Effects of strong network modifiers on Fe<Superscript>3+</Superscript>/Fe<Superscript>2+</Superscript> in silicate melts: an experimental study

The effect of CaO, Na₂O, and K₂O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550?°C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca?<?Na?<?K. Some old controversial conceptions concerning the effect of potassium on Fe³⁺/Fe²⁺ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO₂–TiO₂–Al₂O₃–FeO–Fe₂O₃–MgO–CaO–Na₂O–K₂O–P₂O₅ melts at air conditions.     

Feeding of European cisco (Coregonus albula and C. lucinensis) on the glacial relict crustacean Mysis relicta in Lake Breiter Luzin (Germany)

Lake Breiter Luzin, located in north-eastern Germany, is known for the rare occurrence of sympatric populations of European cisco, Coregonus albula and C. lucinensis. Moreover, the lake is inhabited by the glacial relict crustacean Mysis relicta, currently found in only three other lakes in Germany. In the present study, the role of M. relicta in the diet of ciscoes was investigated. Between 2001 and 2002 ciscoes, mysids and zooplankton were caught in Lake Breiter Luzin and stomach contents of ciscoes were analysed. There were seasonal changes in the food items in the stomachs, largely reflecting changes in prey availability. The main food items were copepods (45–81%) and mysids (5–26%). Cladocerans had high amounts in the diet only in summer. Seasonal changes in selectivity were also noted for most prey groups. There were also some consistent patterns of prey preference, with an overall preference for mysids. In general, the prey composition in cisco stomachs did not show significant diet changes, but there were some significant differences between day and night feeding in single prey groups, such as cladocerans. Diet composition of ciscoes varied with the different depth strata in which the fish were caught. With increasing depth, the proportion of mysids in the diet significantly increased, whereas that of copepods significantly decreased. Between C. albula and C. lucinensis, no distinct differences in feeding were evident. Mysids provided an additional and important food resource to ciscoes, and were mainly consumed when the availability of other prey organisms decreased, as in autumn and in the deeper strata of the water column. However, mysids preyed on the same food organisms as ciscoes, indicating a strong competition for food between fish and mysids.     

The Nigerian manganese-rich iron-formations and their host rocks—from sedimentation to metamorphism

This investigation deals with the Nigerian iron-formations and their host rocks and is based on about 560 mineral analyses (electron-microprobe) and 93 whole-rock analyses (64 iron-formations and 29 host rocks). The manganese-rich and Al-bearing iron-formations occurring in various schist belts of the northern and southern part of West-Nigeria consist of the magnetite-free silicate, the magnetite–silicate and the quartz-rich hematite facies.Iron-formations and host rocks originated from submarine-volcanogenic exhalations enriched in Fe, Mn and CO₂ and from Al₂O₃, SiO₂ and alkali (K₂O and Na₂O)-rich continental-derived pelitic to psammitic material. From these sources and their interaction and controlled by the volcanogenic activity, differently composed protoliths were deposited in the marine basin during the Birimian time. Subsequent metamorphism of greenschist to low amphibolite facies conditions during the Eburnian time led to the formation of the metaprotoliths of the magnetite–silicate (consisting of predominantly magnetite and quartz and subordinate of garnet and amphibole), the silicate facies (consisting of garnet, amphibole and rarely Mn-bearing ilmenite and quartz) and the metasediment phyllite. Garnets are predominantly almandine–spessartine solid solutions, whereas amphiboles are Mn and Ca-bearing grunerite–cummingtonite solid solutions. In the course of a second tectono-metamorphic event of Pan-African age, the magnetite–silicate facies iron-formation/phyllite association was transformed into the hematite facies and muscovite/biotite schists, whereas the silicate facies is characterized by extensive silicification features. The hematite facies and the silicified silicate facies are restricted to southern Nigeria where the second and heterogeneous tectono-metamorphic event is more pronounced (amphibolite facies conditions) than in northern Nigeria.The genesis, summarized as the metamorphic model, shows that the carbonate-rich (siderite, rhodochrosite and subordinate magnesite and calcite) protoliths were metamorphically transformed into the silicate and magnetite–silicate facies. The separation of Mn and Fe, leading to manganese-bearing iron-formations and iron-bearing manganese-formations was explained by varying pH-conditions, under which siderite (pH: 6.8–9.4) and rhodochrosite (pH: 9–11) precipitated.Similar to the Gunfit and Biwabik iron-formations of Minnesota, USA, the iron-formation of Bingi (Maru schist belt), now present in the form of the fayalite bearing silicate facies, was overprinted by contact metamorphism caused by a gabbro intrusion.     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

Molecular characterization of organic matter in sediments from the Keg River formation (Elk Point group), western Canada sedimentary basin

Distributions of free and sulfur-bound biomarkers in organic-rich sediments from the lower and upper Keg River formation (Elk Point group, western Canada) reveal deposition of these sediments under reducing conditions, in agreement with the geological data. The predominance of aryl isoprenoids of Chlorobiaceae origin indicates that photic zone anoxia occurred during time of deposition. A series of novel aryl isoprenoids with a carboxylic acid function was identified by GC–MS and the structure of the predominant 3-methyl-5-(2′,3′,6′-trimethylphenyl)pentanoate was proven by synthesis of an authentic standard. The occurrence of these acids gives evidence that oxidative breakdown at least partially accounts for the diagenetic fate of aromatic carotenoids. Li/EtNH₂ desulfurization of two kerogen concentrates yielded only low amounts of sulfur-bound hydrocarbons, and suggests that either sulfur sequestration was not a predominant process or, more probably, that a major part of the hydrocarbons, initially sulfurized, were released upon maturation, giving further evidence that (poly)sulfide bonds are cleaved at relatively low levels of thermal stress.     

An experimental investigation on diffusion of water in haplogranitic melts

  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz₂₈Ab₃₈Or₃₄ (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D _water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D _water with pressure indicates an average activation volume of about 9 cm³/mole. The diffusivity (in cm²/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by

Über einen ungewöhnlichen Saponit von Raschau i. Sa.

Ohne Zusammenfassung     

Tsunami simulations on several scales

The tsunami event generated by the great Sumatra–Andaman earthquake on 26 December 2004 was simulated with the recently developed model TsunAWI. The model is based on the finite element method, which allows for a very flexible discretization of the model domain. This is demonstrated by a triangulation of the whole Indian Ocean with a resolution of about 14 km in the deep ocean but a considerably higher resolution of about 500 m in the coastal area. A special focus is put on the Banda Aceh region in the Northern tip of Sumatra. This area was heavily hit by the tsunami and the highest resolution in this area is about 40 m in order to include inundation processes in the model simulation. We compare model results to tide gauge data from all around the Indian Ocean, to satellite altimetry, and field measurements of flow depth in selected locations of the Aceh region. Furthermore, we compare the model results of TsunAWI to the results of a nested grid model (TUNAMI-N3) with the same initial conditions and identical bathymetry and topography in the Aceh region. It turns out that TsunAWI gives accurate estimates of arrival times in distant locations and in the same mesh gives good inundation results when compared to field measurements and nested grid results.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.