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Physical review / B 101(24), 245121 (2020). doi:10.1103/PhysRevB.101.245121, We report high-pressure x-ray diffraction, x-ray absorption spectroscopy, and electrical transport measurements on $CuMO_{2}$ $(M = Cr, Mn)$ delafossitelike oxides in an attempt to study their structural and electronic evolution with pressure. Recent studies of the similar $CuFe_{2}$ delafossite has revealed a pressure-induced breaking of the unusual high axial anisotropy resulting in a structural phase transition coinciding with the metal-metal intervalence charge-transfer phenomenon. The present study revealed other possible scenarios responsible for the collapse of the high axial anisotropy and evolution of the O-Cu-O bonds in delafossitelike materials under pressure. Thus in $CuMnO_2$, the O-Cu-O dumbbells tilt with respect to the c axis at $P > 13$ GPa, but in contrast to $CuFeO_2$, the tilting is continuous with pressure increase, justifying a second-order phase transition within the C2/m structure. Meanwhile in $CuCrO_2$ $(R\bar{3}m)$ the first-order structural phase transition to the monoclinic structure (P21/m) is observed at about 26 GPa characterized by the discontinuous bending of the O-Cu-O bond in contrast to the tilting in the case of $CuFeO_2$ and $CuMnO_2$. In both studied systems, we did not find clear evidence of valence transformations, similar to that observed in $CuFeO_2$., Published by Inst., Woodbury, NY

We report high-pressure x-ray diffraction, x-ray absorption spectroscopy, and electrical transport measurements on CuMO2 (M=Cr, Mn) delafossitelike oxides in an attempt to study their structural and electronic evolution with pressure. Recent studies of the similar CuFeO2 delafossite has revealed a pressure-induced breaking of the unusual high axial anisotropy resulting in a structural phase transition coinciding with the metal-metal intervalence charge-transfer phenomenon. The present study revealed other possible scenarios responsible for the collapse of the high axial anisotropy and evolution of the O-Cu-O bonds in delafossitelike materials under pressure. Thus in CuMnO2, the O-Cu-O dumbbells tilt with respect to the c axis at P>13 GPa, but in contrast to CuFeO2, the tilting is continuous with pressure increase, justifying a second-order phase transition within the C2/m structure. Meanwhile in CuCrO2 (R¯3m) the first-order structural phase transition to the monoclinic structure (P21/m) is observed at about 26 GPa characterized by the discontinuous bending of the O-Cu-O bond in contrast to the tilting in the case of CuFeO2 and CuMnO2. In both studied systems, we did not find clear evidence of valence transformations, similar to that observed in CuFeO2.

Bulk Sr2PdO3 was synthesized by a modified solid state reaction and a detailed characterization was carried out using both microscopic and macroscopic experimental techniques. Pd site exhibits an electric field gradient of 5.9(1) ⋅ 1017 V/cm2 due to the anisotropic local atomic configuration. A Curie - paramagnetic susceptibility indicating antiferromagnetic interactions superimposed to a core diamagnetic state is confirmed. A linear volume thermal expansion with a coefficient of 3.0(1) ⋅ 10−5 K−1 at room temperature is extracted. A collection of Einstein oscillators, with an Einstein temperature of about 115 K, is involved in the thermal transport. Large atomic displacements were observed in Sr vibrations. No Pd or Sr valence change is observed up to 900 K. A moderate anharmonicity is identified and quantified in a macroscopic Grüneisen parameter of 2.5(1) at room temperature. The electrical resistivity reveals a semiconducting behaviour. A systematic reduction in electrical resistivity and a change in the conduction mechanism is observed upon thermal cycling which indicates that a peculiar electronic mechanism is involved. © 2018 Elsevier B.V.

Physical review / B 98(5), 054105 (2018). doi:10.1103/PhysRevB.98.054105, The high pressure structural phase diagram of $\mathrm{EuTiO_{3}}$ is revisited by means of single crystal x-ray diffraction at pressures below 30GPa. We report a transition at about 3GPa with a surprisingly small lattice distortion. At 23GPa we have detected a yet unknown transition into a new orthorhombic phase (space group Ibam). Combining our observations on structures obtained on single crystals and polycrystalline samples with complementary methods, such as electrical resistivity and nuclear forward scattering of synchrotron radiation measured on polycrystalline samples, we address issues relevant to chemistry and disorder., Published by APS, Woodbury, NY

The pressure evolution of the local structure of Fe2O3 hematite has been determined by extended x-ray absorption fine structure up to ∼79 GPa. Below the phase-transition pressure at ∼50 GPa, no increasing of FeO6 octahedra distortion is observed as pressure is applied. Above the phase transition, an abrupt decrease of the nearest-neighbor Fe-O distance is observed concomitantly with a strong reduction in the FeO6 distortion. This information on the local structure, used as a test-bench for the different high-pressure forms proposed in the literature, suggests that the orthorhombic structure with space group Aba2, recently proposed by Bykova [Nat. Commun. 7, 10661 (2016)2041-172310.1038/ncomms10661], is the most probable, but puts into question the presence of the P21/n form in the pressure range 54-67 GPa. Finally, the crossover from Fe high-spin to low-spin states with pressure increase has been monitored from the pre-edge region of the Fe K-edge absorption spectra. Its "simultaneous" comparison with the local structural changes allows us to conclude that it is the electronic transition that drives the structural transition and not vice versa.

Solid Oxide Cells are becoming a promising solution for sustainable and renewable power generation. Scandium doped Yttria Stabilized Zirconia is considered one of the best materials used as electrolyte because of its high ionic conductivity and great mechanical and chemical stability under operating conditions. Oxygen bubble formation at grain boundaries of ScYSZ near the anode/electrolyte interface has been observed as a degradation process when running in electrolysis mode at 800 - 900 oC for 24 - 72 hours at high current densities. X-ray diffraction can provide information about structural evolution at different depths of the cell during operation.

International audience; We have performed experiments in the Fe–C system at 2200–3400 K and 25–70 GPa using a multianvil press and laser-heated diamond anvil cell in order to constrain the stability of Fe3C. Iron carbide was observed experimentally as a stable phase using both experimental methods and independently confirmed by thermodynamic calculations. Our results imply that pure iron and carbon cannot coexist in a stable equilibrium at high pressure and high temperature. The high reactivity between metallic iron and the diamond requires a careful design of diamond anvil cell experiments in order to avoid carbon transport to the sample.

An enzyme-linked immunosorbent assay for detecting antibodies to purified protein derivative was evaluated as a rapid method for serodiagnosis of childhood tuberculosis. Its specificity for IgG antibodies was 0.98 as determined in 55 sera from nontuberculous children who showed no significant effect of previous Bacillus Calmette-Guérin vaccination on the production of specific antibodies. Results were negative in 29 of 33 (87.9%) tuberculin-positive children and in 18 of 20 (90.0%) contacts, none of whom had evidence of tuberculosis. The sensitivity of this test was 0.51 as determined in 49 sera from bacteriologically confirmed cases; 17 of 27 smear positive cases and 8 of 22 children with positive cultures were detected. Results were positive in 32 of 114 (28.1%) patients with a diagnosis of tuberculosis not confirmed by microbiology. Consequently whereas a negative result does not rule out tuberculosis, a positive result is a strong indication of the disease. The IgM antibody determination yielded much less discriminative results.

The advent of Mycobacterium tuberculosis strain genotyping has allowed differentiation between disease relapse and exogenous re-infection. We report here a remarkable case of multiply recurrent tuberculosis in a patient living with HIV. Between 1995 and 2009, a young HIV-infected intravenous drug user, who was reluctant to comply with anti-retroviral treatment, underwent at least five tuberculosis episodes caused by three distinct M. tuberculosis strains sharply differentiated by drug susceptibility profile, genotype and infectious source. Eventually, the patient died during a relapse of tuberculosis due to a notorious multidrug-resistant outbreak-strain, which infected him during a prolonged hospitalization in the epicentre of such outbreak. Whether recurrent tuberculosis is due to a new infection or to reactivation of a previous one is a century-long controversial question. In our patient, both conditions alternated throughout his 15 years of living with HIV. Cases such as this might not be exceptional in certain underprivileged suburban areas of Argentina and should raise concern over three pending issues in tuberculosis control policies, namely secondary preventing therapy, institutional infection control and patient follow-up throughout the health network system.

Journal of physics / Condensed matter 30(8), 084004 - (2018). doi:10.1088/1361-648X/aaa73e, Niobium (Nb) is one of the key trace elements used to understand Earth’s formation and differentiation, and is remarkable for its deficiency relative to tantalum in terrestrial rocks compared to the building chondritic blocks. In this context, the local environment of Nb in silica-rich melts and glasses is studied by in situ x-ray absorption spectroscopy (XAS) at high pressure (P) up to 9.3 GPa and 1350 K using resistive-heating diamond-anvil cells. Nb is slightly less oxidized in the melt (intermediate valence between +4 and +5) than in the glass (+5), an effect evidenced from the shift of the Nb-edge towards lower energies. Changes in the pre-edge features are also observed between melt and glass states, consistently with the observed changes in oxidation state although likely enhanced by temperature (T) effects. The oxidation state of Nb is not affected by pressure neither in the molten nor glassy states, and remains constant in the investigated P-range. The Nb–O coordination number is constant and equal to 6.3±0.4 below 5 GPa, and only progressively increases up to 7.1±0.4 at 9.3 GPa, the maximum P investigated. If these findings were to similarly apply to basaltic melts, that would rule out the hypothesis of Nb/Ta fractionation during early silicate Earth’s differentiation, thus reinforcing the alternative hypothesis of fractionation during core formation on reduced pre-planetary bodies., Published by IOP Publ., Bristol

We studied FeCO3 using Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy at pressures up to 54 GPa and temperatures above 2000 K. First-principles calculations of Fe at the K-edge in FeCO3 were performed to support the interpretation of the XANES spectra. The variation of iron absorption edge features with pressure and temperature in FeCO3 matches well with recently reported observations on FeCO3 at extreme conditions, and provides new insight into the stability of Fe-carbonates in Earth's mantle. Here we show that at conditions of the mid-lower mantle, ~50 GPa and ~2200 K, FeCO3 melts and partially decomposes to high-pressure Fe3O4. Carbon (diamond) and oxygen are also inferred products of the reaction. We constrained the thermodynamic phase boundary between crystalline FeCO3 and melt to be at 51(1) GPa and ~1850 K. We observe that at 54(1) GPa, temperature-induced spin crossover of Fe2+ takes place from low to high spin such that at 1735(100) K, all iron in FeCO3 is in the high-spin state. A comparison between experiment and theory provides a more detailed understanding of FeCO3 decomposition observed in X-ray absorption spectra and helps to explain spectral changes due to pressure-induced spin crossover in FeCO3 at ambient temperature.

In this paper we present recent achievements in the field of investigation of the local, electronic and magnetic structure of the matter under extreme conditions of pressure and temperature. These results were obtained thanks to the coupling of a compact laser heating system to the energy-dispersive XAS technique available on the ID24 beamline at the ESRF synchrotron. The examples chosen concern the melting and the liquid structure of 3d metals and alloys under high pressures (HPs) and the observation of temperature-induced spin crossover in FeCO3 at HP.

Journal of applied physics 125(9), 095901 (2019). doi:10.1063/1.5067268, Laser heating in a diamond anvil cell (DAC) is a common method for studying material behavior at high-pressure and high-temperature conditions. It has been previously proven that during continuous wave (CW) laser heating of a sample, carbon of the diamond anvils is mobilized, and its diffusion into the sample can lead to undesirable chemical reactions, which, if not detected, may cause misinterpretations of the results of the experiment. Minimizing the heating time with the use of a pulsed laser (PL) is thought to reduce the risk of possible carbon contamination of the sample; however, this has not been proven experimentally. Here, we report the results of our comparative study of the effect of pulsed and continuous wave (CW) laser heating on the mobilization of carbon and its chemical interaction with iron in a diamond anvil cell. Using X-ray absorption near edge structure spectroscopy, Synchrotron Mössbauer Source spectroscopy, and Synchrotron X-ray diffraction, we examined iron samples that were laser heated in DACs in various pressure transmitting media (neon, argon, and potassium chloride). According to our results, the use of the PL heating does not prevent the sample from carbon contamination. A reaction between carbon and iron happens within a few seconds even at moderate temperatures. We found that one analytical technique was generally insufficient to fully characterize the phase composition of the laser-heated samples., Published by American Inst. of Physics, Melville, NY

The Earth’s crust–mantle boundary, the Mohorovicic discontinuity, has been traditionally considered to be the interface between the magnetic crust and the non-magnetic mantle1. However, this assumption has been questioned by geophysical observations2,3 and by the identification of magnetic remanence in mantle xenoliths4, which suggest mantle magnetic sources. Owing to their high critical temperatures, iron oxides are the only potential sources of magnetic anomalies at mantle depths5. Haematite (α-Fe2O3) is the dominant iron oxide in subducted lithologies at depths of 300 to 600 kilometres, delineated by the thermal decomposition of magnetite and the crystallization of a high-pressure magnetite phase deeper than about 600 kilometres6. The lack of data on the magnetic properties of haematite at relevant pressure–temperature conditions, however, hinders the identification of magnetic boundaries within the mantle and their contribution to observed magnetic anomalies. Here we apply synchrotron Mossbauer source spectroscopy in laser-heated diamond anvil cells to investigate the magnetic transitions and critical temperatures in Fe2O3 polymorphs7 at pressures and temperatures of up to 90 gigapascals and 1,300 kelvin, respectively. Our results show that haematite remains magnetic at the depth of the transition zone in the Earth’s mantle in cold or very cold subduction geotherms, forming a frame of deep magnetized rocks in the West Pacific region. The deep magnetic sources spatially correlate with preferred paths of the Earth’s virtual geomagnetic poles during reversals8 that might not reflect the geometry of the transitional field. Rather, the paths might be an artefact caused by magnetized haematite-bearing rocks in cold subducting slabs at mid-transition zone depths. Such deep sources should be taken into account when carrying out inversions of the Earth’s geomagnetic data9, and especially in studies of planetary bodies that no longer have a dynamo10, such as Mars. Synchrotron Mossbauer source spectroscopy is used to reveal that haematite remains magnetic in cold subducting slabs at the depth of the transition zone in the Earth’s mantle, with implications for the locations of magnetic poles during inversions of the Earth’s magnetic field.

Nature Communications 9(1), 4142 (2018). doi:10.1038/s41467-018-06457-x, A Verwey-type charge-ordering transition in magnetite at 120 K leads to the formation of linear units of three iron ions with one shared electron, called trimerons. The recently-discovered iron pentoxide (Fe$_4$O$_5$) comprising mixed-valent iron cations at octahedral chains, demonstrates another unusual charge-ordering transition at 150 K involving competing formation of iron trimerons and dimerons. Here, we experimentally show that applied pressure can tune the charge-ordering pattern in Fe$_4$O$_5$ and strongly affect the ordering temperature. We report two charge-ordered phases, the first of which may comprise both dimeron and trimeron units, whereas, the second exhibits an overall dimerization involving both the octahedral and trigonal-prismatic chains of iron in the crystal structure. We link the dramatic change in the charge-ordering pattern in the second phase to redistribution of electrons between the octahedral and prismatic iron chains, and propose that the average oxidation state of the iron cations can pre-determine a charge-ordering pattern., Published by Nature Publishing Group UK, [London]

The high pressure structural phase diagram of EuTiO3 is revisited by means of single crystal x-ray diffraction at pressures below 30GPa. We report a transition at about 3GPa with a surprisingly small lattice distortion. At 23GPa we have detected a yet unknown transition into a new orthorhombic phase (space group Ibam). Combining our observations on structures obtained on single crystals and polycrystalline samples with complementary methods, such as electrical resistivity and nuclear forward scattering of synchrotron radiation measured on polycrystalline samples, we address issues relevant to chemistry and disorder.

Before the Archean to Proterozoic Transition (APT) the tectonic regime was dominated by microplates floating on a low viscosity mantle. Such a regime restricted chemical exchange between the shallow and deeper mantle reservoirs. After the APT, a more global convection regime led to deep subduction of slabs. We propose that the improved vertical mixing of the mantle favoured the release to the Earth's surface of an oxygen excess initially trapped in the deep mantle. This excess built up when the primordial lower mantle was left with a high Fe3+/(Fe2++Fe3+) ratio (#Fe3+), after metallic iron segregated down into the core. Our synchrotron-based in situ experiments suggest a primordial Fe3+excess of ∼20 % for the mantle iron. By comparison with the #Fe3+ of the present mantle, this Fe3+excess would correspond to 500-1000 times the O2 content in the Earth's atmosphere. The tectonic transition greatly facilitated the ascent of oxidised lower mantle material towards the Earth's surface, inducing a continuous arrival of O2 at the Earth's surface and into the atmosphere.

The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth’s lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. Here we investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mössbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth’s geotherm at pressures to ∼50 GPa FeCO3 partially dissociates to form various iron oxides. At higher pressures FeCO3 forms two new structures—tetrairon(III) orthocarbonate Fe43+C3O12, and diiron(II) diiron(III) tetracarbonate Fe22+Fe23+C4O13, both phases containing CO4 tetrahedra. Fe4C4O13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth’s lower mantle., Carbonates are shown to exist in the lower mantle as seen in diamond inclusions, but thermodynamic constraints are poorly understood. Here, the authors synthesise two new iron carbonate compounds and find that self-oxidation-reduction reactions can preserve carbonates in the mantle.

The magnetic and structural properties of cobalt were investigated under high pressure (160 GPa) and low temperature (50 K), by synchrotron K-edge x-ray magnetic circular dichroism and x-ray diffraction. A quasihydrostatic equation of state was measured up to 160 GPa. We found that uniaxial stress plays a role in the hexagonal close packed-face centered cubic (hcp-fcc) structural transition pressure. Also, our data provide the first experimental evidence that changes of the $c/a$ ratio pressure derivative are related to the magnetic behavior. The complete extinction of ferromagnetism is observed above 130 GPa in a mixed hcp-fcc phase with no recovery upon cooling to 50 K, indicating that cobalt at 150 GPa is very likely nonmagnetic, i.e., characterized by zero local spin polarization. Density functional theory calculations point out that the K-edge x-ray magnetic circular dichroism (XMCD) signal is related to the $4p$ orbital moment rather than to the total spin moment and allow us to get a deeper insight into the K-edge XMCD measurements interpretation. The combination of novel theoretical results and experimental outputs provides a detailed scenario of the structural and magnetic properties of cobalt at these extreme conditions answering some previously unsolved issues.

Physical review / B covering condensed matter and materials physics 93(20), 201110(2016). doi:10.1103/PhysRevB.93.201110, Magnetic properties of NiO have been studied in the multimegabar pressure range by nuclear forward scattering of synchrotron radiation using the 67.4 keV Mössbauer transition of $^{61}$Ni. The observed magnetic hyperfine splitting confirms the antiferromagnetic state of NiO up to 280 GPa, the highest pressure where magnetism has been observed so far, in any material. Remarkably, the hyperfine field increases from 8.47 T at ambient pressure to ∼ 24 T at the highest pressure, ruling out the possibility of a magnetic collapse. A joint x-ray diffraction and extended x-ray-absorption fine structure investigation reveals that NiO remains in a distorted sodium chloride structure in the entire studied pressure range. Ab initio calculations support the experimental observations, and further indicate a complete absence of Mott transition in NiO up to at least 280 GPa., Published by Inst., Woodbury, NY

Skiagite-rich garnet was synthesized as single crystals at 9.5 GPa and 1100 °C using a multi-anvil apparatus. The crystal structure [cubic, space group Ia 3 d , a = 11.7511(2) A, V = 1622.69(5) A3, D calc = 4.4931 g/cm3] was investigated using single-crystal synchrotron X-ray diffraction. Synchrotron Mossbauer source spectroscopy revealed that Fe2+ and Fe3+ predominantly occupy dodecahedral (X) and octahedral (Y) sites, respectively, as expected for the garnet structure, and confirmed independently using nuclear forward scattering. Single-crystal X-ray diffraction suggests the structural formula of the skiagite-rich garnet to be Fe32+(Fe2+0.234(2)Fe3+1.532(1)Si4+0.234(2))(SiO4)3, in agreement with electron microprobe chemical analysis. The formula is consistent with X-ray absorption near-edge structure spectra. The occurrence of Si and Fe2+ in the octahedral Y-site indicates the synthesized garnet to be a solid solution of end-member skiagite with ~23 mol% of the Fe-majorite end-member Fe32+(Fe2+Si4+)(SiO4)3.