Fission track age of Stibiotantalite from Alto Ligonha,Mozambique

Fossil fission tracks in a stibiotantalite were revealed by etching and used for fission track dating. The fission track age of this specimen (2.3·10⁸ yr.) is much lower than Pb/Pb and Rb/Sr ages of other minerals from the same area. The explanation for this discrepancy could be the only moderate track retentivity of stibiotantalite which is similiar to muscovite.     

Numerical studies of the Kelvin-Hemholtz instability in a coronal jet

Kelvin-Hemholtz(K-H)instability in a coronal EUV jet is studied via 2.5D MHD numerical simulations.The jet results from magnetic reconnection due to the interaction of the newly emerging magnetic field and the pre-existing magnetic field in the corona.Our results show that the Alfv e′n Mach number along the jet is about 5–14 just before the instability occurs,and it is even higher than 14 at some local areas.During the K-H instability process,several vortex-like plasma blobs with high temperature and high density appear along the jet,and magnetic fields have also been rolled up and the magnetic configuration including anti-parallel magnetic fields forms,which leads to magnetic reconnection at many X-points and current sheet fragments inside the vortex-like blob.After magnetic islands appear inside the main current sheet,the total kinetic energy of the reconnection outflows decreases,and cannot support the formation of the vortex-like blob along the jet any longer,then the K-H instability eventually disappears.We also present the results about how the guide field and flux emerging speed affect the K-H instability.We find that a strong guide field inhibits shock formation in the reconnecting upward outflow regions but helps secondary magnetic islands appear earlier in the main current sheet,and then apparently suppresses the K-H instability.As the speed of the emerging magnetic field decreases,the K-H instability appears later,the highest temperature inside the vortex blob gets lower and the vortex structure gets smaller.     

The relationship of the Cocos and Carnegie ridges: age constraints from paleogeographic reconstructions

Paleogeographic restorations for the oceanic crust formed by the Cocos-Nacza spreading center and its precursors were performed to reconstruct the history and ages of the submarine aseismic ridges in the Eastern Pacific Basin, the Carnegie, Coiba, Cocos, and Malpelo ridges. The bipartition of the Carnegie ridge reflects the shift from a precursor to the presently active Cocos-Nazca spreading center. The Cocos ridge is partly composed of products from the Galápagos hotspot but may also contain material from a second center of volcanic activity which is located approximately 600 km NE of Galápagos. The Malpelo ridge is a product of this second hotspot center, whereas the Coiba ridge probably formed at the Galápagos hotspot. The geometric relationship of the Cocos and Carnegie ridges indicates symmetric spreading and a constant northward shift of the presently active Cocos-Nazca spreading center.     

Bioavailability of sediment-borne lead for ragworms (Hediste diversicolor) investigated by lead isotopes

The Seine estuary possesses a heavily industrialised catchment area that contrasts significantly with that possessed by the smaller Authie estuary. For both of these northern French estuaries, Pb isotopic compositions and concentrations have been determined on specimens of Hediste diversicolor (ragworms) and on HCl leachates performed on related mudflat sediment. Three sampling campaigns were completed in 2003. As expected, the reactive Pb obtained by 1 M HCl leaching, shows higher concentrations and a more anthropogenic signature in samples from the Seine estuary than in samples from the Authie. However, neither of the two sites is free from the influence of anthropogenic Pb. Possible contaminant sources are discussed through comparisons with previously published data. For the more highly contaminated Seine estuary, most of the ragworm Pb signatures are similar to those of the sediments. In contrast, ragworms from the Authie site exhibit a higher proportion of anthropogenic Pb than the corresponding sediments. Various hypotheses are discussed to explain this significant discrepancy: (1) analytical artifacts, (2) migration of ragworm populations, (3) diet and feeding behaviour, and as the most likely explanation (4) an unsuitable leaching method for the extraction of bioavailable Pb.     

Ca2Mg(NO3)6×12H2O–structural investigations on a new compound retrieved from chimney deposits of a combined heat and power plant

Phase analysis of incrustations retrieved from chimney deposits of a combined heat and power plant in Malchow/Germany by X-ray powder diffraction gave evidence for the existence of a previously unknown hydrous calcium magnesium nitrate. Optical investigations of the sample showed the presence of colorless platy crystals with a maximum diameter of about 250 μm embedded in a partly polycrystalline and partly glassy matrix. Aided by EDX-analysis and Raman spectroscopy, a single-crystal diffraction study performed at ambient conditions demonstrated that the material represents a phase with composition Ca₂Mg(NO₃)₆×12H₂O. Basic crystallographic data are as follows: trigonal symmetry, space group type R \( \overline{3} \) , a?=?10.5583(5) Å, c?=?19.5351(10) Å, V?=?1885.97(16) ų, Z?=?3, (R(|F|) = 0.0248). The magnesium ions are coordinated by water molecules to form distorted Mg(H₂O)₆-octahedra. The calcium atoms are surrounded by nine ligands. The resulting CaO₉ tricapped trigonal prisms involve oxygen atoms from additional water moieties as well as from three different bidentate nitrate groups, respectively. Hydrogen bonds link one octahedron with two adjacent prisms into trimers. The trimers in turn are stacked in columns running parallel to [001]. Further hydrogen bonding between neighboring columns results in the formation of a three-dimensional network. To our best knowledge, Ca₂Mg(NO₃)₆×12H₂O represents a new structure type. However, column-like topologies with rods consisting of different types of polyhedra have been also observed in other trigonal hydrous nitrates. The structural relationships between these compounds are discussed. It is interesting to note that in previous phase equilibrium studies on the ternary system Ca(NO₃)₂-Mg(NO₃)₂-H₂O no other hydrous double salt has been described. Finally, the results of the structure analysis allowed a qualitative and quantitative phase analysis of the crystalline part of the chimney deposit by the Rietveld method.     

Ein Zusammenhang zwischen der Fällung von Wismutoxychlorid (anorganischer Test von Piccardi) und der Sonnentätigkeit

Zusammenfassung Es wird nachgewiesen, daß die Fällungsgeschwindigkeit von Wismutoxychlorid in sehr engem Zusammenhang steht mit der Sonnenfleckentätigkeit (Korrelationskoeffizient etwa 0,9). Ferner zeigen die Werte der nicht durch einen Faradaykäfig abgeschirmten Fällungen nach chromosphärischen Eruptionen einen Anstieg von mehr als 20%.

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Summary The author proves that the rate of precipitation of bismuth oxychloride shows a very narrow relation with the sunspot activity (correlation coefficient ca. 0,9). Furthermore those precipitations which are not separated by a Farady cage show an ascent of more than 20% after chromospheric eruptions.

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Résumé L'auteur démontre dans ce travail que la vitesse de précipitation du chlorure de bismuth est en rapport très étroit avec l'activité des taches solaires (coefficient de corrélation environ 0,9). D'autre part les précipitations qui ne sont pas isolées au moyen d'une cage de Faraday, indiquent une augmentation de vitesse de plus de 20% après des éruptions chromosphériques.

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Mit 6 Textabbildungen.     

Low-temperature anisotropic diffusion of helium in zircon: Implications for zircon (U-Th)/He thermochronometry

In the last decade the zircon (U-Th)/He (ZHe) thermochronometer has been applied to a variety of geologic problems. Although bulk diffusion coefficients for He in zircon are available from laboratory step-heating experiments, little is known about the diffusion mechanism(s) and their dependence on the crystallographic structure of zircon. Here, we investigate the diffusion of He in perfectly crystalline zircon using atomistic simulation methods that provide insights into the structural pathways of He migration in zircon. Empirical force fields and quantum-mechanical calculations reveal that the energy barriers for He diffusion are strongly dependent on structure. The most favorable pathway for He diffusion is the [0 0 1] direction through the open channels parallel to the c-axis (, activation energy for tracer diffusion of a He atom along [0 0 1]). In contrast, energy barriers are higher in other directions where narrower channels for He diffusion are identified, such as [1 0 0], [1 0 1], and [1 1 0] (ΔE^∗ of 44.8, 101.7, and 421.3 kJ mol⁻¹, respectively). Molecular dynamics simulations are in agreement with these results and provide additional insight in the diffusion mechanisms along different crystallographic directions, as well as the temperature dependence. Below the closure temperature of He in zircon [T_c ∼ 180 °C, Reiners P. W., Spell T. L., Nicolescu S., and Zanetti K. A. (2004) Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar-40/Ar-39 dating. Geochim. Cosmochim. Acta68, 1857-1887], diffusion is anisotropic as He moves preferentially along the [0 0 1] direction, and calculated tracer diffusivities along the two most favorable directions differ by approximately five orders of magnitude (D_[001]/D_[100] ∼ 10⁵, at T = 25 °C). Above this temperature, He atoms start to hop between adjacent [0 0 1] channels, along [1 0 0] and [0 1 0] directions (perpendicular to the c-axis). The diffusion along [1 0 0] and [0 1 0] is thermally activated, such that at higher temperatures, He diffusion in zircon becomes nearly isotropic (D_[001]/D_[100] ∼ 10, at T = 580 °C). These results suggest that the anisotropic nature of He diffusion at temperatures near the closure temperature should be considered in future diffusivity experiments. Furthermore, care should be taken when making geologic interpretations (e.g., exhumation rates, timing of cooling, etc.) from this thermochronometer until the effects of anisotropic diffusion on bulk ages and closure temperature estimates are better quantified.     

On the content and vertical distribution of K,Th and U in the continental crust

The content of K, Th and U in the continental crust is estimated based on the assumption that the concentration of these elements decreases with depth asA_x = A₀e^?x/D [11], withA_x andA₀ the heat production rates at depthx and at the surface, respectively. Taking the weighted mean heat production rate of the intrusive rocks of the upper crust asA₀ = 2.33 μWm^?3, that of the granulites representing the lower crust asA_x = 0.72 μWm^?3, and the mean scale heightD= 9.5km [1] the average vertical distancex = b between these intrusives and granulites is 11.2 km. Withb known and the average concentrations of K, Th and U in granulites and intrusive rocks of the upper crust the scale heights of the vertical distribution of these elements areD_K = 71km,D_Th = 9.5km,D_U = 5.8km. The knowledge of these parameters permits to calculate the average concentrations of these elements in a 33.3 km thick crust:K= 2.19%,Th= 4.43ppm,U= 0.66ppm; Th/U = 6.7 and K/U = 3.3 × 10⁴. The resulting heat flow is 23.0 mW m^?2 which is practically identical with the value deduced from heat flow measurements. Assuming that the Th/U ratio of the entire crust—including the sediments—is 3.9, the high ratio of 6.7 in the crystalline crust indicates that about 7.2 × 10¹² t U were extracted from it. All rocks with Th/U ratios <3.9 are possible sinks of this U. About half that amount is deposited in sedimentary rocks, mainly in black shales. The second important sink are the volcanic rocks of the continental margins.     

Structural investigations of the two polymorphs of synthetic Fe-cordierite and Raman spectroscopy of hexagonal Fe-cordierite

The crystal structures of synthetic hexagonal and orthorhombic Fe-cordierite polymorphs with the space groups P6/mcc and Cccm were refined from single-crystal X-ray diffraction data to R _{1, hex}?=?3.14 % and R _{1, ortho}?=?4.48 %. The substitution of the larger Fe²⁺ for Mg leads to multiple structural changes and an increase of the unit cell volumes, with a, c (hex)?=?9.8801(16) Å, 9.2852(5) Å and a, b, c (ortho)?=?17.2306(2) Å, 9.8239(1) Å, 9.2892(1) Å in the end-members. Furthermore Fe incorporation results in an increase of the volumes of the octahedra, although the diameters of the octahedra in direction of the c-axis decrease in both polymorphs. X-ray powder diffraction analysis indicates a high degree of Al/Si ordering in the orthorhombic polymorph, the Miyashiro distortion index is ~0.24. Estimations of site occupancies based on the determined tetrahedral volumes result in the following values for hexagonal Fe-cordierite: ~73 % Al for T₁ and ~28 % Al for T₂. For the first time Raman spectroscopy was performed on the hexagonal Fe-cordierite polymorph. In the hexagonal Fe-cordierite polymorph most Raman peaks are shifted towards lower wavenumbers when compared with the Mg-end-member.     

A first principles study of the oxidation energetics and kinetics of realgar

Quantum-mechanical calculations allow resolving and quantifying in detail important aspects of reaction mechanisms such as spin transitions and oxygen dissociation that can be the major rate-limiting steps in redox processes on sulfide and oxide surfaces. In addition, this knowledge can help experimentalists in setting up the framework of rate equations that can be used to describe the kinetics of, e.g., oxidation processes. The unique molecular crystal structure of realgar, As₄S₄ clusters held together by van der Waals bonds, allows for a convenient quantum-mechanical (q.m.) cluster approach to investigate the thermodynamics and kinetic pathways of oxidation. The interaction of As₄S₄ clusters with oxygen and co-adsorbed ions provides a model system for understanding the molecular-scale processes that underpin empirically-derived rate expressions, and provides clues to the oxidation mechanisms of other sulfides and oxides. Two activated processes are shown to dominate the kinetics of oxidation by molecular oxygen: (i) a paramagnetic ³O₂ to diamagnetic ¹O₂ spin transition and (ii) oxygen dissociation on the surface, in that order. The activation energies for the spin transition and O₂ dissociation step were determined to be 1.1 eV (106 kJ/mol) and 0.9 eV (87 kJ/mol), respectively, if molecular oxygen is the only reactant on the surface. In the case of As₄S₄, q.m. calculations reveal that ³O₂ transfers its spin to the cluster and forms a low-spin, peroxo intermediate on the surface before dissociating. The adsorption of a hydroxide ion on the surface proximate to the ³O₂ adsorption site changes the adsorption mechanism by lowering the activation energy barriers for both the spin transition (0.30 eV/29 kJ/mol) and the O₂ dissociation step (0.72 eV/69 kJ/mol). Thus, while spin transition is rate limiting for oxidation with O₂ alone, dissociation becomes the rate-limiting step for oxidation with co-adsorption of OH⁻. First-principles, periodic calculations of the realgar surface show that the energetics and structural changes that accompany oxidation of As₄S₄ clusters on the surface are similar to those involving individual As₄S₄ clusters. Thus, assuming that an As₄S₄ cluster with an adsorbed hydroxyl group is a reasonable approximation of the surface of As₄S₄ at high pH, the theoretically calculated oxidation rate (∼1 × 10⁻¹⁰ mol m⁻² s⁻¹) is of the same order as empirically-derived rates from experiments at T = 298 K, pH = 8, and similar dissolved oxygen concentrations. In addition, the co-adsorption of other anions found in alkaline waters (i.e. carbonate, bicarbonate, sulfate, and sulfite) were shown to energetically promote the oxidation of As₄S₄ (on the order of 5-40 kJ/mol depending on the co-adsorbed anion, OH⁻, , , , or , and accounting for changes in the hydration of products and reactants). The effect of the co-adsorbate on the kinetics and thermodynamics of oxidation is due to each adsorbate modifying the electronic and structural environment of the other adsorption site.Activation-energy barriers due to spin transitions are rarely discussed in the literature as key factors for controlling oxidation rates of mineral surfaces, even though the magnitude of these barriers is enough to alter the kinetics significantly. The attenuation of the activation energy by co-adsorbed anions suggests the possibility of pH− or p(co-adsorbate)-dependent activation energies that can be used to refine oxidation rate laws for sulfide minerals and other, especially semiconducting minerals, such as oxides.