Cu 2p absorption spectroscopy as a probe for the site occupancy of (ZnxCu1−x)WO4 solid solution

The solid solution sanmartinite (ZnWO₄)—cuproscheelite (CuWO₄) has been studied using Cu 2p X-ray absorption spectroscopy. While a single L₃ absorption peak is observed for CuWO₄, two distinct L₃ absorption peaks with a separation of ～0.8 eV are observed for the intermediate samples in the solid solution. The two peaks represent distinct Cu sites: one with all CuO₆ next nearest neighbours in the (Cu,Zn)O₆ chains, another having at least one ZnO₆ next nearest neighbour. Both sites show a linear increase in covalency as a function of increasing Cu-content. The relative intensities of the two absorption peaks is dependent upon the Cu-content and has been used to model the site occupancies. The results reveal that the local structural effects can be associated with a composition-dependent structural phase transition from P2/c (ZnWO₄) to P $\bar 1$ (CuWO₄). Deviations from a single-site model are explained in terms of the local environments, and evidence for site preferences and local clustering are explored.     

The emplacement of intermediate volume ignimbrites: A case study from Roccamonfina Volcano,Southern Italy

A model is presented for the emplacement of intermediate volume ignimbrites based on a study of two 6 km³ volume ignimbrites on Roccamonfina Volcano, Italy. The model considers that the flows were slow moving, and quickly deflated from turbulent to non-turbulent conditions. Yield strength and density increased whereas fluidisation decreased with time and runout of the pyroclastic flows. In proximal locations, on the caldera rim, heterogeneous exposures including discontinuous lithic breccias, stratified and cross-stratified units interbedded with massive ignimbrite suggest deposition from turbulent flows. In medial locations thick, massive ignimbrite occurs associated with three types of co-ignimbrite lithic breccia which we interpret as being emplaced by non-turbulent flows. Multiple grading of different breccia/lithic concentration types within single flow units indicates that internal shear occurred producing overriding or overlapping of the rear of the flow onto the slower-moving front part. This overriding of different parts of non-turbulent pyroclastic flows could be caused by at least two different mechanisms: (1) changes in flow regime, such as hydraulic jumps that may occur at breaks in slope; and (2) periods of increased discharge rate, possibly associated with caldera collapse, producing fresh pulses of lithic-rich material that sheared onto the slower-moving part of the flow in front.We propose that ground surge deposits enriched in pumice compared with their associated ignimbrite probably formed by a flow separation mechanism from the top and front of the pyroclastic flow. These turbulent clouds moved ahead of the non-turbulent lower part of the flow to form stratified pumice-rich deposits. In distal regions well-developed coarse, often clast-supported, pumice concentrations zones and coarse intra-flow-unit lithic concentrations occur within the massive ignimbrite. We suggest that the flows were non-turbulent, possessed a relatively high yield strength and may have moved by plug flow prior to emplacement.     

Automatic equipment to monitor groundwater radon

Prototype instrumentation, able to automatically measure groundwater radon content variations, is presented. The equipment is made of stainless steel and has spherical valves with automatic and pneumatic control. The deemanation of the gases from the water is obtained by evacuating a suitable expansion chamber. The instrumentation can make discrete sampling ranging from 1 per hour to 1 per 99 hours. The equipment was tested in the laboratory: the efficiency was measured by means of a²⁶⁶Ra solution. A mean value of (0.65±0.07) count/s/Bq was obtained. A calibration test was carried out by comparing countings from the automatic equipment with those obtained by the standard laboratory cell. Results of an operational check over a period of approximately one year indicate that variations in radon at the calibration site are attributable more to meteorological than to tectonic causes.     

Cesstibtantite—a geologic introduction to the inverse pyrochlores

Summary The crystal structure of cesstibtantite has been solved from diffractometer data collected on samples from Leshaia, Russia and the Tanco pegmatite, Manitoba. Cesstibtantite from the Leshaia pegmatite (type locality) hasa 10.515(2) Å, space groupFd3m, composition Cs_0.31(Sb_0.57Na_0.31Pb_0.02Bi_0.01)_O.91(Ta_1.88Nb_0.12)₂(O_5.69[OH, F]_0.31)₆(OH, F)_0.69, Z 8; its structure was refined toR 3.8,wR 4.3% using 96 observed (F > 3[F]) reflections (MoK). Cesstibtantite from the Tanco pegmatite hasa 10.496(1) Å, space groupFd3m, composition (Cs_0.22K_0.01)_0.23(Na_0.45Sb_0.39Pb_0.14· Ca_0.06Bi_0.02)_1.06(Ta_1.95Nb_0.05)₂(O_5.78[OH,F]_0.22)₆(OH,F)_0.55,Z 8; its structure was refined toR 3.9w R 3.7% using 104 observed reflections. Cesstibtantite differs from the normal pyrochlores in that it contains significant amounts of very large cations such as Cs. As these cations are too large (^VIII[r] > 1.60 Å) for the conventional [8]-coordinated A site, they occupy the [18]-coordinated site, which normally contains monovalent anions. Natural cesstibtantite samples are non-ideal in that both Cs and monovalent anions occur at the site; thus cesstibtantite is intermediate to thenormal pyrochlores (with only monovalent anions at the site) and theinverse pyrochlores (with only large cations at the site).

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Cesstibtantit—eine geologische Einfiihrung in die inversen Pyrochlore

Zusammenfassung Die Kristallstruktur von Cesstibtantit wurde auf der Basis von Diffraktometerdaten von Proben von Leshaia, Russland and dem Tanco Pegmatit, Manitoba, gelöst. Cesstibtantit aus dem Leshaia Pegmatit (Typlokalität) hat a 10.515(2) Å, RaumgruppeFd3m, die Zusammensetzung CS_0.31(Sb_0.57Na_0.31Pb_0.02Bi_0.01)_0.91(Ta_1.88Nb_0.12)₂· (O_5.69OH, F_0.31)₆(OH, F)_0.69 Z 8; die Struktur wurde aufR 3.8,wR 4.3% verfeinert unter Benützung von 96 beobachteten Reflexen. Cesstibtantit vom Tanco Pegmatit hat a 10.496(1) Å, RaumgruppeFd3m, die Zusammensetzung (Cs_0.22K_0.01)_0.23(Na_0.45· Sb_0.39Pb_0.14Ca_0.06Bi_0.02)_1.06(Ta_1.95Nb_0.05)₂(O_5.78OH,F_0.22)₆(OH,F)_0.55,Z 8; seine Struktur wurde aufR 3.9wR 3.7% auf der Basis von 104 beobachteten Rettexen verfeinert. Cesstibtantit unterscheidet sich von normalen Pyrochloren insofern, als er signifikante Mengen von sehr großen Kationen, wie z.B. Cs enthält. Da these Kationen zu groß sind (^VIII r 1.60 Å) für eine konventionelle [8]-koordinierteA Stelle, nehmen she die [18]-koordinierten Positionen ein, welche normalerweise monovalente Anionen enthalten. Natürliche Cesstibtantitproben sind nicht ideal insofern als sowohl Cs als auch monovalente Anionen in der Position vorkommen. Somit ist Cesstibtantit intermediär zu den normalen Pyrochloren (mit nur monovalenten Anionen auf der Position) and den inversen Pyrochloren (mit ausschließlichen großen Kationen an der Position).

     

Tectonometamorphic evolution of the Bohemian Massif: evidence from high pressure metamorphic rocks

The Variscan orogenic belt, of which the Bohemian Massif is a part, is typically recognized for its characteristic low pressure, high temperature metamorphism and a large volume of granites. However, there are also bodies of high pressure rocks (eclogites, garnet peridotites and high pressure granulites) which are small in size but widely distributed throughtout the Massif. Initially the high pressure rocks were considered to be relicts of a much older orogenic event, but the increasing data derived from isotopic and geochronological investigations show that many of these rocks have Palaeozoic protoliths. Metamorphic ages from the high pressure rocks define no single event. Instead, a number of discrete clusters of ages are found between about 430 Ma and the time of the dominant low pressure event at around 320–330 Ma.Most of the eclogite and granulite facies rocks are assigned to allochthonous nappes that arrived close to the end of the low pressure event, but before final granite intrusion. The nappes contain a mixture of different units and the relationship between rocks with high pressure relicts and host gneisses with no apparent signs of deep burial is still problematic. Some of the high pressure rocks retain evidence of multiple stages of partial re-equilibration during uplift. Moreover, it can be shown in certain instances that host gneisses also endured a multistage metamorphic development but with a peak event convergent with one of the breakdown stages in the enclosed rocks with high pressure relicts. It thus appears that the nappe units are composite bodies probably formed during episodic intracrustal thrusting. Fluids derived from prograde dehydration reactions in the newly under thrusting slab are taken to be the catalysts that drove the partial re-equilibrations.On the scale of the whole Massif it can be seen within the units with high pressure relicts that the temperature at the peak recorded pressure and that during the breakdown are variable in different locations. It is interpreted that regional metamorphic gradients are preserved for given stages in the history and thus the present day dismembered nappe relicts are not too far removed from their original spatial distribution in an original coherent unit. From the temperature information alone it is highly probable that the refrigerating underthrusting slab was situated in the north-west. However, this north-west to south-east underthrusting probably represents the major 380–370 Ma event and is no guide to the final thrusting that emplaced the much thinned nappe pile with high pressure relicts.Granite genesis is attributed to the late stage stacking, during the final Himalayan-type collision stage, of thinned crust covered by young, water-rich, sediments — erosion products of the earlier orogenic stages. Regional metamorphism at shallow depths above the voluminous granites was followed by final nappe emplacement which rejuvenated the granite ascent in places. Correspondence to: P. J. O'Brien     

Stable isotope study of carbonate-cemented rocks from the Pobitite Kamani area,north-eastern Bulgaria

The Precipitation of carbonate cements in the Pobitite Kamani area (Lower Eocene) began during early diagenesis of sediments. There is evidence, however, that calcite is still forming today.The negative ¹³C values to –29.2 suggest that the carbonate formed during degradation of ¹²C-enriched organic matter (perhaps partly from oxidation of methane). The ¹⁸O values of –0.9 to –1.6 reflect the marine origin of the early diagenetic carbonate cements. Most of the carbonates, however, formed during late diagenesis (at approximately 1300 m burial depth) and/or recently (after uplift) from percolating groundwaters. These carbonates have an isotopic composition characteristic of carbonates which precipitated from meteoric waters under normal sedimentary temperatures in isotopic equilibrium with ¹²C-enriched soil carbon dioxide.     

Propagation and absorption of cyclotron maser radiation in solar microwave spike bursts

It has been argued that the loss-cone-driven electron cyclotron maser instability can account for the properties of millisecond microwave spike bursts observed during some solar flares. However, as it propagates outward from the corona, maser radiation undergoes gyroresonance absorption when its frequency is a harmonic of the local electron-cyclotron frequency. Existing analytical models using slab geometries predict that this absorption should be sufficiently strong to prevent the radiation from being seen at the observed levels, except under highly restrictive conditions or for unrealistic plasma parameters. A more comprehensive analysis is presented here to determine if and when maser radiation can escape to produce microwave spike bursts. This analysis employs numerical raytracing and incorporates propagation and absorption of fundamental maser emission in a realistic model of a coronal flux loop. It is found that ranges of physical conditions do exist under which maser radiation can escape to an observer and that these conditions are much more limiting for fundamental emission in the extraordinary ()-mode than in the ordinary (o)-mode. Detailed investigation implies that escaping radiation in the -mode is highly directional and chiefly observable toward the center of the solar disk, while escapingo-mode radiation is found to emerge from the corona over a much wider range of directions, with some cases corresponding to radiation observable near the solar limb.     

Coupled atmosphere-ocean models of Titan's past

We have developed a coupled atmosphere and ocean model of Titan's surface. The atmospheric model is a 1-D spectrally-resolved radiative-convective model. The ocean thermodynamics are based upon solution theory. The ocean, initially composed of CH4, becomes progressively enriched in ethane over time. The partial pressures of N2 and CH4 in the atmosphere are dependent on the ocean temperature and composition. We find that the resulting system is stable against a runaway greenhouse. Accounting for the decreased solar luminosity, we find that Titan's surface temperature was about 20 K colder 4 Gyr ago. Without an ocean, but only small CH4 lakes, the temperature change is 12 K. In both cases we find that the surface of Titan may have been ice covered about 3 Gyr ago. In the lakes case condensation of N2 provides the ice, whereas in the ocean case the ocean freezes. The dominant factor influencing the evolution of Titan's surface temperature is the change in the solar constant--amplified, if an ocean is present, by the temperature dependence of the solubility of N2. Accretional heating can dramatically alter the surface temperature; a surface thermal flux of 500 erg cm-2 sec-1, representative of small levels of accretional heating, results in a approximately 20 K change in surface temperatures.     

Discrete emissions and whistler precursors recorded at low latitude ground station Gulmarg

Discrete chorus-type emission and whistler precursors recorded in March 1972 during day time hours at our ground based station Gulmarg are presented. It is shown that discrete chorus type emissions are generated in the equatorial region (L 1.2) during cyclotron resonance interaction between the propagating whistler wave and the gyrating electrons. The whistler precursors are explained in terms of the mechanism suggested by Dowden (1972).     

Multiple flows and the fine structure of the transition region around sunspots

The fine structure in the flow field in the transition region above and surrounding a sunspot is determined fromCIV 1548 line profiles, observed with the High Resolution Telescope and Spectrograph (HRTS) during the Spacelab 2 mission. The observed line profiles show one, two, or three distinct velocity components within the resolution element of 1 × 1. Supersonic flows occur in small regions where the line profile has two or three components. The line component that shows supersonic speed often is weaker than the subsonic line component, which may explain why some observers have been unable to detect the supersonic flow component. The broadening of individual line components shows non-thermal velocities close to 20 km s^–1. This suggests that turbulence is less important than usually considered.The presence of multiple flows, which also occurs in quiet solar regions, suggests that the transition region above sunspots has a sub-arc-second fine structure, perhaps consisting of thin fibrils. The Evershed flow in the transition region appears to have a correspondingly complex character, possibly consisting of sub- and supersonic siphon flows along the individual fibrils. Time changes in the flow field over 5 min may correspond to characteristic times of individual fine structures. Possible explanations of the net downward directed mass flux are presented.