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).     

Fractional Crystallization and Liquid Immiscibility Processes in the Alkaline-Carbonatite Complex of Juqui (So Paulo, Brazil)

The Juqui circular intrusion, which is Cretaceous in age (130–135Ma), crops out in the Precambrian gneissic basement in Brazilover an area of 14 km2. It consists of olivine clinopyroxen-itecumulates (with minor olivine gabbros) in the northeastern sector(74 vol.%), whereas ijolites-melteigites-urtites (4%) and nephelinesyenites with minor essexites and syenodiorites (21%) outlinesubannular concentric patterns with an Mg-carbonatite core (1%), in the southwestern part of the complex. Petrographical, bulk rock, and mineral compositional trendsindicate that the origin of the complex can be largely accountedfor by shallow-level fractional crystallization of a carbonatedbasanitic parental magma. Such a magma was generated deep inthe subcontinental lithosphere by low-degree partial meltingof a garnet-phlogopite peridotite source. Mass-balance calculations in agreement with field volume estimatespermit definition of several fractionation stages of the magmaticevolution under nearly closed-system conditions, with inwarddevelopment of zonally arranged side-wall cumulates. These stagesinvolved: (1) fractionation from basanite to essexite magma(liquid fraction F = 33–5%) by crystallization of olivineclinopyroxenite plus minor olivine alkali gabbro cumulates;(2) derivation of the least differentiated mafic nepheline syenite(F = 5–5 %) from essexitic magma by subtraction of a syenodioriteassemblage; (3) exsolution of a carbonatite liquid (5%) froma CO₂-enriched mafic nepheline syenite magma, which also underwentcontinuous fractionation giving rise to ijolite-melteigite-urtitecumulates. The proportion of cumulus clinopyroxene and biotiteand intercumulus nepheline and alkali feldspar in these lastrocks, as well as the absence of alkalis in carbonatite, maybe attributed, at least in part, to loss of alkali-rich hydrousfluids released during and after the unmixing formation of thetwo conjugate liquids. The KD values determined for Mg-carbonatite/nepheline syeniteare lower (1–4–2–9) for light rare earth elements(LREE) than for REE from Eu to Yb (4–6–7–8),in contrast to recent experimental results (Hamilton et al.,1989). A possible explanation is that Juquia Mg-carbonatiterepresents an alreadydifferentiated magma, which underwent extensivefractionation of LREE-enriched calcite. In this way, the highvariability of K₀ REE patterns observed in several alkaline-carbonatitecomplexes can also be accounted for. The remarkably constant initial ⁸⁷Sr/⁸⁶Sr ratios (mostly between0–7052 and 0–7057) support the interpretation ofthe intrusion as having been generated by fractrional crystallizationand liquid immiscibility from a common parental magma. Iligherisotopic ratios (0–7060–0–7078), found mainlyin dykes and in the border facies of the intrusion, may be dueto contamination by the gecissic basement.     

Westward moving dynamic substorm features observed with the IMAGE magnetometer network and other ground-based instruments

We present the ground signatures of dynamic substorm features with particular emphasis on the event interpretation capabilities provided by the IMAGE magnetometer network. This array covers the high latitudes from the sub-auroral to the cusp/cleft region. An isolated substorm on 11 Oct. 1993 during the late evening hours exhibited many of well-known features such as the Harang discontinuity, westward travelling surge and poleward leap, but also discrete auroral forms, known as auroral streamers, appeared propagating westward along the centre of the electrojet. Besides the magnetic field measurements, there were auroral observations and plasma flow and conductivity measurements obtained by EISCAT. The data of all three sets of instruments are consistent with the notion of upward field-aligned currents associated with the moving auroral patches. A detailed analysis of the electro-dynamic parameters in the ionosphere, however, reveals that they do not agree with the expectations resulting from commonly used simplifying approximations. For example, the westward moving auroral streamers which are associated with field-aligned current filaments, are not collocated with the centres of equivalent current vortices. Furthermore, there is a clear discrepancy between the measured plasma flow direction and the obtained equivalent current direction. All this suggests that steep conductivity gradients are associated with the transient auroral forms. Also self-induction effects in the ionosphere may play a role for the orientation of the plasma flows. This study stresses the importance of multi-instrument observation for a reliable interpretation of dynamic auroral processes.     

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.     

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.     

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.     

Energetic protons from the solar flare of March 24, 1966

Ten to 100 meV protons from the solar flare of March 24, 1966 were observed on the University of California scintillation counter on OGO-I. The short rise and decay times observed in the count rates of the 32 channels of pulse-height analysis show that scattering of the protons by the interplanetary field was much less important in this event than in previously observed proton flares. A diffusion theory in which D = M _r is found to be inadequate to account for the time behavior of the count rates of this event. Small fluctuations of the otherwise smooth decay phase may be due to flare protons reflected from the back of a shock front, which passed the earth on March 23.     

A glancing incidence solar telescope for the soft x-ray region

This paper describes the instrumentation of an Aerobee rocket (NASA 4.95 GS) which was launched from White Sands Missile Range on May 20th 1966, to observe the Sun in the soft X-ray region. The experiment package, which was pointed at the sun by a control system stabilized about all three axes, carried two Wolter type I glancing incidence telescopes to photograph the sun in wavelength regions (determined by bandpass filters) between 3 and 75 Å, and two proportional counters to obtain flux data and rough spectral shapes in the regions 2–11 Å and 8–20 Å. The spatial resolution obtained was about 20 arc seconds. Limb brightening and polar darkening are very pronounced at the longer wavelengths. A tuft of emission was observed at the North Pole in addition to an arch-like structure on the NW limb. Several of the photographs are presented, and some preliminary results are discussed.     

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.