Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.     

China's small town urbanization program: Criticism and adaptation

China's 12,000 designated towns and more than 40,000 rural market towns have experienced a major transformation since the institution of rural reforms in the late 1970s. Rural industrialization based on the concept of leaving the soil but not the village, entering the factory but not the town has contributed to the revitalization of many small towns. But this rural urbanization has also brought about a number of problems in the countryside, leading many to propose the adoption of the concept ofleaving the soil and the village as another basis of China's small town urbanization. This essay attempts to examine this transformation, particularly the recent criticism and adjustment made to the small town urbanization program.     

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).

     

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.     

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.