Mauer – the type site of Homo heidelbergensis: palaeoenvironment and age

The mandible of Homo heidelbergensis was found 1907 in the sand pit Grafenrain at Mauer in coarse fluvial sands 24 m below the surface, deposited in a former course of the Neckar River. These ‘Mauer sands’ are overlain by a series of glacial-climate loess deposits with intercalated interglacial palaeosols, which can be correlated with Quaternary climate history, thus indicating an early Middle Pleistocene age for H. heidelbergensis. The ‘Mauer sands’ are famous for their rather rich mammal fauna, which clearly indicates interglacial climate conditions. The faunal evidence – in particular the micromammals – place the ‘Mauer sands’ into MIS 15 or MIS 13 although most stratigraphic arguments favour correlation to MIS 15 and therefore to an age of ca 600 ka.     

Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Calcium-isotope fractionation in selected modern and ancient marine carbonates

The calcium-isotope composition (δ^44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca²⁺_aq-CaCO₃-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ^44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against ⁴⁴Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ^44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ¹⁸O values and Mg concentrations. The reconstruction of secular variations in the δ^44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ^44/42Ca values of Cretaceous skeletal calcite suggest that the δ^44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.     

Palaeobotanical evidence of wildfires in the Late Palaeozoic of South America – Early Permian, Rio Bonito Formation, Paraná Basin, Rio Grande do Sul, Brazil

Fossil charcoal, as direct evidence of palaeowildfires, has repeatedly been reported from several plant-bearing deposits from the Late Palaeozoic of the Northern Hemisphere. In contrast charcoal reports from the Late Palaeozoic deposits of the Southern Hemisphere are relatively rare in comparison to the Northern Hemisphere. Although the presence of pyrogenic coal macerals has repeatedly been reported from Late Palaeozoic coals from South America, no detailed anatomical investigations of such material have been published so far. Here is presented an anatomical analysis of charcoal originating from Early Permian sediments of the Quitéria Outcrop, Rio Bonito Formation, Paraná Basin, located in the central-eastern portion of Rio Grande do Sul, Brazil. This charcoal comes from two different coaly facies, and it was possible to scrutinize between three types, based on anatomical characters of the charcoal. Two of these charcoal types can be correlated to gymnosperm woods, and the other type corresponds to strongly permineralized bark with characteristic features of lycopsids. The presence of charcoal in different facies, ranging from parautochtonous to allochtonous origin, indicates that different vegetation types, i.e. plants which grew under wet conditions in the lowland as well as in the more dry hinterland, have experienced wildfires. Taking into account previous petrographic and lithological analyses from the facies in which the charcoal occurs and from the conditions of the wood and bark fragments, it was possible to speculate that the intensity of such wildfires most probably corresponds to forest-crown fires. Moreover, it is possible to state that wildfires have been a more or less common element in distinct Late Palaeozoic terrestrial ecosystems in the South American part of Gondwana. The data support previous assumptions on the occurrence of wildfires in the Early Permian of the Paraná Basin which were based solely on coal-petrographic data.     

Phytoreduction and volatilization of mercury by ascorbate in Arabidopsis thaliana, European beech and Norway spruce

Mercury vapor (Hg⁰) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg⁰ emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg⁰ emission from young European beech plants cultivated on a HgCl₂ medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg⁰/h/m² was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg⁰ release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.     

Isoseismals of the strongest Friuli aftershocks of September 1976

Summary Isoseismal maps of the three strongest Friuli aftershocks of September 1976 were compiled using the contributions from European countries within the shaken area. The characteristic features of the macroseismic fields are discussed.     

A method to determine crystallization temperatures of hydrated crystals by intracrystalline oxygen isotope effects

The fractionation of the oxygen isotopes between water molecules from different sites in CuSO₄ · 5H₂O has been measured for crystallization temperatures of 25, 40 and 50°C. The temperature dependence found provides a basis for the determination of crystallization temperatures from such intracrystalline oxygen isotope effects; also for hydrated crystals of mineralogical and geological interest. Necessary suppositions for the application of this method are discussed.     

Compositional zoning of garnet porphyroblasts from the polymetamorphic Wölz Complex, Eastern Alps

We employ garnet isopleth thermobarometry to derive the P–T conditions of Permian and Cretaceous metamorphism in the Wölz crystalline Complex of the Eastern Alps. The successive growth increments of two distinct growth zones of the garnet porphyroblasts from the Wölz Complex indicate garnet growth in the temperature interval of 540°C to 560°C at pressures of 400 to 500 MPa during the Permian and temperatures ranging from 550°C to 570°C at pressures in the range of 700 to 800 MPa during the Cretaceous Eo-Alpine event. Based on diffusion modelling of secondary compositional zoning within the outermost portion of the first garnet growth zone constraints on the timing of the Permian and the Eo-Alpine metamorphic events are derived. We infer that the rocks remained in a temperature interval between 570°C and 610°C over about 10 to 20 Ma during the Permian, whereas the high temperature stage of the Eo-Alpine event only lasted for about 0.2 Ma. Although peak metamorphic temperatures never exceeded 620°C, the prolonged thermal annealing during the Permian produced several 100 µm wide alteration halos in the garnet porphyroblasts and partially erased their thermobarometric memory. Short diffusion profiles which evolved around late stage cracks within the first garnet growth zone constrain the crack formation to have occurred during cooling below about 450°C after the Eo-Alpine event.