Direct quartz-coesite transformation in shocked porous sandstone from Kamil Crater (Egypt)

Coesite, a high-pressure silica polymorph (pressure 3–10 GPa, temperature <3000 K), is a diagnostic feature of shock metamorphism associated with impact cratering on quartz-bearing target rocks. It is preserved as a metastable phase in sedimentary target rocks that experienced peak pressures in excess of ~10 GPa, where it typically occurs as intergranular polycrystalline aggregates of microcrystals embedded in silica glass known as “symplectic regions.” The presence of coesite in the symplectic regions of rocks experiencing shock conditions beyond the limits of the coesite stability field is a controversial issue. Through a combined scanning and transmission electron microscopy and Raman spectroscopy study of shocked quartzarenites from the 45-m-diameter Kamil Crater (southwest Egypt), we show that coesite in symplectic regions forms through direct subsolidus transformation from quartz, in contrast with the prevailing hypothesis for crystalline targets. The quartz-to-coesite transformation takes place during localized shock-wave reverberation at the beginning of the pore collapse process. Complete pore collapse generates the high temperature regimes responsible for the subsequent production of the embedding silica melts, in part at the expense of the previously formed coesite. This work documents the role of pore collapse in producing localized pressure-temperature-time gradients in shocked porous targets, as predicted by numerical models in the literature

3D electron diffraction in nano-geology: present and perspectives

When working on advanced research topics in geosciences, one must often deal with small yields and cryptocrystalline polyphasic samples. Conventional optical and X-ray crystallographic tools may not be sufficient for the proper characterization of these samples. The development of efficient probes able to investigate the nanoworld becomes therefore crucial for pushing forward our understanding about the geochemical and mineralogical processes that regulate Earth and extraterrestrial environments. In the last ten years, electron diffraction (ED) evolved from a qualitative method restricted to few dedicated TEM users, to a robust protocol for phase identification and abinitio structure determination [1]. Such change has been mostly propelled by the development of routines for 3D data collection. This methodology is in principle equivalent to single-crystal X-ray diffraction, but allows sampling crystals of few tens on nanometers. We will show here some examples of recent applications of ED in geosciences, namely how to achieve an easy and relatively fast characterization of minor and cryptocrystalline phases in natural and experimental samples. We were able identify and characterize modulated phases able to carry hydrogen at upper-mantle conditions, to follow aragonite growth from the first nucleation seeds [2] and to identify mineralogical phases and polytypes in non-equilibrated extraterrestrial samples and in impact rocks [3]

Pseudomonas aeruginosa infection in cystic fibrosis caused by an epidemic metallo-β-lactamase-producing clone with a heterogeneous carbapenem resistance phenotype

AbstractAn epidemic IMP-13 metallo-β-lactamase (MBL)-producing Pseudomonas aeruginosa clone, causing infections and even large outbreaks in Italian critical care settings, was detected in a young cystic fibrosis patient. In this patient, the chronic infection was sustained by distinct clonal sub-populations of the MBL-producing P. aeruginosa clone, either susceptible or resistant to carbapenems. These findings underscore the importance of infection prevention practices in cystic fibrosis settings and pose an important diagnostic and therapeutic challenge

Two New Organic Co-Crystals Based on Acetamidophenol Molecules

Herein we present two new organic co-crystals obtained through a simple solution growth process based on an acetamidophenol molecule, either paracetamol or metacetamol, and on 7,7,8,8-tetracyanoquinodimethane (TCNQ). These co-crystals are part of a family of potential organic charge transfer complexes, where the acetamidophenol molecule behaves as an electron donor and TCNQ behaves as an electron acceptor. Due to the sub-micron size of the crystalline domains, 3D electron diffraction was employed for the structure characterization of both systems. Paracetamol-TCNQ structure was solved by standard direct methods, while the analysis of metacetamol-TCNQ was complicated by the low resolution of the available diffraction data and by the low symmetry of the system. The structure determination of metacetamol-TCNQ was eventually achieved after merging two data sets and combining direct methods with simulated annealing. Our study reveals that both paracetamol-TCNQ and metacetamol-TCNQ systems crystallize in a 1:1 stoichiometry, assembling in a mixed-stack configuration and adopting a non-centrosymmetric P1 symmetry. It appears that paracetamol and metacetamol do not form a strong structural scaffold based on hydrogen bonding, as previously observed for orthocetamol-TCNQ and orthocetamol-TCNB (1,2,4,5-tetracyanobenzene) co-crystals

I was not born cubic, said low-temperature metamorphic garnet

Garnet is the paradigmatic cubic mineral of metamorphic and igneous rocks, and is generally regarded as optically isotropic. Nonetheless, evident birefringence is observed, particularly in the rare Ca-Fe3+ hydrogarnets, which is attributed to the coexistence of two or more cubic phases. A weak birefringence, with rare examples of optical sector zoning, has also been documented in much more common Fe2+-Mg-Mn garnets, but an adequate explanation for its cause is, so far, lacking. Here we show that optically anisotropic garnets are much more widespread than previously thought, both in blueschists and blueschist-facies rocks, as well as in lower greenschist-facies phyllites, but they are frequently overlooked when working with conventional, 30-µm-thick thin sections. Utilizing a multi-technique approach including optical microstructural analysis, BSEM, EMPA, EBSD, FTIR, TEM, EDT and single-crystal XRD, we demonstrate here that the birefringence in these garnets is related to their tetragonal symmetry, that it is not due to strain, and that crystals are twinned according to a merohedral law. We also show that the birefringent garnets from blueschists and phyllites are anhydrous, lacking any hydrogarnet component, and have compositions dominated by almandine (58-79%) and grossular (19-30%) with variable spessartine (0-21%) and very low pyrope (1-7%). Considering the widespread occurrence of optically anisotropic OH-free garnets in blueschists and phyllites, their common low-grade metamorphic origin, and the occurrence of optically isotropic garnets with similar Ca-rich almandine composition in higher-grade rocks, we conclude that garnet does not grow with cubic symmetry in low-temperature rocks (< 400 ◦C). The tetragonal structure appears to be typical of Fe-Ca-rich compositions, with very low Mg contents. Cubic but optically sector-zoned garnet in a lower amphibolite-facies metapelite from the eastern Alps suggests that preservation of tetragonal garnet is favored in rocks which did not progress to T> ≈500 ◦C, where transition to the cubic form, accompanied by change of stable chemical composition, would take place. Our data show that the crystal-chemistry of garnet, its thermodynamics and, in turn, its use in unravelling petrogenetic processes in cold metamorphic environments need to be re-assessed

Garnet, the archetypal cubic mineral, grows tetragonal

Garnet is the archetypal cubic mineral, occurring in a wide variety of rock types in Earth’s crust and upper mantle. Owing to its prevalence, durability and compositional diversity, garnet is used to investigate a broad range of geological processes. Although birefringence is a characteristic feature of rare Ca–Fe3+ garnet and Ca-rich hydrous garnet, the optical anisotropy that has occasionally been documented in common (that is, anhydrous Ca–Fe2+–Mg–Mn) garnet is generally attributed to internal strain of the cubic structure. Here we show that common garnet with a non-cubic (tetragonal) crystal structure is much more widespread than previously thought, occurring in low-temperature, high-pressure metamorphosed basalts (blueschists) from subduction zones and in low-grade metamorphosed mudstones (phyllites and schists) from orogenic belts. Indeed, a non-cubic symmetry appears to be typical of common garnet that forms at low temperatures (<450 °C), where it has a characteristic Fe–Ca-rich composition with very low Mg contents. We propose that, in most cases, garnet does not initially grow cubic. Our discovery indicates that the crystal chemistry and thermodynamic properties of garnet at low-temperature need to be re-assessed, with potential consequences for the application of garnet as an investigative tool in a broad range of geological environments

Hexavalent chromium release over time from a pyrolyzed Cr-bearing tannery sludge

Pyrolysis in an inert atmosphere is a widely applied route to convert tannery wastes into reusable materials. In the present study, the Cr(III) conversion into the toxic hexavalent form in the pyrolyzed tannery waste referred to as KEU was investigated. Ageing experiments and leaching tests demonstrated that the Cr(III)–Cr(VI) inter-conversion occurs in the presence of air at ambient temperature, enhanced by wet environmental conditions. Microstructural analysis revealed that the Cr-primary mineral assemblage formed during pyrolysis (Cr-bearing srebrodolskite and Cr-magnetite spinel) destabilized upon spray water cooling in the last stage of the process. In the evolution from the higher to the lower temperature mineralogy, Cr is incorporated into newly formed CrOOH flakes which likely react in air forming extractable Cr(VI) species. This property transforms KEU from an inert waste to a hazardous material when exposed to ordinary ambient conditions

Structure determination, thermal stability and dissolution rate of 6-indomethacin

The structure solution of the δ-polymorph of indomethacin was obtained using three-dimensional electron diffraction. This form shows a significantly enhanced dissolution rate compared with the more common and better studied α- and γ-polymorphs, indicating better biopharmaceutical properties for medicinal applications. The structure was solved in non-centrosymmetric space group P21 and comprises two molecules in the asymmetric unit. Packing and molecule conformation closely resemble indomethacin methyl ester and indomethacin methanol solvate. Knowledge of the structure allowed the rational interpretation of spectroscopic IR and Raman data for δ-polymorph and a tentative interpretation for still unsolved indomethacin polymorphs. Finally, we observed a solid–solid transition from δ-polymorph to α-polymorph that can be driven by similarities in molecular conformation