Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3)

 Premelting effects in gehlenite (Ca₂Al₂SiO₇) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO₃) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol⁻¹ and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.     

A method to predict the group fissuring and faulting caused by regional groundwater decline

Ground fissuring is a recurrent problem in many countries where water extraction surpasses the natural recharge of aquifers. Due to differential settlement, the soil layer undergoes deformation and cracks with serious consequences for civil infrastructure. Here, we propose an approximate analysis of the fissuring process that can be used to predict the location of cracks, which increasingly affect some middle- and large-sized cities in the world. For that purpose, the ground loss theory is applied to sediments overlying a sinusoidal-shaped graben. This analysis shows the existence of a tensile zone at the border of the graben with maximal values on its shoulder where tension cracks are more likely to appear. It also shows that soil deformation under differential settlement may evolve into ground faulting if water withdrawal continues. Finally, when a crack has completely developed, the tensile zone shifts towards the center of the graben, creating a new area for potential cracking and faulting.     

Intercomparison of IRS-P4-MSMR derived geophysical products with DMSP-SSM/I and TRMM-TMI finished products

In this paper, MSMR geophysical products like Integrated Water Vapour (IWV), Ocean Surface Wind Speed (OWS) and Cloud Liquid Water (CLW) in different grids of 50, 75 and 150 kms are compared with similar products available from other satellites like DMSP-SSM/I and TRMMTMI. MSMR derived IWV, OWS and CLW compare well with SSM/I and TMI finished products. Comparison of MSMR derived CLW with that derived from TMI and SSM/I is relatively in less agreement. This is possibly due to the use of 37 GHz in SSM/I and TMI that is highly sensitive to CLW, while 37 GHz channels are not available on MSMR. Monthly comparison of MSMR geophysical products with those from TMI is all carried out for climatological purpose. The monthly comparisons were much better compared to instantaneous comparisons. In this paper, details of the data analysis and comparison results are presented. The usefulness of the MSMR vis-à-vis other sensors is also discussed.     

The effect of acoustic waves on spectral-line profiles in the solar atmosphere: Observations and theory

The fine structure of the FeI λ 532.4185-nm line of neutral iron is studied with high spatial (0.5″) and temporal (9.3 s) resolution using observations of a quiet region at the center of the solar disk. The character of the line asymmetry depends strongly on the nature of the velocity field, i.e., on whether it is due to convective or wave motions. The magnitude of the asymmetry due to acoustic waves is comparable to that due to convective motions. The propagation of acoustic waves in moving granules and intergranular lanes is studied by solving a system of hydrodynamical equations in a three-dimensional model for the solar atmosphere. The temporal variations in the bisector of the line synthesized in a non-LTE approximation agree well with the observational data.     

The possible formation of massive tori in white-dwarf binary systems

Mass exchange in white-dwarf binary systems with mass ratios 0.35–0.55 and total masses exceeding the Chandrasekhar limit could lead to the disruption of the less massive component of the system and the formation of a torus around the more massive component.     

ENSO impacts on salinity in Tampa Bay, Florida

Estuarine salinity distributions reflect a dynamic balance between the processes that control estuarine circulation. At seasonal and longer time scales, freshwater inputs into estuaries represent the primary control on salinity distribution and estuarine circulation. El Niño-Southern Oscillation (ENSO) conditions influence seasonal rainfall and stream discharge patterns in the Tampa Bay, Florida region. The resulting variability in freshwater input to Tampa Bay influences its seasonal salinity distribution. During El Niño events, ENSO sea surface temperature anomalies (SSTAs) are significantly and inversely correlated with salinity in the bay during winter and spring. These patterns reflect the elevated rainfall over the drainage basin and the resulting elevated stream discharge and runoff, which depress salinity levels. Spatially, the correlations are strongest at the head of the bay, especially in bay sections with long residence times. During La Niña conditions, significant inverse correlations between ENSO SSTAs and salinity occur during spring. Dry conditions and depressed stream discharge characterize La Niña winters and springs, and the higher salinity levels during La Niña springs reflect the lower freshwater input levels.     

Rare gas isotopes and parent trace elements in ultrabasic-alkaline-carbonatite complexes, Kola Peninsula: identification of lower mantle plume component

During the Devonian magmatism (370 Ma ago) ∼20 ultrabasic-alkaline-carbonatite complexes (UACC) were formed in the Kola Peninsula (north-east of the Baltic Shield). In order to understand mantle and crust sources and processes having set these complexes, rare gases were studied in ∼300 rocks and mineral separates from 9 UACC, and concentrations of parent Li, K, U, and Th were measured in ∼70 samples. ⁴He/³He ratios in He released by fusion vary from pure radiogenic values ∼10⁸ down to 6 × 10⁴. The cosmogenic and extraterrestrial sources as well as the radiogenic production are unable to account for the extremely high abundances of ³He, up to 4 × 10⁻⁹ cc/g, indicating a mantle-derived fluid in the Kola rocks. In some samples helium extracted by crushing shows quite low ⁴He/³He = 3 × 10⁴, well below the mean ratio in mid ocean ridge basalts (MORB), (8.9 ± 1.0) × 10⁴, indicating the contribution of ³He-rich plume component. Magnetites are principal carriers of this component. Trapped ³He is extracted from these minerals at high temperatures 1100°C to 1600°C which may correspond to decrepitation or annealing primary fluid inclusions, whereas radiogenic ⁴He is manly released at a temperature range of 500°C to 1200°C, probably corresponding to activation of ⁴He sites degraded by U, Th decay.Similar ⁴He/³He ratios were observed in Oligocene flood basalts from the Ethiopian plume. According to a paleo-plate-tectonic reconstruction, 450 Ma ago the Baltica (including the Kola Peninsula) continent drifted not far from the present-day site of that plume. It appears that both magmatic provinces could relate to one and the same deep-seated mantle source.The neon isotopic compositions confirm the occurrence of a plume component since, within a conventional ²⁰Ne/²²Ne versus ²¹Ne/²²Ne diagram, the regression line for Kola samples is indistinguishable from those typical of plumes, such as Loihi (Hawaii). ²⁰Ne/²²Ne ratios (up to 12.1) correlate well with ⁴⁰Ar/³⁶Ar ones, allowing to infer a source ⁴⁰Ar/³⁶Ar ratio of about 4000 for the mantle end-member, which is 10 times lower than that of the MORB source end-member. In (³He/²²Ne)_PRIM versus (⁴He/²¹Ne)_RAD plot the Kola samples are within array established for plume and MORB samples; almost constant production ratio of (⁴He/²¹Ne)_RAD ≅ 2 × 10⁷ is translated via this array into (³He/²²Ne)_PRIM ∼ 10. The latter value approaches the solar ratio implying the non-fractionated solar-like rare gas pattern in a plume source.The Kola UACC show systematic variations in the respective contributions of in situ-produced radiogenic isotopes and mantle-derived isotopes. Since these complexes were essentially plutonic, we propose that the depth of emplacement exerted a primary control on the retention of both trapped and radiogenic species, which is consistent with geological observations. The available data allow to infer the following sequence of processes for the emplacement and evolution of Kola Devonian UACC: 1) Ascent of the plume from the lower mantle to the subcontinental lithosphere; the plume triggered mantle metasomatism not later than ∼700 to 400 Ma ago. 2) Metasomatism of the lithosphere (beneath the central part of the Kola Peninsula), including enrichment in volatile (e.g., He, Ne) and in incompatible (e.g., U, Th) elements. 3) Multistage intrusions of parental melts, their degassing, and crystallisation differentiation ∼370 Ma ago. 4) Postcrystallisation migration of fluids, including loss of radiogenic and of trapped helium. Based on model compositions of the principle terrestrial reservoirs we estimate the contributions (by mass) of the plume material, the upper mantle material, and the atmosphere (air-saturated groundwater), into the source of parent melt at ∼2%, 97.95%, and ∼0.05%, respectively.     

Direct observations of aluminosilicate weathering in the hyporheic zone of an Antarctic Dry Valley stream

This study focused on chemical weathering and bacterial ecology in the hyporheic zone of Green Creek, a McMurdo Dry Valley (Antarctica) stream. An in situ microcosm approach was used to observe dissolution features on the basal-plane surface of muscovite mica. Four mica chips were buried in December 1999 and dug up 39 d later. Atomic force microscopy (AFM) of the basal-plane surfaces revealed small, anhedral ∼10-Å-deep etch pits covering ∼4% of the surfaces, from which an approximate basal-plane dissolution rate of 8.3 × 10⁻¹⁸ mol muscovite cm⁻² s⁻¹ was calculated (on the basis of the geometric surface area) for the study period. This is an integrated initial dissolution rate on a fresh surface exposed for a relatively brief period over the austral summer and should not be compared directly to other long-term field rates. The observation of weathering features on mica agrees with previous stream- and watershed-scale studies in the Dry Valleys, which have demonstrated that weathering occurs where liquid water is present, despite the cold temperatures.AFM imaging of mica surfaces revealed biofilms including numerous small (<1 μm long), rounded, oblong bacteria. The AFM observations agreed well with X-ray photoelectron microscopy results showing increased organic C and N. Bacteriologic analysis of the hyporheic zone sediments also revealed <1-μm-long bacteria. α-Proteobacteria were observed, consistent with the oligotrophic conditions of the hyporheic zone. Nitrate-reducing bacteria were found, in agreement with a previous tracer test at Green Creek that suggested nitrate reduction occurs in the hyporheic zone. The results of this study thus provide direct evidence of dynamic geochemical and microbial processes in the hyporheic zone of a Dry Valley stream despite the extreme conditions; such processes were inferred previously from stream-scale hydrogeochemical studies.