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     

Die Rheingrabenrandverwerfung im Wattkopftunnel bei Ettlingen (Nordschwarzwald)

The Wattkopftunnel, near Ettlingen (Nordschwarzwald), drives through the eastern margin of the Rheingraben. The tunnel passes cenozoic and mesozoic sediments. Early quarternary and tertiary beds are situated west of the main thrust of the Rheingraben. Fossil record indicates upper Oligocene age (Chatt) for parts of the tertiary sediments. At the eastern border of the Rheingraben, wedges of jurassic and middle triassic series are squeezed. East of the Rheingraben the tunnel drives in the lower triassic Bausandstein. The eastern margin of the Rheingraben was investigated in detail during tunneling. Faults of the Rheingraben margin are distributed in an 130 meter wide fault zone in the tunnel. Total stratigraphic separation by the normal faults reaches more than 2 000 meters. The cenozoic sequence suffered synsedimentary to early diagenetic deformation, while the mesozoic series are characterized by ruptural deformation. The fault- and joint system is directed in the rheinische Richtung (SSW-NNE). East of the Rheingraben a second direction occur, running parallel to the lower Albtal (W-E).

     

Palaeoclimatic studies in South Shetland Islands,Antarctica, based on numerous stratigraphic variables in lake sediments

The hitherto longest found lake sediment sequence on Byers Peninsula, Livingston Island, South Shetland Islands, was analysed with respect to lithology, chronology, diatoms, Pediastrum, pollen and spores, mosses, mineralogy, and sediment chemistry. During the ca. 5000 year long development the sediments were influenced by frequent tephra fall-outs. This volcanic impact played a major role in the lake's history during two periods, 4700–4600 and 2800–2500 BP, but was of importance during the lake's entire history with considerable influence on many of the palaeoenvironmentally significant indicators. The large and complex data set was analysed and zonated with different types of multivariate analysis. This resulted in a subdivision of the sequence into 8 time periods and 21 variables. Redundancy analysis (RDA) of this data set, both without and with the tephra periods, and with 4–6 of the variables as explanatory environmental variables, reveal that climatic/environmental signals are detectable. The palaeoclimatic picture that emerged out of the tephra noise suggests that the first 100 years were characterized by mild, humid conditions. This was followed by a less mild and humid climate until ca. 4000 BP when a gradual warming seems to have started, coupled with increased humidity. These mild and humid conditions seem to have reached an optimum slightly after 3000 BP. At ca. 2500 BP a distinct climatic deterioration occurred with colder and drier conditions and long seasons with ice cover. This arid, cold phase probably reached its optimum conditions at ca. 1500 BP, when slightly warmer conditions might have prevailed for a while. Except for the modern sample with rather mild climate, the last 1400 years seem to have been fairly arid and cold, and the effects of the frequent volcanic activity during this period is only vaguely seen in the records.     

The role of bathymetry and directional wave conditions on observed crescentic bar dynamics

Nearshore sandbars are important features in the surf zone of many beaches because they strongly influence the mean circulation and evolving morphology. Due to variations in wave conditions, sandbars can experience cross-shore migration and vary in shape from alongshore uniform (shore-parallel) to alongshore rhythmic (crescentic). Sandbar dynamics have been studied extensively, but existing observational studies usually do not quantify the processes leading to crescentic bar formation and straightening. This study analyses the dynamics of crescentic bar events at the fetch-limited beach of Castelldefels (northwestern Mediterranean Sea, Spain) using 7.5 years of hourly time-exposure video images and detailed wave conditions. The results show that, despite the generally calm wave conditions, the sandbars were very dynamic in the cross-shore and longshore directions. They often migrated rapidly offshore during storms (up to 70 m in one day) and more slowly onshore during post-storm conditions. Crescentic bars were often present at the study site (48% of the time), but only when the sandbar was at least 10 m from the shoreline. They displayed a large variability in wavelengths (100–700 m), alongshore migration speeds (0–50 m/day) and cross-shore amplitudes (5–20 m). Wavelengths increased for larger bar–shoreline distances and the alongshore migration speeds were strongly correlated with the alongshore component of the radiation stresses. Crescentic patterns typically developed during low–medium energetic waves with limited obliquity ( $\theta \lesssim 20$° at 10 m depth), while bar straightening occurred during medium–high energetic waves with strong oblique angles of incidence ( $\theta \gtrsim 15$°). Overall, this study provides further proof for the important role of wave direction in crescentic bar dynamics and highlights the strong dependence of crescentic bar development on the initial bathymetric configuration.     

High-resolution sequence stratigraphy of the Lower Triassic ‘Buntsandstein’ in the Netherlands and northwestern Germany

Detailed log correlations of the largely fluvio-lacustrine Lower Triassic Buntsandstein (Late Permian-Early Anisian), carried out on 80 wells in the Dutch onshore and offshore areas, can be linked to northwest-German high-resolution sequence stratigraphy. The correlations show that cyclic sedimentation occurred in large parts of the basin. Seven 1st-order sequences are recognised, namely the Main Claystone, Rogenstein, Volpriehausen, Detfurth, Hardegsen, Solling and Lower Röt Sequences. They are overlain by the lower part of the Upper Röt–Lower Muschelkalk Sequence. Distinct sequence boundaries have been identified at the bases of four sequences: Volpriehausen, Detfurth, Solling and Upper Röt. The higher-order sequences consist of fining-upwards cycles with a thickness of up to tens of metres. The sequences are laterally persistent and have a characteristic expression on gamma-ray and sonic logs. In the Lower Buntsandstein, they display a uniform character throughout most of the area, with only minor differences in thickness or lithology. NNE-oriented lows and swells were formed during deposition of the Volpriehausen, Detfurth and Hardegsen Sequences. Uplift prior to the deposition of the Solling Sequence caused deep erosion on the swells in the basin and minor erosion in the lows. The high-resolution sequences probably represent alternating, relatively wet and dry climatic periods, with a periodicity of about 100 000 years. An analysis of the sequences suggests that their reduced thickness on the swells is mainly the effect of erosion. This is supported by analyses of the accumulation patterns and rates.     

A multifractal analysis of lidar measured water vapour

Accurate and fast-response measurements of space-time observations of specific humidity were made above a drying land surface at the University of California at Davis, using the Los Alamos water Raman-lidar. In an attempt to quantify the space-time intermittency features of turbulent flows in the lower atmosphere, a multifractal analysis of these water vapour measurements was performed. The structure of the specific humidity, (x, t), was analyzed quantifying a scalar gradient measure both in time and space, for all possible one-dimensional cuts, i.e. and . The results confirm the multifractal nature of this scalar gradient measure (a type of scalar dissipation rate) and show that humidity measurements at fixed times (x) are more intermittent (e.g. have less entropy dimension) than those at fixed locations in space (t). Similar multifractal behaviour of the spatial data, with and without a transformation from the observed wind velocities, supports the validity of Taylor's hypothesis for the studied fields.     

Ozone production due to emissions from vegetation burning

Ozone has been observed in elevated concentrations by satellites over areas previously believed to be background. There is meteorological evidence, that these ozone plumes found over the Atlantic Ocean originate from vegetation fires on the African continent.In a previous study (DECAFE-88), we have investigated ozone and assumed precursor compounds over African tropical forest regions. Our measurements revealed large photosmog layers at altitudes from 1.5 to 4 km. Both chemical and meteorological evidence point to savanna fires up to several thousand km upwind as sources.Here we describe ozone mixing ratios observed over western Africa and compare ozone production ratios from different field measurement campaigns related to vegetation burning. We find that air masses containing photosmog ingredients require several days to develop their oxidation potential, similar to what is known from air polluted by emissions from fossil fuel burning. Finally, we estimate the global ozone production due to vegetation fires and conclude that this source is comparable in strength to the stratospheric input.     

Possible creep-related tilt precursors obtained in the Central Apennines (Italy) and in the Southern Caucasus (Georgia)

Daily averaged tilt component data from two sites of the Central Apennines (Italy) and of the Southern Caucasus (Georgia), respectively, revealed intermediate-term tilts as possible precursors to earthquakes (M=3.0÷4.7) which occurred in the above-mentioned seismic areas within a distance of 50 km from the sites. A good temporal correlation as well as a fair spatial correspondence between these residual tilts (with amplitude and duration of some microradians and months, respectively) and main shocks were pointed out, by removing both secular trends and seasonal thermoelastic effects from the raw tilts. An attempt was made to justify the above-mentioned results, based on the assumption that the observed intermediate-term preseismic tilts are the manifestation of aseismic creep episodes of comparable duration in the fault materials of thrust faults close to the tilt sites. The mechanism refers to a strain field slowly propagating from the preparation focal area to the tilt site, through crustal blocks separated by weak transition zones. This propagation is thought to be the cause of the local aseismic fault slip recorded by the tiltmeters. Previously, both discrete structures and strain propagation effects were revealed in the Central Apennines and are thought also to exist in the Southern Caucasus. As in the past, the rheological properties of fault materials are revealed as viscoelastic ones. In fact, creep equations obtained by applying several viscoelastic models on our data, proved to fit quite well some of the observed tilt precursors, producing viscosity and rigidity values very similar to those reported in literature.Professor Petr Viktorovich Manjgaladze died during the writing of this paper     

Analysis of COMPTEL gamma-ray burst locations and spectra

In its first three years of operation, the COMPTEL instrument on theCompton Gamma-Ray Observatory has measured the locations (mean accuracy 1°) and spectra (0.75-30 MeV) of 18 gamma-ray bursts and continues to observe new events at a rate of 1/month. With good angular resolution and sensitivity at MeV energies, the growing COMPTEL burst catalog is an important new piece of evidence in the on-going GRB mystery. The COMPTEL burst locations are consistent with an isotropic distribution of sources, yet the spatial coincidence of two of the bursts indicates the possibility of repetition. The COMPTEL burst spectra are in most cases consistent with a single power law model with spectral index in the range 2–3. However, two bursts show evidence of a spectral break in the MeV range. Measurement of rapid variability at MeV energies in the stronger bursts provides evidence that either the sources are nearby (within the Galaxy) or the gamma-ray emission is relativistically beamed. We present an overview of analysis results obtained from the COMPTEL burst catalog concentrating on the search for burst repetition and the implications of highly variable MeV emission.     

Near-infrared imaging in H2 of molecular (CO) outflows from young stars

We have imaged several known molecular (CO) outflows in H₂ v=1-0 S(1) and wide-band K in order to identify the molecular shocks associated with the acceleration of ambient gas by outflows from young stars. We detected H₂ line emission in all the flows we observed: L 1157, VLA 1623, NGC 6334I, NGC 2264G, L 1641N and Haro 4-255. A comparison of the H₂ data with CO outflow maps strongly suggests that prompt entrainment near the head of a collimated jet probably is the dominant mechanism for producing the CO outflows in these sources.