Infrared spectroscopic properties of goethite: anharmonic broadening,long-range electrostatic effects and Al substitution

The infrared spectrum and its temperature dependence (20–320 K) were collected on a synthetic goethite sample (α-FeOOH). In addition, the infrared powder absorption spectrum of goethite and aluminum-substituted goethite was computed using ab initio quantum mechanical calculations based on density functional theory. This combined experimental and theoretical approach allows (1) the unequivocal assignment of absorption bands to the corresponding vibrational modes, (2) separate identification of the effects of the particle shape and of the aluminum substitution on the infrared spectrum, and (3) a discussion of the anharmonic properties and the origin of the line broadening in goethite. In particular, the two well-resolved OH bending absorption bands show different temperature evolution. Their detailed analysis suggests that the broadening of the band at ~800 cm^?1 cannot be described solely by a usual three-phonon process. The strong anharmonic behavior of this mode implies the addition of a four-phonon process, such as a pure dephasing process. In our calculations, the effect of the Hubbard U correction is also investigated and found to be most visible on the OH stretching and bending modes, in relation to the associated structural relaxation. The OH stretching frequencies decrease, leading to a better agreement with experimental frequencies, while the OH bending frequencies increase.     

The influence of the plastic potential on plane strain failure

The influence of the shape of the plastic potential in the deviatoric plane on plane strain collapse is investigated. The most commonly employed elastic‐perfect plastic models are considered, which adopt well‐known failure criteria for defining the yield and plastic potential surfaces, namely the von Mises, the Drucker–Prager, the Tresca, the Mohr–Coulomb and the Matsuoka–Nakai criteria. Finally, the conclusions are also extended to strain hardening/softening models. For simple constitutive models based on perfect plasticity, it is shown that the value of the Lode's angle at plastic collapse in plane strain conditions strongly depends on the specific failure surface adopted for reproducing the plastic potential surface. If the value of the Lode's angle at yield coincides with the failure value prescribed by the plastic potential, the stress–strain curves exhibit the typical perfect plastic behaviour with yield coinciding with failure, otherwise the stress changes after yield and the stress‐strain curves resemble those of strain hardening/softening models. The infinite strength which is in some situations exhibited by the Drucker–Prager model in plane strain condition is investigated and explained, and it is shown that this can also affect strain hardening/softening models. Copyright © 2013 John Wiley & Sons, Ltd.     

Itqiy: A study of noble gases and oxygen isotopes including its terrestrial age and a comparison with Zakłodzie

Abstract— We report noble gas, oxygen isotope, ¹⁴C and ¹⁰Be data of Itqiy as well as noble gas, ¹⁴C and ¹⁰Be results for Zak?odzie. Both samples have been recently classified as anomalous enstatite meteorites and have been compared in terms of their mineralogy and chemical composition. The composition of enstatite and kamacite and the occurrence of specific sulfide phases in Itqiy indicate it formed under similar reducing conditions to those postulated for enstatite chondrites. The new results now seem to point at a direct spatial link. The noble gas record of Itqiy exhibits the presence of a trapped subsolar component, which is diagnostic for petrologic types 4–6 among enstatite chondrites. The concentration of radiogenic ⁴He is very low in Itqiy and indicates a recent thermal event. Its ²¹Ne cosmic‐ray exposure age is 30.1 ± 3.0 Ma and matches the most common age range of enstatite chondrites (mostly EL6 chondrites) but not that of Zak?odzie. Itqiy's isotopic composition of oxygen is in good agreement with that observed in Zak?odzie as well as those found in enstatite meteorites suggesting an origin from a common oxygen pool. The noble gas results, on the other hand, give reason to believe that the origin and evolution of Itqiy and Zak?odzie are not directly connected. Itqiy's terrestrial age of 5800 ± 500 years sheds crucial light on the uncertain circumstances of its recovery and proves that Itqiy is not a modern fall, whereas the ¹⁴C results from Zak?odzie suggest it hit Earth only recently.     

Noble gases in enstatite chondrites II: The trapped component

Abstract— The trapped noble gas record of 57 enstatite chondrites (E chondrites) has been investigated. Basically, two different gas patterns have been identified dependent on the petrologic type. All E chondrites of type 4 to 6 show a mixture of trapped common chondritic rare gases (Q) and a subsolar component (range of elemental ratios for E4–6 chondrites: ³⁶Ar/¹³²Xe = 582 ± 270 and ³⁶Ar/⁸⁴Kr = 242 ± 88). E3 chondrites usually contain Q gases, but also a composition with lower ³⁶Ar/¹³²Xe and ³⁶Ar/⁸⁴Kr ratios, which we call sub‐Q (³⁶Ar/¹³²Xe = 37.0 ± 18.0 and ³⁶Ar/⁸⁴Kr = 41.7 ± 18.1). The presence of either the subsolar or the sub‐Q signature in particular petrologic types cannot be readily explained by parent body metamorphism as postulated for ordinary chondrites. We therefore present a different model that can explain the bimodal distribution and composition of trapped heavy noble gases in E chondrites. Trapped solar noble gases have been observed only in some E3 chondrites. About 30% of each group, EH3 and EL3 chondrites, amounting to 9% of all analyzed E chondrites show the solar signature. Notably, only one of those meteorites has been explicitly described as a regolith breccia.     

Noble gases in enstatite chondrites I: Exposure ages,pairing, and weathering effects

Abstract— Cosmic‐ray exposure ages calculated from cosmogenic noble gas nuclides are reported for 57 enstatite (E) chondrites, 43 of them were measured for the first time. With a total of 62 individual E chondrites (literature and this data, corrected for pairing) the observed spectrum of ages ranges between 0.07 and 66 Ma. Three clusters seem to develop at about 3.5, 8, and 25 Ma, respectively. Since the uncertainty of ages is estimated to be ～20% (in contrast to 10 to 15% for ordinary chondrites) and the number of examined samples is still comparatively small, these peaks have to be confirmed by more measurements. Regarding the two subgroups, EH and EL chondrites, no systematic trend is apparent in the distribution of cosmic‐ray exposure ages. Several E chondrites yield significantly lower ³⁸Ar ages compared to those calculated from cosmogenic ³He and ²¹Ne. For these E chondrites, we suggest a reduction of cosmogenic ³⁸Ar as a result of weathering. In order to prove the possible influence of terrestrial alteration on the cosmogenic noble gas record of E‐chondritic material, we simulated terrestrial weathering in an experiment of 12 weeks duration. The treatment showed that a significant amount of cosmogenic ³⁸Ar is lost on Earth by the influence of water.     

Particle size distributions of fault rocks and fault transpression: are they related?

ABSTRACT Laboratory experiments on rock faulting show that processes of particle comminution in fault rocks are influenced by several parameters, including fault strike and normal stress across faults. In nature, normal stress across faults increases with increasing transpressional strike of faults. Accordingly, different structural fabrics and particle size distributions are expected for cataclastic rocks that have developed along faults with different transpressional orientations and comparable displacements within regional-scale strike-slip fault zones. Adjacent bands of cataclastic gouge and breccia were analysed from four small-scale fault zones. All have comparable displacements and very similar protolith (i.e. shallow-water limestone), structure, kinematics, size, and tectonic environment, but different transpressional strikes within the regional-scale left-lateral Mattinata strike-slip fault, Italy. An inverse linear relationship is found between fault transpressional angles and fractal dimensions of particle size distributions from cataclastic rock samples.     

Third-order depositional sequences controlled by synsedimentary extensional tectonics: evidence from Upper Triassic carbonates of the Carnian Prealps (NE Italy)

ABSTRACT The Upper Triassic platform-margin deposits of the Carnian Prealps fail to show the succession of the two global sea-level lowerings predicted for the Norian and Rhaetian by the Haq global sea-level curve. In both cases a relative sea-level rise occurs, a discrepancy that can be explained by an increase in tectonically controlled subsidence, a consequence of the plate-scale rifting in the NW Tethys Gulf preceding oceanic spreading in the Jurassic. Pulses of tectonic subsidence followed by relative quiescence are capable of generating depositional sequences similar in gross geometry and duration to the third-order eustatic cycles of Haq et al . The Late Triassic part of the Exxon global sea-level curve, partly derived from correlatable strata within the same palaeogeographical domain, is likely to reflect pulses of tectonically induced subsidence rather than eustatic sea-level changes.     

Itqiy: A metal‐rich enstatite meteorite with achondritic texture

Abstract— Itqiy is a unique coarse‐grained, metal‐rich enstatite meteorite that was found in the Western Sahara and consists of two rocks together weighing 4.72 kg, which are both completely coated with fusion crust. We report results from our electron microprobe and instrumental neutron activation analysis techniques. Itqiy consists of subhedral, equigranular, millimeter‐sized enstatite, ?25 vol% of millimeter‐sized kamacite and a few tiny intergrowths of sulfides and kamacite. Relic chondrules are absent. Pyroxene (Fs_0.2) is chemically similar to enstatite in EL chondrites, but the metal is closer in composition to that in EH chondrites. Sulfides resemble those in E chondrites but their compositions are distinct from those in both EL and EH chondrites. Itqiy clearly formed under very reducing conditions, but it does not appear to have formed from EH or EL chondrites. Two thermal events can be distinguished. Silicate compositions including rare earth element abundances indicate loss of partial melt and slow cooling. Heterogeneous sulfides indicate a subsequent reheating and quenching event, which may have been due to shock as many enstatite grains show shock stage S3 features.