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     

Combining ordination techniques and geostatistics to determine the patterns of diatom distributions at Lake Lama, Central Siberia

The patterns of spatial variation of diatom assemblages from surface sediments in Lake Lama were quantified using a combined approach of ordination and geostatistics. The aims were (i) to estimate the amount of variation between diatom assemblages within the lake, (ii) to model the spatial variability of the diatom assemblages and their diversity, and (iii) to map the diatom distributions in the lake. A correspondence analysis (CA) separated the diatom assemblages into a planktonic and a periphytic group. Rheophilic taxa were found within the periphytic group. Variogram analysis showed that only the sample scores of the first CA axis and the Shannon diversity index were spatially structured. The range of spatial correlation was estimated to be 55 km for both variables. The diversity and, to a lesser extent, the sample scores had considerable small-scale variability of about 20 and 3%, respectively. Estimates of the first component of the CA and the Shannon index were derived using block-kriging. The maps of the estimates provided a basis for partitioning Lake Lama according to the spatial structures into an eastern and a western basin, a north–south connection between the basins, and a north–south directed tip at the far eastern end. It was shown that variation in diatom assemblages is mainly spatially structured at the catchment scale and that there is a considerable amount of variation at smaller scales. According to the modeled spatial distribution, the assemblages are most likely affected by the lake size, morphology, and the water and nutrient input introduced by rivers. This has to be taken into account when paleolimnological interpretations are drawn from records of complex lake systems like Lake Lama.     

New palaeointensity results from Cretaceous basalt of Inner Mongolia, China

We present new Thellier-Thellier palaeointensity results from three cooling units (32 samples) of Inner Mongolia lava flows (91.7 Ma) emplaced during the Cretaceous Normal Superchron (CNS). Based on rock-magnetic and microscopy observations the magneto-mineralogy of all samples is determined to be primary and unaltered high-Ti titanomagnetite. Accepted palaeointensity determinations, obtained in the 80-200 °C temperature interval, are of good technical quality with positive standard partial thermoremanent magnetisation (pTRM) checks and pTRM-tail checks. Obtained palaeointensity estimates range from 14.7 to 28.0 μT, with virtual axial dipole moments (VADM) of 2.4 to 4.6 (× 10²² Am²). The data agree well with recently published results from the same region and, combining the two datasets, we obtain independent estimates from six different cooling units yielding a time-averaged VADM of 3.2 ± 1.6 (× 10²² Am²). These data suggest a relatively low dipole moment towards the end of the Cretaceous Normal Superchron.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Quantitative climate and vegetation trends since the late glacial on the northeastern Tibetan Plateau deduced from Koucha Lake pollen spectra

Quantitative information on vegetation and climate history from the late glacial-Holocene on the Tibetan Plateau is extremely rare. Here, we present palynological results of a 4.30-m-long sediment record collected from Koucha Lake in the Bayan Har Mountains, northeastern Tibetan Plateau. Vegetation change has been traced by biomisation, ordination of pollen data, and calculation of pollen ratios. The application of a pollen-climate calibration set from the eastern Tibetan Plateau to Koucha Lake pollen spectra yielded quantitative climate information. The area was covered by alpine desert/steppe, characteristic of a cold and dry climate (with 50% less precipitation than today) between 16,700 and 14,600 cal yr BP. Steppe vegetation, warm (∼ 1°C higher than today) and wet conditions prevailed between 14,600 and 6600 cal yr BP. These findings contradict evidence from other monsoon-influenced areas of Asia, where the early Holocene is thought to have been moist. Low effective moisture on the northeastern Tibetan Plateau was likely due to high temperature and evaporation, even though precipitation levels may have been similar to present-day values. The vegetation changed to tundra around 6600 cal yr BP, indicating that wet and cool climate conditions occurred on the northeastern Tibetan Plateau during the second half of the Holocene.     

Bristen granite: a highly differentiated,fluorite-bearing A-type granite from the Aar massif,Central Alps,Switzerland

Bristen granite is a body of fine-grained leucogranite occurring in the Gotthard rail base tunnel in the Central Alps. During construction of the tunnel, Bristen granite (Brgr) has been drilled along a 600 m long section. The aplite-granite belongs to the suite of Variscan granitoid intrusions of the Aar massif and contains a variety of accessory minerals typical of highly differentiated granites. Rock forming fluorite, partly enriched in yttrium (Y) and rare earth elements (REE), is intergrown with the late Y- and REE-bearing carbonate mineral synchysite. The granite contains a variety of Ti- and Y-REE-niobates, thorite, and zircon. Compared with the calc-alkaline central Aar granite (cAgr), Bristen granite is strongly depleted in Ti, P, Mg, Sr, and Ba and shows a remarkable enrichment in incompatible elements such as Rb, Th, U, Nb, Y, HREE and F. Bristen granite is the most evolved granitoid rock of the Aar massif. The composition of Brgr is typical of post-collisional reduced (ferroan) A-type granites. The Brgr melt formed in the lower crust and crystallized from a highly differentiated melt at the cotectic point in the quartz-feldspar system close to 100 MPa and 700 °C. The Brgr intruded as a small isolated stock pre-Variscan gneisses with sharply discordant contacts. The primary igneous host of Nb, Ta, Y, U, Th and REE is biotite in addition to minor amounts of allanite, and zircon. The presence of Y-REE-fluorite, synchysite, parisite and Y- and Ti-niobates and other REE-minerals can be related to reaction of igneous biotite and primary fluorite with hydrothermal fluids. The reaction is associated with alpine metamorphism, because Y-bearing fluorite and synchysite have been reported from Alpine fissures. The transformation of primary biotite to chlorite and muscovite released the heavy metal oxides under lower greenschist facies conditions that formed the Alpine diagnostic mineral stilpnomelane at about 300 °C.