Temperature dependence of the cation distribution in nickel aluminate (NiAl2O4) spinel: a powder XRD study

NiAl₂O₄ is a largely inverse spinel, which in detail shows increasing randomisation with temperature of Ni and Al between the octahedral and tetrahedral cation sites of the spinel structure. We have used powder XRD to determine this cation distribution in various samples of NiAl₂O₄ quenched after annealing between 700 and 1400° C. The inversion parameter (x) can be measured with a precision of ± 0.004 (one standard deviation), and a comparison of different methods of synthesis, X-ray diffraction and refinement techniques, suggests a probable accuracy of better than 0.01. The results are supported by some preliminary single crystal refinements on flux-grown samples.Below 800° C the rate of cation ordering becomes very slow, and, despite reaching an apparently steady state, it is doubtful if our samples attained complete internal equilibrium. Above 1250° C the cation redistribution becomes so fast that the quenching method becomes unreliable. Between 800 and 1250° C inclusive, the degree of inversion changes smoothly from 0.87 at 800° C to 0.79 at 1250° C, and is accompanied by linear changes in u, the oxygen parameter, from 0.2555 to 0.2563 (±0.0002), and a₀, the lattice parameter, from 8.0462 to 8.0522 Å (±0.0002 Å).     

Mineralogical, chemical, and crystallographic properties of supergene jarosite-group minerals from the Xitieshan Pb-Zn sulfide deposit, northern Tibetan Plateau, China

Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K₂O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K_0.29Na_0.19Pb_0.31Fe_2.66Al_0.22(SO₄)_1.65(PO₄)_0.31(AsO₄)_0.04(OH)_7.37. The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO₄ at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO₄)₂ and minor hematite. The decomposition products of NaFe(SO₄)₂ are hematite and Na₂SO₄. Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a?=?7.315 Å and c?=?016.598 Å. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c, but only slightly increase a. The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site.     

Corundum- and kyanite-bearing anatexites from the Precambrian of tanzania

In the Precambrian near Morogoro (East Tanzania) there are anatectic gneisses which are composed of two different domains: (1) Medium grained gneiss with the assemblage (+ rutile + baddeleyite): albite (ab₉₅an₀₃or₀₂) + muscovite + phlogopite_ss + corundum, and albite (ab₈₈an₀₉or₀₃ + kyanite or sillimanite + phlogopite_ss. (2) Coarse grained nests of corundum and antiperthite with minor albite, muscovite, phlogopite, rutile, baddeleyite, and tourmaline. The bulk composition of the antiperthite id ab₇₅an₀₂or₂₃, the composition of the Na-phase ab₉₅an₀₃or₀₂, that of the K-phase ab₁₃an₀₀or₈₇. Phase relationship of the rock can be modelled in the Na-rich, Si-undersaturated part of the KNASH system. P-T conditions are close to the intersection of the melting curve muscovite_ss + H₂O = corundum + liquid with the kyanite-sillimanite transition, i.e. 7.7 kb/695°C assuming a_H2O = 1.     

Improving the efficiency of ant algorithms using adaptive refinement: Application to storm water network design

The ant algorithm is a new evolutionary optimization method proposed for the solution of discrete combinatorial optimization problems. Many engineering optimization problems involve decision variables of continuous nature. Application of the ant algorithm to the optimization of these continuous problems requires discretization of the continuous search space, thereby reducing the underlying continuous problem to a discrete optimization problem. The level of discretization of the continuous search space, however, could present some problems. Generally, coarse discretization of the continuous design variables could adversely affect the quality of the final solution while finer discretization would enlarge the scale of the problem leading to higher computation cost and, occasionally, to low quality solutions. An adaptive refinement procedure is introduced in this paper as a remedy for the problem just outlined. The method is based on the idea of limiting the originally wide search space to a smaller one once a locally converged solution is obtained. The smaller search space is designed to contain the locally optimum solution at its center. The resulting search space is discretized and a completely new search is conducted to find a better solution. The procedure is continued until no improvement can be made by further refinement. The method is applied to a benchmark problem in storm water network design discipline and the results are compared with those of existing methods. The method is shown to be very effective and efficient regarding the optimality of the solution, and the convergence characteristics of the resulting ant algorithm. Furthermore, the method proves itself capable of finding an optimal, or near-optimal solution, independent of the discretization level and the size of the colony used.     

Land use change under conditions of high population pressure: the case of Java

A long history of increases in population pressure in Java has caused agricultural land use to expand and intensify. More recent land use changes caused the conversion of prime agricultural land into residential and industrial area. Results of a dynamic, regional-scale, land use change model are presented, defining the spatial distribution of these land use changes. The model is based on multi-scale modelling of the relations between land use and socio-economic and biophysical determinants. Historical validation showed that the model can adequately simulate the pattern of land use change. Future patterns of land use change between 1994 and 2010 are simulated assuming further urbanization. The results suggest that most intensive land use changes will occur in Java's lowland areas.     

Application of Hilbert‐like transforms for enhanced processing of full tensor magnetic gradient data

Commonly, geomagnetic prospection is performed via scalar magnetometers that measure values of the total magnetic intensity. Recent developments of superconducting quantum interference devices have led to their integration in full tensor magnetic gradiometry systems consisting of planar‐type first‐order gradiometers and magnetometers fabricated in thin‐film technology. With these systems measuring directly the magnetic gradient tensor and field vector, a significantly higher magnetic and spatial resolution of the magnetic maps is yield than those produced via conventional magnetometers. In order to preserve the high data quality in this work, we develop a workflow containing all the necessary steps for generating the gradient tensor and field vector quantities from the raw measurement data up to their integration into high­resolution, low­noise, and artefactless two‐dimensional maps of the magnetic field vector. The gradient tensor components are processed by superposition of the balanced gradiometer signals and rotation into an Earth‐centred Earth‐fixed coordinate frame. As the magnetometers have sensitivity lower than that of gradiometers and the total magnetic intensity is not directly recorded, we employ Hilbert‐like transforms, e.g., integration of the gradient tensor components or the conversion of the total magnetic intensity derived by calibrated magnetometer readings to obtain these values. This can lead to a better interpretation of the measured magnetic anomalies of the Earth's magnetic field that is possible from scalar total magnetic intensity measurements. Our conclusions are drawn from the application of these algorithms on a survey acquired in South Africa containing full tensor magnetic gradiometry data.     

Physico-chemical phenomena in comets—III: The continuum of comet Burnham (1960 II)

The new model of the cometary head proposed in papers I and II is developed and applied to comet Burnham. It takes into account the likely existence of a halo of large icy particles surrounding the nucleus. These particles are steadily stripped from the nucleus by evaporating gases. Their terminal velocity and their rate of evaporation set the size of the halo. The existence of the icy halo influences in two ways the photometric characteristics of the coma. This paper establishes the photometric shape of the continuum as reflected by the icy grains, and compares it to the observed continuum of comet Burnham. Paper IV will compare the predictions of the model with the photometric profile of the molecular emission bands of C₂, in the same comet.     

Acid mine drainage at Cerro Rico de Potosí I: unabated high-strength discharges reflect a five century legacy of mining

Intensive mining and processing of Ag, Sn, Pb and Zn ores have occurred in various locations within and around the city of Potosí, Bolivia since 1545. Surface and subsurface waters, stream sediments and soils are contaminated with various ecotoxic metals in the headwaters of the economically vital, yet highly impacted, upper Rio Pilcomayo watershed. Previous studies have documented downstream trace metal contamination, however, not addressed specific sources. The AMD discharges identified in this study help link downstream pollution to primary origins. The majority of AMD would be considered high-strength due to metal concentrations and acidity orders of magnitude greater than typical AMD. Discharges from both operating and abandoned portals as well as tailings-related deposits displayed a high degree of heterogeneity with total metal concentrations ranging from 0.11 to 7480, <0.022 to 889, <0.0006 to 65.3, <0.001 to 310, 0.12 to 72,100, 0.3 to 402, <0.012 to 34.8, and 0.24 to 19,600 mg/L of Al, As, Cd, Cu, Fe, Mn, Pb and Zn, respectively. Net acidity and pH ranged from −10 to 246,000 mg/L as CaCO₃ equivalent and 0.90–6.94 standard units, respectively. Data were gathered during two sampling events centered around the most extreme periods of the dry and wet seasons of one water-year. Loadings to local streams were marginally greater for most metals in the wet season. If observed loadings are historically representative, Cerro Rico AMD has contributed thousands of tonnes of ecotoxic metals to the upper Rio Pilcomayo over the last five centuries. Metal and hydrogen ion concentrations in the majority of AMD sampled were several orders of magnitude above discharge limits set by the Bolivian government, yet no action has historically or contemporarily been taken.