Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

Segmented seismicity of the M w 6.2 Baladeh earthquake sequence (Alborz Mountains, Iran) revealed from regional moment tensors

The M _w 6.2 Baladeh earthquake occurred on 28 May 2004 in the Alborz Mountains, northern Iran. This earthquake was the first strong shock in this intracontinental orogen for which digital regional broadband data are available. The Baladeh event provides a rare opportunity to study fault geometry and ongoing deformation processes using modern seismological methods. A joint inversion for hypocentres and a velocity model plus a surface-wave group dispersion curve analysis were used to obtain an adapted velocity model, customised for mid- and long-period waveform modelling. Based on the new velocity model, regional waveform data of the mainshock and larger aftershocks (M _w ?≥3.3) were inverted for moment tensors. For the Baladeh mainshock, this included inversion for kinematic parameters. All analysed earthquakes show dominant thrust mechanisms at depths between 14 and 26 km, with NW–SE striking fault planes. The mainshock ruptured a 28° south-dipping area of 24 × 21 km along a north-easterly direction. The rupture plane of the mainshock does not coincide with the aftershock distribution, neither in map view nor with respect to depth. The considered aftershocks form two main clusters. The eastern cluster is associated with the mainshock. The western cluster does not appear to be connected with the rupture plane of the mainshock but, instead, indicates a second activated fault plane dipping at 85° towards the north.     

TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz

Quartz and rutile were synthesized from silica-saturated aqueous fluids between 5 and 20 kbar and from 700 to 940°C in a piston-cylinder apparatus to explore the potential pressure effect on Ti solubility in quartz. A systematic decrease in Ti-in-quartz solubility occurs between 5 and 20 kbar. Titanium K-edge X-ray absorption near-edge structure (XANES) measurements demonstrate that Ti⁴⁺ substitutes for Si⁴⁺ on fourfold tetrahedral sites in quartz at all conditions studied. Molecular dynamic simulations support XANES measurements and demonstrate that Ti incorporation onto fourfold sites is favored over interstitial solubility mechanisms. To account for the P–T dependence of Ti-in-quartz solubility, a least-squares method was used to fit Ti concentrations in quartz from all experiments to the simple expression

Dating lava flows of tropical volcanoes by means of spatial modeling of vegetation recovery

The age of past lava flows is crucial information for evaluating the hazards and risks posed by effusive volcanoes, but traditional dating methods are expensive and time‐consuming. This study proposes an alternative statistical dating method based on remote sensing observations of tropical volcanoes by exploiting the relationship between lava flow age and vegetation cover. First, the factors controlling vegetation density on lava flows, represented by the normalized difference vegetation index (NDVI), were investigated. These factors were then integrated into pixel‐based multi‐variable regression models of lava flow age to derive lava flow age maps. The method was tested at a pixel scale on three tropical African volcanoes with considerable recent effusive activity: Nyamuragira (Democratic Republic of Congo), Mt Cameroon (Cameroon) and Karthala (the Comoros). Due to different climatic and topographic conditions, the parameters of the spatial modeling are volcano‐specific. Validation suggests that the obtained statistical models are robust and can thus be applied for estimating the age of unmodified undated lava flow surfaces for these volcanoes. When the models are applied to fully vegetated lava flows, the results should be interpreted with caution due to the saturation of NDVI. In order to improve the accuracy of the models, when available, spatial data on temperature and precipitation should be included to directly represent climatic variation. Copyright © 2017 John Wiley & Sons, Ltd.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution²³⁰Th_excess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (²³⁰Th), 0.43–1.40 ppm (²³²Th), 0.09–0.49 ppb (²³⁴U) and 1.66–8.24 ppm (²³⁸U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the²³⁰Th_excess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant²³⁰Th_excess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.     

Barium uptake into the shells of the common mussel (Mytilus edulis) and the potential for estuarine paleo-chemistry reconstruction

In this study we test if calcite shells of the common mussel, Mytilus edulis, contain barium in proportion to the water in which they grew. Similar to all bivalves analyzed to date, the [Ba/Ca]_shell profiles are characterized by a relatively flat background [Ba/Ca]_shell, interrupted by sharp [Ba/Ca]_shell peaks. Previous studies have focused on these [Ba/Ca]_shell peaks, but not on the background [Ba/Ca]_shell. We show that in both laboratory and field experiments, there is a direct relationship between the background [Ba/Ca]_shell and [Ba/Ca]_water in M. edulis shells. The laboratory and field data provided background Ba/Ca partition coefficients (D_Ba) of 0.10 ± 0.02 and 0.071 ± 0.001, respectively. This range is slightly higher than the D_Ba previously determined for inorganic calcite, and slightly lower than foraminiferal calcite. These data suggest that M. edulis shells can be used as an indicator of [Ba/Ca]_water, and therefore, fossil or archaeological M. edulis shells could be used to extend knowledge of estuarine dissolved Ba throughputs back in time. Moreover, considering the inverse relationship between [Ba/Ca]_water and salinity, background [Ba/Ca]_shell data could be used as an estuary specific indicator of salinity. The cause of the [Ba/Ca]_shell peaks is more confusing, both the laboratory and field experiments indicate that they cannot be used as a direct proxy of [Ba/Ca]_water or phytoplankton production, but may possibly be caused by barite ingestion.     

Magmato-sedimentary Carboniferous to Jurassic evolution of the western Tauern window,Eastern Alps (constraints from U-Pb zircon dating and geochemistry)

New geochronological U-Pb (LA-ICP-MS) zircon data and geochemical analyses from the Variscan orthogneisses and metavolcanic rocks in the western Tauern window are presented and used to reconstruct the pre-Alpine evolution of this area. The late- and post-Variscan stage in the Tauern window was characterised by distinct magmatic pulses accompanied by the formation of volcano-sedimentary basins. The magmatic activity started in the Visean (335.4 ± 1.5 Ma) with the intrusion of a K-rich, durbachitic biotite-granite (protolith of the Ahorn gneiss). Following a period of exhumation and erosion, Westfalian–Stefanian volcanics were deposited (Grierkar meta-rhyodacite: 309.8 ± 1.5 Ma; Venntal meta-rhyolite: 304.0 ± 3.0 Ma). A renewed magmatic pulse occurred in the Early Permian, producing large volumes of tonalites and granodiorites (Tux meta-granodiorite: 292.1 ± 1.9 Ma). The youngest magmatism is characterised by pyroclastic and tuffitic deposits (Pfitsch meta-rhyolite: 280.5 ± 2.6 Ma; Schönach valley meta-andesite: 279.0 ± 4.8 Ma). This volcanism was probably related to crustal extensional faulting within an intra-continental graben and horst setting, asthenospheric upwelling and heat flow increase due to the onset of the Permian rifting. The Permo-Triassic peneplanation and subsidence is documented by shallow marine and evaporitic deposits. Probably in the Middle Jurassic times, the area was flooded and in the Late Jurassic the whole area was covered by limestones, representing post-rift sediments on the southern European continental margin.     

Model identification for hydrological forecasting under uncertainty

Methods for the identification of models for hydrological forecasting have to consider the specific nature of these models and the uncertainties present in the modeling process. Current approaches fail to fully incorporate these two aspects. In this paper we review the nature of hydrological models and the consequences of this nature for the task of model identification. We then continue to discuss the history (“The need for more POWER‘’), the current state (“Learning from other fields”) and the future (“Towards a general framework”) of model identification. The discussion closes with a list of desirable features for an identification framework under uncertainty and open research questions in need of answers before such a framework can be implemented.     

Composition and sediment dispersal pattern of the Upper Triassic flysch in the eastern Himalayas,China: significance to provenance and basin analysis

International Journal of Earth Sciences - The paleogeography and basin type of Upper Triassic flysch (Langjiexue Group) in the eastern Himalayan Orogen are disputed. In order to shed new light on...