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.     

Effects of onshore and offshore topography on sea breeze circulation: An observational study at eastern Attica,Greece

Field measurements of wind, air temperature and humidity were taken at the eastern part of the Attika district in June 1991, to examine the topographic influences exerted on the local sea breezes. These influences are due either to the elongated Evia island, faced by the northern half of Attica coastline some tens of kilometers offshore, or to the coast-parallel range of Hymettos mountain, rising steeply 12 km onshore. The instrumentation consisted mainly of three tethered meteorological balloons released at characteristic sires (i.e., the coast, a location between shoreline and mountain foot and the mountain top) and three autographic ground-based anemometers operating at selected locations. Data from the ground-based and upper air stations of the Hellenic National Meteorological Service, as well as the diurnal weather maps were also obtained and analyzed. Observations were made under different synoptic wind and the latter was found to determine remarkably the significance of the topographic effects. A preliminary two-dimensional numerical approach was also made concerning the sea breeze capability to reach the Hymettos mountain top in the case of a weak opposing geostrophic flow.     

Isotope and trace element evidence for three component mixing in the genesis of the North Luzon arc lavas (Philippines)

Post-3Ma volcanics from the N Luzon arc exhibit systematic variations in ⁸⁷Sr/⁸⁶Sr (0.70327–0.70610), ¹⁴³Nd/¹⁴⁴Nd (0.51302–0.51229) and ²⁰⁸Pb^*/²⁰⁶Pb^* (0.981–1.035) along the arc over a distance of about 500 km. Sediments from the South China Sea west of the Manila Trench also exhibit striking latitudinal variations in radiogenic isotope ratios, and much of the isotopic range in the volcanics is attributed to variations in the sediment added to the mantle wedge during subduction. However, Pb-Pb isotope plots reveal that prior to subduction, the mantle end-member had high 8/4, and to a lesser extent high 7/4, similar to that in MORB from the Indian Ocean and the Philippine Sea Plate. Th isotope data on selected Holocene lavas indicate a source with unusually high Th/U ratios (4.5–5.5). Combined trace element and isotope data require that three end-members were implicated in the genesis of the N Luzon lavas: (1) a mantle wedge end-member with a Dupal-type Pb isotope signature, (2) a high LIL/HFS subduction component interpreted to be a slab-derived hydrous fluid, and (3) an isotopically enriched end-member which reflects bulk addition (<5%) of subducted S China Sea terrigenous sediment. The ⁸⁷Sr/⁸⁶Sr ratios in the volcanics show a restricted range compared with that in the sediments, and this contrasts with ¹⁴³Nd/¹⁴⁴Nd and ²⁰⁸Pb^*/²⁰⁶Pb^*, both of which have similar ranges in the volcanics and sediments. Such differences imply that whereas the isotope ratios of Nd, Pb and Th are dominated by the component from subducted sediment, those of Sr reflect a larger relative contribution from the slab-derived fluid.     

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).

     

Long-term prediction of intermediate depth earthquakes in the southern Aegean region based on a time-predictable model

Repeat times of strong intermediate depth (60 km h 180 km) earthquakes have been determined by the use of instrumental and historical data for six seismogenic sources in the Benioff zone of the southern Aegean area. For four of these sources, at least two interevent times (three mainshocks) are available for each source. By using the repeat times for these four sources, the following relation has been determined: logT _t = 0.20M _min + 0.19M _p +a, whereT _t is the repeat time (in years),M _min the surface wave magnitude of the smallest earthquake considered,M _p the magnitude of the preceding mainshock and a parameter which varies from source to source. A multilinear correlation coefficient equal to 0.91 was determined for this relation, which indicates that the time predictable model holds to a satisfactory degree for the strong mainshocks of intermediate focal depth in the southern Aegean.By assuming that the ratioT/T _t, whereT is the observed andT _t the calculated repeat time, follows a lognormal distribution, the conditional probabilities for the occurrence of strong (M _s 6.5) and very strong (M _s 7.5) earthquakes during the period 1991–2001 in these four seismogenic sources have been calculated. These probabilities are very high (P > 0.9) for the strong and high (P > 0.5) for the very strong intermediate depth earthquakes which occur in the three sources of the shallower (h < 100 km) part of the Benioff zone where coupling occurs between the front parts of the Mediterranean lithosphere (downgoing) and the Aegean lithosphere.     

Sediment budget-based estimates of trace metal inputs to a Chesapeake estuary

This article evaluates whether a sediment budget for the South River, Maryland, can be coupled with metals data from sediment cores to identify and quantify sources of historic metal inputs to marsh and subtidal sediments along the estuary. Metal inputs to estuarine marsh sediments come from fluvial runoff and atmospheric deposition. Metal inputs to subtidal sediments come from atmospheric deposition, fluvial runoff, coastal erosion, and estuarine waters. The metals budget for the estuary indicates that metal inputs from coastal erosion have remained relatively constant since 1840. Historical variations in metal contents of marsh sediments have probably resulted primarily from increasing atmospheric deposition in this century, but prior to 1900 may reflect changing fluvial sources, atmospheric inputs, or factors not quantified by the budget. Residual Pb, Cu, and Zn in the marsh sediments not accounted for by fluvial inputs was low to moderate in 1840, decreased to near zero circa 1910, and by 1987 had increased to levels that were one to ten times greater than those of 1840. Sources of variability in subtidal cores could not be clearly discerned because of geochemical fluxes, turbulent mixing, and bioturbation within the cores. The sediment-metal budgeting approach appears to be a viable method for delineating metal sources in small, relatively simple estuarine systems like the South River and in systems where recent deposition (for example, prograding marshes) prevents use of deep core analysis to identify background levels of metal. In larger systems or systems with more variable sources of sediment and metal input, however, assumptions and measurement errors in the metal budgeting approach suggest that deep core analysis and normalization techniques are probably preferable for identifying anthropogenic impacts.Field and laboratory research conducted at the Department of Geography, University of Maryland, College Park, Maryland, 20742, USAField and laboratory research conducted at the Marine and Estuarine Environmental Science Program, University of Maryland, College Park, Maryland, 20742, USA     

Late Quaternary palaeolimnology of a tropical marl lake: Wallywash Great Pond,Jamaica

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.     

Paleohydrology and paleoclimate records in a saline prairie lake core: mineral,isotope and organic indicators

This pilot study examines the potential of obtaining a sedimentary record of paleoenvironmental/climatic/hydrologic conditions for saline Redberry Lake in southern Saskatchewan, Canada. The tools are mineralogy, stable isotopes and pigments. The upper meter of an offshore sediment core contains 10 to 20% by weight aragonite (CaCO₃), which apparently precipitated in the water column. The ¹⁸O and ¹³C of the bulk aragonite (corrected for content of detrital calcite) vary by 4 to 5. Enrichment in ¹⁸O in aragonite is significantly correlated with pigment concentrations (chlorophyll a, phaeophytin). The ¹⁸O and pigment data provide evidence for relatively dry and/or warm conditions and high limnetic productivity for the period 2500 to 1500 yrs B.P. After 1500 B.P., the climate was apparently similar to the present, with two episodes of relatively enhanced productivity, dryness and/or warmth, at around 1000 to 900 and 500 to 200 B.P. During the past century, Redberry Lake has decreased approximately 8 m in depth and its salinity has doubled. No clear sedimentary signal was observed in response to these recent hydrologic trends. These changes have not been associated with a significant climate trend in the region, but may have been induced by land use changes in the catchment.This publication is the third of a series of papers presented at the Conference on Sedimentary and Paleolimnological Records of Saline Lakes. This Conference was held August 13–16, 1991 at the University of Saskatchewan, Saskatoon, Canada. Dr. Evans is serving as Guest Editor for this series.     

A stability study of asteroid families near the 3:1 and 5:2 resonance with Jupiter

By using theD-criterion Lindblad (1992) has identified 14 asteroid families from a sample of 4100 numbered asteroids with proper elements from Milani and Kneevi (1990). Taxonomic types and other physical properties for a significant number of objects in five of the families show strong homogeneity within each family, further strengthening their internal relationship.To test the hypothesis of a common origin in, e.g., a catastrophic collision event, we have set out to integrate the orbits of the members of the Maria, Dora and Oppavia-Gefion families over some 10⁶ years. The mean distance for the Maria family is close to the 3:1 mean-motion resonance with Jupiter, while the other two families lie close to the 5:2 resonance.We used a simplified solar system model which included the perturbations by Jupiter and Saturn only and implemented Everhart's variable stepsize integrator RA15. All close encounters between the family members (within 0.1 AU) were recorded as well. Preliminary results from integrations over 4×10⁵ years are presented here.The statistics of close encounters show pronounced peaks for several members within each family, while for others no significant levels above the background of random encounters or even very low frequencies were found. This indicates a subclustering within the families. Quite a lot of very close (<0.005 AU) mutual encounters are found, which suggest that, at least for the larger members in a family, the mutual gravitational interactions could be of some importance for the real orbital evolutions.The encounter statistics between the Dora and Oppavia family members suggest a possible interrelationship between this two groups.     

Generalized Lyapunov exponents indicators in Hamiltonian dynamics: An application to a double star system

The Lyapunov characteristic numbers (LCNs) which are defined as the mean value of the distribution of the local variations of the tangent vectors to the flow (=ln _k ⁱ ) (see Froeschlé, 1984) have been found to be sensitive indicators of stochasticity. So we computed the distribution of these local variations and determined the moments of higher order for the integrable and stochastic regions in a binary star system with =0.5.