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.

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.

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.