Crystal chemistry of a highly disordered Mg-Al natural spinel

Summary A Mg-Al spinel from a xenolith found in the Sacrofano volcanic area (Latium, Italy) was investigated by X-ray single crystal diffraction and electron microprobe. Its main structural parameters were: a₀ = 8.0922(3) Å and the oxygen coordinate u = 0.26213(4), which gave to tetrahedral and octahedral bond distances of 1.9220(6) Å and 1.9299(3) Å respectively. Cation distribution, obtained from structural and chemical data, showed a very high Mg-Al disorder, with an Al(T) content of 0.205 and an inversion parameter, i, of about 0.23. Comparison with the cation distribution of a spinel with similar chemical composition but occurring in chlorite schists (Shishimsk Mountains, Urals, Russia) with a₀ = 8.1003(3) Å and u=0.26330(3), and with data from the literature concerning spinels from metamorphosed limestones (Kalkbro, Sweden) and websteritic dikes (Balmuccia, Italy), all characterized by much lower Mg-Al disorder (i about 0.13–0.12), suggests a completely different thermal history, with rapid cooling rates and consequent high closure temperature of intracrystalline exchange, consistent with the Sacrofano geological environment.

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Kristallchemie eines stark ungeordneten, natürlichen Mg-Al-Spinells

Zusammenfassung Ein Mg-Al-Spinell aus einem Xenolith des Vulkangebiets von Sacrifano (Latium, Italien) wurde mit Röngten-Einkristallmethoden und der Elektronenmikrosonde untersucht. Die wichtigsten Strukturparameter sind a_o = 8,0922(3) Å und die Sauerstoffkoordinate u = 0,26213(4), was zu den tetraedrischen und oktaedrischen Bindungsabständen von 1,9220(6) Å bzw. 1,9299(3) Å führt. Die aus den strukturellen und chemischen Daten erhaltene Kationenverteilung zeigt eine sehr starke Unordnung Mg-Al mit einem Al (T)-Gehalt von 0,205 und einem Inversionsparameteri von ca. 0,23. Der Vergleich mit der Kationenverteilung eines Spinells ähnlicher chemischer Zusammensetzung, aber aus Chloritschiefern (Schischimsk-Berge, Ural, Rußland) mit a₀ = 8,1003(3) Å und u=0,26330(3), sowie mit Literaturdaten über Spinelle aus metamorphen Kalken (Kalkbro, Schweden) und websteritischen Gängen (Balmuccia, Italien), die alle durch eine viel geringere Mg-Al-Unordnung charakterisiert sind (i etwa 0,13–0,12), weist auf eine völlig andere thermische Geschichte hin, und zwar mit rascher Abkühlungsgeschwindigkeit und hoher Schließungstemperatur des intrakristallinen Austausches, was mit den geologischen Verhältnissen von Sacrofino in Übereinstimmung steht.

     

Cycle anatomy and variability in the storm-dominated type cincinnatian (Upper Ordovician): coming to grips with cycle delineation and genesis

Although parasequence and sequence are scale-independent terms, they are frequently applied only to specific scales of cycles. For example, meter-scale cycles are commonly assumed to be parasequences or PACs. In the Upper Ordovician Kope and Fairview Formations of northern Kentucky, we examined a succession of 50 meter-scale cycles that have been variously interpreted as deepening-upward, shallowing-upward, or showing no relationship with water depth. Our analysis shows that these cycles, characterized by shifts in storm-bed proximality, are highly variable in their thickness and internal construction. Most cycles are best considered high-frequency sequences, because deepening-upward intervals are common, and many cycles contain evidence of abrupt basinward shifts in facies as expected at sequence boundaries. A minority fit the parasequence model of shallowing-upward cycles bounded by flooding surfaces. Larger, 20 m scale cycles are defined by systematic thickening and thinning trends of meter-scale cycles. However, meter-scale cycles do not display any systematic trends in cycle anatomy as a function of position within the 20 m cycles or position within the Kope and Fairview Formations. The high cycle variability and the lack of systematic stratigraphic organization with respect to longer-term cyclicity reflect either the irregularity of relative sea-level changes, the poor recording of sea-level changes in this deep-water setting, or the generation of these cycles by climate-induced cyclicity in storm intensity. These three mechanisms would generate similar patterns at the outcrop scale, so it is not possible at the present to distinguish between them.     

Uncertainties in field-line tracing in the magnetosphere. Part II: the complete internal geomagnetic field

The discussion in the preceding paper is restricted to the uncertainties in magnetic-field-iine tracing in the magnetosphere resulting from published standard errors in the spherical harmonic coefficients that define the axisymmetric part of the internal geomagnetic field (i.e. g_n⁰ ± g_n⁰). Numerical estimates of these uncertainties based on an analytic equation for axisymmetric field lines are in excellent agreement with independent computational estimates based on stepwise numerical integration along magnetic field lines. This comparison confirms the accuracy of the computer program used in the present paper to estimate the uncertainties in magnetic-field-line tracing that arise from published standard errors in the full set of spherical harmonic coefficients, which define the complete (non-axisymmetric) internal geomagnetic field (i.e. g_n^m ± g_n^m and h_n^m ± h_n^m). An algorithm is formulated that greatly reduces the computing time required to estimate these uncertainties in magnetic-field-line tracing. The validity of this algorithm is checked numerically for both the axisymmetric part of the internal geomagnetic field in the general case (1 n 10) and the complete internal geomagnetic field in a restrictive case (0 m n, 1 n 3). On this basis it is assumed that the algorithm can be used with confidence in those cases for which the computing time would otherwise be prohibitively long. For the complete internal geomagnetic field, the maximum characteristic uncertainty in the geocentric distance of a field line that crosses the geomagnetic equator at a nominal dipolar distance of 2 R_E is typically 100 km. The corresponding characteristic uncertainty for a field line that crosses the geomagnetic equator at a nominal dipolar distance of 6 R_E is typically 500 km. Histograms and scatter plots showing the characteristic uncertainties associated with magnetic-field-line tracing in the magnetosphere are presented for a range of illustrative examples. Finally, estimates are given for the maximum uncertainties in the locations of the conjugate points of selected geophysical observatories. Numerical estimates of the uncertainties in magnetic-field-line tracing in the magnetosphere, including the associated uncertainties in thelocations of the conjugate points of geophysical observatories, should be regarded as first approximations in the sense that these estimates are only as accurate as the published standard errors in the full set of spherical harmomic coefficients. As in the preceding paper, howerver, all computational techniques developed in this paper can be used to derive more realistic estimates of the uncertainties in magnetic-field-line tracing in the magnetosphere, following further progress in the determination of more accurate standard errors in the spherical harmonic coefficients.Also Visiting Reader in Physics, University of Sussex, Palmer, Brighton, BN1 9QH, UK     

Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.     

Investigation by backscatter radar of artificial irregularities produced in ionospheric plasma heating experiments

The artificial ionospheric turbulence occurs in the ionosphere illuminated by high power HF radio waves. There are a lot of irregularities stretched along the geomagnetic field in this region. The investigation of the artificially disturbed ionospheric region is based on the reception of back scattered signals (BSS) which permits the basic parameters of this region to be estimated and its inhomogeneous structure to be described.Experiments were carried out using ‘Sura’ heating facility in the frequency range of ? = 4.7–9 MHz (ordinary mode) with the effective radiated power P_eff = 50–70 MW beamed vertically upwards. The most important dynamic and statistical BSS characteristics (the built-up time, the relaxation and autocorrelation times, the BSS amplitude spatial correlation function and power spectra) were measured using probe waves in the frequency range of that made it possible to obtain the basic parameters of the artificial irregularities. The model representation of a disturbed region in a form of a periodic structure gives a possibity to evaluate the scale of the structure, the whole size of the disturbance and its power and to calculate the main BSS characteristics.     

The mass accommodation coefficient of ammonia on water

The mass accommodation coefficient of ammonia gas on water has been determined by measuring the absorption rate of 50–200 ppm NH₃ in one atm of air or helium into a liquid jet of 97 µm diameter as function of the exposed jet length, and comparing the results with numerical simulations which treat as the only free parameter. The model considers in detail transport of NH₃ by molecular diffusion, penetration of the gas/water interface, hydrolysis in the acidified water, and transport of the solutes from the surface into the jet. A correction is applied for the time evolution of the jet surface speed, using literature data on the fluid mechanics of liquid jets. The result of nine sets of independent measurements is

Stable boundary layers: observations,models and variability part II: Data analysis and averaging effects

As argued in Part I (Derbyshire, 1995), variability is a key issue in stable boundary layers, and differences in variability between observations and idealized models may imply sytematic biases. Here we discuss how data analysis can be geared to allow for variability and thus consistency with models. Instrumental errors, smoothing methods and vertical discretization are considered. We then show how statistical averaging broadly improves the agreement of heterogeneous results in Part I with the Brost-Wyngaard closure. Recommendations are made for the information needed to analyze apparent differences between homogeneous and heterogeneous stable boundary layers.Part of UK Meteorological Office Atmospheric Processes Research Division     

Mechanisms of shrubland expansion: land use,climate or CO2?

Encroachment of trees and shrubs into grasslands and the thicketization of savannas has occurred worldwide over the past century. These changes in vegetation structure are potentially relevant to climatic change as they may be indicative of historical shifts in climate and as they may influence biophysical aspects of land surface-atmosphere interactions and alter carbon and nitrogen cycles. Traditional explanations offered to account for the historic displacement of grasses by woody plants in many arid and semi-arid ecosystems have centered around changes in climatic, livestock grazing and fire regimes. More recently, it has been suggested that the increase in atmospheric CO₂ since the industrial revolution has been the driving force. In this paper we evaluate the CO₂ enrichment hypotheses and argue that historic, positive correlations between woody plant expansion and atmospheric CO₂ are not cause and effect.Please direct all correspondence to the senior author.     

Geology of the volcanic-hosted Brockman rare-metals deposit,Halls Creek Mobile Zone,northwest Australia. l. Volcanic environment,geochronology and petrography of the Brockman volcanics

Summary Rare-metals mineralization of the Brockman deposit (Halls Creek Mobile Zone, NW Australia) is hosted in a fluorite-bearing, rhyolitic volcaniclastic unit informally termed the Niobium Tuff. The Tuff, more correctly described as a tuffaceous volcaniclastic deposit, is the lowermost unit of a sequence of trachyte-to-rhyolite lavas, trachyandesite subvolcanic rocks, and volcaniclastic units of the Brockman volcanics located within the Halls Creek Group, a thick, early Proterozoic volcano-sedimentary sequence. High precision SHRIMP ion-microprobe zircon dating of the Niobium Tuff gives an eruption age of 1870 ± 4 Ma. Regional geochronological constraints indicate the Niobium Tuff was deposited about 15 Ma before major orogenic activity affected the area. Despite folding, faulting and low-grade metamorphism, the Brockman volcanics show excellent preservation of primary volcanological features, including pillow-lavas and pillow-breccias, that suggest a dominantly subaqueous, below-wave-base emplacement environment. The style of eruption products and magma volume constraints suggest the trachyte-dominated volcanics were erupted from a small shield volcanic complex probably in a rift-related basin in a shallow-marine setting. The tectonic setting was intraplate but differs from most Tertiary to recent trachyte volcanic complexes which are largely subaerial, are built on relatively thick continental crust, and show no post-eruptive orogenic history. Brockman-style rare-metal deposits are characterized by preservation of subaqueous volcanics beneath a thick sedimentary sequence, eruption of early incompatible-element enriched products followed by less differentiated magmas, and fine-grained mineralogy influenced by alteration processes. Prospects exist for discovery of analogous deposits, particularly in early Proterozoic mobile belts and Tertiary intraplate shield volcanic provinces.

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Geologie der an Vulkanite gebundenen Seltene-Metalle-Lagerstätte Brockman, Halls Creek Mobile Zone, Nordwest-Australien. I. Vulkanologie, Geochronologie und Petrographie der Brockman-Vulkanite

Zusammenfassung Selten-Metall-Vererzung der Brockman-Lagerstätten (Halls Creek Mobile Zone, NW Australien) sitzt in einer Fluorit-führenden, rhyolitischen vulkanoklastischen Einheit auf, die informell als der Niob-Tuff bezeichnet wird. Es handelt sich hier um ein vulkanoklastisches Tuff-Sediment; dieses ist die unterste Einheit einer Abfolge vor Trachyt bis Rhyolit-Laven, trachyandesitischen Subvulkaniten and vulkanoklastischen Einheiten der Brockman Vulkanite innerhalb der Halls Creek Gruppe, einer mächtigen frühproterozoischen vulkanosedimentdren Abfolge. Prüzisionsdatierungen des Niob Tuffs mit der SHRIMP Ionen-Mikrosonde ergeben ein Eruptionsalter von 1870 +-4 Millionen Jahren. Regionale geochronologische Zusammenhänge zeigen, daß der Niob Tuff etwa 15 Millionen Jahre vor einer größeren Orogenese, die das Gebiet betroffen hat, abgelagert wurde. Trotz Faltung, Bruchtektonik and niedriggradiger Metamorphose zeigen die Brockman-Vulkanite einen hervorragenden Erhaltungszustand primärer vulkanologischer Erscheinungen. Diese urnfassen auch Kissenlaven und KissenBreckzien, die eine vorwiegend subaquatische Ablagerung in ruhigem Wasser erkennen lassen. Die Art der Eruptionsprodukte and das Magmavolumen zeigen, daß die Trachytdominierten Vulkanite von einem kleinen Schildvulkan stammer, wahrscheinlich in einem Becken in einer Rift-Situation im seichten marinen Milieu. Die tektonische Situation war intraplate, aber unterscheidet sich von den meisten tertiären bis rezenten trachytischen Vulkan-Komplexen, die hauptsächlich subaerisch sind, auf einer relativ mächtigen kontinentalen Kruste aufsitzen, and keine post-eruptive orogene Entwicklung zeigen. Seltene-Metalle-Lagerstatten des Brockman-Typs rind durch die Erhaltung subaquatischer-Vulkanite unterhalb einer machtigen sedimentdren Abfolge gekennzeichnet; welters durch frühe Eruptionsprodukte, die an inkompatiblen Elementen angereichert sind, auf die dann weniger differenzierte Magmen folgten, und schließlich durch einen feinkörnigen Mineralbestand, der vor Umwandlungsprozessen betroffen war. Es besteht die Möglichkeit der Entdeckung analoger Lagerstätten, besonders in frühproterozoischen mobilen Gürteln und in tertidren intraplate Schildvulkan Provinzen.

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