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

P. F. Schofield  C. M. B. Henderson  S. A. T. Redfern  G. van der Laan 《Physics and Chemistry of Minerals》1993,20(6):375-381

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.  相似文献   

The effect of orchard crop structure on the integral length-scale of turbulence     

P. J. Walklate 《Boundary-Layer Meteorology》1993,63(1-2):1-22

The integral length-scalesL for the three orthogonal components of diffusivityK=L are derived from spectral analysis of velocity time series measurements. A 3-D sonic anemometer was used to make these velocity measurements at heights in the range 0.7–7.0 m in and above a 2 m orchard canopy with near-neutral atmospheric boundary-layer stability conditions. The integral length-scale is compared with another length-scale of diffusionL obtained by fitting an exponential model to the auto-correlation spectrumR _E (t) in the region 0.95<R _E (t)<0.5 for smallt. This length-scale is appropriate to a high frequency region of the energy spectrum where turbulent momentum transport becomes diffusion-like and the turbulent energy varies with the inverse square of frequence. This region has been shown by others to determine the magnitude of the dissipation rate of turbulent energy by the action of viscosity even though the dominant dynamics are inviscid. Within the crop, the ratio of the length-scalesL/L were found to be smaller than the values measured above the crop for vertical turbulence. This was attributed to the enhanced decay rate of turbulent energy due to the effect of the airflow interaction with the crop. It is unclear whether similar effects are present in the horizontal plane because of greater scatter in the data, resulting from the more variable nature of the wind direction in the horizontal plane.  相似文献   

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

P. D. Cole  J. E. Guest  A. M. Duncan 《Bulletin of Volcanology》1993,55(7):467-480

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.  相似文献   

Automatic equipment to monitor groundwater radon     

F. Bella  R. Bella  P. F. Biagi  M. Caputo  G. Della Monica  A. Ermini  E. Pettinelli  V. Sgrigna 《Pure and Applied Geophysics》1993,141(1):125-137

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.  相似文献   

Alkaline and ultramafic carbonate lamprophyres in Central Bohemian carboniferous basins,Czech Republic     

Dr. J. Ulrych  Dr. E. Pivec  Dr. K. Zák  Dr. J. Bendl  Dr. P. Bosák 《Mineralogy and Petrology》1993,48(1):65-81

Summary Dykes of alkaline and ultramafic carbonate lamprophyres (monchiquite-ouachitite and aillikite) intrude the Carboniferous sediments of Central Bohemia. Their characteristic feature is the presence of substantial amounts of a sodalite group mineral (presumably haüyne), carbonate and barite. Isotopic compositions of ¹³C (–3.4 to –6.2) and ¹⁸O ( + 13.5 to + 15.9) indicate that the carbonate is of primary magmatic origin and that fluids were formed at temperatures of 500 to 350°C. High contents of CO₂ (3.6 to 17.6 wt.%) and incompatible elements, high LREE/HREE ratios (30.0 to 57.7), and low Rb/Sr (0.025 to 0.078) and⁸⁷Sr/⁸⁶Sr (0.7038 to 0.7042) ratios suggest the ultramafic lamprophyres are related to deep-seated carbonated magmas of mantle origin. Low degree of partial melting ( < 1%) of the mantle peridotite is envisaged, with additional transport of fluids rich in incompatible elements into the crustal chamber. Alkaline lamprophyres are fractionated derivatives which originated from the same source. Magma intrusion from different levels of a magma chamber into fracture zones under horizontal tension without a central intrusion could result in variability in lamprophyre composition (cumulates or evolved derivatives).

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Alkalische und ultramafische Karbonat-Lamprophyre der zentralen böhmischen Karbonbecken, Tschische Republik

Zusammenfassung Alkalische und ultramafische Karbonat-Lamprophyrgänge (Monchiquit-Ouachitit und Aillikit) intrudieren in karbonische Sedimente Zentralböhmens. Sie sind charakterisiert durch das Auftreten von beträchtlichen Mengen an Mineralen der Sodalith-Gruppe (v.a. Haüyn), Karbonaten und Baryt. Ihre Isotopenzusammensetzung von ¹³C (–3.4 bis –6.2) und ¹⁸O (13.5 bis 15.9) zeigt, daß die Karbonate primär magmatischen Ursprungs sind und daß assoziierte Fluide in einem Temperaturbereich von 350 bis 500°C gebildet wurden. Hohe Gehalte an CO₂ (3.6 bis 17.6 Gew. %), inkompatiblen Elementen, hohe LREE/HREE-Verhältnisse (30.0 bis 57.7), sowie niedrige Rb/Sr—(0.025 bis 0.078) und⁸⁷Sr/⁸⁶Sr-(0.7038 bis 0.7042) Verhältnisse lassen vermuten, daß die ultramafischen Lamprophyre mit karbonatischen Magmen des Mantels in Beziehung stehen. Eine niedrige Aufschmelzungsrate ( < 1%) von Mantelperidotit mit zusätzlichem Transport von, an inkompatiblen Elementen angereicherten Fluiden, in die krustale Magmenkammer wird diskutiert. Alkalische Lamprophyre sind als stärker fraktionierte Magmen, die derselben Quelle entstammen, zu verstehen. Die Intrusion der aus verschiedenen Bereichen der Magmenkammer stammenden Magmen in durch horizontale Dehnung verursachte Störungszonen könnte das Fehlen eines zentralen Intrusionskörpers und die unterschiedliche Zusammensetzung der Lamprophyre (Kumulate oder entwickelte Derivate) erklären.

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With 8 Figures  相似文献   

Cesstibtantite—a geologic introduction to the inverse pyrochlores     

T. S. Ercit  P. Černý  F. C. Hawthorne 《Mineralogy and Petrology》1993,48(2-4):235-255

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).

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Tectonometamorphic evolution of the Bohemian Massif: evidence from high pressure metamorphic rocks   总被引：4，自引：0，他引：4  

P. J. O'Brien  D. A. Carswell 《International Journal of Earth Sciences》1993,82(3):531-555

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  相似文献   

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

R. W. Botz  V. Georgiev  P. Stoffers  Kh. Khrischev  V. Kostadinov 《International Journal of Earth Sciences》1993,82(4):663-666

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.  相似文献   

Late Quaternary palaeolimnology of a tropical marl lake: Wallywash Great Pond,Jamaica   总被引：1，自引：0，他引：1  

F. A. Street-Perrott  P. E. Hales  R. A. Perrott  J. C. Fontes  V. R. Switsur  A. Pearson 《Journal of Paleolimnology》1993,9(1):3-22

Wallywash Great Pond (17° 57 N, 77° 48 W, 7 m a.s.l.) is the largest perennial lake in Jamaica. It occupies a fault trough within the karstic White Limestone. The Great Pond is a hardwater lake with a pH of 8.2–8.6 and an alkalinity of 3.6–3.9 meq 1^–1. Its chemistry is strongly influenced by the spring discharge from the limestone. The lake water is subject to degassing, evaporation and bicarbonate assimilation by submerged plants and algae, resulting in marl precipitation. A 9.23 m core (WGP2), taken from a water depth of 2.8 m, was analysed for magnetic susceptibility, loss-on-ignition, carbonate content, mole % MgCO₃ in calcite, and stable isotopes in the fine carbonate fraction. The chronology is based on ten¹⁴C and four U/Th dates. Four main sediment types alternate in the core: marl; organic, calcareous mud; organic mud or peat; and earthy, brown, calcareous mud. The marls represent periods of wet/warm climate during sea-level highstands and the organic deposits, shallower, swampy conditions. In contrast, the brown, calcareous muds were laid down when the lake was dry or ephemeral. The last interglacial (120 000- 106 000 yr BP) is represented by three distinct marl units. After a dry interval, stable, wet/warm conditions set in from 106 000 to 93 000 yr BP. A dry/cool climate prevailed between 93 000 and at least 9500 yr BP. Three subsequent cycles of alternating wet and dry conditions culminated in flooding of the basin by the Black River during the late Holocene. These recent events cannot be accurately dated by¹⁴C due to significant and temporally-variable inputs of dead carbon from the springs.  相似文献   

The history and impact of air pollution at Čertovo Lake,southwestern Czech Republic     

Josef Vesely  Heather Almquist-Jacobson  Lisa M. Miller  Stephen A. Norton  Peter Appleby  Aruna S. Dixit  John P. Smol 《Journal of Paleolimnology》1993,8(3):211-231

This multi-disciplinary investigation documents the longterm effects of atmospheric pollution of metals and acids on a geologically sensitive catchment in the umava Mountains, southwestern Czech Republic, a region with a long history of human disturbance. A 30 cm long sediment core (I) from ertovo Lake was analyzed for natural and artifical radionuclides, metals, diatoms, chrysophytes, and pollen in sediments accumulated during the last 200 years. A second core (II), extending to 95 cm, included sediment judged to be free of atmospheric deposition of pollutants associated with the Industrial Revolution. Chronostratigraphic markers include several changes in the pollen assemblages corresponding to well-documented changes in land-use, and distinct distributions of ¹³⁷Cs, ¹³⁴Cs and ²⁴¹Am from weapons testing and the 1986 nuclear accident at Chernobyl, Russia. These markers corroborate the ²¹⁰Pb dating and, together, produce a reliable chronology extending back nearly to 1800 A.D.Stratigraphic profiles of Cu, Pb, and Zn in Core I are unlike any previously reported in the literature. Concentrations of Cu, Pb, and Zn remain generally above 100, 400, and 200 g g^-1, respectively, for the 200 years represented by Core I. These values are unusually high for sediments from a watershed with no known heavy-metal ore bodies. Accumulation rates for Cu, Pb, and Zn, which include both atmospheric and watershed contributions, are also high (ca 1, > 1 and > 1 g cm^-2 yr^-1, respectively) for the same period, although the anthropogenic contribution of Zn rose from nearly zero at 1800 A.D. The Cu and Pb accumulation rates rose dramatically about 1640 A.D.Accumulation rates of anthropogenically-derived Be, a relatively abundant element in the soft coals of the region, are also elevated by about 0.01 g cm^-2 yr^-1 in sediments of this period. Vanadium accumulation rates increased only since 1980 A.D., presumably along with increased consumption of oil.Diatom assemblages illustrate that the lake was acidic (pH between 4.5 and 5) through at least the past 200 years. The pH declined significantly (from ca 5 to 4) between 1960 and 1985 with a slight increase to 4.5 in the last few years. Recent diatom and chrysophyte assemblages suggest high trace metal concentrations, consistent with the present lake-water chemistry.  相似文献