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Abstract H2O transforms to two forms of superionic (SI) ice at high pressures and temperatures, which contain highly mobile protons within a solid oxygen sublattice. Yet the stability field of both phases remains debated. Here, we present the results of an ultrafast X-ray heating study utilizing MHz pulse trains produced by the European X-ray Free Electron Laser to create high temperature states of H2O, which were probed using X-ray diffraction during dynamic cooling. We confirm an isostructural transition during heating in the 26-69 GPa range, consistent with the formation of SI-bcc. In contrast to prior work, SI-fcc was observed exclusively above ~50 GPa, despite evidence of melting at lower pressures. The absence of SI-fcc in lower pressure runs is attributed to short heating timescales and the pressure-temperature path induced by the pump-probe heating scheme in which H2O was heated above its melting temperature before the observation of quenched crystalline states, based on the earlier theoretical prediction that SI-bcc nucleates more readily from the fluid than SI-fcc. Our results may have implications for the stability of SI phases in ice-rich planets, for example during dynamic freezing, where the preferential crystallization of SI-bcc may result in distinct physical properties across mantle ice layers.

Water and ammonia are major constituents of icy planet interiors, however their phase behaviour under extreme conditions remain relatively unknown. Here, the authors show that ammonia monohydrate transforms under pressure into an alloy composed of molecules as well as ions, owing to a topological frustration.

H 2 O transforms to two forms of superionic (SI) ice at high pressures and temperatures, which contain highly mobile protons within a solid oxygen sublattice. Yet the stability field of both phases remains debated. Here, we present the results of an ultrafast X-ray heating study utilizing MHz pulse trains produced by the European X-ray Free Electron Laser to create high temperature states of H 2 O, which were probed using X-ray diffraction during dynamic cooling. We confirm an isostructural transition during heating in the 26-69 GPa range, consistent with the formation of SI-bcc. In contrast to prior work, SI-fcc was observed exclusively above ~50 GPa, despite evidence of melting at lower pressures. The absence of SI-fcc in lower pressure runs is attributed to short heating timescales and the pressure-temperature path induced by the pump-probe heating scheme in which H 2 O was heated above its melting temperature before the observation of quenched crystalline states, based on the earlier theoretical prediction that SI-bcc nucleates more readily from the fluid than SI-fcc. Our results may have implications for the stability of SI phases in ice-rich planets, for example during dynamic freezing, where the preferential crystallization of SI-bcc may result in distinct physical properties across mantle ice layers., (© 2024. The Author(s).)

In the 2-10 GPa pressure range, ammonia hemihydrate H_{2}O:(NH_{3})_{2} (AHH) is a molecular solid in which intermolecular interactions are ruled by distinct types of hydrogen bonds. Upon heating, the low-temperature ordered P2_{1}/c crystal (AHH-II) transits to a bcc phase (AHH-pbcc) where each site is randomly occupied by water or ammonia. In addition to the site disorder, experiments suggest that AHH-pbcc is a plastic solid, but the physical origin and mechanisms at play for the rotational and site disordering remain unknown. Using large-scale (∼10^{5}  atoms) and long-time (>10  ns) simulations, we show that, as temperature rises above the transition line, orientational disorder sets in, breaking the strongest hydrogen bonds that provide the largest contribution to the cohesion of the ordered AHH-II phase and enabling the molecules to migrate from a crystal site to a neighboring one. This generates a plastic molecular alloy with site disorder while the solid state is overall maintained until melting at a higher temperature. The case of high (P,T) plastic ammonia hemihydrate can be extended to other water-ammonia alloys where a similar interplay between distinct hydrogen bonds occurs.

Solid mixtures of ammonia and water, the so-called ammonia hydrates, are thought to be major components of solar and extra-solar icy planets. We present here a thorough characterization of the recently reported high pressure ( P )-temperature ( T ) phase VII of ammonia monohydrate (AMH) using Raman spectroscopy, X-ray diffraction, and quasi-elastic neutron scattering (QENS) experiments in the ranges 4-10 GPa, 450-600 K. Our results show that AMH-VII exhibits common structural features with the disordered ionico-molecular alloy (DIMA) phase, stable above 7.5 GPa at 300 K: both present a substitutional disorder of water and ammonia over the sites of a body-centered cubic lattice and are partially ionic. The two phases however markedly differ in their hydrogen dynamics, and QENS measurements show that AMH-VII is characterized by free molecular rotations around the lattice positions which are quenched in the DIMA phase. AMH-VII is thus a peculiar crystalline solid in that it combines three types of disorder: substitutional, compositional, and rotational.

Objectives: From the authors' experience, the consumption of a balanced prescription home-prepared diet that includes zucchini (courgette) benefits cats with recurrent urolithiasis, but there is no published evidence to support this. The aim was to study the effects on urinary parameters of (1) a balanced prescription home-prepared diet containing zucchini, and (2) the addition of zucchini to a dry food, compared with two commercial therapeutic diets., Methods: Eight healthy cats were included in a Latin-square designed protocol. Five diets were evaluated: two commercial diets, designed for cats with urinary disorders, one high-moisture (U-WET) and one high-sodium dry (U-DRY); one home-prepared diet (HOME); one commercial dry food for adult maintenance (DRY); and DRY given together with 10 g of zucchini per kg body weight (DRY-Zuc). After a 7-day adaptation period, urine was collected and daily food and water intakes were assessed for 12 days. Urinary parameters, and relative supersaturation (RSS) for calcium oxalate (CaOx) and struvite, were determined. Data underwent repeated measures ANOVA analysis., Results: The digestibility of energy, dry matter, protein and fat was highest with the HOME diet. CaOx RSS was lowest in cats eating the HOME diet, but not significantly different from the U-WET or U-DRY diets. CaOx RSS was lower in cats eating the DRY-Zuc diet than in cats eating the DRY diet. Struvite RSS did not differ significantly among groups., Conclusions and Relevance: This study shows that a balanced prescription home-prepared diet was safe and allowed a very low urinary CaOx RSS. It also showed that adding zucchini to dry food lowered the urine CaOx RSS.

Structural transformation of hot dense water ice is investigated by combining synchrotron x-ray diffraction and a laser-heating diamond anvil cell above 25 GPa. A transition from the body-centered-cubic (bcc) to face-centered-cubic (fcc) oxygen atoms sublattices is observed from 57 GPa and 1500 K to 166 GPa and 2500 K. That is the structural signature of the transition to fcc superionic (fcc SI) ice. The sign of the density discontinuity at the transition is obtained and a phase diagram is disclosed, showing an extended fcc SI stability field. Present data also constrain the stability field of the bcc superionic (bcc SI) ice up to 100 GPa at least. The current understanding of warm dense water ice based on ab initio simulations is discussed in the light of present data.

Ammonia is predicted to be one of the major components in the depths of the ice giant planets Uranus and Neptune. Their dynamics, evolution, and interior structure are insufficiently understood and models rely imperatively on data for equation of state and transport properties. Despite its great significance, the experimentally accessed region of the ammonia phase diagram today is still very limited in pressure and temperature. Here we push the probed regime to unprecedented conditions, up to ∼350  GPa and ∼40 000  K. Along the Hugoniot, the temperature measured as a function of pressure shows a subtle change in slope at ∼7000  K and ∼90  GPa, in agreement with ab initio simulations we have performed. This feature coincides with the gradual transition from a molecular liquid to a plasma state. Additionally, we performed reflectivity measurements, providing the first experimental evidence of electronic conduction in high-pressure ammonia. Shock reflectance continuously rises with pressure above 50 GPa and reaches saturation values above 120 GPa. Corresponding electrical conductivity values are up to 1 order of magnitude higher than in water in the 100 GPa regime, with possible significant contributions of the predicted ammonia-rich layers to the generation of magnetic dynamos in ice giant interiors.

The phase diagram and melting curve of water ice is investigated up to 45 GPa and 1600 K by synchrotron x-ray diffraction in the resistively and laser heated diamond anvil cell. Our melting data evidence a triple point at 14.6 GPa, 850 K. The latter is shown to be related to a first-order solid transition from the dynamically disordered form of ice VII, denoted ice VII^{'}, toward a high-temperature phase with the same bcc oxygen lattice but larger volume and higher entropy. Our experiments are compared to ab initio molecular dynamics simulations, enabling us to identify the high-temperature bcc phase with the predicted superionic ice VII^{''} phase [J.-A. Hernandez and R. Caracas, Phys. Rev. Lett. 117, 135503 (2016).PRLTAO0031-900710.1103/PhysRevLett.117.135503].

The phase diagram and melting behavior of the equimolar water-ammonia mixture have been investigated by Raman spectroscopy, x-ray diffraction, and visual observations from 295 K to 675 K and up to 9 GPa. Our results show non-congruent melting behavior of ammonia monohydrate (AMH) solid below 324 K and congruent melting at higher temperatures. The congruent melting is associated with the stability of a previously unobserved solid phase of AMH, which we named AMH-VII. Another, presumably water-rich, hydrate has also been detected in the range 4 GPa-7 GPa at 295 K on decompression of the high pressure disordered ionico-molecular alloy (DIMA) phase. Comparing our melting data to the literature suggests that non-congruent melting extends from 220 K to 324 K and that the solid phase that borders the fluid between 220 K and 270 K, called AMH-III, is not a proper phase of AMH but a solid solution of ammonia hemihydrate and ice. These results allow us to propose a revised and extended experimental phase diagram of AMH.

The sound velocity and refractive index of pure N 2 and of the equimolar N 2 -CO 2 mixture are measured up to 15 GPa and 700 K in a resistive heating diamond anvil cell. The refractive index vs pressure is obtained by an interferometric method. The adiabatic sound velocity is then determined from the measurement of the Brillouin frequency shift in the backscattering geometry and the refractive index data. No phase separation of the N 2 -CO 2 fluid mixture is observed. The fluid mixture properties are discussed in terms of ideal mixing.

The compression of ammonium azide (AA) has been considered to be a promising route for producing high energy-density polynitrogen compounds. So far though, there is no experimental evidence that pure AA can be transformed into polynitrogen materials under high pressure at room temperature. We report here on high pressure ( P ) and temperature ( T ) experiments on AA embedded in N2 and on pure AA in the range 0-30 GPa, 300-700 K. The decomposition of AA into N2 and NH3 was observed in liquid N2 around 15 GPa-700 K. For pressures above 20 GPa, our results show that AA in N2 transforms into a new crystalline compound and solid ammonia when heated above 620 K. This compound is stable at room temperature and on decompression down to at least 7.0 GPa. Pure AA also transforms into a new compound at similar P - T conditions, but the product is different. The newly observed phases are studied by Raman spectroscopy and X-ray diffraction and compared to nitrogen and hydronitrogen compounds that have been predicted in the literature. While there is no exact match with any of them, similar vibrational features are found between the product that was obtained in AA + N2 with a polymeric compound of N9H formula.

Synchrotron x-ray diffraction measurements of nitrogen are performed up to 120 GPa to determine the melting curve and the structural changes of the solid and liquid phases along it. The melting temperature exhibits a monotonic increase up to the triple point where the epsilon molecular solid, the cubic gauche covalent solid, and the fluid meet at 116 GPa, 2080 K. Above, the stability of the cubic gauche phase induces a sharp increase of the melting curve. The structural data on liquid nitrogen show that the latter remains molecular over the whole probed domain, which contradicts the prediction of a liquid-liquid transition at 88 GPa, 2000 K. These findings thus largely revisit the phase diagram of hot dense nitrogen and challenge the current understanding of this model system.

Water and ammonia are considered major components of the interiors of the giant icy planets and their satellites, which has motivated their exploration under high P-T conditions. Exotic forms of these pure ices have been revealed at extreme (~megabar) pressures, notably symmetric, ionic, and superionic phases. Here we report on an extensive experimental and computational study of the high-pressure properties of the ammonia monohydrate compound forming from an equimolar mixture of water and ammonia. Our experiments demonstrate that relatively mild pressure conditions (7.4 GPa at 300 K) are sufficient to transform ammonia monohydrate from a prototypical hydrogen-bonded crystal into a form where the standard molecular forms of water and ammonia coexist with their ionic counterparts, hydroxide (OH - ) and ammonium [Formula: see text] ions. Using ab initio atomistic simulations, we explain this surprising coexistence of neutral/charged species as resulting from a topological frustration between local homonuclear and long-ranged heteronuclear ionisation mechanisms.

Background and Objectives: Doppler-based renal resistive index (RI) might help in distinguishing transient from persistent acute kidney injury (AKI). The main objective of these systematic review and meta-analysis was to investigate the diagnostic performance of RI in predicting short-term reversibility of AKI., Study Design: A systematic review of the literature was performed. Relevant studies were identified in Pubmed and Cochrane databases covering the years 1985 to 2013 and reviewed independently by 3 authors. Renal transplant recipients were excluded from this analysis. The summary estimates were computed using a random-effects model based on the DerSimonian and Lair meta-analytic method., Results: Among the 154 unique articles identified, 9 studies were included. Of the 176 patients in these studies with elevated RI or pulsatility index, 146 (83%) had a persistent AKI vs 44 (16%) of the 273 patients with normal values. Elevated RI or pulsatility index was associated with an increased risk of persistent AKI (odds ratio, 29.85; 95% confidence interval [CI], 8.73-102.16; P < .00001) with significant heterogeneity (I(2) = 75.0%, P < .0001). The pooled sensitivity and specificity were 0.83 (95% CI, 0.77-0.88) and 0.84 (95% CI, 0.79-0.88). The summary positive and negative likelihood ratios were 4.9 (95% CI, 2.44-9.87) and 0.21 (95% CI, 0.11-0.41)., Conclusion: These results suggest that an elevated RI may be a predictor of persistent AKI in critically ill patients. Further studies are warranted, however, to clarify the exact test performance given the marked heterogeneity among the included studies., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Estimation of the quality of commercial diets is a topic of interest for the majority of dog owners. Recently, in a French consumer association magazine, an evaluation of eight dog commercial dry diets (from super-premium, basic-nutrition, private-label and economy brands) according to several nutritional criteria was published. The aims of the study were: (1) to evaluate the apparent digestibility of these diets; (2) to score these diets according to digestibility results; and (3) to compare these data with the scoring of the magazine. Six adult Beagle dogs were enrolled for the digestibility trials. Diets were scored according to energy, crude protein and crude fat (CF) apparent digestibility coefficients, digestible protein-to-energy ratios and ash content. Each of the five criteria was scored from 4 to 20 points. The ranges of crude protein, CF, crude fibre and ash content were 20·9-30·6 %, 6·8-19·7 %, 2·2-3·3 % and 4·6-9·7 % on a DM basis, respectively. The ranges of energy, crude protein and CF apparent digestibility coefficients were 72·6-87·7 %, 70·4-82·5 % and 76·1-95·4 %, respectively. The range of the protein-to-energy ratio was 10-14 digestible crude protein per MJ metabolisable energy. Little overlap in the scoring systems was found, but the private-label brand and economy brand diets presented the lowest scores in the two systems. These results showed that the evaluation of commercial diets should take into account multiple nutritional aspects. In particular, analytical and biological (digestibility) criteria should be considered as complementary in the evaluation of dry dog commercial diets.

We report the first application of a multichannel collimator (MCC) to perform quantitative structure factor measurements of dense low-Z fluids in a diamond anvil cell (DAC) using synchrotron x-ray diffraction. The MCC design, initially developed for the Paris-Edinburgh large volume press geometry, has been modified for use with diamond anvil cells. A good selectivity of the diffracted signal of the dense fluid sample is obtained due to a large rejection of the Compton diffusion from the diamond anvils. The signal to background ratio is significantly improved. We modify previously developed analytical techniques for quantitative measurement of the structure factor of fluids in DACs [J. H. Eggert, G. Weck, P. Loubeyre, and M. Mezouar, Phys. Rev. B 65, 174105 (2002)] to account for the contribution of the MCC. We present experimental results on liquids argon and hydrogen at 296 K to validate our method and test its limits, respectively.

The properties of mixtures of carbon dioxide with helium or neon have been investigated as a function of CO(2) concentration and pressure up to 30 GPa at room temperature. The binary phase diagrams of these mixtures are determined over the full range of CO(2) concentrations using visual observations and Raman scattering measurements. Both diagrams are of eutectic type, with a fluid-fluid miscibility gap for CO(2) concentrations in the range [5, 75] mol. % for He and [8, 55] mol. % for Ne, and a complete separation between the two components in the solid phase. The absence of alloys or stoichiometric compounds for these two binary systems is consistent with the Hume-Rothery rules of hard sphere mixtures. The Raman spectra and x-ray diffraction patterns of solid CO(2) embedded in He or Ne for various initial concentrations have been measured up to 30 GPa and 12 GPa, respectively. The frequencies of the Raman modes and the volume of solid phase I are identical, within error bars, to those reported for 100% CO(2) samples, thus confirming the total immiscibility of CO(2) with He and Ne in the solid phase. These results demonstrate the possibility to perform high-pressure experiments on solid CO(2) under (quasi-)hydrostatic conditions using He or Ne as pressure transmitting medium.

We report the experimental discovery of a new phase of ammonia ice, stable at pressures above 57 GPa and temperatures above 700 K. The combination of our experimental results and ab initio molecular dynamics simulations reveal that this new phase is a superionic conductor, characterized by a large proton diffusion coefficient (1.0×10(-4) cm(2)/s at 70 GPa, 850 K). Proton diffusion occurs via a Grotthuss-like mechanism, at a surprisingly lower temperature than in water ice. This may have implications for the onset of superionicity in the molecular ice mixtures present in Jovian planets. Our simulations further suggest that the anisotropic proton hopping along different H bonds in the molecular solid may explain the formation of the recently predicted ionic phase at low temperatures.

The structure of polymeric carbon dioxide (CO2-V) has been solved using synchrotron x-ray powder diffraction, and its evolution followed from 8 to 65 GPa. We compare the experimental results obtained for a 100% CO2 sample and a 1 mol % CO2/He sample. The latter allows us to produce the polymer in a pure form and study its compressibility under hydrostatic conditions. The high quality of the x-ray data enables us to solve the structure directly from experiments. The latter is isomorphic to the β-cristobalite phase of SiO2 with the space group I42d. Carbon and oxygen atoms are arranged in CO4 tetrahedral units linked by oxygen atoms at the corners. The bulk modulus determined under hydrostatic conditions, B0=136(10)  GPa, is much smaller than previously reported. The comparison of our experimental findings with theoretical calculations performed in the present and previous studies shows that density functional theory very well describes polymeric CO2.

The high pressure (P)-high temperature (T) phase diagram of solid ammonia has been investigated using diamond anvil cell and resistive heating techniques. The III-IV transition line has been determined up to 20 GPa and 500 K both on compression and decompression paths. No discontinuity is observed at the expected location for the III-IV-V triple point. The melting line has been determined by visual observations of the fluid-solid equilibrium up to 9 GPa and 900 K. The experimental data are well fitted by a Simon-Glatzel equation in the covered P-T range. These transition lines and their extrapolations are compared to the reported ab initio calculations.