Mineral chemistry of gersdorffite – A powerful tool in the differentiation of hydrothermal systems

Gersdorffite from two mineralization types (post-Variscan vein deposits, strata-bound mineralization) was investigated in the Niederberg area Rhenish Massif. In the ternary Ni–Co–Fe space gersdorffite from post-Variscan vein deposits displays a tight cluster with the highest Ni-contents ranging from 0.825 to 0.962 atoms per formula unit (a.p.f.u.). As/S ratios comprise a narrow range from 0.875 to 1.012. In contrast gersdorffite from the strata-bound mineralization displays a substitutional trend. Co and Fe substitute for Ni in a ± fixed ratio. Ni ranges between 0.494 and 0.836 a.p.f.u. As/S ratios (1.025–1.211) display a wider range and indicate higher As-contents relative to gersdorffite from post-Variscan vein deposits. Based on these results, two different hydrothermal fluid systems can be identified in the Niederberg area forming gersdorffite in both mineralization types. The hydrothermal fluids circulating in the post-Variscan vein deposits were homogeneous (high Ni-activities, lower As fugacities) and mixing occurred far away from the site of deposition whereas the fluids of the strata-bound mineralization were more heterogeneous (decreasing Ni-activities) with moderate elevated As fugacities. With respect to the post-Variscan vein deposits in the Niederberg area the results are compatible with earlier findings.Comparison with available gersdorffite analyses from adjacent areas (borehole Viersen, Ramsbeck deposit) reveal that gersdorffite compositions provide a reliable tool in distinguishing between different hydrothermal systems on a regional scale in the northern Rhenish Massif. However, gersdorffite compositions cannot be used to discriminate between Variscan and post-Variscan deposits with confidence.The country rocks in the Niederberg area are possible sources for Ni, Co and Fe during gersdorffite formation of the strata-bound mineralization. However, due to the remarkable homogeneity of gersdorffite compositions of the post-Variscan vein deposits irrespective of age and composition of the immediate adjacent host-rocks it is assumed that these host-rocks are not the source of the metals. Reduced Zechstein sulfate is assumed to be the source of sulfur. The As source remains unknown.Due to conflicting experimental data concerning the gersdorffite solid solution field it is not possible to derive reliable formation temperatures for the strata-bound mineralization. However, gersdorffite compositions of the post-Variscan vein deposits are compatible with low formation temperatures (<300 °C) in accordance with earlier findings.     

The role of land surface dynamics in glacial inception: a study with the UVic Earth System Model

The first results of the UVic Earth System Model coupled to a land surface scheme and a dynamic global vegetation model are presented in this study. In the first part the present day climate simulation is discussed and compared to observations. We then compare a simulation of an ice age inception (forced with 116 ka BP orbital parameters and an atmospheric CO₂ concentration of 240 ppm) with a preindustrial run (present day orbital parameters, atmospheric [CO₂] = 280 ppm). Emphasis is placed on the vegetations response to the combined changes in solar radiation and atmospheric CO₂ level. A southward shift of the northern treeline as well as a global decrease in vegetation carbon is observed in the ice age inception run. In tropical regions, up to 88% of broadleaf trees are replaced by shrubs and C₄ grasses. These changes in vegetation cover have a remarkable effect on the global climate: land related feedbacks double the atmospheric cooling during the ice age inception as well as the reduction of the meridional overturning in the North Atlantic. The introduction of vegetation related feedbacks also increases the surface area with perennial snow significantly.     

Understanding the statistical properties of the percent model affinity index can improve biomonitoring related decision making

The percent model affinity (PMA) index is used to measure the similarity of two probability profiles representing, for example, an ideal profile (i.e. reference condition) and a monitored profile (i.e. possibly impacted condition). The goal of this work is to study the effects of sample size, evenness, true value of the index and number of classes on the statistical properties of the estimator of the PMA index. We derive and extend previous formulas of the expectation and variance of the estimator for estimated monitored profile and fixed reference profile. Using the obtained extension, we find that the estimator is asymptotically unbiased, converging faster when the profiles differ. When both profiles are estimated, we calculate the expectation using transformation rules for expectation and in addition derive the formula for the estimator’s variance. Since the computation of the probabilities in the variance formula is slow, we study the behavior of the variance with simulation experiments and assess whether it could be approximated with the variance for the fixed reference profile. Finally, we provide a set of recommendations for the users of the PMA index to avoid the most common caveats of the index.     

Metal island growth and dynamics on molybdenite surfaces

In order to understand the adsorption mechanism of metal atoms to semiconducting surfaces, we have studied, as a model system, the vapor phase adsorption of Ag, Au, and Cu on the (001) surface of molybdenite (MoS₂) and the subsequent surface diffusion of these adsorbates. Our scanning tunneling microscopy (STM) images show that, depending on the type of metal atom that is adsorbed, islands of a characteristic size (2 nm for Ag, 8 to 10 nm for Cu, two distinct sizes of 2 nm and 8 to 10 nm for Au), shape (well rounded in the lateral extension) and thickness (one monolayer for Ag, 1 to 1.5 nm for Cu) are formed during the initial stages of deposition. Whole islands are observed to surface diffuse without loss of size or shape. Despite the relatively large size of the copper islands on molybdenite, these islands surface diffuse extensively, suggesting that the Cu-S interaction is weak. Surface diffusion is only hindered once individual islands start to coalesce. As copper islands accumulate, the size and shape of the original islands can still be recognized, supporting the conclusion that these characteristics are constant and that monolayer growth occurs by the aggregation of islands across the surface.The strength and the nature of the Ag-S(MoS₂) bond were further investigated by using molecular orbital calculations, ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). By applying quantum mechanical approaches using a two-dimensional periodic molybdenite slab and hexagonal MoS₂ clusters of different sizes with metal atoms adsorbed to them, it is possible to calculate the electron transfer between the mineral surface and the metal atom as well as the adsorption energy as a function of surface coverage. In addition, we used the results from the quantum mechanical runs to derive empirical potentials that model the characteristics of the forces within the crystal, within the adsorbed islands, and the metal and mineral surface. The combination of quantum mechanical calculations and empirical force field calculations explain the electronic structure and the highest stability of Ag islands that have seven atoms in diameter, which exactly agrees with the size of experimentally observed islands. UPS results also suggest that a specific new state is formed (approximately 4.5 eV into the valence band) which may describe the Ag-S bond because it does not occur in pure silver or molybdenite.This study shows how the combination of microscopic (STM), spectroscopic (STS, UPS), compositional (X-ray photoelectron spectroscopy, XPS) and molecular modeling (quantum mechanical and empirical) techniques is a useful approach to understand the nature of the metal to sulfide bond. Further insights may be gained concerning the natural association of certain metals with sulfides.     

A Sr isotope study on fluorite and siderite from post-orogenic mineral veins in the eastern Harz Mountains,Germany

Rb–Sr isotope data for siderite and fluorite from sediment-hosted epithermal mineral veins in the eastern Harz Mountains (Germany) are presented. Several fluorite and siderite-bearing paragenetic stages have been proposed for these veins, with the most important mineralization being related to a quartz–sulfide and a subsequent calcite–fluorite–quartz stage, which occurred at 226±1 and 209±2 Ma, respectively. Our Rb–Sr data do not permit the identification of distinct generations of siderite and fluorite, but rather reveal straight internal mixing relations, reflecting mixing of fluids or differential fluid–rock interaction processes. This indicates merely two significant phases of mineral deposition related to the quartz–sulfide and calcite–fluorite–quartz stages. It is shown that the Paleozoic sedimentary host rocks of the veins are the most likely source for the siderite Sr, whereas fluorite displays a two-component mixture between sedimentary Sr and radiogenic Sr derived from locally occurring Permian metavolcanic rocks. Editorial handling: B. Lehmann     

Creep in geodynamic processes

From the connnection between the homologous temperature T/T_m and the viscosity a stabilization effect at viscosities of about 10²³ poise is achieved for T/T_m = 0.6–0.7. This most probably is the steady-state temperature in the upper mantles of terrestrial planets of similar composition and should be a function of pressure only. Solid-state convection in the (larger) planets is connected with deviations of temperature and viscosity from their steady-state values. Viscosity values are obtained from the uplift data of deglaciated shield areas and from the temperature and strain-rate values of oceanic plate movements. Differences in the homologous temperature of 0.1 between both regions result in differences in viscosity by two orders of magnitude, assuming the crystal size of the material to be equal. The lower viscosity values for oceanic regions may explain the absence of seismicity and the generally faster spreading rates of purely oceanic plates. From the analysis of the uplift data two creep laws are indicated. Also the temperature (T = 0.7 T_m) and the crystal size in the upper mantle (0.1–1 cm) has been obtained from these data. Diffusion creep with a linear relationship between stress and strain rate seems to be important for small stresses, below one bar. This kind of creep apparently exists during the final stage of isostatic uplift and in most parts of the oceanic asthenospheric flow. Dislocation or power-law creep prefers larger stresses like those found in regions of fast uplift, in descending oceanic plates, active plate marginsand perhaps in the depth range of reverse flow.