The bonding of ferrous iron to sulfur and oxygen in tetrahedral coordination: A comparative study using SCF Xα scattered wave molecular orbital calculations

Molecular quantum mechanical calculations have been performed on high-spin ferrous iron tetrahedrally coordinated to sulfur and oxygen, respectively. The molecular orbital energies obtained from the calculations are compared with experimental optical and X-ray emission spectra. Good agreement was found between calculated and experimental spectral transition energies for the optical absorption spectra of Fe²⁺ in sphalerite, of Fe²⁺ in FeAl₂O₄, staurolite and (Zn, Fe)O, and for the FeKβ X-ray emission spectra of FeCr₂O₄. This both clarified interpretation of the spectra and established the validity of the calculations. Distinct differences occur in the molecular orbital structures of the sulfide and oxide clusters. In the sulfide, the crystal field type (mainly Fe 3d) molecular orbitals lie within the nonbonding (mainly S 3p) orbitais in energy, whereas in the oxide, they lie well above the 02p nonbonding orbitals. This also results in a wider valence band in the oxide than in the sulfide. The crystal field type (Fe 3d) molecular orbitais have more ligand character in the sulfide than the oxide and the chalcophilic properties of iron are partly attributed to this observation.     

Direct luminescence chronology of the Epipaleolithic Kebaran site of Nahal Hadera V,Israel

We report direct luminescence ages for the culture‐bearing sediments of the Kebaran site of Nahal Hadera V (NHV) in the coastal plain of Israel. Although the site contains, in addition to rich lithic deposits, plentiful mammalian bone, it has proved to be undatable using radiocarbon dating, in spite of the fact that the cultural context places the time of occupation well within the range of radiocarbon dating. In contrast, luminescence dating of the site sediments proved successful. Luminescence ages were determined using the single aliquot additive‐dose (SAA) method, applied to sand‐sized quartz extracts to determine past equivalent doses (D_e). Dose rates (R) were calculated using thick source alpha counting for the uranium (U) and thorium (Th) concentrations and x‐ray fluorescence analysis for the potassium (K₂0) concentration. Of the five samples collected at the site, four represent cultural and subcultural deposits and the fifth represents the geological substrate for the archaeological deposit, a quartz‐rich, carbonate‐cemented dune sand known as aeolianite or kurkar. The luminescence age of the kurkar is 42.7 ± 6.3 ka. Human occupation of the site occurred between 21.3 ka and 14.0 ka ago, during the Last Glacial Maximum. © 2003 Wiley Periodicals, Inc.     

Application of Compositional Techniques in the Field of Crystal Chemistry: A Case Study of Luzonite, a Sn-Bearing Mineral

Out-of-equilibrium crystallization often produces complex compositional variability in minerals, generating zoning and other mixing phenomena. The appropriate microchemical characterization of the resulting out-of-equilibrium patterns is of critical importance in understanding the overall physical and chemical properties of the host crystalline phases. In this framework, the modeling of compositional changes assumes a fundamental role. However, when compositional data are used, their management with standard exploratory, statistical, graphical, and numerical tools may give misleading results attributable to the phenomenon of induced correlations. To avoid these problems, methods able to extract compositional data from their constrained space (the simplex) in order to apply standard statistics, have to be adopted. As an alternative, the use of tools having properties able to work in the simplex geometry has to be considered. A luzonite single crystal (ideal composition, Cu₃AsS₄) exhibiting concentric and sector zoning was studied using electron probe microanalysis in order to understand the mechanisms which give rise to chemical variability and conditions in the developing environment. Compositional variations were determined by collecting data along three different transects. The major and minor elements (Cu, As, S, Fe, Sb, Sn) were analyzed with the aim of characterizing their patterns of association in the crystal and, hence, crystal evolution. The whole covariance structure as well as the chemical relationships between the successive zones was investigated by means of compositional methods, considering both data transformation and the stay in the simplex approach. Results indicate that the crystal grew under quiescent conditions, where chemical control was primarily exercised by the mineral’s surface and only minor effects were due to changes in the composition of the surrounding fluid. Consequently, an oscillatory uptake of chemical components occurred in which a competition between famatinite-like (Cu₃SbS₄) and kuramite-like (Cu₃SnS₄) domains characterized the As-poor zones.     

Modeling global Hammond landform regions from 250‐m elevation data

In 1964, E.H. Hammond proposed criteria for classifying and mapping physiographic regions of the United States. Hammond produced a map entitled “Classes of Land Surface Form in the Forty‐Eight States, USA”, which is regarded as a pioneering and rigorous treatment of regional physiography. Several researchers automated Hammond?s model in GIS. However, these were local or regional in application, and resulted in inadequate characterization of tablelands. We used a global 250 m DEM to produce a new characterization of global Hammond landform regions. The improved algorithm we developed for the regional landform modeling: (1) incorporated a profile parameter for the delineation of tablelands; (2) accommodated negative elevation data values; (3) allowed neighborhood analysis window (NAW) size to vary between parameters; (4) more accurately bounded plains regions; and (5) mapped landform regions as opposed to discrete landform features. The new global Hammond landform regions product builds on an existing global Hammond landform features product developed by the U.S. Geological Survey, which, while globally comprehensive, did not include tablelands, used a fixed NAW size, and essentially classified pixels rather than regions. Our algorithm also permits the disaggregation of “mixed” Hammond types (e.g. plains with high mountains) into their component parts.     

“A Place of Pain and Gain”: Exploring the Dynamics of Resistance in the Creation of Sengwe Tshipise Wilderness Corridor,Southeast Zimbabwe

This article examines the relationship between place attachment and resistance during participatory planning of the Sengwe Tshipise Wilderness Corridor, located in southeast Zimbabwe, a region that falls within the Great Limpopo Transfrontier Conservation Area. Field research was conducted from July to December 2013 using 69 semistructured interviews, seven focus-group discussions, and analysis of secondary data. By following the dominant narratives articulated by villagers affected by this Corridor, we illustrate the multiple ways in which place attachment becomes part of everyday politics of resistance. Results show that a strong place-based identity is at the center of narratives deployed by villagers displaced by war, conservation, and veterinary fencing restrictions. Through deploying this place-based identity, communities collectively influenced both the spatial extent of the corridor and institutional governance arrangements. This article contributes to debates on the role of community agency in the implementation of transfrontier conservation areas.     

THE INTERPRETATION AND MAPPING OF VEGETATION AND OTHER GROUND SURFACE FEATURES FROM AIR PHOTOGRAPHS OF MOUNTAINOUS AREAS IN NORTH WALES

The paper describes work undertaken in North Wales in 1967 and 1968 in which panchromatic and colour air photographs were used in the mapping of vegetation and in the study of other ground surface features. The problems of relating a priori classification schemes to the categories distinguished by air photo-interpretation are discussed and the case stated for developing classifications which enable more benefit to be derived from the advantages of air photo-ecology.     

A COMPARISON OF FILM TYPE AND THE IMPORTANCE OF SEASON FOR INTERPETATION OF COASTAL MARSHLAND VEGETATION

A study of coastal marshland using panchromatic vertical aerial photography suggested that October was the best season of the year for the interpretation of vegetation while February was most suitable for examining topographical or pedological features. False colour film was used to isolate certain plants from bare mudflats where it was impossible to identify these by differences in texture or height.