The high-pressure behaviour of inderborite [ideally CaMg[B3O3(OH)5]2(H2O)4⋅2H2O, space group C2/c with a ≈ 12.14, b ≈ 7.43, c ≈ 19.23 Å and β ≈ 90.3° at room conditions] has been studied by two in situ single-crystal synchrotron X-ray diffraction experiments up to ~10 GPa, using He as pressure-transmitting fluid. Between 8.11(5) and 8.80(5) GPa, inderborite undergoes a first-order phase transition to its high-pressure polymorph, inderborite-II (with a ≈ 11.37, b ≈ 6.96, c ≈ 17.67 Å, β ≈ 96.8° and ΔV ≈ 7.0%, space group unknown). The isothermal bulk modulus (KV0 = β−1P0,T0, where βP0,T0 is the volume compressibility coefficient) of inderborite was found to be KV0 = 41(1) GPa. The destructive nature of the phase transition prevented any structure resolution of inderborite-II or even the continuation of the experiments at pressures higher than 10.10(5) GPa. In the pressure range 0–8.11(5) GPa, the compressional anisotropy of inderborite, indicated by the ratio between the principal components of the Eulerian finite unit-strain ellipsoid, is ɛ1:ɛ2:ɛ3 = 1.4:1.05:1. The deformation mechanisms at the atomic scale in inderborite are here described. Our findings support the hypothesis of a quasi-linear correlation between the total H2O content and P-stability range in hydrated borates, as the pressure at which inderborite undergoes the phase transition falls in line with most of the hydrate borates studied at high-pressure so far.

The effect of pressure on the naturally occurring hydroxide-perovskite stottite, FeGe(OH)6, has been studied in situ by micro-Raman spectroscopy to 21 GPa at 300 K. The ambient spectrum contains six OH-stretching bands in the range 3064 3352 cm–1. The presence of six non-equivalent OH groups is inconsistent with space group P42/n. In view of this inconsistency a new ambient structure determination of stottite from Tsumeb was carried out, but this did not allow the clear rejection of P42/n symmetry. However, a successful refinement was also carried out in space group P2/n, a subgroup of P42/n, which allows for six non-equivalent O atoms. The two refinements are of comparable quality and do not allow a choice to be made based purely on the X-ray data. However, taken with the ambient and 150 K Raman spectra, a good case can be made for stottite having P2/n symmetry at ambient conditions. On this basis, the pressure induced spectroscopic changes are interpreted in terms of a reversible phase transition P2/n ↔ P42/n.

The crystal structure of the high-pressure phase-II of cristobalite has been solved by neutron diffraction (space group P21/c, a = 8.3780(11) Å, b = 4.6018(6) Å, c = 9.0568(13) Å, β = 124.949(7)°, at P = 3.5 GPa). This phase corresponds to a distortion of the high-temperature cubic β-phase, rather than of the ambient temperature and pressure tetragonal α-phase.

Synchrotron X-ray diffraction (XRD) is a powerful technique to study in situ and in real-time the structural and kinetic processes of pressure-induced phase transformations. This paper presents the experimental set-up developed at beamline ID27 of the ESRF to perform time-resolved angle dispersive XRD in the Paris-Edinburgh cell. It provides a practical guide for the acquisition of isobaric-isothermal kinetic data and the construction of transformation-time plots. The interpretation of experimental data in terms of reaction mechanisms and transformation rates is supported by an overview of the kinetic theory of solid-solid transformations, with each step of data processing illustrated by experimental results of relevance to the geosciences. Reaction kinetics may be affected by several factors such as the sample microstructure, impurities or differential stress. Further high-pressure kinetic studies should investigate the influence of such processes, in order to acquire kinetic information more akin to natural or technological processes.

Ultrahigh-pressure and -temperature (P-T) experimental techniques have progressed rapidly in recent years. By combining them with X-ray diffraction measurements at synchrotron radiation facilities, it is now possible to examine deep Earth mineralogy in situ at relevant high P-T conditions in a laser-heated diamond anvil cell (DAC). The lowermost part of the mantle, known as the D″ layer, has long been enigmatic because of a number of unexplained seismological features. Nevertheless, the discovery of a phase transition from MgSiO3 perovskite to ‘post-perovskite’ above 120 GPa and 2400 K indicates that post-perovskite is a principal constituent in the lowermost mantle, which is compatible with seismic observations. The ultrahigh P-T conditions of the Earth’s core have not been accessible by static experiments, but the structure and phase transition of Fe and Fe-alloys are now being examined up to 400 GPa and 6000 K by laser-heated DAC studies.

Structural refinements of lawsonite have been obtained at pressures up to 16.5 GPa using angle-dispersive powder diffraction with synchrotron radiation on a natural sample contained in a diamond anvil cell. Lawsonite compresses smoothly and relatively isotropically up to 10 GPa. Its bulk modulus is 126.1(6) GPa (for K’ = 4), consistent with previous results. A trend of decreasing Si–O–Si angle indicates that compression is accommodated partly through the narrowing of the cavities containing Ca and H2O in the [001]ortho direction. At 10–11 GPa there is a phase transition from Cmcm to P21/m symmetry. The occurrence of a mixed-phase region, spanning >1 GPa, indicates that the transition is first order in character. The phase transition occurs through a shearing of (010)ortho sheets containing AlO6 octahedral chains in the [100]ortho direction, which causes an increase in βmono. Across the transition, the number of oxygens coordinated to Ca increases from 8 to 9, causing an increase in the average Ca–O bond length. The compressibility of P21/m lawsonite could not be determined due to solidification of the methanol/ethanol pressure-transmitting medium. On the basis of an experiment in which the P21/m lawsonite structure was heated to 200°C at 12.0 GPa, we predict a shallow positive P-T slope for the phase transition, and therefore no stability field for P21/m lawsonite in the Earth.

Recent experimental and theoretical studies provide new insight into the variety of high-pressure transformations in minerals that comprise the Earth’s deep mantle and core. Representative examples of reconstructive, displacive, electronic and magnetic transformations studied by new diamond-anvil cell techniques are examined. Despite reports for various transitions in (Mg,Fe)SiO3-perovskite, the stability field of the orthorhombic phase expands relative to magnesiowüstite + SiO2 with increasing pressure and temperature. The partitioning of Fe and Mg between Mg-rich silicate perovskite magnesiowüstite depends strongly on pressure, temperature, bulk Fe/Mg ratio, and ferric iron content. The soft-mode transition in SiO2 from the rutile- to CaCl2-type structure, originally documented by X-ray powder diffraction, Raman scattering, and first-principles theory has been explored in detail by single crystal diffraction, and transitions to higher-pressure forms have been examined. The effect of H on the transformations of various nominally anhydrous phases and transitions in dense hydrous Mg-silicates are also examined. New studies of the phase diagram of FeO include the transition to rhombohedral and higher-pressure NiAs polymorphs, and provide prototypical examples of coupled structural, electronic, and magnetic transitions. High-spin/low-spin transitions in FeO have been examined by high-resolution X-ray emission spectroscopy to 150 GPa, and the results are compared with similar studies of Fe2O3 and FeS. Finally, laser-heating studies to above 150 GPa and 2500K show that (hcp) ε-Fe has a large P-T stability field. Radial XRD measurements carried out at room temperature to 220 GPa have constrained the elasticity, rheology and sound velocities of ε-Fe at core pressures.

Ambient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.

Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.

The VF3-type compound GaF3 has been studied by high-pressure angle-dispersive X-ray diffraction in the pressure range from 0.0001 to 10 GPa. The compression mechanism was found to be highly anisotropic. The c-axis shows little pressure dependence (≈0.4%), but exhibits negative linear compressibility up to ≈3 GPa where it achieves its maximum length. In contrast, the length of the a-axis is reduced by ≈8.8% at the highest measured pressure and an anomalous reduction in the linear compressibility is observed at 4 GPa. The zero pressure bulk modulus B0 was determined to B0 = 28(1) GPa. The compression mechanism of GaF3 is discussed in terms of deformation of an 8/3/c2 sphere-packing model. The volume reduction of GaF3 is mainly achieved through coupled rotations of the GaF6 octahedra within the entire measured pressure range, which reduces the volume of the cubooctahedral voids. In addition, the volume of the GaF6 octahedra also decreases for p ≲ 4.0 GPa, but remains constant above this pressure. The volume reduction of the GaF6 octahedra is accompanied by an increasing octahedral strain. Isosurfaces of the procrystal electron density are used for visualization of the cubooctahedral voids at different pressures.

Recent efforts to characterize the nanoscale structural and chemical modifications induced by energetic ion irradiation in nuclear materials have greatly benefited from the application of synchrotron-based x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques. Key to the study of actinide-bearing materials has been the use of small sample volumes, which are particularly advantageous, as the small quantities minimize the level of radiation exposure at the ion-beam and synchrotron user facility. This approach utilizes energetic heavy ions (energy range: 100 MeV–3 GeV) that pass completely through the sample thickness and deposit an almost constant energy per unit length along their trajectory. High energy x-rays (25–65 keV) from intense synchrotron light sources are then used in transmission geometry to analyze ion-induced structural and chemical modifications throughout the ion tracks. We describe in detail the experimental approach for utilizing synchrotron radiation (SR) to study the radiation response of a range of nuclear materials (e.g., ThO2 and Gd2TixZr2−xO7). Also addressed is the use of high-pressure techniques, such as the heatable diamond anvil cell, as a new means to expose irradiated materials to well-controlled high-temperature (up to 1000 °C) and/or high-pressure (up to 50 GPa) conditions. This is particularly useful for characterizing the annealing kinetics of irradiation-induced material modifications.

Although density functional theory (DFT) calculations have been widely used in many areas of the geosciences for the last 15 years, arguably the most successful application of these methods has been when they are used to understand the properties of minerals and melts in the Earth's pressures of the Earth's 6000 K and 360GPa) are so extreme that experiments under these conditions are very difficult. DFT calculations have been used to provide invaluable estimates of physical parameters that are fundamental to understanding the dynamics and evolution of the Earth. In particular, DFT calculations have helped provide estimates of the mineralogy and chemistry of the Earth's core, the high-temperature and pressure elasticity of the stable crystal phases in the mantle, the effect of defects on physical properties of mantle minerals, and, most recently, the discovery of a new phase of (Mg, Fe)SiO3 just above the core. These and other applications of DFT in the geosciences are described and their implications discussed.

High-pressure injection injuries to the hand are work-related injuries that can take a devastating toll on the functionality of the affected extremity. Chemical injections are a surgical emergency. Injuries involving only water injection are rarer and have variable management strategies. We report a case of high-pressure injection hand injury due to water only. The patient was managed non-operatively with parenteral antibiotics, narcotics and elevation, with good outcome. We present a review of the literature on high-pressure injection injury.

We have simulated the shock Hugoniot of copper and uranium based on the results of first principles electronic structure calculations. The room temperature isotherm has been obtained by evaluating the accurate ground state total energies at various compressions, and the thermal and electronic excitation contributions were obtained by adopting isotropic models using the results obtained by the band structure calculations. Our calculations ensure smooth consideration of pressure ionization effects as the relevant core states are treated in the semi-core form at the ambient pressure. The pressure variation of the electronic Grüneisen parameter was estimated for copper using the band structure results, which leads to good agreement of the simulated shock Hugoniot with the measured shock data. The simulation results obtained for U are also compared with the experimental data available in literature and with our own data.

Bovine β-lactoglobulin was hydrolyzed with trypsin or chymotrypsin before, during and after treatment at 600 MPa and pH 6·8 for 10 min at 30, 37 and 44 °C. The extent of β-lactoglobulin hydrolysis under pressure was noticeably higher than at atmospheric pressure, particularly when chymotrypsin was used. Addition of proteases at ambient pressure to previously pressure-treated β-lactoglobulin gave only a modest increase in proteolysis with respect to the untreated protein. Products of enzyme hydrolysis under pressure were separated by reverse-phase HPLC, and were found to be different from those obtained at atmospheric pressure when chymotrypsin was used. The residual immunochemical reactivity of the products of combined pressure-enzyme treatment was assessed on the unresolved hydrolysates by ELISA tests using polyclonal and monoclonal antibodies, and on individual hydrolytic fractions by Western Blotting using sera of paediatric patients allergic to whey proteins in cow milk. The immunoreactivity of the whole hydrolysates was related to their content of residual intact β-lactoglobulin, and no immunochemical reactivity was found for all the products of chymotrypsin hydrolysis under pressure. The results indicate that chymotrypsin effectively hydrolysed hydrophobic regions of β-lactoglobulin that were transiently exposed during the pressure treatments and that were not accessible in the native protein or in the protein that had been previously pressure treated.

Rare garnet phenocrysts and garnet-bearing xenoliths occur in high-silica, metaluminous to peraluminous andesites and dacites (and their high-level intrusive quartz diorite equivalents) from a Miocene calc-alkaline province in Northland, New Zealand. These garnets are among the most Ca-rich (17–28 mol% grossular) garnets of igneous origin so far recorded in calc-alkaline suite rocks. Associated minerals are dominant hornblende and plagioclase and minor augite, occurring as phenocrysts in xenoliths and as inclusions in the garnet. This mineralogy points to the I-type character of the garnet-bearing host magma compositions, and contrasts this garnet occurrence with the more frequently recorded grossular-poor (3–10 mol%) garnets with hypersthene, plagioclase, biotite and cordierite, found in S-type volcanic and intrusive host rocks.

Detailed experimental work on a glass prepared from one of the garnet-bearing dacites closely constrains the conditions under which the natural phenocryst and xenolith mineral assemblages formed. This work was conducted over a pressure-temperature range of 8–20 kbar, 800–1050°C with 3–10 wt% of added H2O, defining overall phase relationships for these conditions. Importantly, amphibole only appears at temperatures of 900°C or less and clinopyroxene at >900°C (with 3wt% H2O). Orthopyroxene occurs with garnet at lower pressure (∼15 kbar with 3wt% H2O; ∼>10kbar with 5wt% H2O). Absence of orthopyroxene from the natural garnet-bearing assemblages indicates pressures above these limits during crystallisation. Plagioclase is markedly suppressed (with respect to temperature) with increasing H2O content, and for pressures of 10–15 kbar, the maximum H2O content possible in the magma with retention of clinopyroxene and plagioclase together (as evident in xenoliths) is 5–6 wt%. Finally, the lack of quartz in any of the xenoliths suggests magma H2O content higher than 3% (where quartz appears with amphibole at 900°C), since the quartz liquidus temperature decreases with increasing H2O content, and with decreasing pressure. In experiments with 5wt% H2O, a quartz-free field of crystallisation of garnet-clinopyroxene-amphibole-plagioclase occurs between 10 and 15 kbar and temperatures between 850 and 900°C. In addition, detailed experimentally-determined garnet compositional trends, together with ferromagnesian mineral compositional data for specific experiments with 5 wt% H2O added and run at 10-13 kbar and ∼900°C, suggest that the natural assemblages formed at these conditions. This implies that the parental dacitic magma must have been derived at mantle depths (the Northland crust is ∼25 km thick), and any basaltic or basaltic andesite precursor must have contained ∼2–3 wt% H2O.

The unique nature of the Northland volcanics and high-level intrusives, preserving evidence of relatively grossular-rich garnet fractionation in the high-pressure crystallisation history of an originally mantle-derived magma, is attributed to a combination of unusually hydrous conditions in the source region, complex tectonic history involving obduction and subduction, possible incorporation of crustal slivers in a mantle-crust interaction zone, and relatively thin (∼25 km) crust.