Mössbauer studies of phosphate glasses for the immobilisation of toxic and nuclear wastes

Various iron-containing phosphate glasses were investigated by Mössbauer spectroscopy. Iron was found to occur predominantly as Fe³⁺ in all glasses, and largely occupied sites with distorted octahedral coordination for both redox states. Using a base glass of nominal composition 60 P₂O₅–40 Fe₂O₃ (mol%), stepwise molar replacement of Fe₂O₃ by (0.67 Na₂O?×?0.33 Al₂O₃) increased the redox ratio, Fe²⁺/ΣFe, from 0.13 at 40% Fe₂O₃ to 0.25 at 10% Fe₂O₃. The centre shift increased and quadrupole splitting decreased by up to ～20% over this range, interpreted as a decrease in the average distortion of Fe sites from cubic symmetry, and an increase in average iron coordination. Literature revealed that recoil-free fraction ratio f (Fe³⁺)?/?f (Fe²⁺)?≈?1.3 in iron phosphate glasses, and this was considered when assessing redox. Mössbauer parameters of these and other glasses demonstrated a combination of structural stability and compositional flexibility which makes them so suitable for waste immobilisation.     

Monitoring structural transformation of hydroxy-sulphate green rust in the presence of sulphate reducing bacteria

The activities of bacterial consortia enable organisms to maximize their metabolic capabilities. This article assesses the synergetic relationship between iron reducing bacteria (IRB), Shewanella putrefaciens and sulphate reducing bacteria (SRB) Desulfovibrio alaskensis. Thus, the aim of this study was first to form a biogenic hydroxy-sulpahte green rust GR2( $ {\text{SO}}_{{\text{4}}} ^{{2 - }} The activities of bacterial consortia enable organisms to maximize their metabolic capabilities. This article assesses the synergetic relationship between iron reducing bacteria (IRB), Shewanella putrefaciens and sulphate reducing bacteria (SRB) Desulfovibrio alaskensis. Thus, the aim of this study was first to form a biogenic hydroxy-sulpahte green rust GR2() through the bioreduction of lepidocrocite by S. putrefaciens and secondly to investigate if sulfate anions intercalated in the biogenic GR2() could serve as final electron acceptor for a sulfate reducing bacterium, D. alaskensis. The results indicate that the IRB lead to the formation of GR2() and this mineral serve as an electron acceptor for SRB. GR2() precipitation and its transformation was demonstrated by using X-ray diffraction (DRX), M?ssbauer spectroscopy (TMS) and transmission electron spectroscopy (TEM). These observations point out the possible acceleration of steel corrosion in marine environment in presence of IRB/SRB consortia.     

The Orientation of the Antiferromagnetic Order in FePS3

Hyperfine Interactions - Mössbauer spectroscopy was performed on FePS3. Magnetic moments of a single crystal were found to be parallel to the z-axis at temperatures below 96 K. The internal...     

Mössbauer spectroscopy of ordinary chondrites: an analysis of the metal phases

Mössbauer spectroscopy was used for the analysis of the metal part in various ordinary chondrites. One and two magnetic sextets were used to fit the metal subspectra and the main Fe–Ni–Co phases with different nickel and/or cobalt concentrations were proposed in different chondrites.     

The effect of the sputtering process ambient on the magnetic state and phase composition of the film nanocomposites (Fe0.45Co0.45Zr0.10) x (Al2O3)1−x

The effect of oxygen-containing ambient arising at sputtering of granular nanocomposites (Fe_0.45Co_0.45Zr_0.10) _x (Al₂O₃)_1−x (30 at.%≤x≤65 at.%) on their magnetic state and phase composition has been investigated. It was shown that the presence of oxygen resulted in the formation of oxide shells preventing the ferromagnetic interaction between Co_0.45Fe_0.45Zr_0.10 nanoparticles and also the formation of metallic percolative net beyond the percolation threshold (as opposed to the films prepared in pure argon atmosphere).     

Synthesis and characterisation of the Fe(II–III) hydroxy-formate green rust

A new methodology was envisioned in order to prepare green rust compounds build on organic anions that could intervene in microbiologically influenced corrosion processes of iron and steel. The formate ion was chosen as an example. The formation of rust was simulated by the oxidation of aqueous suspensions of Fe(OH)₂ precipitated from Fe(II) lactate and sodium hydroxide, in the presence of sodium formate to promote the formation of the corresponding green rust. The evolution of the precipitate with time was followed by transmission Mössbauer spectroscopy at 15 K. It was observed that the initial hydroxide was transformed into a new GR compound. Its spectrum is composed of three quadrupole doublets, D ₁ (δ?=?1.28 mm s^?1, Δ?=?2.75 mm s^?1) and D ₂ (δ?=?1.28 mm s^?1, Δ?=?2.48 mm s^?1) that correspond to Fe(II) and D ₃ (δ?=?0.49 mm s^?1, Δ?=?0.37 mm s^?1) that corresponds to Fe(III). The relative area of D ₃, close to the proportion of Fe(III) in the GR, was found at 28.5?±?1.5% (～2/7). Raman spectroscopy confirmed that the intermediate compound was a Fe(II–III) hydroxy-formate, GR(HCOO^?).     

Mössbauer spectroscopy of green shale from banded iron formation

A green shale from the Precambrian banded iron formation of the Bonai Range, Eastern India, is examined by transmission Mössbauer spectroscopy. The constituent phases are identified to be chlorite, siderite and magnetite. The fractional resonance area of each constituent is computed and the ferrous-ferric ratio determined. The variation of this ratio over the sample is examined. Intensity of the magnetite lines reveals that deviation from stoichiometry is negligible. The observations suggest a transition within short range from silicate-rich facies to carbonate-oxide-rich facies in the studied section.     

Mössbauer and magnetic study of Mn2+- and Cr3+-substituted spinel magnesioferrites of the composition Mg1−xMnxFe2−2xCr2xO4

Chromium and manganese co-substituted spinel magnesioferrites of the composition Mg_1?x Mn _x Fe_2?2x Cr_2x O₄ (x?=?0.0, 0.1, 0.2, 0.3, and 0.5) were investigated with X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic measurements. The cation distribution inferred suggests that Mn²⁺ and Cr³⁺ ions dominantly occupy the A- and B-sites respectively. The gradual decrease of the hyperfine fields and Curie temperatures with increasing x reflects a gradual weakening in the AB exchange interaction. Mössbauer data of the sample with x = 0.5 is suggestive of cation clustering and/or superparamagnetism. The magnetization data is suggestive of Yafet-Kittel-type canted magnetism.     

Mössbauer study of the stability of quasicrystalline phases: Al78Fe22 and Al82Fe18

A quasicrystal of Al-Fe with a stoichiometric composition very close to a crystalline phase is shown to transform to the crystalline phase with simple thermal cycling from 300 K through 78 K and 300 K.     

Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2x Al x Cr x O4

In order to study the effect of substitution of Fe³⁺ by Al³⁺ and Cr³⁺ in Li_0.5Fe_2.5O₄ on its structural and magnetic properties, the spinel system Li_0.5Al _x Cr _x Fe_2.5?2x O₄ (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and ⁵⁷Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al³⁺ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5).     

Effect of Precipitation Temperature and Number of Iron Atoms per Molecule on the Structure of Hydrated Iron(III) Oxyhydroxide Ferritin Cores Synthesised in vitro

Hyperfine Interactions - Horse spleen apoferritin was reconstituted with varying numbers of iron atoms per protein shell at 25 and 50°C. Samples with mean particle sizes ranging from...     

Mössbauer,X-ray fluorescence and paleomagnetic studies of deep-sea sediments from the Peru Basin: two million years of sedimentation history

Summary Sediment cores with different sub-bottom depths (I: 45 cm and II: 700 cm) from the Peru Basin have been investigated. From the depth profile of the relative amount of Fe(II) a redox zone is obtained which correlates with the organic carbon flux into the sediment (core I). M?ssbauer parameters suggest that the iron in the sediments is mainly contained in clay minerals and to varying extent also in goethite. Paper presented at ICAME-95, Rimini, 10–16 September 1995.     

Effect of FeCl3 and acetone on the structure of Na–montmorillonite studied by Mössbauer and XRD measurements

⁵⁷Fe Mössbauer spectroscopy, X-ray diffraction, X-ray fluorescence spectroscopy and infrared spectroscopy were used to study the effect of FeCl₃ and acetone on the structure of a Na–bentonite. XRD indicated the incorporation of Fe³⁺ ions into the interlayer space since the basal lattice spacing of montmorillonite increased to 1.6 from 1.24 nm after treatment with FeCl₃ dissolved in acetone. Interlayer Na⁺ ions could be exchanged to Fe³⁺. Magnetically split Mössbauer subspectra with internal magnetic fields 41 and 46 T at 74 K, were associated with two main Fe³⁺ microenvironments within the interlayer regions. The resultant Fe–montmorillonite was successfully applied as a catalyst in the preparation of 1,1-diacetates from aromatic aldehydes and acetic acid anhydride.     

Study of the [Fe(OMe)(dpm)2]2 dimer in the presence of a magnetic field by using Mössbauer spectroscopy

We present a Mössbauer study of a S = 0 ground state magnetic Fe(III)-dimer in the presence of an applied 5 T longitudinal magnetic field, between 7.6 and 33 K. The values obtained for the isomer shift and the quadrupolar splitting are comparable with the ones of Fe(III) ions coordinated to eight oxygen ions. Regarding the spin dynamics, both intramultiplet and intermultiplet transitions are considered. In the chosen temperature range the rate of the former transitions is constant, within the errors, while the rate of the latter ones quickly increases with the temperature.     

Defects induced by electron irradiation in hollandite ceramics, specific radioactive cesium-host wasteforms: a 57Fe Mössbauer study

Several single phase hollandite ceramics having Ba²⁺ _x Cs⁺ _y (C = Al,Fe)³⁺ _2x+y Ti⁴⁺ _8?2x?y O₁₆ composition have been synthesized and irradiated under external electron beams simulating the β-irradiation of radioactive cesium. These samples have been characterized by ⁵⁷Fe transmission Mössbauer spectroscopy. Mössbauer results show that the irradiation modifies the local arrangements of Ba cations around Fe³⁺ ions by atomic displacement of Ba ions.     

Iron overload diseases: the chemical speciation of non-heme iron deposits in iron loaded mammalian tissues

⁵⁷Fe Mössbauer spectra of iron overloaded human spleen, rat spleen and rat liver tissue samples at 78 K were found to consist of a quadrupole doublet (major component) with magnetic sextet (minor component with fractional spectral area F _s). The distributions of F _s for spleen tissue from two different clinically identifiable groups (n = 7 and n = 12) of thalassemic patients were found to be significantly different. The value of F _s for dietary-iron loaded rat liver was found to rise significantly with age/duration (up to 24 months) of iron loading.     

Nuclear Resonance Vibrational Spectroscopy (NRVS) of Fe–S model compounds, Fe–S proteins, and nitrogenase

We have used nuclear resonance vibrational spectroscopy (NRVS) to examine the nature of the Fe–S unit. Specifically, vibrational characteristics have been determined, and through incremental steps in model system complexity, applied to analysis of the enzyme nitrogenase. This stepwise strategy demonstrates NRVS as a viable bioinorganic tool, and will undoubtedly increase the application of synchrotron spectroscopy to biological problems.     

The effect of Al-content and crystallinity on the magnetic properties of goethites

This paper reviews a profound Mössbauer study on the magnetic properties of goethites with varying crystallinity and Al-content. It has been found that both the cluster-ordering and the superferromagnetic models reproduce the temperature dependencies of the average hyperfine fields quite well. However, the magnetic transition temperatures predicted by the cluster-ordering model are in better agreement with those measured from thermoscan experiments. On the other hand, it has been found that the hyperfine field of maximum probability at low temperatures follows the spin–wave law for antiferromagnets. Linear relationships between the saturation hyperfine fields, the inter-sublattice exchange interactions, and the Néel temperatures to the Al-content and crystallinity could be derived. On the other hand, applied-field Mössbauer spectroscopy seems to suggest that the anisotropy field can differentiate between poor crystallinity and Al-content, and that a certain degree of ferrimagnetism occurs at higher Al-contents.     

Mössbauer study of two different aged rock types in the Vredefort structure, South Africa

The Vredefort Structure in South Africa was recently inscribed into the list of World Heritage sites as the oldest and largest recognised impact structure on earth. Due to upliftment of more than 30 km of the Archaean basement core and subsequent exposure of the deeply eroded central portion of the crater a unique opportunity exists to study rocks of the crust, especially those that have undergone recrystallization due to various thermal metamorphic events over time. Two rock types occurring in the central uplifted part of the impact structure were studied. One was a typical Archaean iron formation of sedimentary origin. The other rock studied, adjacent to this much older rock, is a homogeneous, medium grained recrystallized norite of immediately pre- or post-impact age, indicating a possible mafic igneous activity related to impact. Microscopy, XRD and Mössbauer analyses were performed on both samples.     

Spectroscopic studies of the corrosion of model iron electrodes in carbonate and phosphate buffer solutions

We have extended our unenhanced (non-SERS) Raman spectroscopic investigations to include a study of the corrosion of an iron electrode in carbonate and phosphate buffer solutions. The measurements have been supported by electrochemical investigations (via cyclic voltammetry), enabling oxidation and reduction reactions to be systematically followed at variable applied potentials. In a carbonate buffer (pH = 9.4) the surface oxidation led to the formation of a ‘green rust’ (a hydrated hydroxy-carbonate), followed by the α- and β-forms of FeOOH and an underlying magnetite layer formed on the cathodic (reduction) cycle. In a phosphate buffer (pH = 7.7) the surface was passivated by hydrated phosphates of iron [identified as FePO₄ · xH₂O and Fe₃(PO₄)₂·8H₂O]. The formation of oxides (Fe₂O₃ and Fe₃O₄) were inferred from voltammetry, but spectral identification was more difficult because of broad, ill-defined spectra. Despite the challenges of using unenhanced Raman spectroscopy, we believe that the effort was worthwhile, the reactions identified being more likely to be relevant to real electrochemical environments. Copyright © 2008 John Wiley & Sons, Ltd.