Thermodynamic data from redox reactions at high temperatures. IV. Calibration of the Re-ReO2 oxygen buffer from EMF and NiO+Ni-Pd redox sensor measurements

The chemical potential of oxygen defined by the equilibrium:

The effect of sulfur on the partitioning of Ni and other first-row transition elements between olivine and silicate melt

The effect of sulfur dissolved as sulfide (S²⁻) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S²⁻ were varied from zero to sulfide saturation, reaching 4100 μg g⁻¹ S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S²⁻ in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M²⁺, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S²⁻ nor of Mg#^ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S²⁻ depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10⁻³ (±1.3 × 10⁻³) K per μg g⁻¹ of S²⁻, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO₂ content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10⁻³. The ratio / is well constrained at 0.611 ± 0.016.     

The qualitative zoning record of minerals. A method for determining the duration of metamorphic events?

Summary The efficacy of ion exchange in petrological systems, for example the Fe-Mg exchange between garnet and biotite, is a function of grainsize, temperature, rates of temperature change and diffusion parameters. The combination of these variables determines the final zoning profile of minerals. Therefore, zoning profiles may be used to derive one of these variables if the others are known. For example, a mineral grain that experienced a short thermal event may still preserve a zoning profile characteristic of the heating path. In contrast, if that grain experienced a long thermal event it may develop a zoning profile typical of the cooling path. Conversely, for the same temperature-time cycle, large grains may not completely equilibrate at the metamorphic peak, and in smaller grains any previous record may have been erased. This is commonly observed in natural rocks where different grains within one thin section preserve often qualitatively different zoning profiles. Thus, a critical grainsize,l _crit, may exist that separates grains with qualitatively different zoning profiles so that grains of sizel > l _crit still retain zoning information about the heating path and grains of sizel <l _crit contain only information about the cooling path. If the critical grainsize can be measured and an independent estimate for the peak metamorphic temperature exists, the duration of the thermal event may, in principle, be estimated.The applicability of this method to natural garnets is hampered by a range of uncertainties. However, a parameterisation of the critical grain size may be used to illustrate the relative importance of grain size, temperature and event duration to the equilibration of minerals. In this paper, the critical grainsize is parameterized for various temperature-time cycles and its dependence on diffusion parameters is discussed. It is shown that, for Barrovian conditions,l _crit between 0.1 and 1 mm separates garnets retaining prograde information from garnets retaining cooling path information. For illustration, we compare the results with the critical grainsize of garnets from two metamorphic terranes, the Prydz Bay region (Antarctica) and the Koralm complex (Eastern Alps). Despite the large range of uncertainties attached to the method, it is shown that the critical grainsize of garnets in both terranes is consistent with a very short duration of the last thermal event that affected the two regions.

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Die qualitative Form von Zonierungsprofilen in Mineralen. Information über die Dauer metamorpher Ereignisse?

Zusammenfassung Zonierungsprofile von Paragenesen im Ionenaustausch, zum Beispiel das Fe-Mg Austauschsgleichgewicht zwischen Granat und Biotit, sind eine Funktion von (i) Korngröße, (ii) Temperatur, (iii) Kühl- und Heizgeschwindigkeit sowie (iv) den Diffusionskonstanen. Es sollte daher möglich sein, Zonierungsprofile dazu zu verwenden, einen dieser Parameter zu bestimmen, wenn die anderen bekannt sind. Zonierungsprofile von Kristallen die ein kurzes thermisches Ereignis erfahren haben, mögen daher prograde Information beinhalten, wogegen derselbe Kristall ein retrogrades Profil aufweisen mag, wenn er einem langlebigen thermischen Ereignis unterlag (prograd und retrograd ist hier als: bei ansteigender Temperatur und bei abfallender Temperatur definiert). In Kristallen die dem gleichen Temperatur-Zeitpfad unterworfen waren, könnten kleine Körner nur die Kühlgeschichte dokumentieren, wogegen große noch Zonierungsinformation vom Heizpfad aufweisen. In natürlichen Gesteinen wird das oft dadurch beobachtet, daß verschiedene Körner auseinem Dünnschliff qualitativ verschiedene Zonierungsprofile aufweisen. Es ist daher möglich eine kritische Korngöße,l _crit, zu definieren, die Korngrößen mit qualitativ verschiedenen Zonierungsprofilen voneinander trennt. Körner mit einem Durchmesserl > l _crit haben, zumindest teilweise, noch prograde Profile, wogegen Körner mitl <l _crit nur retrograde Information dokumentieren. Wenn man diese kritische Korngröße messen kann, sollte sie dazu benutzt werden können, etwas über die Dauer des thermischen Ereignisses auszusagen.Die Anwendbarkeit dieser Methode ist durch eine Reihe von Fehlern limitiert. Nichtsdestotrotz, ist eine Parameterisierung der kritischen Korngröße nützlich um die relative Wichtigkeit von Korngröße, Temperatur und Zeit, für die Entwicklung von Zonierungsprofilen, zu illustrieren. Unser Modell kann dazu benutzt werden, um die Größenordnung von Granaten abzuschätzen, die noch prograde Information dokumentieren können. Die Abhängigkeit der kritischen Korngröße von Diffusionsparametern und der Form des Temperatur-Zeit Pfades wird ebenfalls diskutiert. Es wird gezeigt, daß für Metamorphose in der mittleren Grünschiefer und Amphibolit fazies,l _crit zwischen 0.1 and 1 mm prograd zonierte von retrograd zonierten Granaten trennt. Um das Modell zu illustrieren, werden die Ergebnisse auf die Prydz Bay Region (Antarktis) und den Koralm Komplex (Ostalpen) angewendet. Trotz der großen Fehlergrenzen der Methode glauben wir zeigen zu können, daß die kritische Korngröße beider Terrains andeutet, daß das letzte thermische Ereignis in beiden Gebieten kurzlebig war.

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With 5 Figures     

Environmental Monitoring and Peat Assessment Using Multivariate Analysis of Regional-Scale Geochemical Data

A compositional multivariate approach was used to analyse regional-scale soil geochemical data obtained as part of the Tellus Project generated by the Geological Survey of Northern Ireland. The multi-element total concentration data presented comprise X-ray fluorescence (XRF) analyses of 6862 rural soil samples collected at 20-cm depth on a non-aligned grid at one site per \(2\,\hbox {km}^{2}\). Censored data were imputed using published detection limits. Each soil sample site was assigned to the regional geology map, resulting in spatial data for one categorical variable and 35 continuous variables comprised of individual and amalgamated elements. This paper examines the extent to which soil geochemistry reflects the underlying geology or superficial deposits. Since the soil geochemistry is compositional, log-ratios were computed to adequately evaluate the data using multivariate statistical methods. Principal component analysis (PCA) and minimum/maximum autocorrelation factors (MAF) were used to carry out linear discriminant analysis (LDA) as a means to discover and validate processes related to the geologic assemblages coded as age bracket. Peat cover was introduced as an additional category to measure the ability to predict and monitor fragile ecosystems. Overall prediction accuracies for the age bracket categories were 68.4 % using PCA and 74.7 % using MAF. With inclusion of peat, the accuracy for LDA classification decreased to 65.0 and 69.9 %, respectively. The increase in misclassification due to the presence of peat may reflect degradation of peat-covered areas since the creation of superficial deposit classification.     

Exploring the gap of the digital divide

While much of the literature related to the digital divide focuses on either technology penetration in developed countries or the introduction of new technology to the poor and disadvantaged in the developing world, this paper pays attention to the middle-classes in a developing country which is connected to the Internet but under poor conditions. The digital divide is examined by investigating how the uneven distribution of Internet connection influences distance education students’ participation in higher education. Empirically, the paper is informed by a qualitative study of distance education in Indonesia. The main conclusion is that while in more peripheral areas students may not gain much from the use of new technology, the use of this technology may be useful for the further development of such regions. In central areas the new technology seems to contribute to students’ study situations more effectively and the daily environment empowers the students’ study activities, rather than vice versa.     

The structural vulnerability in the framework of natural hazard risk analyses and the exemplary application for storm loss modelling in Tyrol (Austria)

In the context of natural hazard-related risk analyses, different concepts and comprehensions of the term risk exist. These differences are mostly subjected to the perceptions and historical backgrounds of the different scientific disciplines and results in a multitude of methodological concepts to analyse risk. The target-oriented selection and application of these concepts depend on the specific research object which is generally closely connected to the stakeholders’ interests. An obvious characteristic of the different conceptualizations is the immanent various comprehensions of vulnerability. As risk analyses from a natural scientific-technical background aim at estimating potential expositions and consequences of natural hazard events, the results can provide an appropriate decision basis for risk management strategies. Thereby, beside the preferably addressed gravitative and hydrological hazards, seismo-tectonical and especially meteorological hazard processes have been rarely considered within multi-risk analyses in an Alpine context. Hence, their comparative grading in an overall context of natural hazard risks is not quantitatively possible. The present paper focuses on both (1) the different concepts of the natural hazard risk and especially their specific expressions in the context of vulnerability and (2) the exemplary application of the natural scientific-technical risk concepts to analyse potential extreme storm losses in the Austrian Province of Tyrol. Following the corresponding general risk concept, the case study first defines the hazard potential, second estimates the exposures and damage potentials on the basis of an existing database of the stock of elements and values, and third analyses the so-called Extreme Scenario Losses (ESL) considering the structural vulnerability of the potentially affected elements at risk. Thereby, it can be shown that extreme storm events can induce losses solely to buildings and inventory in the range of EUR 100–150 million in Tyrol. However, in an overall context of potential extreme natural hazard events, the storm risk can be classified with a moderate risk potential in this province.     

Initiation and development of pull-apart basins with Riedel shear mechanism: insights from scaled clay experiments

Typical pull-apart structures were created in scaled clay experiments with a pure strike-slip geometry (Riedel type experiments). A clay slab represents the sedimentary cover above a strike-slip fault in the rigid basement. At an early stage of the development of the deformation zone, synthetic shear fractures (Riedel shears) within the clay slab display dilatational behaviour. With increasing basal displacement the Riedel shears rotate and open further, developing into long, narrow and deep troughs. The shear displacement and the low angle with the prescribed principal basal fault set them apart from tension gashes. At a more evolved stage, synthetic segments (Y-shears) parallel to the basal principal fault develop and accommodate progressive strike-slip deformation. The Y-shears connect the tips of adjacent troughs developed from the earlier Riedel shears, resulting in the typical rhomb-shaped structures characteristic for pull-apart basins. The Strait of Sicily rift zone, with major strike-slip systems being active from the Miocene to the Present, comprises pull-apart basins at different length scales, for which the structural record suggests development by a mechanism similar to that observed in our experiments.     

The south-western Black Forest and the Upper Rhine Graben Main Border Fault: thermal history and hydrothermal fluid flow

The thermal history of the south-westernmost Black Forest (Germany) and the adjacent Upper Rhine Graben were constrained by a combination of apatite and zircon fission-track (FT) and microstructural analyses. After intrusion of Palaeozoic granitic plutons in the Black Forest, the thermal regime of the studied area re-equilibrated during the Late Permian and the Mesozoic, interrupted by enhanced hydrothermal activity during the Jurassic. At the eastern flank of the Upper Rhine Graben along the Main Border Fault the analysed samples show microstructural characteristics related to repeated tectonic and hydrothermal activities. The integration of microstructural observations of the cataclastic fault gouge with the FT data identifies the existence of repeated tectonic-related fluid flow events characterised by different thermal conditions. The older took place during the Variscan and/or Mesozoic time at temperatures lower than 280°C, whereas the younger was probably contemporary with the Cenozoic rifting of the Upper Rhine Graben at temperatures not higher than 150°C.     

Modification of fluid inclusions in quartz by deviatoric stress I: experimentally induced changes in inclusion shapes and microstructures

Fluid inclusions in quartz are known to modify their shapes and microstructures (textures) during weak plastic deformation. However, such changes have not been experimentally demonstrated and criteria are not available to relate them to paleostress conditions. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. Strains of up to 1% cause the inclusions to develop irregular shapes and to generate microcracks in crystallographic planes oriented subperpendicular to the major compression axis, σ ₁. The uniform alignment of the microcracks imparts a planar fabric to the samples. The microcracks heal and form swarms of tiny satellite inclusions. These new inclusions lose H₂O by diffusion, thereby triggering plastic deformation of the surrounding quartz via H₂O-weakening. Consequently, the quartz samples deform plastically only in domains originally rich in inclusions. This study shows that fluid inclusions deformed by deviatoric stresses may indeed record information on paleostress orientations and that they play a key role in facilitating crystal-plastic deformation of quartz.