Electron paramagnetic resonance of Sc3+-stabilized CO 3 3− molecule-ion in natural calcite

Electron paramagnetic resonance (EPR) spectra of CO ₃ ^3– molecule-ions stabilized by Sc³⁺ in natural calcite were identified and studied at X-band frequencies and room temperature. The principal values of the g-tensor (g _xx= 1.9997, g _yy = 2.0030, g _zz = 1.9972) and the direction cosines of the g and A tensors for CO ₃ ^3– -Sc³⁺ center were found to be close to that for the well-known CO ₃ ^3– -Y³⁺ center. A quantitative comparison of different impurity contents in calcite samples and analysis of the intensities of forbidden transitions were used to identify Sc³⁺. An estimation of the unpaired electron spin density on the nuclei of paramagnetic centers confirms that both centers, CO ₃ ^3– -Sc³⁺ and CO ₃ ^3– -Y³⁺, have the same nature.     

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.     

RADON DEPTH MIGRATION1

A depth migration method is presented that uses Radon-transformed common-source seismograms as input. It is shown that the Radon depth migration method can be extended to spatially varying velocity depth models by using asymptotic ray theory (ART) to construct wavefield continuation operators. These operators downward continue an incident receiver-array plane wave and an assumed point-source wavefield into the subsurface. The migration velocity model is constrained to have longer characteristic wavelengths than the dominant source wavelength such that the ART approximations for the continuation operators are valid. This method is used successfully to migrate two synthetic data examples:

• 1 a point diffractor, and
• 2 a dipping layer and syncline interface model.

It is shown that the Radon migration method has a computational advantage over the standard Kirchhoff migration method in that fewer rays are computed in a main memory implementation.     

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.     

Isotope and trace element evidence for three component mixing in the genesis of the North Luzon arc lavas (Philippines)

Post-3Ma volcanics from the N Luzon arc exhibit systematic variations in ⁸⁷Sr/⁸⁶Sr (0.70327–0.70610), ¹⁴³Nd/¹⁴⁴Nd (0.51302–0.51229) and ²⁰⁸Pb^*/²⁰⁶Pb^* (0.981–1.035) along the arc over a distance of about 500 km. Sediments from the South China Sea west of the Manila Trench also exhibit striking latitudinal variations in radiogenic isotope ratios, and much of the isotopic range in the volcanics is attributed to variations in the sediment added to the mantle wedge during subduction. However, Pb-Pb isotope plots reveal that prior to subduction, the mantle end-member had high 8/4, and to a lesser extent high 7/4, similar to that in MORB from the Indian Ocean and the Philippine Sea Plate. Th isotope data on selected Holocene lavas indicate a source with unusually high Th/U ratios (4.5–5.5). Combined trace element and isotope data require that three end-members were implicated in the genesis of the N Luzon lavas: (1) a mantle wedge end-member with a Dupal-type Pb isotope signature, (2) a high LIL/HFS subduction component interpreted to be a slab-derived hydrous fluid, and (3) an isotopically enriched end-member which reflects bulk addition (<5%) of subducted S China Sea terrigenous sediment. The ⁸⁷Sr/⁸⁶Sr ratios in the volcanics show a restricted range compared with that in the sediments, and this contrasts with ¹⁴³Nd/¹⁴⁴Nd and ²⁰⁸Pb^*/²⁰⁶Pb^*, both of which have similar ranges in the volcanics and sediments. Such differences imply that whereas the isotope ratios of Nd, Pb and Th are dominated by the component from subducted sediment, those of Sr reflect a larger relative contribution from the slab-derived fluid.     

Fluid-rock interaction between syenites and marbles at Stephen Cross Quarry,Québec,Canada: petrological and stable isotope data

Grenville dolomitic marbles and calc-silicates at Stephen Cross Quarry, Québec, underwent contact metamorphism and metasomatism associated with the intrusion of the Wakefield syenite at ambient pressures of 0.4GPa at 1090–1070Ma. Fluid infiltration produced exoskarns, calcite+periclase+forsterite±diopside±orthoclase assemblages in the marbles, and quartz±calcite±wollastonite±diopside±anorthite assemblages in the calc-silicates. Phase-equilibria in the CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ system suggest that fluid infiltration occurred close to the thermal peak of contact metamorphism (715–815°C) and that the fluids hadXCO₂0.15. In the metasediments, ¹⁸O values of calcite (Cc) are as low as 8.6, suggesting that the fluids were in isotopic equilibrium with the syenites (¹⁸O =8.8–10.2). Marble ¹³C(Cc) values are-0.1 to-3.2; the lack of correlation between ¹³C(Cc) and ¹⁸O(Cc) is consistent with the infiltration of water-rich fluids. The resetting of stable isotopes and the mineralogical changes can be explained by time-integrated fluid fluxes of up to 110 m³/m² (4×10⁶ mol/m²), corresponding to actual fluxes of 3×10^-11 to 3×10^-12 m³/m²-s and intrinsic permeabilities of 10^-18 to 10^-20 m² for fluid flow lasting 0.1-1Ma. Marble ¹⁸O(Cc) values do not correlate well with distance from the syenite, and fluids were probably channelled across lithological layering. The correlation between the degree of resetting of marble ¹⁸O(Cc) values with the abundance of submillimetre-wide veins, suggests that fluid focussing may have resulted from variations in fracture density. Late, lower temperature (<500°C), fluid flow formed serpentine (Serp) and brucite (Br) from periclase and forsterite. ¹⁸O(Br) and ¹⁸O(Scrp) values correlate with ¹⁸O(Cc), suggesting that retrogression involved only limited volumes of fluid. The observation that ¹⁸O(Cc-Br) and ¹⁸O(Cc-Serp) values are higher in marbles that have lower ¹⁸O(Cc) values is interpreted as indicating that fluid flow persisted to lower temperatures in those rocks due to higher intrinsic permeabilities. Calcite in the syenite was also formed by the influx of fluids during cooling. Syenite ¹⁸O(Cc) values are approximately in isotopic equilibrium with the high-temperature silicate minerals, suggesting that again only minor volumes of fluid were involved. In detail fluid flow was prolonged and complex, creating problems for the application of quantitative fluid flow models.This paper is a contribution to IGCP 304, Lower Crustal Processes     

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     

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.

     

Sea level and diagenesis: a case study on Pleistocene beaches,Whalebone Bay,Bermuda

Pleistocene fluctuations of sea level have left marine and aeolian limestones intercalated with glacial red soils on the Bermuda Carbonate Platform (Atlantic, 64°50W, 32°20N). Successive eustatic highstands of similar amplitude drowned the tectonically stable platform and piled up similar sets of sediments. Up to three Pleistocene beaches are stacked in shorelines sections. Post-depositional diagenetic histories of these beaches can be linked to repeated changes in sea level and pore waters.This paper presents field evidence and petrographic results (microscope, X-ray, cathodoluminescence, SEMEDAX) for the diagenetic histories of two superimposed Pleistocene beaches in Whalebone Bay, Bermuda North Shore. The younger beach was deposited during isotopic stage 5e, about 120 ka ago. The age of the older beach may be isotopic stage 9 or older.Diagenesis drastically altered the older beach before the stage 5e transgression. Primary high-Mg calcite (HMC) and aragonite were no longer present. Marine skeletal grains were instead leached or recrystallized to low-Mg calcite (LMC). Primary and secondary pore space were largely reduced by LMC cement. Lines of needle relics reminiscent of marine aragonite cement occur as inclusions within syntaxial rim cements around echinoderm grains, indicating that a marine influence had at least once interrupted this period of freshwater alteration. Finally, before the rocks became buried by the sediments of the younger beach, a crust of marine, bladed HMC cement was precipitated throughout the pore space.The younger beach consists of skeletal grains that are, apart from the effects of non-selective dissolution, essentially unaltered. The sediments are only weakly lithified by cryptocrystalline LMC showing an alveolar texture, tangential fibres and other features characteristic of calichification. A younger post-depositional marine influence is not recorded.These results suggest that, under favourable conditions, diagenetic processes can document sea-level fluctuations. The recorded fluctuations, however, are difficult to assess because even major sea-level highstands may not produce a diagenetic imprint. Correspondence to: R. Vollbrecht     

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).