Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

Die alpidischen Stockwerke der südlichen Ägäis

Zusammenfassung Im Bereich der südlichen Ägäis überlagern vier allochthone Stockwerke den autochthonen Plattenkalk (Perm-Oligozän). Die allochthonen Serien entstammen ursprünglich konzentrisch angeordneten mesozoisch-alttertiären Faziesräumen der zentralen Ägäis. Die tektonische Abfolge aus neritischen Karbonaten, pelagischen Karbonaten und einem vulkano-sedimentären Komplex, die durch inkompetente Zwischenmittel (Mélange) getrennt werden, besteht über den gesamten Bogen. Fazielle und stratigraphische Merkmale sowie die Art der Deformation ermöglichen die Korrelation der Teilprofile des südägäischen Deckenstapels und dessen Anknüpfung an die südwestliche Türkei. Die kinematische Analyse des Deckenbaus führt zu dem Bild eines sich ausbreitenden Mantel-Diapirs, an dessen geneigter Grenzfläche ein gravitativer Transport ausgelöst wurde.

---

In the realm of the Southern Aegean Arc four allochthonous units are piled up above the autochthonous Cherty Limestone (Permian-Oligocene). The allochthonous units are derived from different Mesozoic to Paleogene facies zones which originally were arranged in concentric belts in the Central Aegean Sea. The nappe pile consists — from bottom to top — of neritic carbonates, pelagic carbonates and a volcano-sedimentary complex along the entire arc. These competent units are separated by incompetent members of mainly flyschoid sediments, acting as lubricants. The intercalated sediments were deformed to mélanges due to tectonic transport. Facies analysis, stratigraphy and the style of deformation lead to a correlation of type sections of the southern Aegean nappe pile and its relation to the southwestern part of Turkey. The nappe transport is caused by diapiric uplift and lateral shifting of a thermal dome. A radial gravity transport occurred on its inclined boundary plane.

---

Résumé Dans la région de l'Egée méridionale le Calcaire en plaquettes, en position autochthone (Permian-Oligocène) repose sous quatre unités allochthones. Les séries allochthones proviennent de différentes zones de faciès mésozoique-paléogène qui à l'origine étaient disposées concentriquement dans l'Égée centrale. Les nappes sont constituées tout le long de l'arc entier pour des carbonates néritiques, des carbonates pélagiques et un complexe volcano-sédimentaire. Ces unités compétentes sont séparées par des formations incompétentes, notamment des sédiments flyschoides qui ont servi de lubrificant. Ces sédiments intercalés ont été déformés en mélanges par le transport tectonique. Des caractéristiques de faciès et d'ordre stratigraphique, et le style de la déformation rendent possible la corrélation entre les fractions des nappes sud-égéennes et leur rattachement au sud-ouest de la Turquie. Le transport des nappes est lié au déploiement latéral de l'enveloppe d'un dôme diapirique, qui a déclanché un transport radial, par gravité, le long de sa base inclinée.

---

4 (-). - - . - , (Mélange). , - - . , .

---

---

Diese Untersuchungen wurden im Rahmen des Schwerpunktprogrammes Geodynamik des mediterranen Raumes der Deutschen Forschungsgemeinschaft durchgeführt und gefördert. Ausgehend von einer Geländetätigkeit auf Kreta in den Jahren 1973–1975 erfolgten im Herbst 1975 Vergleichsbegehungen auf dem Peloponnes, auf Rhodos und den Kykladen. Von den Mitarbeitern des Institutes für Geologie und Paläontologie der TU Braunschweig übernahmen dankenswerterweise FrauBeddies und FrauBusch die Niederschrift des Manuskriptes sowie Übersetzungsarbeiten. HerrStosnach führte freundlicherweise die Reinzeichnung der Abbildungen und Fotoarbeiten aus.     

Die Phasenkontrastmikroskopie als Hilfsmittel zur Bestimmung feinkörniger,speziell dünner,transparenter Minerale.

Zusammenfassung Es wird mit Hilfe von Zeigerdiagrammen eine anschauliche Darstellung vom Zustandekommen der Phasenkontrasterscheinungen gegeben. An Hand theoretischer Überlegungen und experimenteller Versuche wird die besondere Eignung der Phasenkontrastmikroskopie für die Bestimmung der Brechzahl transparenter dünner Teilchen nach der Immersionsmethode nachgewiesen. Daraus ergeben sich Vorteile für die mikroskopische Beurteilung der Minerale in Tonfraktionen. Das wird an zwei praktischen Beispielen gezeigt. Der Vergleich der Ergebnisse der mit dem Phasenkontrastverfahren durchgeführten Tonuntersuchungen mit den auf röntgenographischem Wege erzielten läßt eine gute Übereinstimmung erkennen.     

Desalinization of running waters: III. Changes in the structure of diatom assemblages caused by a decreasing salt load and changing ion spectra in the river Wipper (Thuringia, Germany)

Salt-loaded effluents were introduced into the river Wipper during the mining period for almost a century. Beginning with the year 1990, the waste water load was strongly reduced due to the termination of the potash industry. Prior to 1990, monthly means of the chloride concentrations at times exceeded 6,000 mg l⁻¹ in the strongly polluted sections. Maximum concentrations reached twice these values. Up to 1998, mean annual chloride concentrations decreased to values below 2,000 mg l⁻¹. This led to more balanced fluctuations in salinity which had been pronounced before, depending on discharge and short-term changes in production. Similarly, the physiologically adverse ion conditions improved due to decrasing potassium and increasing calcium proportions.

In 1963/64, 1986 and 1998, samples of epilithic, epiphytic and epipsammic diatoms were taken at locations of different salinities along the river and examined for the effects of the salinization on the structure of the diatom assemblages. These structures changed in dependence on salinity. Increasing salt concentrations coincided with decreasing oligohalophilic and increasing mesohalophilic and polyhalophilic species numbers. Above a chloride concentration of about 3,000 mg l⁻¹, the proportion of the latter exceed that of the former (halobion index > 50). Corresponding to different conditions of salinization along the river, characteristic diatom assemblages occur differring from each other and which are specific for the river section. Spring and autumn aspects of the diatom assemblages show also salt-dependent differences. The assemblages found in 1998 after decrease of salinization have changed markedly in comparison to those from 1963/64 and 1986. Halobiontic species predominating formerly occurred only occasionally or not at all. They were replaced by oligohalobic-indifferent forms.

An ecological assessment of the changes was performed based on the halobion index calculated from all the samples. For the strongly salinized section of the river Wipper, a shift from -mesohalobic/polyhalobic conditions in 1963/64 and 1986 to -oligohalobic/β-mesohalobic conditions in 1998 was found. However, constant -oligohalobic conditions are still not given. With regard to the transition from -oligohalobic (limnetic) to β-mesohalobic (brackish) conditions, a maximum chloride concentration of 600 mg l⁻¹ was found. To guarantee -oligohalobic conditions, a maximum chloride concentration of 400 mg l⁻¹ should not be exceeded.     

Genesis and distribution of mineral waters as a consequence of recent lithospheric dynamics: the Rhenish Massif,Central Europe

Three major, interdependent processes control the genesis and distribution of mineral and thermal waters in the Rhenish Massif, Central Europe: (a) Magmatic processes in the upper mantle provide most of the CO₂ to produce bicarbonate waters in shallow aquifers. (b) Extension of the brittle upper crust enables the ascent of sodium chloride waters. (c) Uplift and erosion shape the massif's relief, which determines the extent of flow systems and the distribution of thermal springs. The chemistry of mineral waters further depends on the aquifers' mineral composition. A comprehensive set of hydrological, chemical, tectonic and geophysical data on the Rhenish Massif has been compiled. It was used to classify the mineral waters and to map the spatial distribution of water properties. The composition of cuttings from several representative wells producing different water types shows that the hydrothermal alteration of the aquifer rocks consists mainly of kaolinization of chlorite and dissolution of feldspar. Numerical transport simulations favour two modes of groundwater flow: topography-driven flow and the pressure-driven ascent of basement brines along active faults. Thermal convection is less important.     

Nocturnal drainage flow on simple slopes

Observations of nocturnal slope flow have been made at two sites with quite different topography and vegetation. In both cases, continuous measurements of wind and temperature profiles were made from towers that extended through the depth of the katabatic flow. At the simpler site, which approximates a tilted plane, three towers were located at different distances down the slope to measure the development of slope flow with downslope distance.Slope flow depth, downslope wind speed, and temperature deficit are found to change with downslope distance at rates that are consistent with the predictions of Manins and Sawford's (1979) layer-averaged model of slope flow, while measured entrainment rates are found to be comparable to those predicted by Ellison and Turner's (1959) laboratory experiments. The depth of slope flow is found to be roughly 0.05 times the vertical drop from the top of the slope, a relationship that also follows from combining Manins and Sawford's model and Ellison and Turner's laboratory data. Analysis of the wind spectra and a simple numerical model suggest that the turbulent kinetic energy profiles in slope flow are dependent on the speed and direction of the ambient wind and can differ substantially from those found over flat terrain. At the more complex of the two measurement sites, the occurrence of slope flow was found to correlate well with a dimensionless number 5 that is a function of the ridge-top wind speed and of the strength and depth of the inversion and that is an estimate of the ratio of the buoyancy deficit to the external horizontal pressure gradient.Prepared for the U.S. Department of Energy under Contract DE-AC06-76RLO 1830     

Gas chromatographic determination of peroxyacetyl nitrate: Two convenient calibration techniques

Two procedures for the calibration of an electron capture detector (ECD) for peroxyacetyl nitrate (PAN) are discussed. One is based on the first-order decay rate of the the PAN mixing ratio in conditioned glass storage vessels. The other method makes use of the photochemical generation of PAN in mixtures of acetone and NO₂ in air. For this purpose a Penray Hg lamp was inserted into a glass vessel filled with 1 atmosphere of air containing 10 ppm NO₂ and 1% acetone. After 3 min of irradiation, the average PAN mixing ratio formed was 8.87±0.25 ppmv as determined in six separate runs.     

Ground-motion scenarios on Mt. Etna inferred from empirical relations and synthetic simulations

Ground motion scenarios for Mt. Etna are created using synthetic simulations with the program EXSIM. A large data set of weak motion records is exploited to identify important input parameters which govern the modeling of wave propagation effects, such as Q-values, high frequency cut-off and geometrical spreading. These parameters are used in the simulation of ground motion for earthquakes causing severe damage in the area. Two seismotectonic regimes are distinguished. Volcano-tectonic events, though being of limited magnitude (M_max ca. 5), cause strong ground shaking for their shallow foci. Being rather frequent, these events represent a considerable threat to cities and villages on the flanks of the volcano. A second regime is related to earthquakes with foci in the crust, at depths of 10–30 km, and magnitudes ranging from 6 to 7. In our synthetic scenarios, we chose two examples of volcano-tectonic events, i.e. the October 29, 2002, Bongiardo event (I = VIII) and the May 8, 1914, Linera earthquake (I = IX–X). A further scenario regards the February 20, 1818 event, considered representative for stronger earthquakes with foci in the crust. We were able to reproduce the essential features of the macroseismic field, in particular accounting for the possibility of strong site effects. We learned that stress drop estimated for weak motion events is probably too low to explain the intensity of ground motion during stronger earthquakes. This corresponds to findings reported in the literature claiming an increase of stress drop with earthquake size.