Synthetic zeolites formed from expanded perlite: Type,formation conditions and properties

Summary The starting material used was expanded perlite with a grain size < 40 m (74.5 wt.% SiO₂; 12.5 wt.% Al₂O₃). This material is a waste product obtained during the production of expanded perlite. The experiments were carried out with KOH solutions, mixtures of KOH and NaOH solutions (1:1) as well as NaOH solutions in the concentration range 0.5 N to 6.0 N at temperatures of between 100° and 140°C and with reaction periods of 2 hours to 13 days in closed system. In the experiments with KOH containing solutions zeolite ZK-19 (phillipsite), W (merlinoite), G (chabazite) and F (edingtonite) formed. Without addition of aluminium high percentages of zeolite ZK-19 (80–100 wt.%) and zeolite W (90–100 wt.%) were obtained. The addition of aluminium rendered possibly the formation of 90 to 100 wt.% of zeolite G and 85 to 100 wt.% of zeolite F, respectively. In the experiments with NaOH solutions analcime, zeolite Na-Pc (gismondine), zeolite HS (sodalite hydrate) and zeolite A formed. High percentages of zeolite Na-Pc (90–100 wt.%), zeolite HS (up to 100 wt.%) and analcime (up to 100 wt.%) were synthesized without addition of aluminium. The formation of high percentages of zeolite A (95–100 wt.%), however, needs the addition of aluminium, NaCI and seed crystals. The temperature stability of the zeolites decreases in the following sequence: K-F > K-W K-ZK-19 (Na), K-W Na, K-F G_si-rich (Na), K-ZK-19 >> Na-Pc G_si-poor. Zeolite A has a very good temperature stability up to temperatures of } 550 °C similar to that of zeolite K-W. At higher temperatures, however, its stability is very poor. The NH₄ ⁺-exchange capacities (meq/g) of the different zeolites amount to the following values: ZK-19:2.8 - 3.2; W:3.0 - 3.2; G:2.3 - 3.6; A:3.1 - 3.2; Na-Pc:3.5 - 3.6; F : 3.9 - 4.8.

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Zeolithsynthese aus Blähperlit—Art, Bildungsbedingungen und Eigenschaften

Zusammenfassung Ausgangsmaterial der experimentellen Untersuchungen war Blähperlit mit einer Korngröße < 40 ,m (74,5 Gew.-% SiO₂; 12,5 Gew.-% Al₂O₃). Dieses Material ist ein Abfallprodukt, das bei der Produktion von Blähperlit anfällt. Die Experimente wurden mit KOH-Lösungen, Lösungsgemischen aus KOH und NaOH (1:1) sowie mit NaOH-Losungen im Konzentrationsbereich 0,5 n-6,0 n bei Temperaturen von 100° – 140°C und über Reaktionszeiten von 2 Stunden bis zu 13 Tagen im geschlossenen System durchgeführt. In den Experimenten mit KOH-hältigen Lösungen bildeten sich die Zeolithe ZK-19 (Phillipsit), W (Merlinoit), G (Chabasit) und F (Edingtonit). Hohe Prozentgehalte an Zeolith ZK-19 (80 – 100 Gew.-%) und Zeolith W (90–100 Gew.-%) entstehen nur ohne Zugabe von Aluminium. Die Bildung von 90–100 Gew.-% Zeolith G bzw. 85–100 Gew. % Zeolith F ist dagegen durch die Zugabe von Aluminium möglich. In den Experimenten mit NaOH-Lösungen bildeten sich die Zeolithe Analcim, Na-Pc (Gismondin), HS (Sodalithhydrat) und Zeolith A. Hohe Prozentanteile an Zeolith Na-Pc (90–100 Gew.-%), HS (bis zu 100 Gew. %) und Analcim (bis zu 100 Gew.-%) wurden ohne Aluminium-Zugabe synthetisiert. Die Bildung von hohen Gehalten an Zeolith A (95–100 Gew. %) ist jedoch nur unter Zugabe von Aluminium, NaCl und Kristallkeimen möglich.Die Temperaturbeständigkeit der Zeolithe nimmt in der folgenden Reihenfolge ab: K-F > K-W - K-ZK-19 (Na), K-W Na, K-F G_si-reich (Na), K-ZK-19 >> Na-Pc G_si-am. Zeolith A weist bis zu Temperaturen von etwa 550°C eine gute Temperaturbeständigkeit auf, die in etwa der von Zeolith K-W entspricht. Bei höheren Temperaturen ist die Beständigkeit jedoch sehr gering.Die NH⁴⁺-Austauschkapazitäten (mÄqu/g) der verschiedenen Zeolithe erreichen folgende Werte: ZK-19:2,8 - 3,2; W:3,0 - 3,2; G:2,3 - 3,6; A:3,1 - 3,2; Na-Pc:3,5 -3,6; F:3,9 - 4,8.

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With 2 Figures     

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).

     

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.

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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.

     

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.     

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.     

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.     

Origin of the hydrocarbon component of carbonaceous chondrites: the star-meteorite connection

We report the results of an experiment that produced a residue which closely matches the hydrocarbon component of the Murchison carbonaceous chondrite. This experiment suggests that the parent material of the meteoritic component originated as polycyclic aromatic hydrocarbon species in carbon stars during their later stages of evolution. The experiments also indicate that the pathway from those formation sites to eventual incorporation into the meteorite parent body involved hydrogenation in a plasma in the solar nebula or in H II regions prior to the solar nebula. This model is consistent with what is known about the meteoritic hydrocarbon component including deuterium abundance, the observation of cosmic infrared emission bands best attributed to polycyclic aromatic hydrocarbon molecules, and the inherent stability of these molecules that allows their formation in stars and subsequent survival in the interstellar medium.     

Čerenkov radiation within the Earth's upper atmosphere

A brief review of erenkov radiation within the upper atmospheric plasma has been presented. Different attempts in this context are systematically discussed. The results of analysis about the nature and characteristics of VLF hisses in terms of incoherent erenkov radiation are given in a concise manner. The occurrence of resonance cone has also been reported.     

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.