Extraktion und Verteilung der Aminosäuren in einigen kretazischen Kernproben

Zusammenfassung In 45 Sedimentproben wurde die Verteilung von 16 Aminosäuren quantitativ bestimmt. Durch aufeinanderfolgende Hydrolysen des gleichen Gesteins mit verschiedenen Säuren ließen sich zwei Arten von Aminosäurenverbindungen ermitteln. Aus den Verhältniswerten dieser löslichen, bereits mit 6-N-Salzsäure freisetzbaren Aminosäuren und der kerogengebundenen mit 12 N HCl zugänglichen Komponente lassen sich über die thermische Beanspruchung und den Reifungszustand eines Sedimentes Schlüsse ziehen. Diese stimmen mit den Ergebnissen der durchgeführten Thermalversuche überein und erklären sich durch eine Änderung der Bindungsform der Aminosäuren am Kerogen. Durch zunehmende thermische Beanspruchung erhöht sich der kerogengebundene Aminosäurenanteil, während das Verhältnis zwischen neutralen und nicht neutralen Aminosäuren abnimmt.

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The distribution of 16 aminoacids in 45 sedimentsamples has been determined. Two separate groups of aminoacids could be isolated by successive treatment of the same rock with different acids i. e. rather loosely bound aminoacids isolated by 6 N HCl hydrolysis and aminoacids incorporated in the kerogen, which could be recovered only upon 12 N HCl treatment. From the ratio of these groups conclusions may be drawn with respect to the thermal history and maturity of a sediment. The conclusions have been verified by thermal experiments and may be explained by a modification of the way of compound of the aminoacids with the kerogen. With increasing thermal influence the strongly combined aminoacid fraction becomes relatively predominant. At the same time the ratio of neutral and other aminoacids in these fractions decreases.

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Résumé Le rendement de l'extraction des amino-acides présents dans la roche est fonction de la solubilité de la roche, donc de la pétrographie des échantillons. C'est pourquoi on déminéralise la roche d'abord à l'aide d'acide chlorhydrique, puis d'acide fluorhydrique; on élimine ensuite les constituants bitumineux à l'aide d'acide formique. Le kérogène ainsi isolé fait l'objet de l'hydrolyse proprement dite, laquelle est entreprise par traitements successifs à l'HCl 6 N et à l'HCl 12 N. Ce double traitement a pour effet de séparer des fractions faiblement et fortement combinées.La fraction obtenue par hydrolyse à l'HCl 6 N représente les amino-acides liés au kérogène par adsorption superficielle; la fraction 12 N HCl contient les amino-acides qui étaient intimement incorporés dans le kérogène, en faisant partie de la structure. Cette dernière fraction devient relativement de plus en plus importante avec l'âge et la maturation croissantes; par traitement thermique d'échantillons récents, traitement simulant le vieillissement et la maturation, on constate la même chose. La part des amino-acides neutres diminue, avec la température et la profondeur croissantes, dans la fraction 12 N; elle augmente dans la fraction 6 N.Des échantillons mésozoiques provenant d'un forage profond d'Aquitaine ont été analysés. Les concentrations totales en amino-acides sont en corrélation avec les concentrations en fossiles. D'autre part, dans le partie inférieure du forage (donc la partie dont on peut penser qu'elle est la plus évoluée), on voit le rapport amino-acides neutres/amino-acides totaux diminuer avec la profondeur. Il est à noter que des changements nets dans ce rapport coïncident avec des limites stratigraphiques.

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. 45 , 16 . : 1) 6 HCI II) 12 HCI. .

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Herrn Professor Dr.Roland Brinkmann zum 70. Geburtstag gewidmet.

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Der Direktion derSocièté Nationale Des Pétroles D'Aquitaine, Pau, danke ich für die Ermöglichung dieser Arbeiten und die Genehmigung ihrer Veröffentlichung, den Herren Doktoren G.Kulbicki und B.van der Weide für die vielseitigen Anregungen und Diskussionen. Herrn Prof. Dr. E. T.Degens bin ich für die Durchsicht des Manuskriptes sehr dankbar.     

Isotopic evidence (Sr/Sr, δLi) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and ⁸⁷Sr/⁸⁶Sr ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light δ⁷Li values, partly close to those of hydrothermal vent fluids (δ⁷Li: +11.9‰), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 °C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments.     

On the Effect of Surface Heat-Flux Heterogeneities on the Mixed-Layer-Top Entrainment

We used a set of large-eddy simulations to investigate the effect of one-dimensional stripe-like surface heat-flux heterogeneities on mixed-layer top entrainment. The profiles of sensible heat flux and the temporal evolution of the boundary-layer depth revealed decreased entrainment for small heat-flux amplitudes and increased entrainment for large heat-flux amplitudes, compared to the homogeneously-heated mixed layer. For large heat-flux amplitudes the largest entrainment was observed for patch sizes in the order of the boundary-layer depth, while for significantly smaller or larger patch sizes entrainment was similar as in the homogeneous case. In order to understand the underlying physics of this impact, a new approach was developed to infer local information on entrainment by means of the local flux divergence. We found an entrainment maximum over the centre of the stronger heated surface patch, where thermal energy is accumulated by the secondary circulation (SC) that was induced by the surface heterogeneity. Furthermore, we observed an entrainment maximum over the less heated patch as well, which we suppose is to be linked to the SC-induced horizontal flow convergence at the top of the convective boundary layer (CBL). For small heat-flux amplitudes a counteracting effect dominates that decreases entrainment, which we suppose is the horizontal advection of cold air in the lower, and warm air in the upper, CBL by the SC, stabilizing the CBL and thus weakening thermal convection. Moreover, we found that a mean wind can reduce the heterogeneity-induced impact on entrainment. If the flow is aligned perpendicular to the border between the differentially-heated patches, the SC and thus its impact on entrainment vanishes due to increased horizontal mixing, even for moderate wind speeds. However, if the flow is directed parallel to the border between the differentially-heated patches, the SC and thus its impact on entrainment persists.     

Late Cretaceous reactivation of major crustal shear zones in northern Namibia: constraints from apatite fission track analysis

Namibia's passive continental margin records a long history of tectonic activity since the Proterozoic. The orogenic belt produced during the collision of the Congo and Kalahari Cratons in the Early Proterozoic led to a zone of crustal weakness, which became the preferred location for tectonism during the Phanerozoic. The Pan-African Damara mobile belt forms this intraplate boundary in Namibia and its tectonostratigraphic zones are defined by ductile shear zones, where the most prominent is described as the Omaruru Lineament–Waterberg Thrust (OML–WT). The prominance of the continental margin escarpment is diminished in the area of the Central and Northern Zone of the Damara belt where the shear zones are located. This area has been targeted with a set of 66 outcrop samples over a 550-km-long, 60-km-broad coast-parallel transect from the top of the escarpment in the south across the Damara sector to the Kamanjab Inlier in the north. Apatite fission track age and length data from all samples reveal a regionally consistent cooling event. Thermal histories derived by forward modelling bracket this phase of accelerated cooling in the Late Cretaceous. Maximum palaeotemperatures immediately prior to the onset of cooling range from ca. 120 to ca. 60 °C with the maximum occurring directly south of the Omaruru Lineament. Because different palaeotemperatures indicate different burial depth at a given time, the amount of denudation can be estimated and used to constrain vertical displacements of the continental crust. We interpret this cooling pattern as the geomorphic response to reactivation of basement structures caused by a change in spreading geometry in the South Atlantic and South West Indian Oceans.     

Towards urbanisation of the non-hydrostatic numerical weather prediction model Lokalmodell (LM)

Numerical weather prediction models are increasingly employed for providing meteorological data for urban air quality applications. Model resolution, physiographic parameters and surface-layer parameterisations need to be adapted to the requirements of the urban boundary layer. The Lokalmodell of the German Weather Service was triple-nested down to a horizontal grid resolution of 1.1 km, urbanised physiographic parameters were implemented, and an additional anthropogenic heat source was introduced. Results of a sensitivity study for a spring dust episode in Helsinki show a clear urbanisation effect of these measures on temperature, humidity and the partitioning of surface fluxes, leading to an increased Bowen ratio and heat storage and an urban heat island effect.     

Aerosol climatology for the planetary boundary layer derived from regular lidar measurements

Regular aerosol extinction and backscatter measurements using a UV Raman Lidar have been performed for almost 3 years in Hamburg in the frame of the German Lidar Network. A set of 92 aerosol extinction and 164 aerosol backscatter profiles has been used for statistical investigations. Mean values and variances of the aerosol extinction and backscatter in the boundary layer have been calculated. Large fluctuations during the whole year have been found. The measured aerosol extinction over Hamburg shows a seasonal cycle with highest values in early fall and a second less prominent peak in spring.An analysis of the data using back trajectories showed a dependence of the aerosol extinction on the origin of the air mass. The residence time of the air mass over industrialized areas was found to be an important parameter for the measured aerosol extinction at Hamburg. However, only a small part of the total variability could be explained by the air mass origin.For 75 cases of aerosol extinction measurements under cloud-free conditions, the aerosol backscatter profile and therefore, the lidar ratio as a function of altitude could be determined. Winter measurements of the lidar ratio are often close to model results for maritime aerosol, the summer measurements are close to the model results for urban or continental aerosols.The high quality of the data has been proven by intercomparisons with other lidar systems and with star photometer measurements of the aerosol optical depth during the Lindenberg Aerosol Characterization Experiment (LACE'98) field campaign.     

Anomalous phosphorus episodes during Callovian-Oxfordian times in the Kachchh Basin,western India: Implications for palaeoclimate,productivity, and weathering

The Upper Callovian-Oxfordian strata of the Kachchh Basin, western India, record three positive excursions of phosphorus. They have been documented in three sections of the Chari Formation from different parts of the basin. Corroboration of field and petrographic data with trends of major and trace elemental data and elemental ratios of the strata revealed that these excursions were coeval with reduced chemical weathering in the source area and significant reduction of siliciclastic influx to the depositional sites. The study also revealed the intrabasinal source of P, and minor sea-level fluctuations and resultant episodic sediment recycling as the causative factors. Considering the geographic locations of the three sections, the phosphorus anomalies seem to be controlled by a regional and/or basin-scale process, if not linked with global signals. Temporal resolution of these anomalies suggests that the processes were episodic and related to short term climate/relative sea-level cycles, the durations of which could be unraveled with high-resolution biostratigraphic data.     

Long-term effects of anthropogenic CO<Subscript>2</Subscript> emissions simulated with a complex earth system model

A new complex earth system model consisting of an atmospheric general circulation model, an ocean general circulation model, a three-dimensional ice sheet model, a marine biogeochemistry model, and a dynamic vegetation model was used to study the long-term response to anthropogenic carbon emissions. The prescribed emissions follow estimates of past emissions for the period 1751–2000 and standard IPCC emission scenarios up to the year 2100. After 2100, an exponential decrease of the emissions was assumed. For each of the scenarios, a small ensemble of simulations was carried out. The North Atlantic overturning collapsed in the high emission scenario (A2) simulations. In the low emission scenario (B1), only a temporary weakening of the deep water formation in the North Atlantic is predicted. The moderate emission scenario (A1B) brings the system close to its bifurcation point, with three out of five runs leading to a collapsed North Atlantic overturning circulation. The atmospheric moisture transport predominantly contributes to the collapse of the deep water formation. In the simulations with collapsed deep water formation in the North Atlantic a substantial cooling over parts of the North Atlantic is simulated. Anthropogenic climate change substantially reduces the ability of land and ocean to sequester anthropogenic carbon. The simulated effect of a collapse of the deep water formation in the North Atlantic on the atmospheric CO₂ concentration turned out to be relatively small. The volume of the Greenland ice sheet is reduced, but its contribution to global mean sea level is almost counterbalanced by the growth of the Antarctic ice sheet due to enhanced snowfall. The modifications of the high latitude freshwater input due to the simulated changes in mass balance of the ice sheet are one order of magnitude smaller than the changes due to atmospheric moisture transport. After the year 3000, the global mean surface temperature is predicted to be almost constant due to the compensating effects of decreasing atmospheric CO₂ concentrations due to oceanic uptake and delayed response to increasing atmospheric CO₂ concentrations before.