A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.     

Radiometric constraints on hydrothermal circulation in cooling granite plutons

Improved precision of radiometric dating of ore deposits can provide information about the thermal history of hydrothermal circulation in cooling plutons. In Jales a Hercynian porphyritic two-mica granite and pre-Ordovician mica schists are cut and intensely altered by the Campo gold-quartz vein. The unaltered granite must be younger than 320 ± 6 Ma, and gives mica Rb-Sr ages of 308.5 ± 2.4 (1) Ma (muscovite) and 294.5 ± 1.1 Ma (biotite). Alteration muscovites from the granite give a weighted mean Rb-Sr age of 308.1 ± 1.5 Ma, and a mean ³⁹Ar-⁴⁰Ar age of 300.7 ± 2.8 Ma. Alteration muscovites from the mica schists give similar ³⁹Ar-⁴⁰Ar ages, averaging 303.0 ± 2.8 Ma. The results suggest that circulation of the Campo mineralising fluids took place no more than 2–4 Ma after the granite cooled through the muscovite Rb-Sr closure temperature, about 500 °C, and that subsequent cooling to biotite closure at about 300 °C took place at less than 14°C/Ma. The mean cooling rate following emplacement was 15 to 25 °C/Ma. The most detailed comparable published data, for the Cornubian ore field, imply much faster cooling rates.     

Powder- and single crystal Mössbauer spectroscopy on synthetic fayalite

Mössbauer measurements on synthetic iron orthosilicate Fe₂SiO₄ (fayalite) were carried out in the antiferromagnetic spin state below T _N 65 K. The Mössbauer parameters isomer shift , inner magnetic field H(0), angle between H(0) and the z-component of the electric field gradient (efg), quadrupole splitting QS and asymmetry parameter were determined as a function of temperature. These parameters could be attributed to the two crystallographic sites M1 and M2.The smaller isomer shift on M1 with respect to M2 displays the more covalent character of the Fe-O bond on M1, which is supported by previous neutron diffraction experiments. H(0) shows a Brillouin-type behaviour with different fields on the two crystallographic sites (stronger on M1) and a small discontinuity at T = 23 K which corresponds with previous magnetic measurements. The quadrupole splitting is equal on both sites within error bars, in agreement with previous theoretical results and in contradiction to previous Mössbauer refinements published elsewhere.     

Mineralogical and geochemical compositions of modern bivalve shells from the Mediterranean coast of Egypt

The stable isotopic composition (¹³C and ¹⁸O) and elemental (Sr and Mg) of marine molluscs are presented for Carditacea and Solenacea shells collected off the Mediterranean coast of Egypt. Based on shell microstructures and mineralogy, the bivalve shells are preserved in their original mineralogy and chemistry.The Sr and Mg concentrations of the bivalve shells have mean values of 1960 ppm and 226 ppm respectively. The stable isotopic composition generally show high values of ¹⁸O and ¹³C. The ¹⁸O values range from +0.1 to –1.8 PDB and most shells are highly enriched in¹³C; averaging +2.5 PDB. These elemental and isotopic signatures are analogous to modern marine bivalves from other localities.The oxygen and carbon isotopes, together with the calculated temperatures, suggest that the aragonitic bivalve shells were precipitated in isotopic equilibrium from warm marine waters.     

Diagenesis of vascular plant organic matter components during burial in lake sediments

Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither ¹³C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.     

The age of the Kagenfels granite (northern Vosges) and its bearing on the intrusion scheme of late Variscan granitoids

In the Saxothuringian part of the Vosges (France), a first series of Variscan plutonic rocks (diorites to granites) has been intruded by several younger granites. Rocks of both the older generations have been cross-cut by the late orogenic Kagenfels granite. The averages of the hitherto published mineral ages of the earlier rock generations are 331 and 334 Ma, respectively, whereas Rb-Sr and K-Ar dates around 290 Ma have been reported for the Kagenfels granite. Because of the unlikely large age hiatus, a redetermination of the intrusion age of the Kagenfels granite formation appeared to be irrevocable. The newly obtained mineral ages on the Kagenfels granite (K-Ar and ⁴⁰Ar/³⁹Ar biotite ages as well as single zircon radiogenic ²⁰⁷Pb/²⁰⁶Pb data: 331 ± 5 Ma) are about 40 Ma older than the previous results. They are interpreted as giving the time of emplacement of the Kagenfels granite during the latest Visan. The mineral ages of the earlier plutonic rocks in this part of the Variscan Orogeny in all probability are not significantly different from their ages of intrusion. Therefore the age concordance of all three granitoid generations constrains a rather narrow time interval of orogenic magmatism close to the Lower-Upper Carboniferous boundary.     

Solar structure in terms of Gauss' hypergeometric function

Hydrostatic equilibrium and energy conservation determine the conditions in the gravitationally stabilized solar fusion reactor. We assume a matter density distribution varying non-linearly through the central region of the Sun. The analytic solutions of the differential equations of mass conservation, hydrostatic equilibrium, and energy conservation, together with the equation of state of the perfect gas and a nuclear energy generation rate = ₀ ⁿ T ⁿT ^m ,are given in terms of Gauss' hypergeometric function. This model for the structure of the Sun gives the run of density, mass, pressure, temperature, and nuclear energy generation through the central region of the Sun. Because of the assumption of a matter density distribution, the conditions of hydrostatic equilibrium and energy conservation are separated from the mode of energy transport in the Sun.     

TheROSAT survey of extreme UV sources: a new window on the universe

This paper discusses the first all-sky suvey of cosmic extreme ultra-violet sources, discovered by theROSAT Wide Field Camera. Details of the instrument and the survey are presented, with comparisons made to previous selected surveys in the X-ray regime. The subsequent optical identification program is described, and the major results summarized. I then discuss the main classes of EUV emitters: active chromosphere stars and hot white dwarfs, and describe the importance of EUV obserevations in understanding the astrophysics of these objects. Many bright, and relatively nearby, sources have been identified with hitherto unrecognized active stars, representing the extremes in chromospheric and coronal activity, be it binary or age related. Many new hot DA white dwarfs have also been indentified, and the most exciting result in this area is the discovery that significant traces of heavier elements (e.g. C, N, O, Si, Fe & Al) exist in their atmospheres, substantially increasing their EUV opacities. The importance of hot white dwarfs as standard candles in probing the local interstellar medium is also discussed. Miscellaneous counterparts (AGN, PNN, O-B stars and CVs) that make up the rest of the sample of EUV sources are also briefly mentioned. I conclude the paper with a discussion of the new magnetic cataclysmic variables discovered at SAAO, which have been the subject of intensive follow-up observations.     

Interferometric observations of HCN and CN towards carbon stars

Using the IRAM interferometer we have observed four carbon stars (U Cam, CIT6, Y CVn, IRC+40540) in the HCN(J=1 0) and CN(N=1 0) lines. Here we present some results for CIT6 and U Cam.