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 elastic properties of single-crystal fayalite as determined by dynamical measurement techniques

We present new elasticity measurements on single-crystal fayalite and combine our results with other data from resonance, pulse superposition interferometry, and Brillouin scattering to provide a set of recommended values for the adiabatic elastic moduliC _ij and their temperature variations. We use a resonance method (RPR) with specimens that were previously investigated by pulse superposition experiments. The nineC _ij of fayalite are determined from three new sets of measurements. One set of our newC _ij data is over the range 300–500 K. We believe that the relatively large discrep ncies found in someC _ij are due in large part to specimen inhomogeneities (chemical and microstructural) coupled with differences in the way various techniques sample, rather than only systematic errors associated with experimental procedures or in the preparations of the specimens.Our recommendeaC _ij's (GPa) and (C _ij/T) _p (GPa/K) are: The resulting values for the isotropic bulk and shear moduli,K _s and , and their temperature derivatives are:K _s=134(4) GPa; =50.7(0.3) GPa; (K _s/T) _p =–0.024(0.005) GPa/K; and (/T) _p =–0.013(0.001) GPa/K. An important conclusion is thatK _s increases as the Fe/(Fe+Mg) ratio in olivine is increased.     

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.     

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.     

Fossil carotenoids and paleolimnology of meromictic Mahoney Lake,British Columbia,Canada

Vertical distribution of fossil carotenoids in a sediment core from meromictic Mahoney Lake was studied. Besides okenone and demethylated okenone, lutein and zeaxanthin and-carotene isomers were identified. No carotenoids typical for purple nonsulfur or green sulfur bacteria were detected. The ratio of zeaxanthin to lutein (above 1:1 in all samples) indicates a dominance of cyanobacteria over green algae in the phytoplankton assemblages of the past. Okenone, which is found exclusively in Chromatiaceae, was the dominating carotenoid in all sediment zones.The oldest sediment layers containing okenone were deposited 11 000 years ago. Between 9000 and 7000 and since 3000 years b.p., Chromatiaceae reached a considerable biomass in the lake. Vertical changes in okenone concentration were not related to changes of paleotemperatures. In contrast, okenone concentrations decreased during periods of volcanic ash input. During most of the lake history, however, mean okenone concentrations were positively correlated with sedimentation rates. This indicates that vertical changes of okenone concentration in the sediment reflect past changes of purple sulfur bacterial biomass in the lake.According to these results, the past limnology of Mahoney Lake resembled that of the present with a sulfide-containing monimolimnion and a well-developed population of okenone-bearing purple sulfur bacteria.     

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

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).

---

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.

---

---

With 8 Figures     

Crystal-chemistry of clinopyroxene from Sunda volcanic arc

Summary The crystal-chemistry of clinopyroxene from a suite of Sunda arc volcanic rocks was investigated by X-ray structure refinement and microprobe analysis. Relationships with clinopyroxene from volcanic rocks of the intraplate environment were highlighted.Sunda clinopyroxenes were distinguished into two groups. The first consists of clinopyroxene from SiO₂-saturated rock types and crystal rim from SiO₂-undersaturated rock types, the second of crystal core from SiO₂-undersaturated rock types. The crystal chemical behaviour of the two groups differs significantly, mainly in the geometrical relationships between M2 and T sites. While in the first group M2-O3 and T-O3 bond lengths shorten and lengthen respectively due to Ca and Al^IV increase, in the second group in which M2 site is almost fully coordinated by Ca, -O3 bond lengths are forced to lengthen in spite of low Al^IV content, in order to mantain the local charge balance around the O3 oxygens.It is noteworthy that Sunda clinopyroxene shows strong analogies with that from basaltic rocks from the Ethiopian plateau and K-rich lavas from the Roman Province respectively, reflecting similarities between the composition and mineralogical assemblages of the host rocks, although they all came from different tectonic environments. A relationship between intracrystalline Mg-Fe 2+ disorder and the explosive character of the volcanism is demonstrated.

---

Kristallchemie von Klinopyroxenen aus Gesteinen des Vulkanbogens der Sunda-Inseln

Zusammenfassung Die Kristallchemie von Klinopyroxenen aus einer Serie von vulkanischen Gesteinen des Sunda-Bogens wurde mit Röntgen-Strukturverfeinerungen und Mikrosonden-analysen untersucht. Beziehungen zu Klinopyroxenen vulkanischer Gesteine aus intra-Plattenpositionen werden beleuchtet. Die Sunda-Klinopyroxene wurden in zwei Gruppen eingeteilt. Die erste umfaßt Klinopyroxene SiO₂-gesättigter Gesteinstypen und Kristallsäume SiO₂-untersättigter Gesteinstypen, die zweite Kristallkerne SiO₂-untersättigter Gesteinstypen. Das kristallchemische Verhalten der beiden Gruppen unterscheidet sich beträchtlich, hauptsächlich in den geometrischen Beziehungen zwischen den M2 und T Positionen. Während in der ersten Gruppe die M2-O3 und T-O3 Bindungsldngen durch Zunahme von Ca und Al^IV kleiner bzw. größer werden, sind in der zweiten Gruppe die T-O3 Bindungslängen trotz niedrigen Al^IV Gehaltes zu einer Vergrößerung gezwungen, damit um die O3 Atome der lokale Ladungsausgleich erhalten bleibt.Es ist bemerkenswert, daß die Sunda-Klinopyroxene große Analogien zu denen aus basaltischen Gesteinen des Abessinischen Plateaus und aus K-reichen Laven sowohl der Römischen Provinz als auch des Westafrikanischen Grabens zeigen. Dies spiegelt Ähnlichkeiten zwischen Zusammensetzung und Mineralbestand der Muttergesteine wider, obwohl sie all aus tektonisch unterschiedlichen Positionen kommen.Eine Beziehung zwischen intrakristalliner Mg-Fe²⁺ Unordnung und dem explosiven Charakter des Vulkanismus wird aufgezeigt.

     

Corona textures in Proterozoic olivine melanorites of the Equeefa Suite,Natal Metamorphic Province,South Africa

Summary Olivine-plagioclase and phlogopite-plagioclase coronas have been identified from olivine melanorites of the Mid- to Late Proterozoic Equeefa Suite in southern Natal, South Africa. Olivine, in contact with plagioclase, is mantled by a shell of clear orthopyroxene, in turn rimmed by pale green (pargasitic) clinoamphibole. Locally a third rim, composed of a fine pargasite-spinel symplectite is developed adjacent to the plagioclase. The second corona reaction has produced greenish-brown pargasite at phlogopite-plagioclase interfaces. A third, less obvious reaction, between olivine and phlogopite is also noted. Analytical data of all the mineral phases present, along with the coronas, are given. Two-pyroxene thermometry yields magmatic core temperatures ( 1120°C), with rim compositions indicating equilibration at 850°C. Consistent with this, the modelled olivine-plagioclase reaction occurs between 830–1050°C with a_waterbetween 0.1 and 1.0 at 7 kbar. The three reactions took place during a prolonged history of cooling and partial hydration of the magmatic olivine melanorites from over 1000°C down to 600°C. The P-T conditions indicated by the reactions suggest this cooling process was essentially isobaric, indicating that the area was not subjected to rapid uplift or burial throughout this entire period.

---

Korona-Texturen in proterozoischen Olivin-Melanoriten der Equeefa Suite, Natal Metamorphic Province, Südafrika

Zusammenfassung Aus Olivin-Melanoriten der mittel- bis spätproterozoischen Equeefa Suite im südlichen Natal, Südafrika, wurden Olivin-Plagioklas und Phlogopit-Plagioklas-Koronartexturen beobachtet. Olivin, der mit Plagioklas im Kontakt steht, wird von einem klaren Saum vom Orthopyroxen ummantelt, der seinerseits von blaßgrünem (pargasitischem) Klinoamphibol umsäumt wird. Stellenweise ist ein dritter Saum, bestehend aus feinkörnigem symplektitischem Pargasit-Spinell im Kontakt mit Plagioklas ausgebildet. Die zweite koronabildende Reaktion resultiert in Bildung eines grünbraunen Pargasites an Phlogopit-Plagioklas Kornkontakten. Eine dritte, weniger auffällige Reaktion zwischen Olivin und Phlogopit wurde ebenfalls beobachtet. Zwei-Pyroxen-Thermometrie ergab magmatische Temperaturen der Kernbereiche ( 1120°C) und belegt eine Gleichgewichtseinstellung in den Randzonen bei ca. 850°C. Olivin-Plagioklas-Modellreaktionen liegen ebenfalls in einem Temperaturbereich von 830–1050°C bei Wasseraktivitäten von 0.1 bis 1.0 und einem Druck von 7 kbar. Die drei Reaktionen liefen im Zuge einer länger andauernden Abkühlung unter teilweiser Hydratisierung der magmatischen Melanorite in einem Temperaturbereich von 1000°C bis ca. 600°C ab. Die aus den Reaktionen ableitbaren P-T-Bedingungen sprechen für eine im wesentlichen isobare Abkhlungsgeschichte und zeigen, daß dieses Gebiet wáhrend dieser gesamten Periode keiner raschen Hebung bzw. keiner Versenkung unterworfen worden ist.

     

The arrangement in mean elements space of the periodic orbits close to that of the Moon

In a simplified model of the Earth-Moon-Sun system based on the restricted circular 3-dimensional 3-body problem, it is possible to find numerically a set of 8 periodic orbits whose time evolutions closely resemble that of the Moon's orbit. These orbits have a period of 223 synodic months (i.e. the period of the Saros cycle known for more than two millennia as a means of predicting eclipses), and are characterized by a secular rotation of the argument of perigee . Periodic orbits of longer durations exhibiting this last feature are very abundant in Earth-Moon-Sun dynamical models. Their arrangement in the space of the mean orbital elements- for various values of the lunar mean motion is presented.     

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.