Search

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 P1̅) structural phase transition occurring in szomolnokite between 5.0(1) and 6.6(1) GPa and a previously unknown triclinic-monoclinic (P1̅ 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 P1̅ 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. [ABSTRACT FROM AUTHOR]

• We measure the melting and solid phase relations of Fe 0.8 Ni 0.1 Si 0.1 up to 83 GPa. • Independent melt detection techniques show excellent agreement and reproducibility. • Synchrotron Mössbauer spectroscopy detects the very first onset of melting. • X-ray diffraction constrains in-situ sample pressure evolution during heating. • 10 mol% Si decreases the melting temperature of Fe 0.9 Ni 0.1 by up to 500 K at 150 GPa. 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 (<60 GPa) and flattens the hcp-fcc phase boundary. Extrapolating our results, we constrain the location of the hcp-fcc-liquid quasi-triple point at 147±14 GPa and 3140±90 K, which implies a melting temperature reduction of 500 K compared with Fe 0.9 Ni 0.1. The results demonstrate the advantages of combining complementary experimental techniques in investigations of melting under extreme conditions. [ABSTRACT FROM AUTHOR]

The composition of ultralow velocity zones (ULVZs) remains an open question, despite advances in both seismology and experimental work. We investigate the hypothesis of iron-rich (Mg,Fe)O (magnesiowüstite) as a cause of ULVZ seismic signatures. We report new quasi-hydrostatic X-ray diffraction measurements to constrain the equation of state of (Mg0.06Fe0.94)O with fit parameters V0 = 9.860 ± 0.007 Å3, K0T = 155.3 ± 2.2 GPa, K'0T = 3.79 ± 0.11, as well as synchrotron Mössbauer spectroscopy measurements to characterize the high-pressure magnetic and spin state of magnesiowüstite. We combine these results with information from previous studies to calculate the elastic behavior at core–mantle boundary conditions of magnesiowüstite, as well as coexisting bridgmanite and calcium silicate perovskite. Forward models of aggregate elastic properties are computed, and from these, we construct an inverse model to determine the proportions of magnesiowüstite that best reproduce ULVZ observations within estimated mutual uncertainties. We find that the presence of magnesiowüstite can explain ULVZ observations exhibiting 1:2 VP:VS reduction ratios relative to the Preliminary Reference Earth Model (PREM), as well as certain 1:3 VP:VS reductions within estimated uncertainty bounds. Our work quantifies the viability of compositionally distinct ULVZs containing magnesiowüstite and contributes to developing a framework for a methodical approach to evaluating ULVZ hypotheses. [ABSTRACT FROM AUTHOR]