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.     

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.     

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.     

The Panafrican Stratoid Granites of Madagascar: Alkaline Magmatism in a Post-Collisional Extensional Setting

A major alkali province of late Panafrican age occupies centralMadagascar and takes the form of a thick sequence of ‘stratoid’(sheet-like)granites emplaced in a mid-crustal gneissic basement This alkalinemagmatism has been interpreted as a consequence of extensionaltectonics accompanying the collapse of the Mozambique belt.The rocks belong to three petrographic types: subsolvus granites,hypersolvus alkaline granites and syenites. Major and traceelement analyses have typical A-type characteristics. Two distinctmagmatic suites are recognized: a mildly alkaline suite includingall the subsolvus granites and a strongly alkaline suite includingthe hypersolvus alkaline granites and the syenites. We proposethat the mildly alkaline suite was derived from a granodioriticcrustal protolith. Some of the strongly alkaline granites andthe quartz syenites display low ¹⁸O isotopic signatures of around+6.The parental magmas for this suite are most probably of mantlederivation. The more evolved compositions are consistent withcrystal fractionation processes. Contemporaneous alkaline silicicplutonismoccurs in many parts of the Panafrican belt of Eastern Africa;however, sheet-like intrusions have rarely been described. Asa large-scale province, the nearest analogues of the stratoidgranites of Madagascar are the rapakivi granites of earlierProterozoic age in Scandinavia and Greenland. KEY WORDS: alkaline granite; Madagascar; Panafrican; pastcollisional magmatism ^*Corresponding author     

Episode 49 of the Pu'u 'O'o-Kupaianaha eruption of Kilauea volcano-breakdown of a steady-state eruptive era

The Pu'u 'O'o-Kupaianaha eruption (1983-present) is the longest lived rift eruption of either Kilauea or neighboring Mauna Loa in recorded history. The initial fissure opening in January 1983 was followed by three years of episodic fire fountaining at the Pu'u 'O'o vent on Kilauea's east rift zone 19km from the summit (episodes 4–47). These spectacular events gave way in July 1986 to five and a half years of nearcontinuous, low-level effusion from the Kupaianaha vent, 3km to the cast (episode 48). A 49th episode began in November 1991 with the opening of a new fissure between Pu'u 'O'o and Kupaianaha. this three week long outburst heralded an era of more erratic eruptive behavior characterized by the shut down of Kupaianaha in February 1992 and subsequent intermittent eruption from vents on the west flank of Pu'u 'O'o (episodes 50 and 51). The events occurring over this period are due to progressive shrinkage of the rift-zone reservoir beneath the eruption site, and had limited impact on eruption temperatures and lava composition.     

A search for ultra-high energy counterparts to gamma-ray bursts

A small air shower array operating over many years has been used to search for ultra-high energy (UHE) gamma radiation ( 50 TeV) associated with gamma-ray bursts (GRBs) detected by the BATSE instrument on the Compton Gamma-Ray Observatory (CGRO). Upper limits for a one minute interval after each burst are presented for seven GRBs located with zenith angles < 20°. A 4.3 excess over background was observed between 10 and 20 minutes following the onset of a GRB on 11 May 1991. The confidence level that this is due to a real effect and not a background fluctuation is 99.8%. If this effect is real then cosmological models are excluded for this burst because of absorption of UHE gamma rays by the intergalactic radiation fields.     

Analysis of COMPTEL gamma-ray burst locations and spectra

In its first three years of operation, the COMPTEL instrument on theCompton Gamma-Ray Observatory has measured the locations (mean accuracy 1°) and spectra (0.75-30 MeV) of 18 gamma-ray bursts and continues to observe new events at a rate of 1/month. With good angular resolution and sensitivity at MeV energies, the growing COMPTEL burst catalog is an important new piece of evidence in the on-going GRB mystery. The COMPTEL burst locations are consistent with an isotropic distribution of sources, yet the spatial coincidence of two of the bursts indicates the possibility of repetition. The COMPTEL burst spectra are in most cases consistent with a single power law model with spectral index in the range 2–3. However, two bursts show evidence of a spectral break in the MeV range. Measurement of rapid variability at MeV energies in the stronger bursts provides evidence that either the sources are nearby (within the Galaxy) or the gamma-ray emission is relativistically beamed. We present an overview of analysis results obtained from the COMPTEL burst catalog concentrating on the search for burst repetition and the implications of highly variable MeV emission.     

Search for low energyν e,μ,τ andv e,μ,τ in coincidence with BATSE gamma ray bursts

A search for low energy neutrinos of all flavours in correlation with 553 ray bursts detected by BATSE aboard the Compton Observatory has been performed by the LSD (Liquid Scintillator Detector) neutrino telescope. No excess ofe,, orv _e,, candidate has been detected by LSD during the time interval in which BATSE detected the 90% of the photon flux for any of the GRBs analyzed. Upper limits on the neutrino fluxes are given in the paper.     

Magnetically-aided evolution of protoplanetary disks

We investigate the global evolution of a turbulent protoplanetary disk incorporating the effects of Maxwell stress due to a large-scale magnetic field permeating the disk. A magnetic field is produced continuously by an dynamo and the resultant Maxwell stress assists the viscous stress in p roviding the means for disk evolution. The most striking feature of magnetized disk evolution is the presence of the surface density bulge located in the magnetic gap, the region of the disk where the degree of ionization is too low to allow for coupli ng between the magnetic field and the gas. The bulge persists for a time of the order of 10⁵–10⁶ yr. The presence and persistence of the surface density bulge may have important implications for the process of planet formation and the overall characteristics of resultant planetary systems.Operated by USRA under contract No. NASW-4574 with NASA.     

New kinematic distances of NGC 7009 and BD+30°3639 from UV and radio data

Measurements of the equivalent width of the interstellar Lyman line from IUE spectra in the direction of the planetary nebulae NGC 7009 and BD+30°3639 are used to infer the H column density in these directions. Hydrogen 21 cm profiles are also used in connection with the ultraviolet data so that the expected rotation velocities and distances can be determined. The results are compared with recently published distances, in an attempt to distinguish between the short and long PN distance scales as applied to these objects.