Iron oxidation state in the Fe‐rich layer and silica matrix of Libyan Desert Glass: A high‐resolution XANES study

Abstract— Libyan Desert Glass (LDG) is an enigmatic type of glass that occurs in western Egypt in the Libyan Desert. Fairly convincing evidence exists to show that it formed by impact, although the source crater is currently unknown. Some rare samples present dark‐colored streaks with variable amounts of Fe, and they are supposed to contain a meteoritic component. We have studied the iron local environment in an LDG sample by means of Fe K‐edge highresolution X‐ray absorption near edge structure (XANES) spectroscopy to obtain quantitative data on the Fe oxidation state and coordination number in both the Fe‐poor matrix and Fe‐rich layers. The pre‐edge peak of the high‐resolution XANES spectra of the sample studied displays small but reproducible variations between Fe‐poor matrix and Fe‐rich layers, which is indicative of significant changes in the Fe oxidation state and coordination number. Comparison with previously obtained data for a very low‐Fe sample shows that, while iron is virtually all trivalent and in tetrahedral coordination (^[4]Fe³⁺) in the low‐Fe sample, the sample containing the Fe‐rich layers display a mixture of tetra‐coordinated trivalent iron (^[4]Fe³⁺) and penta‐coordinated divalent iron (^[5]Fe²⁺), with the Fe in the Fe‐rich layer being more reduced than the matrix. From these data, we conclude the following: a) the significant differences in the Fe oxidation state between LDG and tektites, together with the wide intra‐sample variations in the Fe‐oxidation state, confirm that LDG is an impact glass and not a tektite‐like glass; b) the higher Fe content, coupled with the more reduced state of the Fe, in the Fe‐rich layers suggests that some or most of the Fe in these layers may be directly derived from the meteoritic projectile and that it is not of terrestrial origin.     

Vertical distribution of dust particles in the Earth's atmosphere during the 1998 Leonids

Abstract— Photometric observations of the twilight sky were carried out during Leonids 1998. The obtained vertical distributions of aerosol between 20 and 140 km demonstrate the processes of the intrusion of fine meteor dust and its subsequent intra-atmospheric dynamics. The characteristic radii of two fractions of the meteor dust particles were estimated by their sedimentation velocities. They varied within r_p = 0.006–0.06 μm and r_p = 19–81 μm limits depending on an assumed particle density within ρ_p = 0.4–4.0 g cm^?3. The assumption of ρ_p = 2.0 g cm^?3 gave radii of the two fractions to be 0.01 and 30 μm, respectively.     

Simulation and modeling of rainfall radar measurements for hydrological applications

A procedure is described for the simulation of rainfall radar reflectivity (absolute and differential) measurements by dual linear polarization meteorological radars. The basic requirement that the proposed procedure aims at satisfying is that radar data obtained at the end of the process be correlated in a physically plausible manner to the rainfall field at ground, the latter being generated by means of a stochastic space-time rainfall model. The main goal of the model is to give the possibility to easily check the accuracy of radar rainfall estimates derived by means of procedures and algorithms aimed at minimizing or compensating for the effects of measurement errors associated with several types of meteorological events, with particular reference to requirements of hydrogeological forecast systems. Within the limits imposed by the validity of the adopted model, an analysis was carried out indicating general criteria that may be adopted to achieve a better accuracy in rainfall estimates and a full exploitation of the advantages offered by the radar dual polarization measurement technique.     

The local structure of Ca-Na pyroxenes. II. XANES studies at the Mg and Al K edges

X-ray absorption spectra at the Mg and Al K edges have been recorded using synchrotron radiation on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c end members and intermediate members of the solid solution series (C-omphacites) are different from those of the intermediate members having P2/n symmetry (P-omphacites). Differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra calculated via the full multiple-scattering formalism, starting from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. Atomic clusters with at least 89 atoms, extending to more than 0.60 nm away from the Mg or Al absorbers, are needed to reproduce the experimental spectra. This shows that in the clinopyroxene systems XANES detects medium- rather than short-range order-disorder relationships. Theoretical spectra match the experimental ones well for all features in the regions from 16 to 60 eV above threshold. Experimental near-edge features in the first 16 eV are also reproduced, albeit less accurately. Certain near-edge features of C-omphacites reflect the octahedral arrangement of the back-scattering six O atoms nearest neighbours of the probed atom (Mg or Al) located at site M1 of the crystal structure, thus being indicators of short-range order. Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased complexity of the structure and the greater local disorder around the probed atom induced by the two alternative M1, M11 configurations of the six O atoms forming the first coordination shells. Mg and Al are confirmed to be preferentially partitioned in the M1 and M11 site of the P-omphacite crystal structure, however with a certain degree of local disorder. The relative heights of certain prominent features are directly related to sample composition in terms of Di:Jd ratio in the Al K-edge spectra, whereas they show abrupt variations in the Mg K-edge spectra. They demonstrate that XANES is directly related to composition and may be used to distinguish C- from P-omphacites. Received: 24 November 1998 / Revised, accepted: 10 June 1999     

Iron local structure in tektites and impact glasses by extended X-ray absorption fine structure and high-resolution X-ray absorption near-edge structure spectroscopy

The local structure of iron in three tektites has been studied by means of Fe K-edge extended X-ray absorption fine structure (EXAFS) and high-resolution X-ray absorption near-edge structure (XANES) spectroscopy in order to provide quantitative data on <Fe-O> distance and Fe coordination number. The samples studied are a moldavite and two australasian tektites. Fe model compounds with known Fe oxidation state and coordination number were used as standards in order to extract structural information from the XANES pre-edge peak. EXAFS-derived grand mean <Fe-O> distances and Fe coordination numbers for the three tektite samples are constant within the estimated error (<Fe-O > =2.00 Å ± 0.02 Å, CN = 4.0 ± 0.4). In contrast to other data from the literature on Fe-bearing silicate glasses, the tektites spectra could not be fitted with a single Fe-O distance, but rather were fit with two independent distances (2 × 1.92 Å and 2 × 2.08 Å). High-resolution XANES spectra of the three tektites display a pre-edge peak whose intensity is intermediate between those of staurolite and grandidierite, thus suggesting a mean coordination number intermediate between 4 and 5. Combining the EXAFS and XANES data for Fe, we infer the mean coordination number to be close to 4.5.Comparison of the tektites XANES spectra with those of a suite of different impact glasses clearly shows that tektites display a relatively narrow range of Fe oxidation state and coordination numbers, whereas impact glasses data span a much wider range of Fe oxidation states (from divalent to trivalent) and coordination numbers (from tetra-coordinated to esa-coordinated). These data suggest that the tektite production process is very similar for all the known strewn fields, whereas impact glasses can experience a wide variety of different temperature-pressure-oxygen fugacity conditions, leading to different Fe local structure in the resulting glasses. These data could be of aid in discriminating between tektite-like impact glasses and impact glasses sensu strictu.     

Analysis of radar and raingauge measurements for a critical meteorological event in Tuscany

In this paper, some considerations are given to the employment of C-band polarimetric weather radars for rainfall estimates. The most common error sources are discussed, such as ground clutter and propagation attenuation effects, together with decorrelation in the sampling at the ground between radar and raingauge measurements, which can be quite significant in radar systems located in hilly regions, as is the case of the Arno basin in Tuscany. Since the main objective from a hydrological point of view is the estimate of rainfall at ground, integrations and comparisons are needed between radar and raingauge data, which are characterized by different time and space sampling. The paper is then focussed mainly on this problem and a technique is presented in order to improve radar based rainfall estimates through the integration with raingauge data, in order to enhance the correlation between the two types of measurements. Such a method is finally applied to a serious meteorological event which affected the Arno basin on October 1992.     

Iron oxidation state in impact glass from the K/T boundary at Beloc,Haiti, by high‐resolution XANES spectroscopy

Abstract— We examined the local iron environment in nine impact glasses from the Cretaceous‐Tertiary (K/T) boundary section at Beloc, Haiti, which formed as the result of impact melting during the Chicxulub impact event. The samples have been analyzed by Fe K‐edge high‐resolution X‐ray absorption near edge structure (XANES) spectroscopy to obtain data on both the Fe oxidation state and the coordination number. The pre‐edge peak of our high‐resolution XANES spectra display noticeable variations indicative of significant changes in the Fe oxidation state spanning a wide range from about 20 to 75 mol% trivalent Fe. All data plot along the same trend, falling between two mixing lines joining a point calculated as the mean of a group of tektites studied so far (consisting of four‐ and five‐coordinated Fe²⁺) to ^[4]Fe³⁺ and ^[5]Fe³⁺, respectively. Thus, the XANES spectra can be interpreted as a mixture of ^[4]Fe²⁺, ^[5]Fe²⁺, ^[4]Fe³⁺, and ^[5]Fe³⁺. There is no evidence for six‐fold coordinated Fe; however, its presence in small amounts cannot be excluded from XANES data alone. Our observations can be explained by two possible scenarios: either these impact glasses formed under very reducing conditions and, because of their small size, were easily oxidized in air while still molten, or they formed under a variety of different oxygen fugacities resulting in different Fe oxidation states. In the first case, the oxidation state and coordination number would imply similar formation conditions as splash‐form tektites, followed by progressive oxidation.     

Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state

The Fe oxidation state and coordination number of 29 impact glass spherules recently recovered from the Transantarctic Mountains (Antarctica) have been determined by X‐ray absorption near edge structure (XANES) spectroscopy. Based on geochemical, isotopic, and fission track data, these spherules are considered as microtektites from the Australasian tektite/microtektite strewn field. Their find location is the farthest so far discovered from the possible source crater region, and their alkali content is the lowest compared with other published data on Australasian microtektite glasses. The Fe³⁺/(Fe²⁺+Fe³⁺) ratio, determined from the analysis of the pre‐edge peak energy position and integrated intensity, is below 0.1 (±0.04) for all the samples, and is comparable to that of most tektites and microtektites from the Australasian strewn field. Also, the pre‐edge peak integrated intensity, which is sensitive to the average Fe coordination geometry, is comparable to that of other Australasian microtektites reported in the literature. The agreement of the Fe oxidation state and coordination number, between the Transantarctic Mountain microtektites (TAM) and the Australasian tektites and microtektites, further confirms the impact origin of these glass spherules and provides an independent suggestion that they represent a major extension southeastward of the Australasian strewn field. The fact that similar redox conditions are observed in tektites and microtektites within the Australasian strewn field regardless of the distance from the source crater area (up to approximately 11000 km) could be an important constraint for better understanding the different processes affecting microtektite formation and transport. The fact that the Fe oxidation state of microtektites does not increase with distance, as in the case of North American microtektites, means that thermal and redox histories of Australasian and TAM microtektites could differ significantly from those of North American microtektites.     

Keck infrared observations of Saturn's main rings bracketing Earth's August 1995 ring plane crossing

We present results of near-infrared (2.26 μm) observations of Saturn's main rings taken with the W.M. Keck telescope during August 8-11, 1995, surrounding the time that Earth crossed Saturn's ring plane. These observations provide a unique opportunity to study the evolution of the ring brightness in detail, and by combining our data with Hubble Space Telescope (HST) results (Nicholson et al., 1996, Science 272, 453-616), we extend the 12-hour HST time span to several days around the time of ring plane crossing (RPX). In this paper, we focus on the temporal evolution of the brightness in Saturn's main rings. We examine both edge-on ring profiles and radial profiles obtained by “onion-peeling” the edge-on data. Before RPX, when the dark (unlit) face of the rings was observed, the inner C ring (including the Colombo gap), the Maxwell gap, Cassini Division and F ring region were very bright in transmitted light. After RPX, the main rings brighten rapidly, as expected. The profiles show east-west asymmetries both before and after RPX. Prior to RPX, the evolution in ring brightness of the Keck and HST data match one another quite well. The west side of the rings showed a nonlinear variation in brightness during the last hours before ring plane crossing, suggestive of clumping and longitudinal asymmetries in the F ring. Immediately after RPX, the east side of the rings brightened more rapidly than the west. A quantitative comparison of the Keck and HST data reveals that the rings were redder before RPX than after; we ascribe this difference to the enhanced multiple scattering of photons passing through to the unlit side of the rings.