Intraplate deformation and 3D rheological structure of the Rhine Rift System and adjacent areas of the northern Alpine foreland

The lithosphere of the Northern Alpine foreland has undergone a polyphase evolution during which interacting stress-induced intraplate deformation and upper mantle thermal perturbations controlled folding of the thermally weakened lithosphere. In this paper we address relationships among deeper lithospheric processes, neotectonics and surface processes in the Northern Alpine foreland with special emphasis on tectonically induced topography. We focus on lithosphere memory and neotectonics, paying special attention to the thermo-mechanical structure of the Rhine Graben System and adjacent areas of the northern Alpine foreland lithosphere. We discuss implications for mechanisms of large-scale intraplate deformation and links with surface processes and topography evolution.     

Localization of mining-induced horizontal fractures along rock layer interfaces in overburden: field measurements and prediction

The locations of mining-induced horizontal fractures along rock interfaces in the overburden of Donetsk Coal Basin were identified using an original experimental device. The device traps methane from horizontal fracture zone (100–fold coal seam thickness) over an active longwall mining excavation. Presence or absence of horizontal fractures along rock layer interfaces is correlated with physical characteristics of the overburden, such as thickness, uniaxial compressive strength of overburden rock layers, location of rock layer interfaces and thickness of extracted coal seams. As a result, a combined criterion based on these physical characteristics is proposed to predict the presence of overburden horizontal fracturing in coal mine operations.     

Development of an integrated conceptual model for the rational management of the transboundary Nestos River, Greece

This paper provides a detailed analysis of the geologic, hydrologic and hydrogeologic characteristics of Nestos River basin, which is formed within the Greek mountainous part of the river. The quantitative analysis was mainly based on the data of the river flow in different gauging points across the rivercourse as well as on the data of groundwater discharge from karst springs of the mountainous area while important conclusions were made regarding the hydraulic connection between the surface waters of the river and the groundwater of the karst aquifers of the basin. The qualitative analysis has shown that the quality of both surface waters and groundwaters of the investigated basin is high, whereas, no sources of contamination were indicated during this research. The possible effects of the two large dams of Platanovrisi and Thesavros are also analysed as they strongly affect the quantitative and qualitative regime of the river delta.     

H2S fluxes from Mt. Etna, Stromboli, and Vulcano (Italy) and implications for the sulfur budget at volcanoes

We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO₂/H₂S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H₂S flux of 6 to 9 t · d⁻¹ for the summit crater. For Mt. Etna and Stromboli, we found SO₂/H₂S molar ratios of ≈20 and ≈15, respectively, which combined with SO₂ flux measurements, suggest H₂S emission rates of 50 to 113 t · d⁻¹ and 4 to 8 t · d⁻¹, respectively. We observe that “source” and plume SO₂/H₂S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H₂S emission.     

Calculation of the UV-visible spectra and the stability of Mo and Re oxysulfides in aqueous solution

Erickson and Helz (2000) established that molybdate, MoO₄⁻², is quickly and completely transformed to thiomolybdate, MoS₄⁻², by reaction with sulfide. They monitored the equilibria and kinetics of this process by measuring the UV-visible spectra of solutions containing the different oxythiomolybdate species. There is interest in the analogous reactions for the ReO₄⁻ species but little experimental data. We have therefore calculated quantum-chemically the equilibrium constants in solution for the sulfidation reactions of both MoO₄⁻² and ReO₄⁻, as well as recalculating their UV-visible charge-transfer spectra. Calculations using configuration interaction singles and time-dependent hybrid Hartree-Fock density functional methods give good absolute values and trends in UV-vis energies for both series. For MoO₄⁻² the calculated equilibrium constants for the various sulfidation steps match reasonably well against the experimental values (within two log K units). For the ReO₄⁻ sulfidation reaction the first two steps are considerably less favorable than for MoO₄⁻², suggesting that the “geochemical switch” of Erickson and Helz, a rapid transformation of oxyanion to thioanion highly dependent on sulfide concentration, will be less effective in the Re case. However, both our calculations and experiment indicate that ReO₄⁻ and ReS₄⁻ are both easier to reduce than their Mo analogs, so that reduction of these Re(VII) species will be the preferred mechanism for their removal from seawater. A previous suggestion that the neutral species MoO₄H₂ is actually the hydrated octahedral Mo(OH)₆ species is found to be incorrect, but the MoO₃(OH₂)₃ species, a highly distorted six-coordinate complex, is almost competitive in energy with MoO₄H₂ plus two H₂O.     

Lithium isotopes in the system Qz-Ms-fluid:An experimental study

The fractionation of lithium isotopes among quartz, muscovite, and a chloride-bearing aqueous fluid has been investigated experimentally at 400°-500°C and 50-100 MPa. Experiments were performed for 15-60 days in cold seal vessels with natural mineral specimens. Lithium was introduced primarily through the fluid, which also contained KCl and HCl. In most runs, the fluid was prepared with the L-SVEC standard (δ⁷Li = 0) and was 1 M in total chloride with K/Li/H = 100/10/1. In two experiments, a ⁶Li spike was employed. The experiments demonstrate that quartz and muscovite are susceptible to pronounced, rapid shifts in Li isotopic composition by diffusion through interaction with a Li-bearing fluid, particularly at 500°C. At 500°C, fractionation factors were determined to be Δ_{quartz-aqueous} ≅ +8 to + 12‰ and Δ_{muscovite-aqueous} ≅ +18 to + 20‰. An intermineral fractionation factor is given by Δ_{muscovite-quartz} ≈ +9‰. At 400°C, the results suggest Δ_{quartz-aqueous} ≈ +4 to + 6‰. The study provides evidence of systematic fractionation in lithium isotopes at the temperatures of some magmatic processes, such as those associated with porphyry-type ore systems and pegmatites.