Mössbauer Investigation of Characteristic Distribution of Iron Oxides in Sediments from the Antarctica

Sediments from the Admiralty Bay, King George Island, Antarctica, were investigated by ⁵⁷Fe Mössbauer spectroscopy, X-ray diffractometry, and radiometry. Quartz, feldspar, chlorite, calcite, dolomite, mica, kaolinite, hematite and magnetite were identified as constituent minerals in the sediment samples. The phase composition and the iron distribution among the crystallographic sites of iron-bearing minerals (silicates, magnetite and hematite) of samples from different location have been derived from the complex Mössbauer spectra. At different locations sediments had significant characteristic differences in the mineral composition, in the iron distribution among the crystallographic site of silicates, and in the specific radioactivity of Cs radionuclides. These results indicate differences in the rock formation and alteration by the sediments in this maritime part of Antarctica. There is a much higher amount of iron oxides in the sediments from south part of the geological fault across the Admiralty Bay than in the north part. This can be associated with much more alteration in the rocks in the south part compared to the northern one. This finding can contribute to the question of the history of the formation and alteration of volcanic rocks in the border of Antarctica.     

Quantitative multielemental analysis of titaniferous magnetites

Two representative titaniferous magnetite samples procured from Moulabhanj, Orissa, India have been studied by PIXE, EDXRF, Mössbauer spectroscopy, and XRD techniques. Major iron-bearing phases identified in the samples by Mössbauer spectroscopy and XRD are magnetite, hematite, ferrous ilmenite and ferric ilmenite. The Fe²⁺/Fe³⁺ ratio and the relative percentages of different minerals were determined from the resonance areas of Mössbauer spectra. Quantitative multielemental analysis was carried out by energy dispersive X-ray fluorescence (EDXRF) and proton induced X-ray emission (PIXE). Nineteen minor and trace elements have been quantified by EDXRF whereas by PIXE eighteen elements have been analyzed quantitatively. Concentrations of trace elements determined by EDXRF and PIXE were used in interpreting the physico-chemical condition of the depositional basin.     

Mössbauer and X-ray Investigation of Clay Minerals Originated from Libya

⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffractometry were used to study clay mineral samples originated from two different regions (Um-arrazm and Alkawasim) of Libya in order to get information about their mineralogical composition to assess their potential for use in the Libyan oil industry. In the samples originated from Um-arrazm calcite, akaganeite and nontronite while in the samples originated from Alkawasim quartz, akaganeite, montmorillonite, kaolinite, illite, mica and hematite were identified with different ratios by using diffraction method. The differences in the phase composition of iron-containing phases of samples from different localities have reflected in the complex Mössbauer spectra at both 300 K and 80 K. For the samples originated from Um-arrazm the Mössbauer parameters of subspectra were identified as nontronite and akaganeite.     

Chemical reduction of hematite with starch

Chemical reduction of hematite with starch in air at elevated temperature was investigated using X-ray powder diffraction, FT-IR and ⁵⁷Fe Mössbauer spectroscopies. On heating the starting mixture for 0.5 and 2 hours at 300 °C, magnetite and a small fraction of hematite were identified by XRD. With the heating time prolonged up to 24 hours, magnetite reoxidized and hematite was obtained again. The formation of magnetite was observed even at 580 °C. However, the magnetite formed at this temperature was substoichiometric, as shown by XRD and Mössbauer spectroscopy. Characteristic IR bands of oxide phases were monitored by FT-IR spectroscopy. Chemical reduction of hematite with starch into a Fe⁰ state was not observed in any sample.     

A new analytical method for 32P: Liquid scintillation counting with solvent extraction

⁵⁷Fe Mössbauer spectroscopy has been applied to the ultramafic rocks collected from the Jinchuan nickel deposit in China to elucidate their mineralization process. Their Mössbauer spectra consisted of two sextets ascribable to magnetite, two doublets ascribable to Fe²⁺ and Fe³⁺ in chromite, and one doublet ascribable to olivine. The closest sample to the ore body did not contain chromite and contained a doublet ascribable to pyrite and a sextet ascribable to pyrrhotite. The valence and site distribution of iron species suggested low oxygen fugacity for the formation of the Jinchuan nickel deposit.     

Mössbauer spectroscopic and X-ray diffraction study of the thermal decomposition of natural siderite and goethite

Thermal decomposition of natural siderite and goethite has been studied using Mössbauer spectroscopy and X-ray diffraction. Hematite and magnetite were the principal compounds formed during high temperature treatment of siderite. Natural goethite transformed to hematite at high temperatures. The crystal structures, stoichiometry and the nuclear magnetic properties of Fe-oxides formed are discussed.     

Iron speciation related to color of Jurassic sedimentary rocks in Turpan Basin, northwest China

Mesozoic-Cenozoic reddish and green beds are widely distributed in northwest China. Mössbauer spectroscopy revealed that the composition of iron species varies with color in the middle-upper Jurassic sedimentary rocks from the Turpan Basin. Three main kinds of iron species were identified: (1) ferric iron of hematite (hem-Fe³⁺), (2) paramagnetic ferric iron (para-Fe³⁺), and (3) paramagnetic ferrous iron (para-Fe²⁺). Pyrite iron (pyr-Fe²⁺) was revealed only in a few samples. In general, there is a direct correlation between rock color, iron species and total iron content, however, in detail, this relationship is more complicated. The reddish rocks contain higher contents of total iron and hem-Fe³⁺, whereas the gray rocks contain much more para-Fe²⁺. However, relatively low hematite content cannot give red color to rocks, probably due to suppression by other pigments such as organic matter in black or chlorite in green. The dark or green rocks normally contain either only paramagnetic Fe²⁺ and paramagnetic Fe³⁺ species or these two species associated with hematite Fe³⁺, but the relative content of hematite species is lower. The variations of different iron species control lithological properties such as color and also may reflect the sedimentary conditions. Moreover, iron speciation in these rocks is one of the main factors, which result the color features of rocks in remote sensing imagery.This revised version was published online in November 2005 with corrections to the Cover Date.     

Characterization of the precipitates formed during the denitration of simulated HRLW

The denitration of several chemical compositions of simulated HRLW (highly radioactive liquid waste) was performed using formic acid as reducing agent. Precipitates formed during the denitration of simulated HRLW were analyzed using X-ray diffraction and⁵⁷Fe Mössbauer spectroscopy. Goethite and amorphous fraction were the principal phases in these precipitates. It was found that the chemical composition of simulated HRLW and the experimental conditions of denitration have more influence on the crystallinity and the particle size than on the phase composition of the precipitates. Thermal treatment of denitrated precipitates caused the solid state transformation of goethite+amorphous fraction into hematite. The values of hyperfine magnetic field (HMF) of hematite were decreased, thus indicating the substitution of Fe³⁺ ions with other metal cations.     

Mössbauer study of iron reduction in hematite containing mineral originated from Aswan area in Egypt

Mössbauer spectroscopy was used to study iron reduction in mineral originated from Aswan area in Egypt. The Mössbauer spectra of samples heat treated at 1000 °C in hydrogen atmosphere show a gradually reduction process of hematite. The main phase of sample aged for 1 h is magnetite, while alpha-iron as well as some silicates and wustite type oxide can be detected in sample aged for 3 h. Further aging of sample results in dissolution of alloying elements /Si, Al/, being present in the samples. This process starts already in samples aged at 1000 °C for 4 h, but it is more expressive in minerals heat treated at 1200 °C or 1300 °C, when all paramagnetic phases disappeared.     

Characterization of silica supported Rh-Fe catalysts by Mössbauer technique

Silica supported Rh–Fe catalysts were characterized by means of in situ⁵⁷Fe Mössbauer spectroscopy. The Mössbauer spectra indicated that iron on the silica support existed either as Fe/O/ in the Rh–Fe alloy or as Fe³⁺ in Rh–Fe metal cluster compounds. The (Fe³⁺/Fe/O/) ratio and Mössbauer parameters were found to depend on the (Fe/Rh) atomic ratio in the catalysts. Such dependence corresponded to the change of catalytic properties of the supported Rh–Fe catalyst with the varying (Fe/Rh) ratio.     

57Fe Mössbauer spectroscopic characterisation of a ferromanganese nodule from the Central Indian Ocean

The iron bearing phases present in a ferromanganese nodule from the Central Indian Ocean have been determined using⁵⁷Fe Mössbauer spectroscopy. The Mössbauer results have been corroborated by XRD, IR and TG-DTA studies. The Mössbauer spectrum of a ferromanganese nodule shows a broad line width which indicates the presence of more than one iron bearing paramagnetic oxide or oxyhydroxide phases where iron is present as Fe³⁺. -FeOOH has been distinctly characterised as one of the iron bearing phases in the nodule. Other oxyhydroxide and oxide phases of iron in the nodule have been ruled out. A typical paramagnetic doublet persists even at very high temperature which has been proposed to be due to iron(III)phosphate. Formation of solid solution of Mn₂O₃–Fe₂O₃ has been observed in the heat treated nodule at 1073 K, which has been characterised by the Mössbauer technique.     

Mössbauer spectroscopy of some volcanic glasses from the Pampa Region,Córdoba,Argentina

Mössbauer spectroscopy has been applied to the study of volcanic glasses and closely associated clay minerals which were carefully separated from the sediments of the Pampe Region, Córdoba, Argentina. The parameters of volcanic glass samples show the presence of a high content of Fe²⁺ in octahedral coordination and some Fe³⁺ in tetrahedral and octahedral coordination. No remarkable difference has been found with a pure volcanic glass sample taken as a reference. In the clay samples, the only clay mineral found was illite.     

Mössbauer, vibrational spectroscopic and solution X-ray diffraction studies of the structure of iron(III) complexes formed with indole-3-alkanoic acids in acidic aqueous solutions

The chemical reactions between iron(III) and indole-3-acetic (IAA), -propionic (IPA), and -butyric (IBA) acids were studied in acidic aqueous solutions. The motivation of this work was that IAA is one of the most powerful natural plant-growth-regulating substances (phytohormones of the auxin series). Mössbauer spectra of the frozen aqueous solutions of iron(III) with indole-3-alkanoic acids as ligands (L), showed parallel reactions between Fe³⁺ and the ligands. Partly, it resulted in a complex formation which precipitated in aqueous solution and partly, in a redox process with iron(II) and the oxidised indole-3-alkanoic acids as products. The Mössbauer parameters of the Fe²⁺ species suggested a hexaaquo coordination environment. The chemical composition and coordination structure of the precipitated complexes were investigated using elemental analysis, Mössbauer spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopic techniques. The complexes were soluble in some organic solvents. So, Mössbauer, FTIR and solution X-ray diffraction measurements were carried out on the solution of complexes in acetone, hexadeutero acetone and methanol, respectively. The data obtained supported the existence of the μ-dihydroxo-bridging structure of the dimer: [L₂Fe<(OH)₂>FeL₂] (where L is indole-3-propionate, -acetate or -butyrate).     

Structural studies on some iron 8-oxi-quinolinates using Mössbauer spectroscopy

Using Mössbauer spectroscopy the quinolinates of iron/II/ and iron/III/ have been studied. In iron/II/ quinolinate three sublattices were evidenced, two of them being attributed to Fe²⁺ ions and the third to Fe³⁺ impurities. In the iron/III/ quinolinate five structural sublattices were found, two of them containing Fe³⁺ ions, the other two Fe²⁺ ions and the fifth may be attributed to the interstitial Fe³⁺ ions.     

57Fe- and119Sn-Mössbauer effect of oxide glasses

Coordination number of network-former (NWF) and formation of nonbridging oxygen (NBO) at the site neighboring to NWF can be estimated from Mössbauer measurements, since small amounts of Fe³⁺ and Sn⁴⁺ substitute NWF in several oxide glasses. Gamma-ray or thermal neutron irradiation of oxide glasses causes electron or charge transfer from oxygen to the Mössbauer ions, and the probability depends on the fraction of NBO. On the contrary, -ray irradiation of phosphate glasses results in oxidation of Fe²⁺ to Fe³⁺ since iron plays a role of network modifier (NWM) at interstitial sites. Debye temperature _D obtained from low-temperature Mössbauer measurements reflects the site occupation of Mössbauer ions in glasses. A linear relationship between glass transition temperature (T _g ) and quadrupole splitting () of Fe³⁺,T _g — rule, is also effective for determining the site occupation of Mössbauer ions.     

Characterization of Natural Chromite Samples from Ophiolite Complexes in the Philippines by 57Fe Mössbauer Spectroscopy

Mössbauer spectroscopy was applied to natural chromite samples from ophiolite complexes in the Philippines. Chemical and structural characterization of the chromite samples was also carried out using X-ray absorption fine structure (XAFS), X-ray diffraction (XRD) and X-ray fluorescence spectrometry (XRF). The Mössbauer spectra of the samples consisted of quadrupole doublets ascribable to Fe³⁺ in octahedral site, Fe³⁺ in tetrahedral site, and Fe²⁺ in tetrahedral site. The relative percentage of Fe³⁺ and Fe²⁺ ions suggested that these Philippine samples were formed under relatively high oxygen fugacity.     

151Eu and57Fe Mössbauer and X-ray diffraction study of high temperature Tl-containing superconductor

⁵⁷Fe and¹⁵¹Eu Mössbauer spectroscopy and X-ray diffractometry measurements were performed with europium and iron containing Tl₂(Ca_0.8Eu_0.2)Ba₂(Cu_0.98Fe_0.02)₂O₈ and EuBa₂Cu₃O_7-d high temperature superconductor samples in order to study the effect of europium incorporated in a Tl-containing high temperature superconductor. Significant differences have been found between the⁵⁷Fe Mössbauer spectra of Tl-containing samples with and without Eu or between the¹⁵¹Eu Mössbauer spectra of Tl-containing and 1-2-3 type superconductors. The results can be interpreted by assuming that Eu can be localized at the Ca site in the Tl-containing superconductor.     

Mösbauer chemical phase characterization of iron aerosols

⁵⁷Fe Mössbauer spectroscopy has been employed to characterize the chemical composition of iron aerosols collected from three distinct groups of sites representing remote, urban and industrially active areas. The Mössbauer spectra clearly show this environmental difference. The fact that the spectra of the samples collected from the remote areas are quite similar to those of clay minerals corroborates the view that iron aerosols are soil derived. Similarly the predominant presence of -Fe₂O₃ and Fe₃O₄ in the close vicinity of industrial activities suggests that the Mössbauer spectroscopy can help identify the anthropogenic processes against the natural ones.Work performed under the Punjab States Research Scheme NPC-5.     

Mössbauer Study of the Structure of Fe - Zircon System

Iron-doped silicate (zircon), prepared by a ceramic method with the addition of LiF as mineralizer, was analyzed by X-ray powder diffraction (XRD) and ⁵⁷Fe Mössbauer spectroscopy to obtain information on the solid solution formation. The results of X-ray diffraction and Mössbauer spectroscopy have shown that only a small fraction of iron, about 1.5 mol%, is incorporated in the zircon structure as paramagnetic Fe³⁺ species while the remaining Fe³⁺ cations form magnetic -Fe₂O₃ particles which are trapped within the zircon matrix.     

Radioactive waste treatment products studied by Mössbauer spectroscopy II. Iron hydroxide precipitation systems

Different iron hydroxide precipitation processes simulating radioactive waste, treatment have been investigated by Mössbauer spectroscopy at room temperature and at 80 K. Magnetic oxides (hematite or magnetite) partially affected by superparamagnetic relaxation have been observed. The crystallization degree and the particle size depend on the concentration and the addition order of chemicals. Much smaller particles were precipitated with Ca(OH)₂ than with NaOH as neutralization reagent.