Jan Filip

The targeted antibacterial and antifungal properties of magnetic nanocomposite of iron oxide and silver nanoparticles.

Two types of magnetic binary nanocomposites, Ag@Fe(3)O(4) and γ-Fe(2)O(3)@Ag, were synthesized and characterized and their antibacterial activities were tested. As a magnetic component, Fe(3)O(4) (magnetite) nanoparticles with an average size of about 70 nm and monodisperse γ-Fe(2)O(3) (maghemite) nanoparticles with an average size of 5 nm were used. Nanocomposites were prepared via in situ chemical reduction of silver ions by maltose in the presence of particular magnetic phase and molecules of polyacrylate serving as a spacer among iron oxide and silver nanoparticles. In the case of the Ag@Fe(3)O(4) nanocomposite, silver nanoparticles, caught at the surfaces of Fe(3)O(4) nanocrystals, were around 5 nm in a size. On the contrary, in the case of the γ-Fe(2)O(3)@Ag nanocomposite, ultrafine γ-Fe(2)O(3) nanoparticles surrounded silver nanoparticles ranging in a size between 20 and 40 nm. In addition, the molecules of polyacrylate in this nanocomposite type suppress considerably interparticle magnetic interactions as proved by magnetization measurements. Both synthesized nanocomposites exhibited very significant antibacterial and antifungal activities against ten tested bacterial strains (minimum inhibition concentrations (MIC) from 15.6 mg/L to 125 mg/L) and four candida species (MIC from 1.9 mg/L to 31.3 mg/L). Moreover, acute nanocomposite cytotoxicity against mice embryonal fibroblasts was observed at concentrations of higher than 430 mg/L (Ag@Fe(3)O(4)) and 292 mg/L (γ-Fe(2)O(3)@Ag). With respect to the non-cytotoxic nature of the polyacrylate linker, both kinds of silver nanocomposites are well applicable for a targeted magnetic delivery of silver nanoparticles in medicinal and disinfection applications.

Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching.

Acid mine water from in situ chemical leaching of uranium (Straz pod Ralskem, Czech Republic) was treated in laboratory scale experiments by zero-valent iron nanoparticles (nZVI). For the first time, nZVI were applied for the treatment of the real acid water system containing the miscellaneous mixture of pollutants, where the various removal mechanisms occur simultaneously. Toxicity of the treated saline acid water is caused by major contaminants represented by aluminum and sulphates in a high concentration, as well as by microcontaminants like As, Be, Cd, Cr, Cu, Ni, U, V, and Zn. Laboratory batch experiments proved a significant decrease in concentrations of all the monitored pollutants due to an increase in pH and a decrease in oxidation-reduction potential related to an application of nZVI. The assumed mechanisms of contaminants removal include precipitation of cations in a lower oxidation state, precipitation caused by a simple pH increase and co-precipitation with the formed iron oxyhydroxides. The possibility to control the reaction kinetics through the nature of the surface stabilizing shell (polymer vs. FeO nanolayer) is discussed as an important practical aspect.

Mechanisms and Efficiency of the Simultaneous Removal of Metals and Cyanides by Using Ferrate(VI): Crucial Roles of Nanocrystalline Iron(III) Oxyhydroxides and Metal Carbonates

The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates.

Facile fabrication of tin-doped hematite photoelectrodes – effect of doping on magnetic properties and performance for light-induced water splitting

We present a new, easily scalable method for the deposition of nanocrystalline hematite photoelectrodes based on the spin-coating of a mixed solution containing tin(II) and iron(III) chlorides followed by thermal treatment. Our facile approach does not require any additional film-forming organic species and allows simple control of the photoelectrochemical performance of the electrode by adjusting the degree of tin doping. When annealed at 650 °C a strong increase in the water oxidation photocurrent is observed with increasing tin concentration. The maximum performance (0.45 mA cm−2 at 1.43 V vs. RHE) was found at the highest possible tin loading (20 : 100, Sn : Fe). The contrasting performance of electrodes annealed at 650 °C and 800 °C suggests different activation processes for dopant diffusion and activation. The doping of tin into the crystal structure of hematite thin films is directly evidenced by X-ray photoelectron spectroscopy and indirectly by changes in the intrinsic magnetic parameters (Morin temperature, Neel temperature) of the hematite films. The magnetization measurements thus represent a potential technique to quantify doping amounts in hematite.

Remarkable efficiency of ultrafine superparamagnetic iron(III) oxide nanoparticles toward arsenate removal from aqueous environment.

Arsenates, when present in water resources, constitute a risk to human health. In order to remove them, various technologies have been developed; out of them, sorption approach is widely adopted employing a wide spectrum of suitable sorbent materials. Nanoparticles of iron oxide are frequently used due to a high surface area and ability to control them by external magnetic field. In this work, we report on a simple and cheap synthesis of ultrafine iron(III) oxide nanoparticles with a narrow size distribution and their exploitation in the field of arsenate removal from aqueous environment. It is shown that the adsorption capacity is enhanced by a mesoporous nature of nanoparticle arrangement in their system due to strong magnetic interactions they evolve between nanoparticles. A complete arsenate removal is achieved at Fe/As ratio equal to ∼20/1 and at pH in the range from 5 to 7.6. Under these conditions, the arsenates are completely removed within several minutes of treatment. Among iron-oxide-based nanosystems synthesized and employed in arsenate remediation issues so far, our assembly of iron(III) oxide nanoparticles shows the highest Freundlich adsorption coefficient and equilibrium sorption capacity under conditions maintained. Taking into account simple and low-cost preparation procedure, product high yields, almost monodispersed character, room-temperature superparamagnetic behavior, and strong magnetic response under small applied magnetic fields, the synthesized iron(III) oxide nanoparticles can be regarded as a promising candidate for exploitation in the field of removing undesired toxic pollutants from various real water systems.

Attenuation of dissolved metals in neutral mine drainage in the Zambian Copperbelt

Behaviour of metals like Cu and Co was studied in nearly neutral (pH ≥ 6.4) mine drainage seepage in a stream downgradient of a tailing dam at Chambishi site in the Copperbelt of Zambia. They are attenuated by precipitation of ferruginous ochres that incorporate significant quantities of metals. Using chemical analysis, X-ray powder diffraction and Mössbauer spectroscopy, we show that the ochres are composed mostly of amorphous ferric hydroxide. Close to the seepage face, the total Fe content of ochres increases due to precipitation of amorphous ferric hydroxide, but total Fe in sediment decreases further downstream. The stream then flows through wetland (dambo) where the remaining fraction of metals is removed. During rainy periods, increased flow rate may result in re-suspension of ochres, increasing thus the mobility of metals. Major ions like sulphate are conservative at the start of the dry period (May), but gypsum may probably precipitate later at the end of the dry period. Sequential extractions of bulk sediments indicate that Mn behaves differently to Fe, with a trend of increasing Mn with distance from the tailing dam. There is much more Fe than Mn in residual (Aqua Regia) fraction, indicating that amorphous ferric hydroxides are transformed to more crystalline phases deeper in sediment. Environmental impact of mine drainage is relatively limited due to its neutral character.

Mössbauer and Magnetic Studies of Nanocrystalline Iron, Iron Oxide and Iron Carbide Powders Prepared from Synthetic Ferrihydrite

Mossbauer spectroscopy and magnetic measurements were used for an analysis of nanocrystalline iron oxides (hematite α‐Fe2O3, magnetite Fe3O4), Hagg carbide (Fe5C2), and α‐Fe prepared by thermal treatment of synthetic ferrihydrite in various atmospheres. The transformation of ferrihydrite precursor was monitored by the measurements of temperature dependence of magnetic moment (thermomagnetic curves). Under optimized temperature and time, hematite nanoparticles were prepared by heating in vacuum. Application of hydrogen atmosphere yielded magnetite or α‐Fe. Annealing in ethylene resulted in the formation of iron carbides.

High Temperature Decomposition of Almandine and Pyrope in Reducing Atmosphere

Thermal decomposition of two garnets of near end‐member composition—almandine (Fe2.85Mg0.15)(Al1.99)Si2.99O12 and pyrope (Mg2.22Fe0.47Ca0.33)(Cr0.11Fe0.06Al1.81)Si2.98O12—has been carried out in reducing atmosphere (forming gas: 10% of H2 in N2). High‐temperature behavior of both samples was monitored using simultaneous thermogravimetry and differential scanning calorimetry. The decomposition of almandine and pyrope turned out to proceed at slightly different temperatures above 1000 °C. Therefore, two series of samples were prepared based on the results of thermal analysis: almandine heated up to 950 °C, 1070 °C and 1200 °C, and pyrope heated up to 1000 °C, 1100 °C, 1125 °C and 1200 °C. The identification of the decomposition products was performed by X‐ray powder diffraction and Mossbauer spectroscopy. The common feature of the decomposition of both garnets is the presence of metallic iron and spinel phase, while the other products include fayalite, cristobalite, and cordierite for almandine; and enstati...

In-field 57Fe Mössbauer spectroscopy below spin-flop transition in powdered troilite (FeS) mineral

Powdered troilite (FeS), extracted from the Cape York IIIA octahedrite meteorite, was investigated employing in-field 57Fe Mossbauer spectroscopy. The study identified a typical behavior of polycrystalline antiferromagnetic material under external magnetic fields. The in-field evolution of the 57Fe Mossbauer spectra showed that the spin-flop transition in the FeS system occurs at a field higher than 5 T.

Removal of arsenate and antimonate by acid-treated Fe-rich clays

Iron impurities in clays degrade the quality in many aspects, but available Fe oxides can significantly improve adsorption affinity of clays to anionic particles. Two natural Fe-rich clays (kaolin and bentonite) were treated in 0.5 M HCl (pH = 1.1) and 0.15 M (COOH)2 (pH = 1.2), and then used to adsorb AsV/SbV oxyanions from model solutions. After acid leaching, the equilibrium sorption capacities (qmax) increased from 2.3 × 10-3 to 39.2 × 10-3 mmol g-1 for AsV and from 2.4 × 10-3 to 40.1 × 10-3 mmol g-1 for SbV, more than doubling the adsorption yields (≈95%) of both oxyanions. Leaching in 0.5 M HCl enhanced both AsV and SbV adsorption, whereas leaching in 0.15 M (COOH)2 mainly improved the adsorption of SbV. Bentonite, which contained fewer crystalline forms of Fe, exhibited better sorption properties for both oxyanions. The leaching of Fe followed first-order kinetics, whereas the adsorption of AsV/SbV followed second-order kinetics. Acid leaching of Fe-rich clays can be used for the preparation of highly selective anionactive sorbents.