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).     

Deep structure of the Racha earthquake source zone from seismic tomography data

The Racha earthquake of 1991 was the strongest of the earthquakes recorded in the Caucasus. It was studied by an international epicentral expedition. Unique data gathered by this expedition included records of aftershocks whose swarm was very intense. A 3-D velocity model is obtained from analysis of these data by the method of local earthquake tomography. The ancient crystalline basement and the sedimentary-volcanic Mesozoic-Cenozoic cover could be identified from cross sections of the P wave field. The eastern and western boundaries of an uplift in the basement of the Dzirulskii Massif are delineated. Linear low velocity heterogeneities correlating with the active Kakheti-Lechkhumi fault zone and two Trans-Caucasian linear fault zones are discovered in the basement. The cloud of aftershock hypocenters is shown to correlate with a reflector coinciding with the cover-basement interface.     

Anaerobic Metabolism in Tidal Freshwater Wetlands: I. Plant Removal Effects on Iron Reduction and Methanogenesis

For energetic reasons, iron reduction suppresses methanogenesis in tidal freshwater wetlands; however, when iron reduction is limited by iron oxide availability, methanogenesis dominates anaerobic carbon mineralization. Plants can mediate this microbial competition by releasing oxygen into the rhizosphere and supplying oxidized iron for iron reducers. We utilized a plant removal experiment in two wetland sites to test the hypothesis that, in the absence of plants, rates of iron reduction would be diminished, allowing methanogenesis to dominate anaerobic metabolism. In both sites, methanogenesis was the primary anaerobic mineralization pathway, with iron reduction dominating only early and late in the growing season in the site with a less organic soil. These patterns were not influenced by the presence of plants, demonstrating that plants were not a key control of microbial metabolism. Instead, we suggest that site conditions, including soil chemistry, and temperature are important controls of the pathways of anaerobic metabolism.     

Late Quaternary paleoclimate of western Alaska inferred from fossil chironomids and its relation to vegetation histories

Fossil Chironomidae assemblages (with a few Chaoboridae and Ceratopogonidae) from Zagoskin and Burial Lakes in western Alaska provide quantitative reconstructions of mean July air temperatures for periods of the late-middle Wisconsin (～39,000–34,000 cal yr B.P.) to the present. Inferred temperatures are compared with previously analyzed pollen data from each site summarized here by indirect ordination. Paleotemperature trends reveal substantial differences in the timing of climatic warming following the late Wisconsin at each site, although chronological uncertainty exists. Zagoskin Lake shows early warming beginning at about 21,000 cal yr B.P., whereas warming at Burial Lake begins ～4000 years later. Summer climates during the last glacial maximum (LGM) were on average ～3.5 °C below the modern temperatures at each site. Major shifts in vegetation occurred from ～19,000 to 10,000 cal yr B.P. at Zagoskin Lake and from ～17,000 to 10,000 cal yr B.P. at Burial Lake. Vegetation shifts followed climatic warming, when temperatures neared modern values. Both sites provide evidence of an early postglacial thermal maximum at ～12,300 cal yr B.P. These chironomid records, combined with other insect-based climatic reconstructions from Beringia, indicate that during the LGM: (1) greater continentality likely influenced regions adjacent to the Bering Land Bridge and (2) summer climates were, at times, not dominated by severe cold.     

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.     

Cosmic‐ray rejection for single spectroscopic CCD images by means of template matching

This article describes a novel algorithm for cosmic‐ray rejection in single spectroscopic CCD images. This algorithm is based on a variation of template matching. It focuses on identifying those pixels belong to spectra, while other conventional algorithms tried to locate the cosmic‐ray hits directly. The main principle is applying template matching to find suspicious blocks, which is followed by surface patching to locate the legitimate pixels accurately. Therefore, the rest pixels are the ones corrupted by cosmic‐ray hits. Meanwhile, almost all the parameters are automatically extracted from the images. Examples of its performance are given for both simulated and observed images. It shows an advantage of significantly low false alarm rate with relatively high detection rate (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of a eutrophic tidal basin: part 1—factors affecting the distribution and biomass of macroalgae

The distribution and biomass of macroalgae, principally Enteromorpha spp., have been estimated in Langstone Harbour, a 19 km² tidal basin in southenrn England. Comprehensive mapping was carried out annually at the time of maximum biomass and monthly mapping of selected areas allowed seasonal changes to be studied. Aerial false-colour photography and ground-level mapping were used for assessing the area and density of cover of macroalgae, but have identified no continuous trends between 1973 and 1982. In nine years, some 48% of the intertidal mudflat has supported >75% macroalgal cover at some stage, but generally only one-third of this potential has been achieved annually. The average peak biomass was determined by a stratified sampling method and varied about a mean of 38.5 g dry weight per square metre and showed significant annual differences. The processes controlling macroalgal growth and distribution reviewed, but, in general, factors other than nutrient availability are effective in determining areas supporting high macroalgal cover in any particular year.     

Initial volatilization temperatures and average volatilization rates of coal — Their relationship to coal rank and other characteristics

Two thermal parameters, initial volatilization temperature (IVT) and average volatilization rate (AVR), have been determined by thermogravimetric analysis in argon for 38 coal samples ranging in rank from lignite to low-volatile bituminous. Both IVT and AVR are correlated with percent volatile matter and vitrinite reflectance.The IVT values increase gradually from about 250 to 445°C with increasing rank; however, a change in slope is observed in the region of high-volatile bituminous coals (from about 340°C to about 380°C) when IVT's are plotted against percent volatile matter or percent fixed carbon. The changes in slope near 340°C and near 380°C occur at “coalification jumps” recognized on the basis of changes in the optical and chemical character of the macerals. In general, AVR values decrease gradually with increasing rank for the lignite and sub-bituminous coals and for the medium- and low-volatile bituminous coals; however, a sharp increase in AVR occurs in high-volatile bituminous coals. The change in slope of the IVT curves and sharp increase in the AVR values for high-volatile bituminous coals reflect the development of new, higher vapor pressure organic compounds produced during this stage of the coalification process.A plot of AVR vs IVT reveals three regions which correspond to: (1) lignite and sub-bituminous coals; (2) high-volatile bituminous coals; and (3) medium- to low-volatile bituminous coals.     

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.     

Effect of Silica Activity on OH- IR Spectra of Olivine: Implications for Low-aSiO2 Mantle Metasomatism

Hydrogen solubility and hydroxyl substitution mechanism in olivineat upper-mantle conditions are not only a function of pressure,temperature, water fugacity and hydrogen fugacity, but are alsoinfluenced by silica activity. Olivine synthesized in equilibriumwith magnesiowüstite displays hydroxyl stretching bandsin the wavenumber range from 3640 to 3430 cm^–1. In contrast,olivine in equilibrium with orthopyroxene shows absorption bandsin a narrower wavenumber range from 3380 to 3285 cm^–1.The two fundamentally different spectra are assigned to hydroxylin tetrahedral and octahedral sublattices, respectively. Olivinein equilibrium with orthopyroxene is also less capable of incorporatinghydroxyl, relative to olivines in equilibrium with magnesiowüstite,by about a factor of ten. A comparison of spectra obtained aspart of this study with hydroxyl spectra of natural mantle olivinesshows that the latter display hydroxyl stretching patterns reminiscentof equilibrium with magnesiowüstite, although undoubtedlyolivine in the Earth’s mantle coexists with orthopyroxene.This may be attributed to a metasomatic overprint by a low-silicafluid and/or melt that was in reaction relationship with orthopyroxene.A likely metasomatic agent is a carbonatitic melt. When carbonatiticmelts decompose to oxides and CO₂, they may temporarily imposea low-aSiO₂ environment inherited by the olivine structure.If this suggestion proves true, Fourier transform IR spectroscopymay be used to fingerprint metasomatic episodes in the lithosphericmantle. KEY WORDS: FTIR spectrometry; olivine; mantle; metasomatism; water