Towards the establishment of a reliable proxy for the reactive surface area of smectite

Reactive surface area is one of the key parameters for studying the kinetics of mineral dissolution. The common practice in experimental kinetics is to normalize the dissolution rate to the surface area measured by the BET method. The relationship between BET surface area and the reactive surface area is not trivial in minerals such as smectites, which possess both internal and external surface areas, and in which the dissolution is controlled by the chemical attack on the edge surface. The present study examines two proxies for the reactive surface area of the Clay Mineral Society reference smectite SAz-1: BET surface area and the edge surface area measured using AFM.Since smectites are very microporous, their BET surface area is strongly influenced by the degassing procedure. It is demonstrated that outgassing the smectite powder at 135°C in a 15 mL min⁻¹ N₂ gas flow for at least 24 hours minimizes contribution from micropores to less than 11% of the BET surface area.Following dissolution experiments in solutions with a low electrolyte concentration, the BET surface area increased from 34 ± 2 m² g⁻¹ in raw SAz-1 to 127 ± 13 m² g⁻¹ in SAz-1 sample recovered from dissolution experiments. This increase in BET surface area is explained by a decrease in the average size of the smectite aggregates, and by an increase in microporosity due to the depletion in the major interlayer cation, i.e., Ca²⁺. As the BET surface area of the raw smectite sample includes considerably less microporosity compared to the BET surface area of the smectite recovered from dissolution experiments, the former is a better approximation of the external surface area of the dried sample powder.AFM measurements show that there is no correlation between the specific external surface area of the sample and its specific edge surface area. This observation is explained by the platy morphology of the smectite particle in which the specific external surface area depends linearly on the height reciprocal, whereas the specific edge surface area is independent of the particles height and depends linearly on the sum of the reciprocals of the length of the axes. Therefore, there is no reason to expect a correlation between the BET and the edge surface area. Our results show that the edge surface area (4.9 ± 0.7 m² g⁻¹) of the smectite particles cannot be predicted based on its external surface area (136 ± 20 m² g⁻¹). Therefore, the BET surface area cannot serve as a proxy for the reactive surface area. We suggest using AFM measurements of the specific edge surface area as an alternative proxy for the reactive surface area of smectite.     

Vegetation and climate changes in northwestern Russia during the Lateglacial and Holocene inferred from the Lake Ladoga pollen record

The new pollen record from the upper 12.75 m of a sediment core obtained in Lake Ladoga documents regional vegetation and climate changes in northwestern Russia over the last 13.9 cal. ka. The Lateglacial chronostratigraphy is based on varve chronology, while the Holocene stratigraphy is based on AMS ¹⁴C and OSL dates, supported by comparison with regional pollen records. During the Lateglacial (c. 13.9–11.2 cal. ka BP), the Lake Ladoga region experienced several climatic fluctuations as reflected in vegetation changes. Shrub and grass communities dominated between c. 13.9 and 13.2 cal. ka BP. The increase in Picea pollen at c. 13.2 cal. ka BP probably reflects the appearance of spruce in the southern Ladoga region at the beginning of the Allerød interstadial. After c. 12.6 cal. ka BP, the Younger Dryas cooling caused a significant decrease in spruce and increase in Artemisia with other herbs, indicative of tundra‐ and steppe‐like vegetation. A sharp transition from tundra‐steppe habitats to sparse birch forests characterizes the onset of Holocene warming c. 11.2 cal. ka BP. Pine forests dominated in the region from c. 9.0 to 8.1 cal. ka BP. The most favourable climatic conditions for deciduous broad‐leaved taxa existed between c. 8.1 and 5.5 cal. ka BP. Alder experiences an abrupt increase in the local vegetation c. 7.8 cal. ka BP. The decrease in tree pollen taxa (especially Picea) and the increase in herbs (mainly Poaceae) probably reflect human activity during the last 2.2 cal. ka. Pine forests have dominated the region since that time. Secale and other Cerealia pollen as well as ruderal herbs are permanently recorded since c. 0.8 cal. ka BP.     

Fluid inclusion evidence for impact‐related hydrothermal fluid and hydrocarbon migration in Creataceous sediments of the ICDP‐Chicxulub drill core Yax‐1

Fluid inclusions studies in quartz and calcite in samples from the ICDP‐Chicxulub drill core Yaxcopoil‐1 (Yax‐1) have revealed compelling evidence for impact‐induced hydrothermal alteration. Fluid circulation through the melt breccia and the underlying sedimentary rocks was not homogeneous in time and space. The formation of euhedral quartz crystals in vugs hosted by Cretaceous limestones is related to the migration of hot (>200 °C), highly saline, metal‐rich, hydrocarbon‐bearing brines. Hydrocarbons present in some inclusions in quartz are assumed to derive from cracking of pre‐impact organic matter. The center of the crater is assumed to be the source of the hot quartz‐forming brines. Fluid inclusions in abundant newly‐formed calcite indicate lower cyrstallization temperatures (75–100 °C). Calcite crystallization is likely related to a later stage of hydrothermal alteration. Calcite precipitated from saline fluids, most probably from formation water. Carbon and oxygen isotope compositions and REE distributions in calcites and carbonate host rocks suggest that the calcite‐forming fluids have achieved close equilibrium conditions with the Cretaceous limestones. The precipitation of calcite may be related to the convection of local pore fluids, possibly triggered by impact‐induced conductive heating of the sediments.     

Reverse time migration of CMP-gathers an effective tool for the determination of interval velocities

One of the most important steps in the conventional processing of reflection seismic data is common midpoint (CMP) stacking. However, this step has considerable deficiencies. For instance the reflection or diffraction time curves used for normal moveout corrections must be hyperbolae. Furthermore, undesirable frequency changes by stretching are produced on account of the dependence of the normal moveout corrections on reflection times. Still other drawbacks of conventional CMP stacking could be listed.One possibility to avoid these disadvantages is to replace conventional CMP stacking by a process of migration to be discussed in this paper. For this purpose the Sherwood-Loewenthal model of the exploding reflector has to be extended to an exploding point model with symmetry to the lineP _EX M whereP _EX is the exploding point, alias common reflection point, andM the common midpoint of receiver and source pairs.Kirchhoff summation is that kind of migration which is practically identical with conventional CMP stacking with the exception that Kirchhoff summation provides more than one resulting trace.In this paper reverse time migration (RTM) was adopted as a tool to replace conventional CMP stacking. This method has the merit that it uses the full wave equation and that a direct depth migration is obtained, the velocityv can be any function of the local coordinatesx, y, z. Since the quality of the reverse time migration is highly dependent on the correct choice of interval velocities such interval velocities can be determined stepwise from layer to layer, and there is no need to compute interval velocities from normal moveout velocities by sophisticated mathematics or time consuming modelling. It will be shown that curve velocity interfaces do not impair the correct determination of interval velocities and that more precise velocity values are obtained by avoiding or restricting muting due to non-hyperbolic normal moveout curves.Finally it is discussed how in the case of complicated structures the reverse time migration of CMP gathers can be modified in such a manner that the combination of all reverse time migrated CMP gathers yields a correct depth migrated section. This presupposes, however, a preliminary data processing and interpretation.     

Plate and intraplate processes of Hercynian Europe during the late paleozoic

It is speculated that until Late Carboniferous time the region of Hercynian Europe was occupied by an elongated island arc system underlain by a segment of continental crust. In the Upper Carboniferous, two subduction zones are assumed to have extended from the north and south beneath Hercynian Europe. An extensive zone of hot, partially molten upper mantle lay above and between these, and diapiric uprise of portions of this material led to separation of mafic magmas, widespread partial melting in the lower and middle crust, high temperature-low pressure metamorphism in crustal rocks, and regional uplift and extension of the crust, as indicated by intermontane troughs and their associated volcanic rocks.In Visean to Westphalian time Hercynian Europe collided with both the large neighbouring plates North America-Europe and Africa. During these diachronous collisions and owing to reduced rigidity of the relatively hot island arc crust, the irregular continental margins of the larger and thicker continental plates induced oroclinal bending of Hercynian Europe. After the collision processes had been terminated, processes of upper mantle activity continued, causing further crustal uplift and even, enhanced crustal extension for several tens of million years into the Lower Permian. Decline of the upper mantle activity beneath Hercynian Europe is indicated by crustal subsidence and formation of a peneplain in Permian time followed by the Upper Permian transgression of both the Zechstein sea and the Tethys sea which mark the end of the Hercynian geodynamic cycle.     

Mediterrane Trias — Grundzüge und Probleme

Zusammenfassung Die mediterrane oder alpine Trias wurde im 19. Jh. nahezu als Standard-Typus der marinen Entwicklung dieses Systems aufgefaßt. Sie lieferte fast ausschließlich die Faunenfolgen zur biochronologischen Gliederung; Schicht- und Fazies-Bezeichnungen wurden aus dem alpinen Raum bis nach Südostasien übertragen. Eine gewisse Sonderstellung maß man nur ihren Ammonoideen-Faunen zu. Ihre Erforschung schien bald nach der Jahrhundertwende abgeschlossen.Seit zwei Jahrzehnten wird jedoch die Gliederung der mediterranen Trias mit Hilfe der Ammonoidea völlig revidiert. Darüber hinaus konnten neue biochronologische Standards von der phylogenetischen Entwicklung anderer Organismen-Gruppen (Conodonten, Ostracoden, Foraminiferen, Holothurien, Dasycladaceen, Sporen und Pollen) abgeleitet werden. Die marinen Sequenzen des Mittelmeerraumes haben dabei eine wesentliche Rolle gespielt.Zahlreiche moderne Fazies-Analysen, auf die nur kursorisch verwiesen wird, erlauben, die paläogeographischen Konturen im Westteil der triassischen Tethys schärfer zu sehen und ihre geotektonische Entwicklung plattentektonisch zu deuten. Ausgehend von permischen Vorzeichnungen öffneten sich ozeanische Arme im Norden (Vardar-Zone, wahrscheinlich mit Fortsetzung bis in die Alpen) und Süden (Sizilien, Alboran). Dabei wurden einige Mikroplatten von Afrika bzw. Europa abgespalten, von denen die Adria-Platte und ihre geotektonische Differenzierung während der Trias diskutiert werden.

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In a first period of exploration, until the beginning of our century, the Mediterranean or Alpine Triassic advanced to be a standard type of the marine development of that period. It served as well as the base for a world-wide biochronological division as for the deviation of facies types.Nevertheless the subdivision of the Triassic with the help of ammonoids was revised during the past decades, and new biochronological standards were derived from the phylogenetic evolution of other taxa: conodonts, ostracodes, foraminifera, holothuroids, dasycladacean algae, and from the palynological record. For these investigations, the Mediterranean region is again of special importance.The results of modern facies analysis which are not reviewed extensely in this paper, allow to discern the palaeogeographic contures in the western part of the Triassic Tethys with more accuracy and to sketch the outlines of a plate tectonic interpretation. Following to Permian configurations two deep branches of this oceans developed, one to the north (Vardar zone, probably to the Alps) and another in the south (Sicily-Alboran). Several microplates were split off from Africa and Europe. The geotectonic differentiation of one of them (Adria microplate) is discussed.

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Résumé Au 19ième siècle le Trias méditerranéen ou «alpin» a presque partout été considé ré comme type standard du développement marin de ce système. La subdivision biochronologique est largement basée sur ses faunes, et sa nomenclature stratigraphique fut transférée aux autres régions. Concernant les ammonoïdes, le Trias méditerranéen a, en effet, pris une position spéciale. Au début de notre siècle leur exploration semblait bientôt être achevée.Depuis vingt ans on travaille cependant à la révision de la subdivision du Trias sur la base des ammonoïdes. De plus de nouveaux standards biochronologiques ont pu être établis sur la base de l'évolution d'autres taxa (conodontes, ostracodes, foraminifères, holothuroïdes, algues, spores et pollens). Au cours de ces recherches les séries marines ont joué un rôle important.De nombreuses analyses de faciès dont il n'a été fait mention qu'en passant, permettent de voir plus distinctement dans la région de la Téthys les contours paléogéographiques et d'interpréter, selon la théorie de la tectonique de plaques, leur évolution géotectonique. Tracés déjà au Permien, deux bras océaniques s'ouvraient dans la Téthys occidentale, l'un marqué par la zône du Vardar et allant probablement jusqu'aux Alpes et l'autre dans région de Sicile et de Tunisie. Au cours de ce processus, plusieurs microplaques furent séparées de l'Afrique ainsi que de l'Europe. L'exemple de la microplaque adriatique et son évolution géotectonique au cours du Trias sont brièvement discutés.

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SEAWAT 2000: modelling unstable flow and sensitivity to discretization levels and numerical schemes

A systematic analysis shows how results from the finite difference code SEAWAT are sensitive to choice of grid dimension, time step, and numerical scheme for unstable flow problems. Guidelines to assist in selecting appropriate combinations of these factors are suggested. While the SEAWAT code has been tested for a wide range of problems, the sensitivity of results to spatial and temporal discretization levels and numerical schemes has not been studied in detail for unstable flow problems. Here, the Elder-Voss-Souza benchmark problem has been used to systematically explore the sensitivity of SEAWAT output to spatio-temporal resolution and numerical solver choice. A grid size of 0.38 and 0.60% of the total domain length and depth respectively is found to be fine enough to deliver results with acceptable accuracy for most of the numerical schemes when Courant number (Cr) is 0.1. All numerical solvers produced similar results for extremely fine meshes; however, some schemes converged faster than others. For instance, the 3rd-order total variation-diminishing method (TVD3) scheme converged at a much coarser mesh than the standard finite difference methods (SFDM) upstream weighting (UW) scheme. The sensitivity of the results to Cr number depends on the numerical scheme as expected.     

Self‐purification in Upland and Lowland Streams

Ecological investigations at four streams in Saxony‐Anhalt have shown that there are considerable differences between the self‐purification power of upland and lowland streams. This result is reflected in chemistry and in microbiology. The structure of the bottom substrate mainly influences the degree of self‐purification in connection with rate of flow and flow velocity. The results and differences are demonstrated using the example of Katzsohlbach in the landscape unit “Mittel‐ and Unterharz” and the stream Olbe in the landscape unit “Magdeburger Börde”.