Quantitative analysis of H2O and CO2 in cordierite using polarized FTIR spectroscopy

We report a FTIR (Fourier transform infrared) study of a set of cordierite samples from different occurrence and with different H₂O/CO₂ content. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMPA (electron microprobe analysis), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm. According to the EMPA data, the Si/Al ratio is always close to 5:4; X _Mg ranges from 76.31 to 96.63, and additional octahedral constituents occur in very small amounts. Extraframework K and Ca are negligible, while Na reaches the values up to 0.84 apfu. SIMS shows H₂O up to 1.52 and CO₂ up to 1.11 wt%. Optically transparent single crystals were oriented using the spindle stage and examined by FTIR micro-spectroscopy under polarized light. On the basis of the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO₂ molecules in the structural channels. The IR spectra also show the presence of small amounts of CO in the samples. Refined integrated molar absorption coefficients were calibrated for the quantitative microanalysis of both H₂O and CO₂ in cordierite based on single-crystal polarized-light FTIR spectroscopy. For H₂O the integrated molar coefficients for type I and type II water molecules (ν₃ modes) were calculated separately and are ^[I]ε?=?5,200?±?700?l?mol^?1?cm^?2 and ^[II]ε?=?13,000?±?3,000?l?mol^?1?cm^?2, respectively. For CO₂ the integrated coefficient is $ \varepsilon_{{{\text{CO}}_{ 2} }} $ ?=?19,000?±?2,000?l?mol^?1?cm^?2.     

Integration of Markov mesh models and data assimilation techniques in complex reservoirs

We present a methodology that allows conditioning the spatial distribution of geological and petrophysical properties of reservoir model realizations on available production data. The approach is fully consistent with modern concepts depicting natural reservoirs as composite media where the distribution of both lithological units (or facies) and associated attributes are modeled as stochastic processes of space. We represent the uncertain spatial distribution of the facies through a Markov mesh (MM) model, which allows describing complex and detailed facies geometries in a rigorous Bayesian framework. The latter is then embedded within a history matching workflow based on an iterative form of the ensemble Kalman filter (EnKF). We test the proposed methodology by way of a synthetic study characterized by the presence of two distinct facies. We analyze the accuracy and computational efficiency of our algorithm and its ability with respect to the standard EnKF to properly estimate model parameters and assess future reservoir production. We show the feasibility of integrating MM in a data assimilation scheme. Our methodology is conducive to a set of updated model realizations characterized by a realistic spatial distribution of facies and their log permeabilities. Model realizations updated through our proposed algorithm correctly capture the production dynamics.     

A Reliable Method for Determining the Oxidation State of Manganese at the Microscale in Mn Oxides via Raman Spectroscopy

Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X‐ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal‐chemical information at the local scale. In this work, we compare a large set of Raman data from well‐characterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co‐ordinated Mn²⁺ is recognised by a band around 530 cm^?1, Mn³⁺ by a band around 580 cm^?1 and Mn⁴⁺ by a band around 630 cm^?1, while tetrahedrally co‐ordinated Mn²⁺ is recognisable by a band around 650 cm^?1. Strongly distorted Mn³⁺ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.     

Undrained Monotonic Response and Instability of Medium-Dense Sandy Soil

A series of undrained monotonic triaxial compression tests were performed on natural, medium-dense (relative density (RD) = 50%) Chlef sand containing 0.5% of non-plastic fines, under different confining pressures of 50 kPa, 100 kPa, and 200 kPa. This article focuses on distinctive states of the monotonic undrained response of sands, namely the critical state, the phase transformation state, the quasi-steady state, and the state of undrained instability (onset of flow liquefaction). Specimens were prepared using dry funnel pluviation and wet deposition to investigate the effect of the initial sand fabric on these states. The present data suggest that the initial fabric of the sand appears to have a significant effect on the undrained behavior in the early stages of shearing, with its influence vanishing at large strains. Wet deposition specimens demonstrate considerably larger undrained instability state strength than their dry funnel pluviation counterparts, and a unique critical state locus is reached by both dry funnel pluviation and wet deposition.     

Nebular emission-line profiles of Type Ib/c supernovae – probing the ejecta asphericity

In order to assess qualitatively the ejecta geometry of stripped-envelope core-collapse supernovae (SNe), we investigate 98 late-time spectra of 39 objects, many of them previously unpublished. We perform a Gauss-fitting of the [O  i ]  λλ6300, 6364  feature in all spectra, with the position, full width at half maximum and intensity of the  λ6300  Gaussian as free parameters, and the  λ6364  Gaussian added appropriately to account for the doublet nature of the [O  i ] feature. On the basis of the best-fitting parameters, the objects are organized into morphological classes, and we conclude that at least half of all Type Ib/c SNe must be aspherical. Bipolar jet models do not seem to be universally applicable, as we find too few symmetric double-peaked [O  i ] profiles. In some objects, the [O  i ] line exhibits a variety of shifted secondary peaks or shoulders, interpreted as blobs of matter ejected at high velocity and possibly accompanied by neutron-star kicks to assure momentum conservation. At phases earlier than ∼200 d, a systematic blueshift of the [O  i ]  λλ6300, 6364  line centroids can be discerned. Residual opacity provides the most convincing explanation of this phenomenon, photons emitted on the rear side of the SN being scattered or absorbed on their way through the ejecta. Once modified to account for the doublet nature of the oxygen feature, the profile of Mg  i ]  λ4571  at sufficiently late phases generally resembles that of [O  i ]  λλ6300, 6364  , suggesting negligible contamination from other lines and confirming that O and Mg are similarly distributed within the ejecta.