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.     

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.     

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.     

Ozone production due to emissions from vegetation burning

Ozone has been observed in elevated concentrations by satellites over areas previously believed to be background. There is meteorological evidence, that these ozone plumes found over the Atlantic Ocean originate from vegetation fires on the African continent.In a previous study (DECAFE-88), we have investigated ozone and assumed precursor compounds over African tropical forest regions. Our measurements revealed large photosmog layers at altitudes from 1.5 to 4 km. Both chemical and meteorological evidence point to savanna fires up to several thousand km upwind as sources.Here we describe ozone mixing ratios observed over western Africa and compare ozone production ratios from different field measurement campaigns related to vegetation burning. We find that air masses containing photosmog ingredients require several days to develop their oxidation potential, similar to what is known from air polluted by emissions from fossil fuel burning. Finally, we estimate the global ozone production due to vegetation fires and conclude that this source is comparable in strength to the stratospheric input.     

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.     

Internal morphology, habit and U-Th-Pb microanalysis of amphibolite-to-granulite facies zircons: geochronology of the Ivrea Zone (Southern Alps)

Several types of growth morphologies and alteration mechanisms of zircon crystals in the high-grade metamorphic Ivrea Zone (IZ) are distinguished and attributed to magmatic, metamorphic and fluid-related events. Anatexis of pelitic metasediments in the IZ produced prograde zircon overgrowths on detrital cores in the restites and new crystallization of magmatic zircons in the associated leucosomes. The primary morphology and Th-U chemistry of the zircon overgrowth in the restites show a systematic variation apparently corresponding to the metamorphic grade: prismatic (prism-blocked) low-Th/U types in the upper amphibolite facies, stubby (fir-tree zoned) medium-Th/U types in the transitional facies and isometric (roundly zoned) high-Th/U types in the granulite facies. The primary crystallization ages of prograde zircons in the restites and magmatic zircons in the leucosomes cannot be resolved from each other, indicating that anatexis in large parts of the IZ was a single and short lived event at 299 ± 5 Ma (95% c. l.). Identical U/Pb ages of magmatic zircons from a metagabbro (293 ± 6 Ma) and a metaperidotite (300 ± 6 Ma) from the Mafic Formation confirm the genetic context of magmatic underplating and granulite facies anatexis in the IZ. The U-Pb age of 299 ± 5 Ma from prograde zircon overgrowths in the metasediments also shows that high-grade metamorphic (anatectic) conditions in the IZ did not start earlier than 20 Ma after the Variscan amphibolite facies metamorphism in the adjacent Strona–Ceneri Zone (SCZ). This makes it clear that the SCZ cannot represent the middle to upper crustal continuation of the IZ. Most parts of zircon crystals that have grown during the granulite facies metamorphism became affected by alteration and Pb-loss. Two types of alteration and Pb-loss mechanisms can be distinguished by cathodoluminescence imaging: zoning-controlled alteration (ZCA) and surface-controlled alteration (SCA). The ZCA is attributed to thermal and/or decompression pulses during extensional unroofing in the Permian, at or earlier than 249 ± 7 Ma. The SCA is attributed to the ingression of fluids at 210 ± 12 Ma, related to hydrothermal activity during the breakup of the Pangaea supercontinent in the Upper Triassic/Lower Jurassic. Received: 7 July 1998 / Accepted: 4 November 1998     

Empirical Relationships for Debris Flows

The assessment of the debris flow hazard potential has to rely on semi-quantitative methods. Due to the complexity of the debris-flow process, numerical simulation models of debris flows are still limited with regard to practical applications. Thus, an overview is given of empirical relationships that can be used to estimate the most important parameters of debris-flow behavior. In a possible procedure, an assessment of a maximum debris-flow volume may be followed by estimates of the peak discharge, the mean flow velocity, the total travel distance, and the runout distance on the fan. The applicability of several empirical equations is compared with available field and laboratory data, and scaling considerations are used to discuss the variability of the parameters over a large range of values. Some recommendations are made with regard to the application of the presented relationships by practicing engineers, apart from advocating field reconnaissance and searching for historic events wherever possible.