High-pressure Ice Research Articles

Investigation of high-pressure planetary ices by cryo-recovery. II. High-pressure apparatus, examples and a new high-pressure phase of MgSO4·5H2O.

An apparatus is described for the compression of samples to ∼2 GPa at temperatures from 80 to 300 K, rapid chilling to 80 K whilst under load and subsequent recovery into liquid nitro-gen after the load is released. In this way, a variety of quenchable high-pressure phases of many materials may be preserved for examination outside the high-pressure sample environment, with the principal benefit being the ability to obtain high-resolution powder diffraction data for phase identification and structure solution. The use of this apparatus, in combination with a newly developed cold-loadable low-temperature stage for X-ray powder diffraction (the PheniX-FL), is illustrated using ice VI (a high-pressure polymorph of ordinary water ice that is thermodynamically stable only above ∼0.6 GPa) as an example. A second example using synthetic epsomite (MgSO4·7H2O) reveals that, at ∼1.6 GPa and 293 K, it undergoes incongruent melting to form MgSO4·5H2O plus brine, contributing to a long-standing debate on the nature of the high-pressure behaviour of this and similar highly hydrated materials. The crystal structure of this new high-pressure polymorph of MgSO4·5H2O has been determined at 85 K in space group Pna21 from the X-ray powder diffraction pattern of a sample recovered into liquid nitro-gen and is found to differ from that of the known ambient-pressure phase of MgSO4·5H2O (pentahydrite, space group ), consisting of corner-sharing MgO6-SO4 ion pairs rather than infinite corner-sharing chains.

Investigation of high-pressure planetary ices by cryo-recovery. I. An apparatus for X-ray powder diffraction from 40 to 315 K, allowing 'cold loading' of samples.

A low-temperature stage for X-ray powder diffraction in Bragg-Brentano reflection geometry is described. The temperature range covered is 40-315 K, with a temperature stability at the sample within ±0.1 K of the set point. The stage operates by means of a Gifford-McMahon (GM) closed-cycle He refrigerator; it requires no refrigerants and so can run for an extended period (in practice at least 5 d) without intervention by the user. The sample is cooled both by thermal conduction through the metal sample holder and by the presence of He exchange gas, at ambient pressure, within the sample chamber; the consumption of He gas is extremely low, being only 0.1 l min-1 during normal operation. A unique feature of this cold stage is that samples may be introduced into (and removed from) the stage at any temperature in the range 80-300 K, and thus materials which are not stable at room temperature, such as high-pressure phases that are recoverable to ambient pressure after quenching to liquid nitro-gen temperatures, can be readily examined. A further advantage of this arrangement is that, by enabling the use of pre-cooled samples, it greatly reduces the turnaround time when making measurements on a series of specimens at low temperature.

A New Desalination Pump Helps Define the pH of Ocean Worlds

Abstract We study ocean exoplanets, for which the global surface ocean is separated from the rocky interior by a high-pressure ice mantle. We describe a mechanism that can pump salts out of the ocean, resulting in oceans of very low salinity. Here we focus on the H2O–NaCl system, though we discuss the application of this pump to other salts as well. We find our ocean worlds to be acidic, with a pH in the range of 2–4. We discuss and compare between the conditions found within our studied oceans and the conditions in which polyextremophiles were discovered. This work focuses on exoplanets in the super-Earth mass range (∼2 M ⊕), with water composing at least a few percent of their mass. However, the principle of the desalination pump might extend beyond this mass range.

28p-YD-13 高圧氷VII相における水素結合対称化

28p-YD-13 高圧氷VII相における水素結合対称化

Experimental evidence of low-density liquid water upon rapid decompression

Water is an extraordinary liquid, having a number of anomalous properties which become strongly enhanced in the supercooled region. Due to rapid crystallization of supercooled water, there exists a region that has been experimentally inaccessible for studying deeply supercooled bulk water. Using a rapid decompression technique integrated with in situ X-ray diffraction, we show that a high-pressure ice phase transforms to a low-density noncrystalline (LDN) form upon rapid release of pressure at temperatures of 140-165 K. The LDN subsequently crystallizes into ice-Ic through a diffusion-controlled process. Together with the change in crystallization rate with temperature, the experimental evidence indicates that the LDN is a low-density liquid (LDL). The measured X-ray diffraction data show that the LDL is tetrahedrally coordinated with the tetrahedral network fully developed and clearly linked to low-density amorphous ices. On the other hand, there is a distinct difference in structure between the LDL and supercooled water or liquid water in terms of the tetrahedral order parameter.

Hypercooling Temperature of Water is about 100 K Higher than Calculated before.

For deeply supercooled liquids the transition from a two-stage freezing process to complete solidification in just one freezing step occurs at the hypercooling temperature, a term that seems to be almost unknown in water research; to our knowledge, it has only been mentioned by Dolan et al. for high-pressure ice. The reason for the absence of this expression may be that the best estimate to be found in the literature for the hypercooling temperature of water is about -160 °C (113 K). This temperature is far below the limit of experimentally realizable degrees of supercooling near -40 °C (233 K), which marks the homogeneous nucleation temperature TH of common pure water; in fact, it is even below the glass-transition temperature (133 K). Here we show that, surprisingly, a more thorough analysis taking into account the temperature dependence of the heat capacities of water and ice as well as of the enthalpy of freezing shows that the hypercooling temperature of water is about -64 °C or 209 K, almost 100 K higher than estimated before. One of the most exciting consequences is that existing experiments are already able to reach these degrees of supercooling, and it is our prediction that a transition in the freezing behavior occurs at these temperatures.

First principles centroid molecular dynamics simulation of high pressure ices.

The nuclear quantum effects (NQEs) on the structural, elastic, electronic, and vibrational properties of high pressure ices (HPIs) VIII, VII, and X at 270 K were investigated via first principles centroid molecular dynamics (CMD). Our simulations clearly show that even at relatively high temperature of 270 K, the NQEs play a definite role in the pressure-induced proton order (ice VIII)-disorder (ice VII) transition occurring at ∼30 GPa in our H2O ice and the subsequent transition to the symmetric phase ice X suggested to occur at ∼80 GPa. The internal pressure computed at constant NVT conditions shows that the NQEs manifest themselves in the equation of state of HPIs. Our employed approach based on first principles CMD for computing vibrational spectra is proved to be able to reproduce well the overall features of the measured infrared and Raman spectra.

2D IR spectroscopy of high-pressure phases of ice.

We present experimental and simulated 2D IR spectra of some high-pressure forms of isotope-pure D2O ice and compare the results to those of ice Ih published previously [F. Perakis and P. Hamm, Phys. Chem. Chem. Phys. 14, 6250 (2012); L. Shi et al., ibid. 18, 3772 (2016)]. Ice II, ice V, and ice XIII have been chosen for this study, since this selection covers many aspects of the polymorphism of ice. That is, ice II is a hydrogen-ordered phase of ice, in contrast to ice Ih, while ice V and ice XIII are a hydrogen-disordered/ordered couple that shares essentially the same oxygen structure and hydrogen-bonded network. For the transmission 2D IR spectroscopy, a novel method had to be developed for the preparation of ultrathin films (1-2 μm) of high-pressure ices with good optical quality. We also simulated 2D IR spectra based on molecular dynamics simulations connected to a vibrational exciton picture. These simulations agree with the experimental results in a semi-quantitative manner for ice II, while the same approach failed for ice V and ice XIII. From the perspective of 2D IR spectroscopy, ice II appears to be more inhomogeneously broadened than ice Ih, despite its hydrogen-order, which we attribute to the fact that ice II is structurally more complex with four distinguishable hydrogen bonds that mix due to exciton coupling. Ice V and ice XIII, on the other hand, behave as expected with the hydrogen-disordered case (ice V) being more inhomogenously broadened. Furthermore, in all hydrogen-ordered forms (ice II and ice XIII), cross peaks could be identified in the anisotropic 2D IR spectrum, whose signs reveal the relative direction of the corresponding excitonic states.

Kinetically Controlled Two-Step Amorphization and Amorphous-Amorphous Transition in Ice.

We report the results of insitu structural characterization of the amorphization of crystalline ice Ih under compression and the relaxation of high-density amorphous (HDA) ice under decompression at temperatures between 96 and 160K by synchrotron x-ray diffraction. The results show that ice Ih transforms to an intermediate crystalline phase at 100K prior to complete amorphization, which is supported by molecular dynamics calculations. The phase transition pathways show clear temperature dependence: direct amorphization without an intermediate phase is observed at 133K, while at 145K a direct Ih-to-IX transformation is observed; decompression of HDA shows a transition to low-density amorphous ice at 96K and ∼1 Pa, to ice Ic at 135K and to ice IX at 145K. These observations show that the amorphization of compressed ice Ih and the recrystallization of decompressed HDA are strongly dependent on temperature and controlled by kinetic barriers. Pressure-induced amorphous ice is an intermediate state in the phase transition from the connected H-bond water network in low pressure ices to the independent and interpenetrating H-bond network of high-pressure ices.

Two-phase convection in Ganymede’s high-pressure ice layer — Implications for its geological evolution

Ganymede, the largest moon in the solar system, has a fully differentiated interior with a layer of high-pressure (HP) ice between its deep ocean and silicate mantle. In this paper, we study the dynamics of this layer using a numerical model of two-phase ice–water mixture in two-dimensional Cartesian geometry. While focusing on the generation of water at the silicate/HP ice interface and its upward migration towards the ocean, we investigate the effect of bottom heat flux, the layer thickness, and the HP ice viscosity and permeability. Our results suggest that melt can be generated at the silicate/HP ice interface for small layer thickness ( ≲ 200 km) and high values of heat flux ( ≳ 20 mW m−2) and viscosity ( ≳ 1015 Pa s). Once generated, the water is transported through the layer by the upwelling plumes. Depending on the vigor of convection, it stays liquid or it may freeze before melting again as the plume reaches the temperate (partially molten) layer at the boundary with the ocean. The thickness of this layer as well as the amount of melt that is extracted from it is controlled by the permeability of the HP ice. This process constitutes a means of transporting volatiles and salts that might have dissolved into the melt present at the silicate/HP ice interface. As the moon cools down, the HP ice layer becomes less permeable because the heat flux from the silicates decreases and the HP ice layer thickens.

Outcomes of the collapse of a large bubble in water at high ambient pressures.

Presented here are observations of the outcomes of the collapses of large single bubbles in H_{2}O and D_{2}O at high ambient pressures. Experiments were carried out in a high-pressure spherical resonator at ambient pressures of up to 30 MPa and acoustic pressures up to 35 MPa. Monitoring of the collapse events and their outcomes was accomplished using multiframe high-speed photography. Among the observations to be presented are the temporal and spatial evolution of light emissions produced by the collapse events, which were observed to last on the order of 30 ns and have time independent radii on the order of 30μm; the production of Rayleigh-Taylor jets which were observed to travel distances of up to 70μm at speeds in excess of 4500 m/s; the entrainment of the light emitting regions in the jets' remnants; the production of spheroidal objects around the collapse points of the bubbles, far from any surface of the resonator; and the traversal and emergence of the Rayleigh-Taylor jets through the spherical objects. These spheroidal objects appear to behave as amorphous solids and form at locations where hydrodynamics predicts pressures in excess of the known transition pressures of water into the high-pressure crystalline ices, Ice-VI and Ice-VII.

Salt partitioning between water and high-pressure ices. Implication for the dynamics and habitability of icy moons and water-rich planetary bodies

Water-rich planetary bodies including large icy moons and ocean exoplanets may host a deep liquid water ocean underlying a high-pressure icy mantle. The latter is often considered as a limitation to the habitability of the uppermost ocean because it would limit the availability of nutrients resulting from the hydrothermal alteration of the silicate mantle located beneath the deep ice layer. To assess the effects of salts on the physical properties of high-pressure ices and therefore the possible chemical exchanges and habitability inside H2O-rich planetary bodies, we measured partitioning coefficients and densities in the H2O–RbI system up to 450 K and 4 GPa; RbI standing as an experimentally amenable analog of NaCl in the H2O-salt solutions. We measured the partitioning coefficient of RbI between the aqueous fluid and ices VI and VII, using in-situ Synchrotron X-ray Fluorescence (XRF). With in-situ X-ray diffraction, we measured the unit-cell parameters and the densities of the high-pressure ice phases in equilibrium with the aqueous fluid, at pressures and temperatures relevant to the interior of planetary bodies. We conclude that RbI is strongly incompatible towards ice VI with a partitioning coefficient Kd(VI-L)=5.0(±2.1)⋅10−3 and moderately incompatible towards ice VII, Kd(VII-L)=0.12(±0.05). RbI significantly increases the unit-cell volume of ice VI and VII by ca. 1%. This implies that RbI-poor ice VI is buoyant compared to H2O ice VI while RbI-enriched ice VII is denser than H2O ice VII. These new experimental results might profoundly impact the internal dynamics of water-rich planetary bodies. For instance, an icy mantle at moderate conditions of pressure and temperature will consist of buoyant ice VI with low concentration of salt, and would likely induce an upwelling current of solutes towards the above liquid ocean. In contrast, a deep and/or thick icy mantle of ice VII will be enriched in salt and hence would form a stable chemical boundary layer on top of the silicate mantle. Such a contrasted dynamics in the aqueous–ice VI–ice VII system would greatly influence the migration of nutrients towards the uppermost liquid ocean, thus controlling the habitability of moderate to large H2O-rich planetary bodies in our solar system (e.g., Ganymede, Titan, Calisto) and beyond.

Isothermal equation of state and high-pressure phase transitions of synthetic meridianiite (MgSO4·11D2O) determined by neutron powder diffraction and quasielastic neutron spectroscopy

We have collected neutron powder diffraction data from MgSO4·11D2O (the deuterated analogue of meridianiite), a highly hydrated sulfate salt that is thought to be a candidate rock-forming mineral in some icy satellites of the outer solar system. Our measurements, made using the PEARL/HiPr and OSIRIS instruments at the ISIS neutron spallation source, covered the range 0.1 < P < 800 MPa and 150 < T < 280 K. The refined unit-cell volumes as a function of P and T are parameterized in the form of a Murnaghan integrated linear equation of state having a zero-pressure volume V 0 = 706.23 (8) Å3, zero-pressure bulk modulus K 0 = 19.9 (4) GPa and its first pressure derivative, K′ = 9 (1). The structure's compressibility is highly anisotropic, as expected, with the three principal directions of the unit-strain tensor having compressibilities of 9.6 × 10−3, 3.4 × 10−2 and 3.4 × 10−3 GPa−1, the most compressible direction being perpendicular to the long axis of a discrete hexadecameric water cluster, (D2O)16. At high pressure we observed two different phase transitions. First, warming of MgSO4·11D2O at 545 MPa resulted in a change in the diffraction pattern at 275 K consistent with partial (peritectic) melting; quasielastic neutron spectra collected simultaneously evince the onset of the reorientational motion of D2O molecules with characteristic time-scales of 20–30 ps, longer than those found in bulk liquid water at the same temperature and commensurate with the lifetime of solvent-separated ion pairs in aqueous MgSO4. Second, at ∼ 0.9 GPa, 240 K, MgSO4·11D2O decomposed into high-pressure water ice phase VI and MgSO4·9D2O, a recently discovered phase that has hitherto only been formed at ambient pressure by quenching small droplets of MgSO4(aq) in liquid nitrogen. The fate of the high-pressure enneahydrate on further compression and warming is not clear from the neutron diffraction data, but its occurrence indicates that it may also be a rock-forming mineral in the deep mantles of large icy satellites.

A generalized Bayesian inference method for constraining the interiors of super Earths and sub-Neptunes

We aim to present a generalized Bayesian inference method for constraining interiors of super Earths and sub-Neptunes. Our methodology succeeds in quantifying the degeneracy and correlation of structural parameters for high dimensional parameter spaces. Specifically, we identify what constraints can be placed on composition and thickness of core, mantle, ice, ocean, and atmospheric layers given observations of mass, radius, and bulk refractory abundance constraints (Fe, Mg, Si) from observations of the host star's photospheric composition. We employed a full probabilistic Bayesian inference analysis that formally accounts for observational and model uncertainties. Using a Markov chain Monte Carlo technique, we computed joint and marginal posterior probability distributions for all structural parameters of interest. We included state-of-the-art structural models based on self-consistent thermodynamics of core, mantle, high-pressure ice, and liquid water. Furthermore, we tested and compared two different atmospheric models that are tailored for modeling thick and thin atmospheres, respectively. First, we validate our method against Neptune. Second, we apply it to synthetic exoplanets of fixed mass and determine the effect on interior structure and composition when (1) radius, (2) atmospheric model, (3) data uncertainties, (4) semi-major axes, (5) atmospheric composition (i.e., a priori assumption of enriched envelopes versus pure H/He envelopes), and (6) prior distributions are varied. Our main conclusions are: [...]

Heat transport in the high-pressure ice mantle of large icy moons

While the existence of a buried ocean sandwiched between surface ice and high-pressure (HP) polymorphs of ice emerges as the most plausible structure for the hundreds-of-kilometers thick hydrospheres within large icy moons of the Solar System (Ganymede, Callisto, Titan), little is known about the thermal structure of the deep HP ice mantle and its dynamics, possibly involving melt production and extraction. This has major implications for the thermal history of these objects as well as on the habitability of their ocean as the HP ice mantle is presumed to limit chemical transport from the rock component to the ocean. Here, we describe 3D spherical simulations of subsolidus thermal convection tailored to the specific structure of the HP ice mantle of large icy moons. Melt production is monitored and melt transport is simplified by assuming instantaneous extraction to the ocean above. The two controlling parameters for these models are the rheology of ice VI and the heat flux from the rock core. Reasonable end-members are considered for both parameters as disagreement remains on the former (especially the pressure effect on viscosity) and as the latter is expected to vary significantly during the moon’s history. We show that the heat power produced by radioactive decay within the rock core is mainly transported through the HP ice mantle by melt extraction to the ocean, with most of the melt produced directly above the rock/water interface. While the average temperature in the bulk of the HP ice mantle is always relatively cool when compared to the value at the interface with the rock core (∼ 5 K above the value at the surface of the HP ice mantle), maximum temperatures at all depths are close to the melting point, often leading to the interconnection of a melt path via hot convective plume conduits throughout the HP ice mantle. Overall, we predict long periods of time during these moons’ history where water generated in contact with the rock core is transported to the above ocean.

NMR spectroscopy of some electrolyte solutions to 1.9 GPa

Nuclear-magnetic resonance (NMR) spectra of CsCl and LaCl3 in D2O/H2O solutions were collected up to pressures of 1.9GPa using a new NMR probe design that considerably extends the pressure range available for geochemical experiments. The longitudinal-relaxation times (T1) for 2H compare well with those reported in the previous studies of Lee et al. (1974), who examined lower pressures, and indicate that the probe functions properly. In some experiments, 133Cs and 1H NMR spectra could be taken on solutions to pressures well beyond the nominal freezing pressure of D2O or H2O to form Ice VI (near 0.9GPa). Freezing to form the high-pressure ice is kinetically slow on an experimental time scale (minutes to hours). The data indicate that the electrolyte concentrations increase the freezing pressure of the solution. This result means that solution NMR spectra can be collected at pressures that are nearly twice the nominal freezing pressure of pure D2O or H2O. Pulsed-magnetic-field-gradient NMR methods are used to independently measure the self-diffusion coefficient of H2O in these solutions, which yields estimates of solution viscosity via the Stokes–Einstein relation. The increased viscosity accounts for the pressure variation of T1 values as rates of molecular tumbling are affected. Accounting for such changes is essential if NMR spectral line widths are used to infer pressure-enhanced rates of geochemical reactions, such as interconversion of aqueous complexes.

Constraints on dissipation in the deep interiors of Ganymede and Europa from tidal phase-lags

Jupiter’s satellites are subject to strong tidal forces which result in variations of the gravitational potential and deformations of the satellites’ surfaces on the diurnal tidal cycle. Such variations are described by the Love numbers $$k_2$$ and $$h_2$$ for the tide-induced potential variation due to internal mass redistribution and the radial surface displacement, respectively. The phase-lags $$ \phi _{k_2}$$ and $$ \phi _{h_2}$$ of these complex numbers contain information about the rheological and dissipative states of the satellites. Starting from interior structure models and assuming a Maxwell rheology to compute the tidal deformation, we calculate the phase-lags in application to Ganymede and Europa. For both satellites we assume a decoupling of the outer ice-shell from the deep interior by a liquid subsurface water ocean. We show that, in this case, the phase-lag difference $$\varDelta \phi = \phi _{k_2}- \phi _{h_2}$$ can provide information on the rheological and thermal state of the deep interiors if the viscosities of the deeper layers are small. In case of Ganymede, phase-lag differences can reach values of a few degrees for high-pressure ice viscosities $${<}10^{14}$$ Pa s and would indicate a highly dissipative state of the deep interior. In this case $$\varDelta \phi $$ is dominated by dissipation in the high-pressure ice layer rather than dissipation within the ice-I shell. These phase lags would be detectable from spacecraft in orbit around the satellite. For Europa $$\varDelta \phi $$ could reach values exceeding $$20^\circ $$ and phase-lag measurements could help distinguish between (1) a hot dissipative silicate mantle which would in thermal equilibrium correspond to a very thin outer ice-I shell and (2) a cold deep interior implying that dissipation would mainly occur in a thick (several tens of km) outer ice-I shell. These measurements are highly relevant for ESA’s Jupiter Icy Moons Explorer (JUICE) and NASA’s Europa Multiple Flyby Mission, both targeted for the Jupiter system.

Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds.

It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty » high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl∙RH2O and LiBr∙RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random.

A new structural relaxation pathway of low-density amorphous ice

Low-density amorphous (LDA) ice is involved in critical cosmological processes and has gained prominence as one of the at least two distinct amorphous forms of ice. Despite these accolades, we still have an incomplete understanding of the structural diversity that is encompassed within the LDA state and the dynamic processes that take place upon heating LDA. Heating the high-pressure ice VIII phase at ambient pressure is a remarkable example of temperature-induced amorphisation yielding LDA. We investigate this process in detail using X-ray diffraction and Raman spectroscopy and show that the LDA obtained from ice VIII is structurally different from the more "traditional" states of LDA which are approached upon thermal annealing. This new structural relaxation pathway involves an increase of structural order on the intermediate range length scale. In contrast with other LDA materials the local structure is more ordered initially and becomes slightly more disordered upon annealing. We also show that the cascade of phase transitions upon heating ice VIII at ambient pressure includes the formation of ice IX which may be connected with the structural peculiarities of LDA from ice VIII. Overall, this study shows that LDA is a structurally more diverse material than previously appreciated.

Water-rich planets: How habitable is a water layer deeper than on Earth?

Water is necessary for the origin and survival of life as we know it. In the search for life-friendly worlds, water-rich planets therefore are obvious candidates and have attracted increasing attention in recent years. The surface H2O layer on such planets (containing a liquid water ocean and possibly high-pressure ice below a specific depth) could potentially be hundreds of kilometres deep depending on the water content and the evolution of the proto-atmosphere.We study possible constraints for the habitability of deep water layers and introduce a new habitability classification relevant for water-rich planets (from Mars-size to super-Earth-size planets). A new ocean model has been developed that is coupled to a thermal evolution model of the mantle and core. Our interior structure model takes into account depth-dependent thermodynamic properties and the possible formation of high-pressure ice.We find that heat flowing out of the silicate mantle can melt an ice layer from below (in some cases episodically), depending mainly on the thickness of the ocean-ice shell, the mass of the planet, the surface temperature and the interior parameters (e.g. radioactive mantle heat sources). The high pressure at the bottom of deep water–ice layers could also impede volcanism at the water–mantle boundary for both stagnant lid and plate tectonics silicate shells.We conclude that water-rich planets with a deep ocean, a large planet mass, a high average density or a low surface temperature are likely less habitable than planets with an Earth-like ocean.