Phosphoric acid fractionation factors for smithsonite and cerussite between 25 and 72°C

The intramolecular kinetic oxygen isotope fractionation between CO₂ and CO₃²⁻ during reaction of phosphoric acid with natural smithsonite (ZnCO₃) and cerussite (PbCO₃) has been determined between 25 and 72°C. While cerussite decomposes in phosphoric acid within a few hours at 25°C, smithsonite reacts very slowly with the acid at 25°C providing yields of CO₂ < 25% after 2 weeks. The low yields result in a low precision for oxygen isotope measurements of the acid-liberated CO₂ (±1.65‰, 1σ, n = 9). The yield and reproducibility of oxygen isotope values of the acid-liberated CO₂ from smithsonite can be improved, the latter to ∼±0.15‰, by increasing the reaction temperature to 50°C for 12 h or to 72°C for 1 h. Our new phosphoric acid fractionation factor for natural cerussite at 25°C deviates significantly from a previously published value on synthetic material. The temperature dependence of the oxygen isotope factionation factor, α between acid-liberated CO₂ and carbonate at 25 to 72°C is given by the following equations

     

Area-Averaged Surface Fluxes Over the Litfass Region Based on Eddy-Covariance Measurements

Micrometeorological measurements (including eddy-covariance measurements of the surface fluxes of sensible and latent heat) were performed during the LITFASS-2003 experiment at 13 field sites over different types of land use (forest, lake, grassland, various agricultural crops) in a 20 × 20 km² area around the Meteorological Observatory Lindenberg (MOL) of the German Meteorological Service (Deutscher Wetterdienst, DWD). Significant differences in the energy fluxes could be found between the major land surface types (forest, farmland, water), but also between the different agricultural crops (cereals, rape, maize). Flux ratios between the different surfaces changed during the course of the experiment as a result of increased water temperature of the lake, changing soil moisture, and of the vegetation development at the farmland sites. The measurements over grass performed at the boundary-layer field site Falkenberg of the MOL were shown to be quite representative for the farmland part of the area. Measurements from the 13 sites were composed into a time series of the area-averaged surface flux by taking into account the data quality of the single flux values from the different sites and the relative occurrence of each surface type in the area. Such composite fluxes could be determined for about 80% of the whole measurement time during the LITFASS-2003 experiment. Comparison of these aggregated surface fluxes with area-averaged fluxes from long-range scintillometer measurements and from airborne measurements showed good agreement.     

The influence of trench migration on slab penetration into the lower mantle

A two-dimensional numerical convection model in cartesian geometry is used to study the influence of trench migration on the ability of subducted slabs to penetrate an endothermic phase boundary at 660 km depth. The transient subduction history of an oceanic plate is modelled by imposing plate and trench motion at the surface. The viscosity depends on temperature and depth. A variety of styles of slab behaviour is found, depending predominantly on the trench velocity. When trench retreat is faster than 2–4 cm/a, the descending slab flattens above the phase boundary. At slower rates it penetrates straight into the lower mantle, although flattening in the transition zone may occur later, leading to a complex slab morphology. The slab can buckle, independent of whether it penetrates or not, especially when there is a localised increase in viscosity at the phase boundary. Flattened slabs are only temporarily arrested in the transition zone and sink ultimately into the lower mantle. The results offer a framework for understanding the variety in slab geometry revealed by seismic tomography.     

Study of metal sorption/desorption processes on competing sediment components with a multichamber device

A new multichamber device was developed to study sorption/desorption reactions of metals on different competing sediment components and the influence of environmental factors on these reactions. The system consists of a central chamber connected with six external chambers and separated by 0.45-μm-diameter membranes. The diffusion kinetics of metals between the single chambers were determined. Equilibrium was attained within 24 h. Algal cell walls (Scenedesmus quadricauda), bentonite, aluminium oxide, managese oxide, quartz powder, and goethite were used as model sediment components. Determination of metal sorption on the solid phases resulted in a significant enrichment on the algal cell walls, particularly for Cu and Cd. It was concluded that sorption depends not only on ion exchange but also on complexing reactions which lead to relatively stable surface binding. A second series of experiments investigated the effect of seawater on sediment components and dredged mud. Cadmium was remobilized from all solid components, but Cu was not remobilized from algal cell walls and bentonite. The dominant role of organic substrates in the binding of metals such as Cd andCu is of particular relevance for the transfer of these elements into biological systems. Even relatively small percentages of organic substrates, if involved in metabolic processes, may constitute a major pathway by which metals are transferred within the food chain.     

Minimum friction velocity and heat transfer in the rough surface layer of a convective boundary layer

A simple model is deduced for the surface layer of a convective boundary layer for zero mean wind velocity over homogeneous rough ground. The model assumes large-scale convective circulation driven by surface heat flux with a flow pattern as it would be obtained by conditional ensemble averages. The surface layer is defined here such that in this layer horizontal motions dominate relative to vertical components. The model is derived from momentum and heat balances for the surface layer together with closures based on the Monin-Obukhov theory. The motion in the surface layer is driven by horizontal gradients of hydrostatic pressure. The balances account for turbulent fluxes at the surface and fluxes by convective motions to the mixed layer. The latter are the dominant ones. The model contains effectively two empirical coefficients which are determined such that the model's predictions agree with previous experimental results for the horizontal turbulent velocity fluctuations and the temperature fluctuations. The model quantitatively predicts the decrease of the minimum friction velocity and the increase of the temperature difference between the mixed layer and the ground with increasing values of the boundary layer/roughness height ratio. The heat transfer relationship can be expressed in terms of the common Nusselt and Rayleigh numbers, Nu and Ra, as Nu ~ Ra^{% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaSGbaeaaca% aIXaaabaGaaGOmaaaaaaa!3779!\[{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}\]}. Previous results of the form Nu ~ Ra^{% MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaaSGbaeaaca% aIXaaabaGaaG4maaaaaaa!377A!\[{1 \mathord{\left/ {\vphantom {1 3}} \right. \kern-\nulldelimiterspace} 3}\]} are shown to be restricted to Rayleigh-numbers less than a certain value which depends on the boundary layer/roughness height ratio.     

Heat flow during the carboniferous and mesozoic of the Northwest German Basin

The temperature history of the Northwest German Basin has been reconstructed using a one-dimensional computer model that accounts for compaction-related changes of physical rock properties, depth, temperature and maturity of organic matter. Maturity has been modelled by empirically relating vitrinite reflectance to time-temperature history. Heat flow values for the Mesozoic and Carboniferous have been obtained by matching measured and computed vitrinite reflectance. For Mesozoic samples agreement between measured and computed maturity can be achieved with a heat flow between 37 and 50 mW/m² (0.9 and 1.2 hfu). There is no systematic areal variation. Carboniferous samples are matched best at heat flows between 70 and 96 mW/m² (1.7 and 2.3 hfu), corresponding to geothermal gradients between 50 and 80 °C/km depending on lithology and compaction. Areal variation follows patterns subparallel to the structural grain of the Variscan orogeny. Mesozoic heat flow is compatible with heat flow in stable platform areas. Carboniferous heat flow and its geotectonic setting are best in agreement with present-day back-arc areas underlain by continental crust.

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Zusammenfassung Die Temperaturgeschichte des Nordwestdeutschen Bekkens wurde mittels eines eindimensionalen Computermodells rekonstruiert, das auch kompaktionsbezogenen Änderungen der physikalischen Gesteinseigenschaften, der Tiefe und der Temperatur gerecht wird. Die Reife wurde simuliert, indem Vitrinitreflexion und Zeit-Temperatur Verlauf empirisch miteinander korelliert wurden. Die Wärmeflußwerte für das Karbon und das Mesozoikum wurden dadurch ermittelt, daß gemessene und berechnete Vitrinitreflexion in optimale Übereinstimmung gebracht wurden. Für das Mesozoikum kann eine Übereinstimmung bei Wärmeflußwerten zwischen 37 und 50 mW/m² (0.9 und 1,2 hfu), für das Karbon für Werte zwischen 70 und 96 mW/m² (1.7 und 2.3 hfu) erzielt werden, was je nach Lithologie und Kompaktionszustand einem Geothermalgradienten zwischen 50 und 80 °C/km entspricht. Nur für die karbonischen Daten ist eine systematische räumliche Änderung der Werte erkennbar. Der Wärmefluß im Mesozoikum entspricht dem in heutigen stabilen Plattformgebieten. Wärmefluß und geotektonische Position im Karbon sind vergleichbar mit solchen heutigen »back-arc« Gebieten, die von kontinentaler Kruste unterlagert sind.

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Résumé L'histoire thermique du bassin allemand nord-occidental a été simulée sur ordinateur au moyen d'un modéle unidimensionnel; ce modèle tient compte des changements introduits par la compaction dans les propriétés physiques de roches, de la profondeur, de la température et de l'évolution de la matière organique. Pour modéliser cette évolution, on a établi une corrélation entre la réflectance de la vitrinite et l'histoire thermique. Les valeurs du flux de chaleur pour le Mésozoïque et le Carbonifère ont été obtenues par ajustement entre la réflectance de la vitrinite observée et calculée. Pour les échantillons mésozoïques, les valeurs calculées et mesurées s'accordent le mieux pour un flux compris entre 37 et 50 mW/m2 (0.9 et 1,2 HFU). Il n'y a pas de variation régionale systématique. Pour le Carbonifère, le meilleur accord donne un flux siuté entre 70 et 96 mW/m2 (1,7 et 2,3 HFU), ce qui correspond à des gradients géothermiques de 50 et 80 °C/Km, selon la lithologie et le degré de compaction. Il existe dans le Carbonifère, des variations régionales, qui parallélisent les lignes structurales de l'orogène varisque. Le flux de chaleur mésozoïque est compatible avec une situation de plate-forme stable. Le flux de chaleur carbonifère et sa répartition géotectonique fait plutôt penser, dans la nature actuelle, aux régions d'arrière-arc sur croûte continentale.

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, , , . , . . 37–50 mW/m² (0,9 i 1,2 hfu), — 70–96 mW/m² (1,7 2,3 hfu), — — 50 80°/. , . (back-arc), .

     

Early Cretaceous »events« in the evolution of the eastern and western North Atlantic continental margins

At many North Atlantic continental margins, the early Neocomian is characterized by a major stratigraphic turning point from Late Jurassic-Berriasian carbonate bank/pelagic carbonate deposition to Valanginian-Barremian hemipelagic sedimentation with thick Wealden-type deltaic to deep-sea fan sequences. The stratigraphy and structure of the very old, starved passive margin of the Mazagan Plateau and adjacent steep escarpment off Morocco was studied during the French-German CYAMAZ deep diving campaign. The drowning of the Late Jurassic-early Berriasian carbonate platform was strongly influenced by a global late Berriasian sea level fall which was followed by a rapid late Valanginian sea level rise and/or by a major regional blockfaul ting event with accelerated subsidence rates. Upper Berriasian to (?) Hauterivian quartz-bearing bioclastic wackestones document the transition from the carbonate platform to the hemipelagic deposition on the drowned platform margin. Seawards, these deposits are correlated with a deep sea fan sequence. We discuss also an example from the Tarfaya Basin-Fuerteventura area further south. A 300 m thick succession of organic-rich claystone and sandstone turbidites (including m-thick debris flow units) of Hauterivian to Barremian age was an unexpected discovery at DSDP Site 603 off North Carolina (Leg 93). We discuss a tectonically confined fan model with laterally migrating channels, influenced by sea level fluctuations and varying terrigenous supply. During the Valanginian to Barremian time of high-standing (or rising) sea level, shelf construction (Wealden-type deltas) coincided with subdued, resedimentation-starved turbiditic system on the continental rise. Extensive unconsolidated sands, however, reflect sudden input of shelfal material into the basin during a mid-Aptian sea level lowstand (shelf destruction). The following global late Aptian transgression terminated the clastic fan deposition, raised the CCD and started the deposition of organic-rich shales.     

S- and I-type granitoids of North Victoria Land,Antarctica, and their inferred geotectonic setting

In the context of Gondwana North Victoria Land forms the Antarctic conjugate terrain to the East Australian Lachlan Fold Belt, where the distinction between S- and I-type granitoids was first worked out (Chappell &White 1974). Thus the area was considered a good testing ground for the hypothesis when the German Antarctic North Victoria Land Expedition (Ganovex) resumed fieldwork there in 1979/80.It was known at that time that there existed a Cambro/Ordovician and a Devonian/Carboniferous granitoid generation, which, in analogy to Australia, were taken to be related to two different orogenetic events. Our geological, petrographical and geochemical investigations, together with radiometric age dating, revealed that this is true only for the older granite generation. The younger generation is in fact anorogenic. At the same time, it became obvious that the S- and I-type classification did not completely fit the observed field data. At this pointPitcher's (1982) subdivision of the I-types into a »Cordilleran« and a »Caledonian« suite offered a solution to account for the observed irregularities.At about the same time, plate tectonic models based on evidence independent from the granite classification were developed for this part of the active Gondwana margin. This offers the opportunity to crosscheck the tectonic environment derived from the granite classification:The characteristics of the older, Cambro/Ordovician granitoids allow a perfect accommodation in the model of an active margin above a subduction zone as derived from other evidence.For the younger (Devonian/Carboniferous) granitoids, however, the postulated tectonic setting (post-collisional uplift and faulting) could not be verified in North Victoria Land.It is concluded thatPitchers classification is applicable in its petrographic and geochemical aspects but that the tectonic environment postulated for the production of »Caledonian« I-type granitoids may not be the same in all investigated areas.

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Zusammenfassung Im Gondwana Rahmen bildet Nord Victoria Land das antarktische Pendant zur ostaustralischen Lachlan Mobilzone, wo die Einteilung von Graniten in S- und I-Typen entwickelt wurde (Chappell &White 1974). Deshalb war eine überprüfung dieser neu entwickelten Hypothese eines der Arbeitsziele, als die deutschen Nord Victoria Land Expeditionen (Ganovex) dort 1979 ihre Arbeiten aufnahmen. An den bekannten zwei Granitgenerationen der Region wurden geologische, petrographische und geochemische Untersuchungen sowie Altersbestimmungen durchgeführt, deren Ergebnisse sich folgenderma\en zusammenfassen lassen.Die ältere, kambro-ordovizische Granitfolge steht, analog zur Situation in Australien, in enger Beziehung zu einer bedeutenden Orogenese, während sich zur jüngeren, devonisch-karbonischen Suite kein zugehöriges tektonisches Ereignis finden lie\. Dies steht im Gegensatz zur Situation in Australien/Tasmanien.Die S- und I-Typ Klassifikation, auf Nord Victoria Land angewendet, weist ähnliche Widersprüche auf, wie siePitcher (1982) zur Aufteilung der I-Typen in »kordillere« und »kaledonische« Sippen führten.Plattentektonische Modelle, die in den letzten Jahren für diese Region am mobilen Rand Gondwanas unabhängig von der Granitklassifikation nach geologischen und tektonischen Kriterien entwickelt wurden, erlauben es, die vonPitcher entwickelten tektonischen Bildungsmilieus für verschiedene Granit-Typen zu überprüfen:Die Charakteristiken der älteren (kambro-ordovizischen) Granite erlauben ein widerspruchsloses Einfügen in das aus anderen Kriterien abgeleitete Bild eines aktiven Kontinentalrandes über einer Subduktionszone.Für die jüngeren (devonisch-karbonischen) Granite dagegen, die im Charakter den »kaledonischen« I-TypenPitchers entsprechen, sind die für deren Bildung postulierten Vorgänge, nämlich Hebung und Dehnung nach einer Kollision, in Nord Victoria Land nicht erkennbar.Demnach erscheint zwar die KlassifikationPitchers sinnvoll, da sie in ihrer petrographisch-geochemischen Charakterisierung nachvollziehbar ist, aber das abgeleitete tektonische Milieu für die Bildung der »kaledonischen« Typen bedarf einer weiteren überprüfung.

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Résumé Dans le contexte du Gondwana, la Terre Victoria est le pendant antarctique de la zone plissée de Lachlan, en Australie Orientale, où la distinction entre granites S et I a été établie pour la première fois (Chappel &White 1974). C'est pourquoi la vérification de cette hypothèse a été portée au programme de l'expédition allemande à la Terre Victoria en 1979–80 (Ganovex).On connaissait à cette époque l'existence d'une génération cambro-ordovicienne et d'une génération dévono-carbonifère de granitoÏdes qui, par analogie avec l'Australie, avaient été rapportées à deux événements orogéniques différents. Nos investigations géologiques, pétrologiques, géochimiques et géochronologiques montrent que cette conclusion n'est vraie que pour les granites de la première génération. La seconde génération est, en fait, anorogénique. Il s'est avéré en mÊme temps que la répartition en types S et I ne correspond pas exactement aux observations de terrain. Par contre, la distinction introduite parPitcher (1982) parmi les granites I entre une série »de Cordillère« et une série »Calédonienne« peut expliquer les irrégularités que nous observons.Environ à cette époque, des modèles géodynamiques basés sur des considérations indépendantes de la classification des granites ont été proposés pour cette partie de la marge active du Gondwana. Ces modèles permettent de recouper les considérations sur l'environnement tectonique des granites, déduites de leur classification:Les caractères des granitoÏdes anciens, cambro-ordoviciens, s'accordent parfaitement au modèle d'une marge active surmontant une subduction.Par contre, pour les granitoÏdes jeunes, dévono-carbonifères, la situation tectonique postulée (soulèvement et fracturation post-collision) n'a pas pu Être confirmée sur la Terre Victoria.En conclusion, la classification dePitcher est applicable dans ses aspects pétrographiques et géochimiques, mais l'environnement tectonique qui préside à la formation de granitoÏdes de type »Calédonien I« n'est pas nécessairement le mÊme dans toutes les régions étudiées.

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- Lachlan, S I (Chappell & White, 1974). (GANOVEX) 1979 . , , . : - , , , , - , , - . S I , , (Pitcher, 1982) I . , , , , : — - — , . , - , , , , .. ., , - , , , , .