Multiple Enrichment Processes and their Relationships in the Subcrustal Lithosphere Beneath the Eifel (Germany)

Three types of enrichment processes may be distinguished inspinel peridotite mantle xenoliths from the West Eifel (Germany):

1. Enrichmentof light rare earth elements (LREE) occurs in wholerocks andclinopyroxenes in conjunction with the formation ofTi-pooramphiboles (<0•5%) in a low-tempetature suite(900C).
2. Enrichment in high field strength elements (HFSE; Ti and Hf)is associated with strong zoning of TiO₂ in amphibole adjacentto mica hornblendite veins. A reheating from 900 to 1050C associatedwith this vein formation is reflected by the zoning profilesin orthopyroxenes with Ca, Al, and Cr increasing from core torim.
3. Moderate enrichment of LREE without amphibole formationin ahigh-temperature suite (1125C) is observed at the contactofperidotites to pyroxenite veins yielding the same temperature.
4. Based on geochemical and isotopic evidence, enrichment process(1) is inferred to be due to interaction of peridotites fromthe subcrustal lithosphere with low-density fluids. Process(2) represents a subsequent interaction of amphibole-bearingperidotites formed during the first process with basic meltsmoving through a system of cross-cutting dykes and veins. Processes(2) and (3) are linked to the Quaternary West Eifel volcanism.Geothermobarometry of the xenoliths shows that these processesare related to different depth regimes of the lower lithosphere.

     

Stratiform and vein U,Mo and Cu mineralization in the Novoveská Huta area,CSFR

U-Mo and Cu mineralization occurs in horizons as well as in veins in the Permian formations near Novoveská Huta. Ore mineralization is represented by uraninite, U-Ti oxides, coffinite, molybdenite, chalcopyrite, tennantite and pyrite. The isotopic composition of S and C displays a larger variability in the stratiform ores (³⁴S from –32.7 to +2.7 and ¹³C from –27.1 to — 0.5) These data suggest mixing of meteoric solutions with fluids of volcanic origin and a complex history. There is a narrower range of ³⁴S from –18.8 to –4.6 and ¹³C from –6.3 to –2.5% in quartz-carbonate veins with Cu mineralization suggesting a deep source of ore-bearing solutions. The Permian volcanics were a significant source of ore elements.Their contents of U, Mo, Cu and Y are from two to eight times higher than in sedimentary rocks. Accumulations of ore elements in the horizons were formed by the reduction and adsorption processes 240 ± 30 Ma ago according to U-Pb isotopic dating. Due to Alpine tectonism, these low-grade ores (U<0.1 wt%) were remobilized and higher-grade U-Mo ores (U>0.1 wt%) were formed 130 ± 20 Ma ago at temperatures ranging from 110 to 120° C, according to fluid inclusions. Younger veins with Cu mineralization were formed 115 ± 10 Ma according to the model age of Pb at temperatures ranging from 95 to 190°C.     

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.     

The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.     

Fractional crystallization and zoning in igneous feldspars: ideal water-buffered liquid fractionation lines and feldspar zoning paths

Diagrams giving plagioclase and sanidine fractionation paths and liquid fractionation lines under conditions of ideal water-buffered fractional crystallization in the ternary feldspar system were constructed graphically using topological reasoning, and experimental data and calculated phase relationships from the literature. The liquidus lines and solidus or solvus paths are unique at constant P and a _{H 2}O. The composition of a liquid evolves with time and moves along a fractionation line by removal of successive crystal fractions, whereas the compositions of each of the crystal fractions lie on and define a solidus or solvus path. Most but not all such water-buffered lines and paths differ only slightly from those in which water is free to build up during crystallization and a _{H 2}O to increase, as in many rocks. Liquid compositions lying along liquidus fractionation lines are not normally preserved, unless erupted as aphyric lavas. The solidus or solvus paths may be preserved either as overgrowth zones in crystals (zoning paths) or as a series of crystal fractions in layered intrusions. The topologies of the lines and paths depend mainly on the nature of the two-feldspar boundary line separating the plagioclase and sanidine fields which is a function of P _{H 2}O or a _{H 2}O at constant P; increases in either progressively lower the liquidi and solidi and cause larger intersections of the solidi with the solvus. One-feldspar solidus paths at high P and a _{H 2}O are simple, whereas they are complex and may bend back on themselves at low P _{H 2}O or low a _{H 2}O at high P. Two-feldspar paths may be simultaneous (cotectic) or sequential (peritectic). The former are simple and do not meet at high P and a _{H 2}O, the critical solution line lying in the gap; they are complex and may bend back or overlap at low P _{H 2}O or low a _{H 2}O at high P, the position of the critical solution line being hard to determine. Liquids which have simultaneously fractionated two feldspars may fractionate only one towards the end, crystallization changing from subsolvus to hypersolvus. Sequential paths may involve overgrowth of an early feldspar by a later one, usually sanidine overgrowths on plagioclase, but plagioclase overgrowths on sanidine occur. These complexities explain in part the difficulties of unravelling the textural and compositional relationships of ternary feldspars in water-poor felsic igneous rocks (even in the absence of alteration or complex magma dynamics) and of trying to deduce phase relationships from natural occurrences of feldspars.C.R.P.G. contribution number 948     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

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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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.

     

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.     

Passing through resonance: The excitation and dissipation of the lunar free libration in longitude

The acceleration of the mean lunar longitude has a small effect on the periods of most terms in a Fourier expansion of the longitude. There are several planetary perturbation terms that have small amplitudes, but whose periods are close to the resonant period of the lunar libration in longitude. Some of these terms are moving toward resonance, some are moving away from resonance, and the periods of those terms that do not include the Delaunay variables in their arguments are not moving. Because of its acceleration of longitude, the Moon is receding from the Earth, so the magnitude of the restoring torque that the Earth exerts on the rotating Moon is gradually attenuating; thus resonance itself is moving, but at a much slower rate than the periods of the accelerating planetary perturbations. There are five planetary perturbation terms from the ELP-2000 Ephemeris (with amplitudes of 0.00001 or greater) that have passed through resonance in the past two million years. One of them is of special interest because it appears to be the excitation source of a supposed free libration in longitude that has been detected by the lunar laser ranging experiment. The amplitude of the term is only 0.00021 but it could be the source of the 1 amplitude free libration term if the viscoelastic properties of the Moon are similar to those of the Earth.