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Hydrated sulfates have been identified and studied in a wide variety of environments on Earth, Mars, and the icy satellites of the solar system. The subsurface presence of hydrous sulfur-bearing phases to any extent necessitates a better understanding of their thermodynamic and elastic properties at pressure. End-member experimental and computational data are lacking and are needed to accurately model hydrous, sulfur-bearing planetary interiors. In this work, high-pressure X-ray diffraction (XRD) and synchrotron Fourier-transform infrared (FTIR) measurements were conducted on szomolnokite (FeSO4·H2O) up to ~83 and 24 GPa, respectively. This study finds a monoclinic-triclinic (C2/c to P1) structural phase transition occurring in szomolnokite between 5.0(1) and 6.6(1) GPa and a previously unknown triclinic-monoclinic (P1 to P21) structural transition occurring between 12.7(3) and 16.8(3) GPa. The high-pressure transition was identified by the appearance of distinct reflections in the XRD patterns that cannot be attributed to a second phase related to the dissociation of the P1 phase, and it is further characterized by increased H2O bonding within the structure. We fit third-order Birch-Murnaghan equations of state for each of the three phases identified in our data and refit published data to compare the elastic parameters of szomolnokite, kieserite (MgSO4·H2O), and blödite (Na2Mg(SO4)2·4H2O). At ambient pressure, szomolnokite is less compressible than blödite and more than kieserite, but by 7 GPa both szomolnokite and kieserite have approximately the same bulk modulus, while blödite’s remains lower than both phases up to 20 GPa. These results indicate the stability of szomolnokite’s high-pressure monoclinic phase and the retention of water within the structure up to pressures found in planetary deep interiors.

Complex mixtures of sulfates, silicates, and ice have been observed in a variety of planetary environments on Earth, Mars and the icy satellites of the solar system. Characterizing the properties of the corresponding compositional endmembers is important for understanding the interiors of a range of planetary bodies in which these phases are observed. To measure the electronic and vibrational properties of the iron endmember, szomolnokite, (FeSO4⋅H2O), we have performed synchrotron 57Fe nuclear resonant inelastic and forward scattering experiments in the diamond anvil cell up to 14.5 GPa. This pressure range covers depths within Earth’s interior relevant to sulfur cycling in subduction zones and the range of pressures expected within icy satellites interiors. We find evidence of crystal lattice softening, changes in elastic properties, and changes in the electric field gradients of iron atoms associated with two structural transitions occurring within the experimental pressure range. We apply these findings to icy satellite interiors, including discussion of elastic properties and implications for tidal observations.

Many studies have suggested silicon as a candidate light element for the cores of Earth and Mercury. However, the effect of silicon on the melting temperatures of core materials and thermal profiles of cores is poorly understood, due to disagreements among melt detection techniques, uncertainties in sample pressure evolution during heating, and sparsity of studies investigating the combined effects of nickel and silicon on the phase diagram of iron. In this study we develop a multi-technique approach for measuring the high-pressure melting and solid phase relations of iron alloys and apply it to Fe_(0.8)Ni_(0.1)Si_(0.1) (Fe-11wt%Ni-5.3wt%Si), a composition compatible with recent estimates for the cores of Earth and Mercury. This approach combines results (20-83 GPa) from two atomic-level techniques: synchrotron Mössbauer spectroscopy (SMS) and synchrotron x-ray diffraction (XRD). Melting is independently detected by the loss of the Mössbauer signal, produced exclusively by solid-bound iron nuclei, and the onset of a liquid diffuse x-ray scattering signal. The use of a burst heating and background updating method for quantifying changes in the reference background during heating facilitates the determination of liquid diffuse signal onsets and leads to strong reproducibility and excellent agreement in melting temperatures determined separately by the two techniques. XRD measurements additionally constrain the hcp-fcc phase boundary and in-situ pressure evolution of the samples during heating. We apply our updated thermal pressure model to published SMS melting data on fcc-Fe and fcc-Fe_(0.9)Ni_(0.1) to precisely evaluate the effect of silicon on melting temperatures. We find that the addition of 10 mol% Si to Fe_(0.9)Ni_(0.1) reduces melting temperatures by ∼250 K at low pressures (