XANES and Mg isotopic analyses of spinels in Ca‐Al‐rich inclusions: Evidence for formation under oxidizing conditions

Ti valence measurements in MgAl₂O₄ spinel from calcium‐aluminum‐rich inclusions (CAIs) by X‐ray absorption near‐edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti⁺⁴. Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI‐like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti⁺³‐rich if they equilibrated with CAI liquids under near‐solar oxygen fugacities. In igneous inclusions, the seeming paradox of high‐valence spinels coexisting with low‐valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low‐pressure evaporation or by equilibration of spinel with relict Ti⁺⁴‐rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ²⁵Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ²⁵Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ²⁵Mg data are most simply explained by the low‐pressure evaporation model, but this model has difficulty explaining the high Ti⁺⁴ concentrations in spinel.     

New insights into the mineralogy and weathering of the Meridiani Planum meteorite,Mars

Meridiani Planum is the first officially recognized meteorite find on the surface of Mars. It was discovered at and named after the landing site of the Mars Exploration Rover Opportunity. Based on its composition, it was classified as a IAB complex iron meteorite. Mössbauer spectra obtained by Opportunity are dominated by kamacite (α‐Fe‐Ni) and exhibit a small contribution of ferric oxide. Several small features in the spectra have been neglected to date. To shed more light on these features, five iron meteorite specimens were investigated as analogs to Meridiani Planum with a laboratory Mössbauer setup. Measurements were performed on (1) their metallic bulk, (2) troilite (FeS) inclusions, (3) cohenite ((Fe,Ni,Co)₃C) and schreibersite ((Fe,Ni)₃P), and (4) corroded rims. In addition to these room‐temperature measurements, a specimen from the Mundrabilla IAB‐ungrouped meteorite was measured at Mars‐equivalent temperatures. Based on these measurements, the features in Meridiani Planum spectra can be explained with the presence of small amounts of schreibersite and/or cohenite and iron oxides. The iron oxides can be attributed to a previously reported coating on Meridiani Planum. Their presence indicates weathering through the interaction of the meteorite with small amounts of water.     

Photoabsorption in Ganymede’s atmosphere

In the framework of future space missions to Ganymede, a pre-study of this satellite is a necessary step to constrain instrument performances according to the mission objectives. This work aims at characterizing the impact of the solar UV flux on Ganymede’s atmosphere and especially at deriving some key physical parameters that are measurable by an orbiter. Another objective is to test several models for reconstructing the solar flux in the Extreme-UV (EUV) in order to give recommendations for future space missions.Using a Beer–Lambert approach, we compute the primary production of excited and ionized states due to photoabsorption, neglecting the secondary production that is due to photoelectron impacts as well as to precipitated suprathermal electrons. Ions sputtered from the surface are also neglected. Computations are performed at the equator and close to the pole, in the same conditions as during the Galileo flyby. From the excitations, we compute the radiative relaxation leading to the atmospheric emissions. We also propose a simple chemical model to retrieve the stationary electron density. There are two main results: (i) the modelled electron density and the one measured by Galileo are in good agreement. The main atmospheric visible emission is the atomic oxygen red line at 630 nm, both in equatorial and in polar conditions, in spite of the different atmospheric compositions. This emission is measurable from space, especially for limb viewing conditions. The OH emission (continuum between 260 and 410 nm) is also probably measurable from space. (ii) The input EUV solar flux may be directly measured or reconstructed from only two passbands solar observing diodes with no degradation of the modelled response of the Ganymede’s atmosphere. With respect to these results, there are two main conclusions: (i) future missions to Ganymede should include the measurement of the red line as well as the measurement of OH emissions in order to constrain the atmospheric model. (ii) None of the common solar proxies satisfactorily describes the level of variability of the solar EUV irradiance. For future atmospheric planetary space missions, it would be more appropriate to derive the EUV flux from a small radiometer rather than from a full-fledged spectrometer.     

GLONASS ambiguity resolution of mixed receiver types without external calibration

GLONASS processing from mixed receiver types is typically subject to unmodeled inter-frequency phase biases which prevent carrier phase ambiguity parameters from converging to integers. Receiver-dependent values have been proposed to mitigate the contribution of these biases, but are still subject to a number of issues, such as firmware updates. Recent studies have demonstrated that the origin of inter-frequency biases is a misalignment between phase and code observations, and could be calibrated to first order by manufacturers. In this contribution, a calibration-free method for GLONASS ambiguity resolution is presented in which ambiguities naturally converge to integers. A mandatory condition is that two GLONASS satellites with adjacent frequency numbers are observed simultaneously, although this condition can be relaxed once a fixed solution has been obtained. This approach then permits the integration of different receiver types and firmware versions into seamless processing.     

Estimating the Sampling Uncertainty for the Analysis of Solid Refused Fuel

Uncertainty assessment of the parameters used for the reporting in the emissions trading system (ETS) to characterize fuels includes not only the processes in a laboratory but has to be expanded for inclusion of sampling and sample preparation. Analysis of variance was used to allocate the contributing uncertainties to the steps described. Apart from some specific results for sampling methods, it was observed that the uncertainty of sampling was in the same order of magnitude than the analytical and the sample preparation error. Several measures to enhance quality assurance in sampling and sample preparation could be derived from specific results. The results were used in the European Monitoring and Reporting Regulation, which set out the requirements for ETS. Sampling and sample preparation have to be included in uncertainty assessment as well as sampling procedures and sampling plans (including quality assurance) have to be agreed upon by the laboratories, carrying out the analytics of those samples.     

Relations between denudation,glaciation, and sediment deposition: implications from the Plio‐Pleistocene Central Alps

Despite abundant data on the early evolution of the Central Alps, the latest stage exhumation history, potentially related to relief formation, is still poorly constrained. We aim for a better understanding of the relation between glaciation, erosion and sediment deposition. Addressing both topics, we analysed late Pliocene to recent deposits from the Upper Rhine Graben and two modern river sands by apatite fission‐track and (U‐Th‐Sm)/He thermochronology. From the observed age patterns we extracted the sediment provenance and paleo‐erosion history of the Alpine‐derived detritus. Due to their pollen and fossil record, the Rhine Graben deposits also provide information on climatic evolution, so that the erosion history can be related to glacial evolution during the Plio‐Pleistocene. Our data show that Rhine Graben deposits were derived from Variscan basement, Hegau volcanics, Swiss Molasse Basin, and the Central Alps. The relations between glaciation, Alpine erosion, and thermochronological age signals in sedimentary rocks are more complex than assumed. The first Alpine glaciation during the early Pleistocene did not disturb the long‐term exhumational equilibrium of the Alps. Recent findings indicate that main Alpine glaciation occurred at ca. 1 Ma. If true, then main Alpine glaciation was coeval with an apparent decrease of hinterland erosion rates, contrary to the expected trend. We suggest that glaciers effectively sealed the landscape, thus reducing the surface exposed to erosion and shifting the area of main erosion north toward the Molasse basin, causing sediment recycling. At around 0.4 Ma, erosion rates increased again, which seems to be a delayed response to main glaciation. The present‐day erosion regime seems to be dominated by mass‐wasting processes. Generally, glacial erosion rates did not exceed the pre‐glacial long‐term erosion rates of the Central Alps.     

Reversible rock-slope deformations caused by cyclic water-table fluctuations in mountain slopes of the Central Alps, Switzerland

Within the framework of the Gotthard Base Tunnel Project in the Central Alps, Switzerland, geodetic monitoring networks were installed above the tunnel trajectory in alpine valleys. Natural ground-surface deformation recorded in the years prior to the tunneling excavation was seen to contain an unexpectedly large cyclical component of horizontal strain across the valleys, which was seasonal and appeared to be due to elastic processes. The strain is strongly correlated with snow melt and rainstorm precipitation, suggesting the implied rock-mass deformation is driven by changes in water-table elevation within adjacent mountain slopes. The horizontal strains are of the order of 1?C2?·?10^?C5, which is close to the design limits that can be accommodated by hydropower arch dams in the study area. This study investigates these processes in detail and describes a new mathematical model (REROD), which is able to accurately reproduce and predict such natural rock-slope displacements. The model implements a transfer-function approach to predict the valley-crossing strains from rainfall and winter snow height data recorded at nearby meteorological stations. It has been used to estimate and remove the natural strain signal from the net recorded deformation so as to resolve the component due to tunneling.     

Experimental and theoretical study of the vibrational properties of diaspore (α-AlOOH)

Vibrational properties of diaspore, α-AlOOH, have been re-investigated using room-temperature single-crystal Raman spectroscopy and low-temperature powder infrared (IR) transmission spectroscopy. First-principles harmonic calculations based on density functional theory provide a convincing assignment of the major Raman peaks and infrared absorption bands. The large width of the Raman band related to OH stretching modes is ascribed to mode–mode anharmonic coupling due to medium-strength H-bonding. Additional broadening in the powder IR spectrum arises from depolarization effects in powder particles. The temperature dependence of the IR spectrum provides a further insight into the anharmonic properties of diaspore. Based on their frequency and temperature behavior, narrow absorption features at ~2,000 cm⁻¹ and anti-resonance at ~2,966 cm⁻¹ in the IR spectrum are interpreted as overtones of fundamental bending bands.     

Investigating high zircon concentrations in the fine fraction of stream sediments draining the Pan-African Dahomeyan Terrane in Nigeria

Sixteen hundred stream sediments (<150 μm fraction) collected during regional geochemical surveys in central and SW Nigeria have high median and maximum concentrations of Zr that exceed corresponding Zr concentrations found in stream sediments collected from elsewhere in the World with similar bedrock geology. X-ray diffraction studies on a sub-set of the analysed stream sediments showed that Zr is predominantly found in detrital zircon grains. However, the main proximal source rocks (Pan-African ‘Older Granites’ of Nigeria and their Proterozoic migmatitic gneiss country rocks) are not enriched in zircon (or Zr). Nevertheless, U–Pb LA-ICP-MS dating with cathodoluminescence imaging on detrital zircons, both from stream sediment samples and underlying Pan-African ‘Older Granites’ confirms a local bedrock source for the stream sediment zircons. A combination of tropical/chemical weathering and continuous physical weathering, both by ‘wet season’ flash flooding and ‘dry season’ unidirectional winds are interpreted to have effectively broken down bedrock silicate minerals and removed much of the resultant clay phases, thereby increasing the Zr contents in stream sediments. The strong correlation between winnowing index (Th/Al) and Zr concentration across the study area support this interpretation. Therefore, ‘anomalous’ high values of Zr, as well as other elements concentrated in resistant ‘heavy’ minerals in Nigeria’s streams may not reflect proximal bedrock concentrations of these elements. This conclusion has important implications for using stream sediment chemistry as an exploration tool in Nigeria for primary metal deposits associated with heavy minerals.     

Spatial polarization and dynamic pathways of Foreign Direct Investment in China 1990–2009

The spatial and sectoral distribution of Foreign Direct Investment (FDI) in China has changed dramatically in the past two decades. FDI was largely concentrated in the Pearl River Delta (PRD) and other Southern Coastal provinces in early stages and shifted to the Yangtze River Delta (YRD) and the Bohai Economic Rim (BER) sequentially in later stages. It created unique and dynamic paths of the spatial evolution of FDI in China. Although many provinces have received relatively more FDI since the late 2000s, Guangdong and Jiangsu are still the two major recipients of FDI in China, demonstrating and over-arching polarization process. Furthermore, most FDI in China has been in the manufacturing sector, making China well-known as the “World Factory of Manufacturing”. This paper analyses the most recent trends, characteristics and patterns of FDI in China. It portrays the factors that determined the investment location and the dynamic pathways of different kinds of FDI. This paper also foresees the possible changes in spatial and sectoral distribution of FDI in the near future and provides policy suggestions for both China and other developing countries in seeking new FDI inflows and transforming their industrial structures and economies in this particular phase of globalization.