Coupling among the terrestrial sulfur,carbon and oxygen cycles: numerical modeling based on revised Phanerozoic carbon isotope record

Numerical modeling of the terrestrial oxygen budget based on the revised δ¹³C_carb record by Veizeret al. (1980) has shown that total photosynthetic oxygen has varied between ±7% and ±10% of its average reservoir size (～3.2 × 10²² g) during the last 800 myr as a result of oscillations of the sedimentary reservoir of organic carbon. Calculated curves of oxygen evolution display a distinct minimum in the Early Paleozoic framed by two maxima in the Latest Proterozoic and the Mesozoic. The sympathetic relationship observed between the curves of total oxygen evolution and respective functions for the partial reservoir of sulfate-bound oxygen suggests that the O₂ required for an additional conversion of sulfide to sulfate was most probably provided by excess burial of organic carbon, the results of the modeling thus adding credence to current interpretations proposed for the negative correlation between the secular ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{34}\text{S}{}^{32}\text{S}$ trends.     

Shock effects on hydrous minerals and implications for carbonaceous meteorites

New infrared absorption spectra, thermo-gravimetric analyses and optical-and scanning electron microscopy of shock-recovered specimens of antigorite serpentine (Mg₃Si₂O₅(OH)₄) from the pressure range between 25 to 59 GPa are reported. The infrared spectra show systematic changes in absorption peaks related to structural and molecular surface absorbed water. H₂O absorption peaks increase at the expense of OH peaks with increasing shock pressure. Changes in SiO bond vibrational modes with increasing shock pressure parallel those seen for other, non-hydrous minerals. Thermogravimetric analyses of shock-recovered samples determine the amount of shock-induced water loss. For samples shocked in vented assemblies, the data define a relation between shock-induced water loss versus shock pressure. Results for samples shocked in sealed assemblies demonstrate a dependence of water loss on shock pressure and target confinement. For the vented assembly samples, a linear relation between shock pressure and both the length of dehydration interval and the effective activation energy for releasing post-shock structural water in antigorite is found. Optical and scanning electron miscroscopy of shocked antigorite reveal a number of textures thought to be unique to shock loading of volatile-bearing minerals. Gas bubbles, which probably are the result of shock-released H₂O appear to be injected into zones of partial melting. This process may produce the vesicular dark veins which are distributed throughout heavily shocked samples. The present observations suggest several criteria which may constrain possible shock histories of the hydrous matrix phases of carbonaceous condrites. A model is proposed for explaining hydrous alteration processes occurring on carbonaceous chondrite parent bodies in the course of their accretion. We speculate that shock loading of hydrous minerals would release and redistribute free water in the regoliths of carbonaceous chondrite parent bodies giving rise to the observed hydrous alterations.     

Intercomparison of Boron Isotope and Concentration Measurements. Part I: Selection, Preparation and Homogeneity Tests of the Intercomparison Materials

In 1999 the Istituto di Geoscienze e Georisorse (IGG), with the support of the International Atomic Energy Agency (IAEA), undertook the collection, preparation and distribution of eight geological materials intended for a blind interlaboratory comparison of measurements of boron isotopic composition and concentration. The materials came from Italian sources and consist of three natural waters (Mediterranean seawater and two groundwaters) and five rocks and minerals (tourmaline, basalt, obsidian, limestone and clay). The solid materials were crushed, milled and mixed, in preparation for distribution. Extensive assays performed at the IGG on these materials demonstrated that their boron isotopic and chemical compositions are homogeneous.
Additional homogeneity tests were carried out on solid material fragments at the GeoForschungsZentrum Potsdam, with the specific objective of investigating the suitability of some of them for the calibration in situ of micro-analytical techniques. Two materials, B4 (tourmaline) and B6 (obsidian), proved to be isotopically homogeneous and may become excellent references for in situ microanalyses of boron isotopes.
The materials described here were used as the basis of a major laboratory intercomparison study and are now available for further distribution from either the IAEA (solid materials) or the IGG (waters).     

Hydrothermal gases offshore Milos Island, Greece

Hydrothermal fluids emerge from the seafloor of Paleohori Bay on Milos. The gases in these fluids contain mostly CO₂ but CH₄ concentrations up to 2% are present. The stable carbon isotopic composition of the CO₂ (near 0%) indicates an inorganic carbon source (dissociation of underlying marine carbonates). The carbon and hydrogen isotopes of most CH₄ samples are enriched in the heavy species (δ¹³C = −9.4 to −17.8‰; δD = −102 to −189‰) which is believed to be characteristic for an abiogenic production of CH₄ by CO₂-reduction (Fischer-Tropsch reactions). Depletions in the deuterium content of three CH₄ samples (to −377%) are probably caused by unknown subsurface rock alteration processes. Secondary hydrogen isotope exchange processes between methane, hydrogen and water are most likely responsible for calculated unrealistic methane formation temperatures.

We show that excess helium, slightly enriched in ³He, is present in the hydrothermal fluids emerging the seafloor of Paleohori Bay. When the isotopic ratio of the excess component is calculated a ³He/⁴He_excess of 3.6 · 10⁻⁶ is obtained: This indicates that the excess component consists of about one third of mantle helium and two thirds of radiogenic helium. We infer that the mantle-derived component has been strongly diluted by radiogenic helium during the ascent of the fluids to the surface.     

Tectonic style and pressure distribution at the northern margin of the Alps between Lake Constance and the River Inn

Hydrocarbon exploration in the Molasse basin and the Alpine thrust belt has provided new information on the tectonic structure of the foreland margin of the overthrust belt. Two N-S cross-sections show the front of the Folded Molasse as a so-called Triangle Zone in the area north of the Hindelang 1 well (Bavaria) and the Sulzberg 1 well (Vorarlberg). The Triangle Zone was described and defined byJones (1982) for the Alberta Foothills in Canada.Oil and gas wells commonly encountered overpressured zones with pressure gradients up to 2.5 bar/10 m. The pressure profiles from the Sulzberg1, Hindelang1, Staffelsee1, Miesbach 1 and Bromberg 1 wells were analysed stratigraphically and lithologically with respect to the tectonics of the region. It can be concluded that the overpressures in the Foreland Molasse were caused by compaction, where those within the thrust belt were caused by tectonics.

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Zusammenfassung Die von der Erdöl- und Erdgasindustrie im Bereich des Alpennordrandes durchgeführten Untersuchungsarbeiten brachten neue Ergebnisse zum tektonischen Bau. So stellt sich in zwei N-S-Profilen nördlich von Hindelang (Bayern) und über die Tiefbohrung Sulzberg 1 (Vorarlberg) die Stirn der Faltenmolasse als Triangelzone dar, wie sie von Jones (1982) aus den Foothills der Rocky Mountains beschrieben wird.Tiefbohrungen auf Erdöl und Erdgas haben verbreitet überhydrostatische Porendrücke mit Gradienten bis 2,5 bar/10 m angetroffen. Es wurden Druckprofile aus den Bohrungen Sulzberg 1, Hindelang 1, Staffelsee 1, Miesbach 1 und Bromberg 1 nach stratigraphisch-lithologischen Gesichtspunkten analysiert, regionaltektonisch zugeordnet und interpretiert. Es zeigt sich, daß die Überdrücke in der Vorlandmolasse durch Kompaktion entstanden sind, während diejenigen unter den Decken tektonische Ursachen haben.

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Résumé Les travaux d'exploration entrepris par l'industrie du pétrole dans le bassin molassique et dans la bordure septentrionale des Alpes ont conduit à de nouveaux résultats en ce qui concerne les structures tectoniques de cette région. Dans deux profils nord — sud établis dans la région, respectivement au nord de Hindelang (Bavière) et au nord de Sulzberg (Vorarlberg), le front de la molasse plissée se présente comme une »zone triangulaire« du type défini parJones (1982) dans les Foothills d'Alberta au Canada.Des forages pétroliers profonds ont fréquemment recontré des pressions interstitielles hyperhydrostatiques avec des gradients pouvant atteindre 2,5 bars / 10 m.Les profils de pression relevés dans les sondages de Sulzberg 1, Hindelang 1, Staffelsee 1, Miesbach 1 et Bromberg 1 ont été analysés au point de vue stratigraphique et lithologique et placés dans le cadre tectonique de la région. Il en résulte que les surpressions dans la molasse d'avant-pays (Vorlandmolasse) sont dues à la compaction et que celles des formations recouvertes par les nappes sont d'origine tectonique.

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Reconstruction of the late Quaternary paleoenvironments of the Nussloch loess paleosol sequence,Germany, using n-alkane biomarkers

This study contributes to the paleoenvironmental reconstruction of the loess–paleosol sequence of Nussloch, Germany, by using n-alkanes as plant leaf-wax-derived lipid biomarkers. We found that n-alkane patterns and concentrations in the Saalian loess and the last interglacial Eemian paleosol of Nussloch point to very strong degradation and prevailing deciduous vegetation. Degradation effects in the overlying paleosols and loess layers are less pronounced and allow for the application of an end-member mixing model to estimate vegetation changes semi-quantitatively. Our findings highlight the potential for the interpretation of degradation-corrected n-alkane ratios. n-Alkane modelling results for loess layers, paleosols and an in-filled paleochannel dated to ~ 60–32 ka suggest that up to ~ 50% of the n-alkanes were derived from deciduous trees or shrubs. This finding is in agreement with the abundant occurrence of wood fragments and indicates a highly variable and dynamic landscape dominated by tundra shrubland. On the other hand, deciduous trees or shrubs did not contribute significantly to the soil organic matter in the late Weichselian loess layers and the intercalated Gelic Gleysols (~ 32–18 ka).     

Spectroscopic characterisation and crystal field calculations of varicoloured kyanites from Loliondo, Tanzania

Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al₂SiO₅, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr₂O₃, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H₂O with structural OH defects partially replacing the O_B (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe³⁺ (all samples), Mn³⁺ (orange and ochre) and Cr³⁺ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe³⁺ preferably occupies the Al4 site, Cr³⁺ prefers the Al1 and Al2 sites, and Mn³⁺ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me³⁺–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr³⁺ cations.     

The Regensburg Model: reference values for the (I)NDCs based on converging per capita emissions†

A core question still remains after the Paris Agreement: who receives how much of the remaining CO₂ budget (resource/burden/effort sharing), so that the increase in the global average temperature is kept to well below 2°C above pre-industrial levels? If converging per capita emissions serve as a possible answer to this question, the discussion focuses primarily on the approach ‘Contraction and Convergence’ (C&C). The Regensburg Model now offers a further option for the mathematical implementation of converging per capita emissions. The authors identify features common to C&C and differences from C&C. They show that, of the convergence models they examined, the Regensburg Model is the most favourable option for industrialized countries.

Policy relevance

In politics, the concept of converging per capita emissions is often accepted at the abstract level. Civil society in particular can then take politicians at their word wherever they take values calculated using the Regensburg Model as points of reference; then prosperous developed countries in particular whose nationally determined contributions do not come up even to these reference values will find it difficult to justify their contributions.