of the size of the particles upon the sample treatment. While sterilization has supported their growth, incubation with fungus has changed their chemical environment and removed mainly bigger particles.

Identification of spatial magnetic inhomogeneities by nuclear forward scattering of synchrotron radiation.

Spatially confined magnetic inhomogeneities were revealed by measuring nuclear forward scattering time spectra on the same sample in two different geometric arrangements. They differ by 180° rotation of the sample around one of the polarization axes. A basic theoretical description of this phenomenon and its relation to a spatial distribution of nuclei featuring different magnetic moments is provided. From an experimental point of view, the violation of rotational invariance was observed for an inhomogeneous Fe81Mo8Cu1B10 metallic glass. The development of magnetic inhomogeneities and their relation to the evolution of time spectra was studied during thermal annealing.

On the Formation of Nanocrystalline Grains in Metallic Glasses by Means of In-Situ Nuclear Forward Scattering of Synchrotron Radiation.

Application of the so-called nuclear forward scattering (NFS) of synchrotron radiation is presented for the study of crystallization of metallic glasses. In this process, nanocrystalline alloys are formed. Using NFS, the transformation process can be directly observed during in-situ temperature experiments not only from the structural point of view, i.e., formation of nanocrystalline grains, but one can also observe evolution of the corresponding hyperfine interactions. In doing so, we have revealed the influence of external magnetic field on the crystallization process. The applied magnetic field is not only responsible for an increase of hyperfine magnetic fields within the newly formed nanograins but also the corresponding components in the NFS time spectra are better identified via occurrence of quantum beats with higher frequencies. In order to distinguish between these two effects, simulated and experimental NFS time spectra obtained during in-situ temperature measurements with and without external magnetic field are compared.

Antimony leaching from antimony-bearing ferric oxyhydroxides by filamentous fungi and biotransformation of ferric substrate.

Ferric oxyhydroxides are natural scavengers of antimony, thus, they contribute significantly to antimony immobilization in soils and sediments. Recent studies, however, usually omit microbial influence on geochemically stable antimony-ferric oxyhydroxide association. Therefore, we have evaluated fungal contribution to antimony mobility during static cultivation of common soil fungus Aspergillus niger in presence of ferric oxyhydroxides. Our results indicate distinguished effect of fungus on antimony distribution at two different antimony concentrations that were used for antimony pre-adsorbtion onto ferric oxyhydroxides prior to the inoculation. Approximately 36% of antimony was bioextracted by fungus from antimony bearing ferric oxyhydroxide after 14-day cultivation when the 8.9 mg·L-1 antimony concentration was used for pre-adsorption. However, no statistically significant change of antimony content in ferric oxyhydroxides was observed after cultivation when initial 48 mg·L-1 antimony concentration was used for pre-adsorption. As Mössbauer spectroscopy and XRD analysis indicated, nanosized akageneite, goethite, and lepidocrocite enhanced their crystallinity during cultivation, while hematite was identified only after the cultivation. Nevertheless, presence of ferric oxyhydroxides at both initial concentrations enabled transformation of antimony into volatile derivatives, and almost 9.5% of antimony was biovolatilized after cultivation. These results contribute significantly to environmental geochemistry of antimony-ferric oxyhydroxides association and highlight the importance of microbial activity in relation to ferric component of natural geochemical barriers.

Increased Colloidal Stability and Decreased Solubility-Sol-Gel Synthesis of Zinc Oxide Nanoparticles with Humic Acids.

Adding the humic acid coating to the nanoparticles of zinc oxide (ZnO-NP) may improve the properties necessary for their colloidal stability. To show how humic acid coating affects the properties of ZnO-NP, three differently sol-gel synthesized ZnO-NP were synthesized: pristine zinc oxide nanoparticles without coating (p-ZnO-NP) and humic acid coated zinc oxide nanoparticles at two different initial concentrations of 20 mg/L (HA20-ZnO-NP) and 200 mg/L (HA200-ZnO-NP) of humic acids in the starting solution. All ZnO-NP were found to be nanocrystals of mineral zincite exhibiting wurtzite crystal symmetry. Transmission electron microscopy showed that capping by humic acids during synthesis decreased the size of HA20-ZnO-NP and HA200-ZnO-NP compared to p-ZnO-NP nanoparticles. Via experiments, HA20-ZnO-NP were found to dissolve less and have a similar or higher stability than both p-ZnO-NP and HA200-ZnO-NP.

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses.

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic glasses (MGs). Despite their amorphous nature, the identification of hyperfine interactions unveils faint structural modifications. For this purpose, we have employed two techniques that utilize nuclear resonance among nuclear levels of a stable 57Fe isotope, namely Mössbauer spectrometry and nuclear forward scattering (NFS) of synchrotron radiation. The effects of heat treatment upon (Fe2.85Co1)77Mo8Cu1B14 MG are discussed using the results of ex situ and in situ experiments, respectively. As both methods are sensitive to hyperfine interactions, information on structural arrangement as well as on magnetic microstructure is readily available. Mössbauer spectrometry performed ex situ describes how the structural arrangement and magnetic microstructure appears at room temperature after the annealing under certain conditions (temperature, time), and thus this technique inspects steady states. On the other hand, NFS data are recorded in situ during dynamically changing temperature and NFS examines transient states. The use of both techniques provides complementary information. In general, they can be applied to any suitable system in which it is important to know its steady state but also transient states.

Iron oxides in human spleen.

Iron is an essential element for fundamental cell functions and a catalyst for chemical reactions. Three samples extracted from the human spleen were investigated by scanning (SEM) and transmission electron microscopy (TEM), Mössbauer spectrometry (MS), and SQUID magnetometry. The sample with diagnosis of hemosiderosis (H) differs from that referring to hereditary spherocytosis and the reference sample. SEM reveals iron-rich micrometer-sized aggregate of various structures-tiny fibrils in hereditary spherocytosis sample and no fibrils in hemochromatosis. Hematite and magnetite particles from 2 to 6 µm in TEM with diffraction in all samples were shown. The SQUID magnetometry shows different amount of diamagnetic, paramagnetic and ferrimagnetic structures in the tissues. The MS results indicate contribution of ferromagnetically split sextets for all investigated samples. Their occurrence indicates that at least part of the sample is magnetically ordered below the critical temperature. The iron accumulation process is different in hereditary spherocytosis and hemosiderosis. This fact may be the reason of different iron crystallization.

Direct evidence of Fe(V) and Fe(IV) intermediates during reduction of Fe(VI) to Fe(III): a nuclear forward scattering of synchrotron radiation approach.

Identification of unstable high-valent iron species in electron transfer reactions of ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) has been an important challenge in advancing the understanding of the oxidative mechanisms of ferrates. This paper presents the first example of distinguishing various phases differing in the valence state of iron in the solid state reduction of Fe(VI) to Fe(III) oxides at 235 °C using hyperfine parameters, isomer shift and hyperfine magnetic field, obtained from nuclear forward scattering of synchrotron radiation (NFS). The NFS technique enables a fast data accumulation resulting in high time resolution of in situ experiments. The results suggest a reaction mechanism, involving Fe(V) and Fe(IV) species, in the thermal decomposition of K2FeO4 to KFeO2. The present study opens up an approach to exploring the unambiguous identification of Fe(VI), Fe(V), Fe(IV), and Fe(III) in electron-transfer reaction mechanisms of ferrates in solid and aqueous phase systems.

Evolution of structure and local magnetic fields during crystallization of HITPERM glassy alloys studied by in situ diffraction and nuclear forward scattering of synchrotron radiation.

Evolution of structure and local magnetic fields in (Fe(1-x)Co(x))76Mo8Cu1B15 (HITPERM) metallic glass ribbons with various amounts of Co (x = 0, 0.25, 0.5) were studied in situ using diffraction and nuclear forward scattering of synchrotron radiation. It was found that crystallization of all three glasses proceeds in two stages. In the first stage, bcc (Fe,Co) nanocrystals are formed, while in the second stage additional crystalline phases evolve. For all three glasses, the crystallization temperatures at the wheel side were found to be lower than at the air side of the ribbon. The crystallization temperatures were found to decrease with increasing Co content. The lattice parameters of the bcc nanocrystals decrease up to about 550 °C and then increase pointing to squeezing Mo atoms out of the nanograins or to interface effects between the nanocrystals and the glassy matrix. Nuclear forward scattering enabled separate evaluation of the contributions that stem from structurally different regions within the investigated samples including the newly formed nanocrystals and the residual amorphous matrix. Even minor Co content (x = 0.25) has a substantial effect not only upon the magnetic behaviour of the alloy but also upon its structure. Making use of hyperfine magnetic fields, it was possible to unveil structurally diverse positions of Fe atoms that reside in a nanocrystalline lattice with different numbers of Co nearest neighbours.

Bulk metallic glass-like scattering signal in small metallic nanoparticles.

The atomic structure of Ni-Pd nanoparticles has been studied using atomic pair distribution function (PDF) analysis of X-ray total scattering data and with transmission electron microscopy (TEM). Larger nanoparticles have PDFs corresponding to the bulk face-centered cubic packing. However, the smallest nanoparticles have PDFs that strongly resemble those obtained from bulk metallic glasses (BMGs). In fact, by simply scaling the distance axis by the mean metallic radius, the curves may be collapsed onto each other and onto the PDF from a metallic glass sample. In common with a wide range of BMG materials, the intermediate range order may be fit with a damped single-frequency sine wave. When viewed in high-resolution TEM, these nanoparticles exhibit atomic fringes typical of those seen in small metallic clusters with icosahedral or decahedral order. These two seemingly contradictory results are reconciled by calculating the PDFs of models of icosahedra that would be consistent with the fringes seen in TEM. These model PDFs resemble the measured ones when significant atom-position disorder is introduced, drawing together the two diverse fields of metallic nanoparticles and BMGs and supporting the view that BMGs may contain significant icosahedral or decahedral order.