Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part II: synthesis of a S-spiro-like dithiolane triterpenoid

A sulfide with a bicyclic squalene hydrocarbon skeleton present in sediments from various depositional settings and of different geological age has been identified by synthesis of a reference compound. In contrast to previous expectations [cf. Schouten, S., Sinninghe Damsté, J.S., de Leeuw, J.W., 1995. A novel triterpenoid carbon skeleton in immature sulphur-rich sediments. Geochimica et Cosmochimica Acta 59, 953–958; Gug, S., Schaeffer, P., Adam, P., Klein, S., Motsch, E., Albrecht, P., 2009. Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: Synthesis of a dithiane triterpenoid. Organic Geochemistry 40, 876–884.], this sulfide bears two “S-spiro type“ thiolane moities, but not the two thiochromane moieties originally envisaged. The synthesis resulted in the formation of a complex isomeric mixture of compounds, all co-eluting in gas chromatography (GC) in the form of one broad peak, as is the case with the geochemical compound. The spiro-type sulfide was formed by intramolecular sulfurization of a polyunsaturated bicyclic squalene derivative of unknown biological origin. The presence of this sulfide in a number of Triassic to Miocene marine sediments from various and contrasting depositional settings (upwelling environments, shallow continental platforms, lagoonal sub-basins, hypersaline environments), all characterized by strongly anoxic conditions, but with or without photic zone anoxia, indicates that the microorganisms biosynthesizing the precursor bicyclic squalene occupy diverse ecological niches.     

Das Impulsaktinometer

Zusammenfassung Das Impulsaktinometer arbeitet mit Bolometermessbrücken, die nur die kurze Zeit mit Spannung belastet werden, die zur Feststellung des Ausschlages des Brückengalvanometers erforderlich ist. Da stets genügend Zeit zum Abkühlen gegeben ist, können Messbrücken in dieser Schaltung wesentlich höher belastet werden als gewöhnliche Bolometer. Bei der Anwendung dieses Prinzips auf die Messung der direkten Sonnenstrahlung entstehen Aktinometer, die mit unempfindlichen Galvanometern arbeiten. Ihre Abmessungen sind klein genug, dass das eigentliche Aktinometer und das Galvanometer zu einer Einheit zusammengefasst werden können. Hierdurch entstehen Instrumente, die leicht in der Herstellung und im Gewicht sind und aus überall in der Welt käuflichen Materialien angefertigt werden können, Sie haben sich bereits auf Expeditionen bewährt.Der beschriebene Apparat enthält vier Aktinometersysteme für verschiedene Spektralgebiete. Der Aufbau des Gerätes und seine Einzelheiten wie Bolometer, Diaphragmen, Einstellungsvorgänge, Galvanometer, Filter, Schaltung usw. werden besprochen und das Vorgehen bei der Messung behandelt. Es wird auch eine Theorie des Temperaturkoeffizienten gegeben und die Justierung beschrieben. Die Prüfung des Gerätes mit demLinke-Feussner-Aktinometer ergab eine mittlere Abweichung von ±1.3%, die auf Verschiedenheiten bei der Exposition beider Instrumente zurückgeführt werden kann.

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Summary The pulse-actinometer works with bolometers, i. e. with Wheatstone's bridge circuits. The principle of operation of this actinometer is based upon an overloading of those bolometers with a relatively high current. Obviously such a high current can only be connected for a brief period, which, however, has to be sufficiently long for reading the deflection of the galvanometer.This principle makes it possible to use relatively insensitive galvanometers of small size so that they may be built into the case surrounding the whole instrument. The actinometer uses ordinary radio components and its construction is extremely simple and should not present any difficulties. The instrument has successfully been used on various expeditions.The apparatus contains four different actinometer systems for different spectral ranges. The design of the instrument, its properties as bolometers, diaphragms, galvanometer, filters, circuit diagram, and its operation are treated. Furthermore a theory of the temperature coefficient is given and the final adjustement is described in detail. The calibration of the instrument with theLinke-Feussner Actinometer resulted in a deviation of ±1.3%, which can be explained by the differences in the operating procedures of both instruments.

     

Die Weiterentwicklung der Meßtechnik des Wassergehalts des Bodens auf thermischer Grundlage

Zusammenfassung Durch Untersuchungen vonJ. Bracht [3] und dem Verfasser wurde im Jahre 1940 festgestellt, daß die Wärmeleitfähigkeit des Bodens nicht bei allen Bodenarten eindeutig mit dem Wassergehalt zusammenhängt. Es wird eine Erklärung für diese Erscheinung durch die Verscjiedenheit der Wasserablagerung zwischen den Bodenpartikeln bei Wasseraufnahme und Wasserabgabe gegeben. Von allen Wärmekonstanten des Bodens ist nur die Wärmekapazität wahrscheinlich eindeutig abhängig von dem Wassergehalt des Bodens. Diese Größe kann am einfachsten als der Quotient aus der Wärmeleitfähigkeit und der Temperaturleitfähigkeit des Bodens bestimmt werden. Es mu\ also außer der Wärmeleitfähigkeit auch noch die Temperaturleitfähigkeit gemessen werden.In der vorliegenden Arbeit wird ein Verfahren zur Bestimmung dieser letzteren Größe beschrieben. Hierbei wird als Geber das Doppelthermometer benutzt, das zur Messung der Wärmeleitfähigkeit des Bodens vom Verfasser [2] beschrieben wurde. Von den beiden Thermometern dieses Doppelthermometers wird das eine in halbstündigen Intervallen je eine Viertelstunde lang geheizt. Gemessen wird dann außer dem Temperaturunterschied zwischen geheiztem und ungeheiztem Thermometer auch der Temperaturgang des ungeheizten Thermometers allein. Aus dem Temperaturunterschied zwischen beiden Thermometern wird in der üblichen Weise die Wärmeleitfähigkeit und aus der Amplitude des Temperaturganges und seiner Phasenverschiebung gegen die Heizung die Temperaturleitfähigkeit des Bodens berechnet.

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Summary Researches ofJ. Bracht [3] and of the present author have shown in 1940 that the thermal conductivity of the soil is not exactly coherent with the content of water in all kinds of soil. An explanation of this phenomenon is given by the difference of water deposit between the soil particles under conditions of imbilition and desiccation of water. Of all thermal constants of the soil solely the heat capacity probably is distinctly dependent on the water content of the soil. This value can be determined in the simplest manner as the quotient of thermal conductivity and thermal diffusivity of the soil. Beside thermal conductivity therefore thermal diffusivity must be measured too.A procedure for the determination of this last value is developed in this paper. The double thermometer which has been described by the author [2] for measuring the thermal conductivity is used as indicator. One of the two thermometers of this double thermometer is being heated during a quarter of an hour at intervals of half an hour. Beside the difference of temperature between heated and unheated thermometer the variation of temperature of the unheated thermometer itself is measured. Then the thermal conductivity is calculated in the usual manner from the difference of temperature between the two thermometers and the thermal diffusivity of the soil from the amplitude of the temperature variation and its shift of phase against heating.

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Résumé Des recherches deJ. Bracht [3] et de l'auteur en 1940 ont montré que la conductibilité calorifique de certains sols ne dépend pas uniquement de leur teneur en eau. On tente d'expliquer cette anomalie par le fait que l'eau s'insère différemment entre les particules du sol lors de l'imbibition et lors de la dessication. Parmi toutes les constantes calorifiques du sol, la capacité calorifique est probablement la seule qui soit en relation univoque avec la teneur en eau. Cette grandeur peut se définir le plus simplement par le quotient de la conductivité calorifique et de la transmission thermique du sol. Il faut donc mesurer séparément ces deux grandeurs.On décrit dans le présent mémoire un procédé permettant la mesure de la transmission thermique. On se sert comme indicateur du thermomètre double décrit par l'auteur [2] en vue de la mesure de la conductibilité du sol. L'un de ces thermomètres est chauffé pendant un quart d'heure toutes les demi-heures. On note alors non seulement la différence de température entre les deux instruments, mais encore les variations du thermomètre non chauffé: la différence de température permet comme d'ordinaire le calcul de la conductibilité, tandis que l'amplitude de la variation du thermomètre non chauffé et son décalage par rapport à l'autre permettent le calcul de la transmission thermique.

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Mit 4 Textabbildungen.     

Die Pyrenäen im Lichte der Deckentheorie

Ohne Zusammenfassung     

Central European Cenozoic plume volcanism with OIB characteristics and indications of a lower mantle source

Average concentrations of incompatible elements and isotopes of radiogenic Sr, Nd and Pb in a 350 km long belt of Central European volcanics (CECV) resemble those in OIB in general and in OIB from the N Atlantic in particular. This similarity allows to infer comparable sources for CECV and OIB which might have been located in the lower mantle according to seismic tomography and chemistry, with the latter unlike a MORB source. The incompatible element contribution of lower mantle origin can be modelled from primitive mantle minus continental crust and upper mantle inventories. Alkali basaltic magmas from the modelled source are close in composition to CECV and OIB. The continental crust contains almost half of the silicate Earth's content of Rb, K, Pb, Ba, Th and U, which were mobilized to a major extent through dehydration of subducted ocean crust. Related losses from the lower mantle had to be replaced by deep subductions of oceanic lithosphere recognized from their isotopic imprint. From a balance based on Nd isotopes it can be concluded that average CECV contains 60% matter from residual primitive mantle and 40% from deeply subducted lithosphere (including some young upper mantle materials). Plume products from separate CECV regions developed, within 45 Ma, from rather depleted to more primitive isotopic signatures. Four periods of volcanism from Eocene to late Quaternary time are explained as four pulses of an almost stationary ultrafast plume uprise as modelled by Larsen and Yuen (1997). Magma production has increased from the first to the third pulse with the peak during Miocene time in the Vogelsberg region. The final pulse produced the Quaternary Eifel volcanoes. Tectonism from the Alpine orogen has probably triggered the synchronous volcanism of CECV, Massif Central etc. The European lithospheric plate has moved under the control of the opening Atlantic almost in an eastern direction with a velocity of 1 cm per year and has shifted extinct volcanoes off their source channels. Received: 10 July 1998 / Accepted: 10 February 1999     

Implementing a new data model for simulating processes

The paper describes the development of a new methodological approach for simulating geographic processes through the development of a data model that represents a process. This methodology complements existing approaches to dynamic modelling, which focus on the states of the system at each time step, by storing and representing the processes that are implicit in the model. The data model, called nen, focuses existing modelling approaches on representing and storing process information, which provides advantages for querying and analysing processes. The flux simulation framework was created utilizing the nen data model to represent processes. This simulator includes basic classes for developing a domain specific simulation and a set of query tools for inquiring after the results of a simulation. The methodology is prototyped with a watershed runoff simulation.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.