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.     

Eocene-Pliocene time scale and stratigraphy of the Upper Rhine Graben (URG) and the Swiss Molasse Basin (SMB)

We present a general stratigraphic synthesis for the Upper Rhine Graben (URG) and the Swiss Molasse Basin (SMB) from Eocene to Pliocene times. The stratigraphic data were compiled both from literature and from research carried out by the authors during the past 6 years ; an index of the stratigraphically most important localitites is provided. We distinguish 14 geographical areas from the Helvetic domain in the South to the Hanau Basin in the North. For each geographical area, we give a synthesis of the biostratigraphy, lithofacies, and chronostratigraphic ranges. The relationships between this stratigraphic record and the global sea-level changes are generally disturbed by the geodynamic (e.g., subsidence) evolution of the basins. However, global sea-level changes probably affected the dynamic of transgression–regression in the URG (e.g., Middle Pechelbronn Beds and Serie Grise corresponding with sea-level rise between Ru1/Ru2 and Ru2/Ru3 sequences, respectively) as well as in the Molasse basin (regression of the UMM corresponding with the sea-level drop at the Ch1 sequence). The URGENT-project (Upper Rhine Graben evolution and neotectonics) provided an unique opportunity to carry out and present this synthesis. Discussions with scientists addressing sedimentology, tectonics, geophysics and geochemistry permitted the comparison of the sedimentary history and stratigraphy of the basin with processes controlling its geodynamic evolution. Data presented here back up the palaeogeographic reconstructions presented in a companion paper by the same authors (see Berger et al. in Int J Earth Sci 2005).     

Spectroscopy, morphometry, and photoclinometry of Titan's dunefields from Cassini/VIMS

Fine-resolution (500 m/pixel) Cassini Visual and Infrared Mapping Spectrometer (VIMS) T20 observations of Titan resolve that moon's sand dunes. The spectral variability in some dune regions shows that there are sand-free interdune areas, wherein VIMS spectra reveal the exposed dune substrate. The interdunes from T20 are, variously, materials that correspond to the equatorial bright, 5-μm-bright, and dark blue spectral units. Our observations show that an enigmatic “dark red” spectral unit seen in T5 in fact represents a macroscopic mixture with 5-μm-bright material and dunes as its spectral endmembers. Looking more broadly, similar mixtures of varying amounts of dune and interdune units of varying composition can explain the spectral and albedo variability within the dark brown dune global spectral unit that is associated with dunes. The presence of interdunes indicates that Titan's dunefields are both mature and recently active. The spectrum of the dune endmember reveals the sand to be composed of less water ice than the rest of Titan; various organics are consistent with the dunes' measured reflectivity. We measure a mean dune spacing of 2.1 km, and find that the dunes are oriented on the average in an east-west direction, but angling up to 10° from parallel to the equator in specific cases. Where no interdunes are present, we determine the height of one set of dunes photoclinometrically to be between 30 and 70 m. These results pave the way for future exploration and interpretation of Titan's sand dunes.     

The Water Framework Directive: Can more information be extracted from groundwater data? A case study of Seewinkel,Burgenland, eastern Austria

Water protection is one of the most important goals in environmental protection. The Clean Water Act in the USA and the Water Framework Directive (WFD) in Europe are the legal frameworks to facilitate the achievement of this goal. The question is raised of whether more information can be extracted from WFD-related groundwater data. To answer it, a methodology has been developed that is easy to use and could be implemented into official practice. A case study is presented in which the groundwater data of a sodic area in Austria (Seewinkel) is assessed. Eighteen parameters in groundwater sampled from 23 wells (1991–2011) were analyzed. With basic statistics, trend-, cluster-, Wilks’ λ and spatial sampling density analysis, local phosphorus and boron phenomena were described, along with the determining role of sulphate, groundwater flow, and the oxygen gradient in the area. As a final step, the spatial sampling density was determined. Regarding the current set of parameters, all the sampling sites are necessary and only in the case of certain parameters (Ca²⁺, Mg²⁺, K⁺, NO₃ ^?, pH) could one sampling site be abandoned. The methodology applied brings a new perspective to exploring groundwater data collected according to the requirements of the WFD.     

Fifteen days of continuous activity survey at Stromboli volcano, Italy, in late September 2000: Doppler radar, seismicity, infrared, soil humidity, and mapping of the crater region

The intention of our study was to gain new insight into the complex interplay between different types of eruption of the Stromboli volcano by combining detailed field observation with different geophysical methods. We recorded more than 600 eruptions by use of continuous Doppler radar measurements. We detected the onset of the seismic precursor and the beginning of the visible eruption by use of seismic and infrared data. Two soil samples per day were used to monitor the effect of humidity on the eruptive style. We mapped the crater region as a reference base for the long-term morphological changes of the active region and for the exact positions of our measurement systems. Two distinct types of eruption were distinguished from each other on the basis of seismic and radar data - short, wide-angle Strombolian explosions and pulsating, sharp angle fountain-like eruptions. Data and visual observations imply that weather conditions significantly effect volcanic activity. We also interpret the intensification of eruptive activity during our field study as replenishment of the reservoir with a new batch of magma in late September 2000.     

Multi-stage reaction history in different eclogite types from the Pakistan Himalaya and implications for exhumation processes

Metabasites were sampled from rock series of the subducted margin of the Indian Plate, the so-called Higher Himalayan Crystalline, in the Upper Kaghan Valley, Pakistan. These vary from corona dolerites, cropping out around Saif-ul-Muluk in the south, to coesite–eclogite close to the suture zone against rocks of the Kohistan arc in the north. Bulk rock major- and trace- element chemistry reveals essentially a single protolith as the source for five different eclogite types, which differ in fabric, modal mineralogy as well as in mineral chemistry. The study of newly-collected samples reveals coesite (confirmed by in situ Raman spectroscopy) in both garnet and omphacite. All eclogites show growth of amphiboles during exhumation. Within some coesite-bearing eclogites the presence of glaucophane cores to barroisite is noted whereas in most samples porphyroblastic sodic–calcic amphiboles are rimmed by more aluminous calcic amphibole (pargasite, tschermakite, and edenite). Eclogite facies rutile is replaced by ilmenite which itself is commonly surrounded by titanite. In addition, some eclogite bodies show leucocratic segregations containing phengite, quartz, zoisite and/or kyanite. The important implication is that the complex exhumation path shows stages of initial cooling during decompression (formation of glaucophane) followed by reheating: a very similar situation to that reported for the coesite-bearing eclogite series of the Tso Morari massif, India, 450 km to the south-east.     

Bubble-induced porewater mixing: A 3-D model for deep porewater irrigation

Porewater data from vent sites of the northeastern shelf off Sakhalin Island, Sea of Okhotsk, exhibit bottom-water concentrations down to a sediment depth of up to 300 cm. Below this depth, solute concentrations rapidly change due to methanogenesis and anaerobic methane oxidation (AMO). The profile shapes suggest an irrigation-like process that mixes on a meter scale. At these sites active gas emanation into the overlying water column and near-surface gas hydrates are commonly observed. We propose that methane gas bubbles rise through the soft surface sediments and cause mixing of the porewater.Mathematically, the bubble-induced irrigation can be described by eddy diffusion enhancing the diffusive transport of solutes by several orders of magnitude. A 3-D numerical transport-reaction model was developed to investigate the parameters defining the mixing process, such as bubble rise velocity, tube size, tube distribution in the sediment, and ebullition frequency.Model consistency with the field data requires eddy diffusivities ?1 × 10⁵ cm²/a, tube densities of >4 tubes/m² (equivalent to a tube spacing of <40 cm), active gas seepage for more than a few weeks or months, and moderate to low diagenetic reaction rates of solutes. The corresponding methane gas fluxes that are predicted from the results of the model realizations range from 1 × 10³-5 × 10⁵ L/(m² a). Due to bubble mixing, solute fluxes in these sediments are increased by a factor of 3 and the maximum AMO rate by a factor of 7.     

Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.     

Processing and quality control of flux data during LITFASS-2003

Different aspects of the quality assurance and quality control (QA/QC) of micrometeorological measurements were combined to create a comprehensive algorithm which was then applied to experimental data from LITFASS-2003 (Lindenberg Inhomogeneous Terrain—Fluxes between Atmosphere and Surface: a long term Study). Eddy-covariance measurements of the latent heat flux were the main focus of the QA/QC efforts. The results of a turbulence sensor intercomparison experiment showed deviations between the different eddy-covariance systems on the order of 15%, or less than 30 W m⁻², for the latent heat flux and 5%, or less than 10 W m⁻², for the sensible heat flux. In order to avoid uncertainties due to the post-processing of turbulence data, a comprehensive software package was used for the analysis of experimental data from LITFASS-2003, including all necessary procedures for corrections and quality control. An overview of the quality test results shows that for most of the days more than 80% of the available latent heat flux data are of high quality so long as there are no instrumental problems. The representativeness of a flux value for the target land-use type was analysed using a stochastic footprint model. Different methods to calculate soil heat fluxes at the surface are discussed and a sensitivity analysis is conducted to select the most robust method for LITFASS-2003. The lack of energy balance closure, which was found for LITFASS-2003, can probably be attributed to the presence of low-frequency flux contributions that cannot be resolved with an averaging time of 30 min. Though the QA/QC system has been developed for the requirements of LITFASS-2003, it can also be applied to other experiments dealing with similar objectives.