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Title: The compression behavior of blödite at low and high temperature up to ~10GPa: Implications for the stability of hydrous sulfates on icy planetary bodies

Abstract

Recent satellite inferences of hydrous sulfates as recurrent minerals on the surface of icy planetary bodies link with the potential mineral composition of their interior. Blödite, a mixed Mg-Na sulfate, is here taken as representative mineral of icy satellites surface to investigate its crystal structure and stability at conditions of the interior of icy bodies. To this aim we performed in situ synchrotron angle-dispersive X-ray powder diffraction experiments on natural blödite at pressures up to ~10.4 GPa and temperatures from ~118.8 K to ~490.0 K using diamond anvil cell technique to investigate the compression behavior and establish a low-to-high temperature equation of state that can be used as reference when modeling the interior of sulfate-rich icy satellites such as Ganymede. The experimentally determined volume expansivity, α, varies from 7.6 (7) 10 -5 K -1 at 0.0001 GPa (from 118.8 to 413.15 K) to 2.6 (3) 10 -5 K -1 at 10 GPa (from 313.0 to 453.0 K) with a δα/δ P coefficient = -5.6(9)10 -6 GPa -1 K -1. The bulk modulus calculated from the least squares fitting of P-V data on the isotherm at 413 K using a second-order Birch - Murnaghan equation of state is 38(5) GPa, whichmore » gives the value of δK/δ T equal to 0.01(5) GPa K -1. The thermo-baric behavior of blödite appears strongly anisotropic with c lattice parameter being more deformed with respect to a and b. Thermogravimetric analyses performed at ambient pressure showed three endotherms at 413 K, 533 K and 973 K with weight losses of approximately 11%, 11% and 43% caused by partial dehydration, full dehydration and sulfate decomposition respectively. Interestingly, no clear evidence of dehydration was observed up to ~453 K and ~10.4 GPa, suggesting that pressure acts to stabilize the crystalline structure of blödite. The data collected allow to write the following equation of state, V(P, T) = V 0[1 + 7.6(7)10 - 5ΔT - 0.026(3)P - 5.6(9)10 - 6PΔT-6.6(9)10 - 6PΔT)] from which the density of blödite can be determined at conditions of the mantle of the large icy satellites of Jupiter. Blödite has higher density, bulk modulus and thermal stability than similar hydrous sulfates (e.g. mirabilite and epsomite) implying, therefore, a different contribution of these minerals to the extent of deep oceans in icy planets and their distribution over the local geotherms.« less

Authors:
ORCiD logo; ORCiD logo; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1340734
Resource Type:
Journal Article
Resource Relation:
Journal Name: Icarus; Journal Volume: 285
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; 58 GEOSCIENCES; Blödite; High pressure; Icy satellite; Sulfate; In situ angle-dispersive X-ray diffraction; Synchrotron

Citation Formats

Comodi, Paola, Stagno, Vincenzo, Zucchini, Azzurra, Fei, Yingwei, and Prakapenka, Vitali. The compression behavior of blödite at low and high temperature up to ~10GPa: Implications for the stability of hydrous sulfates on icy planetary bodies. United States: N. p., 2017. Web. doi:10.1016/j.icarus.2016.11.032.
Comodi, Paola, Stagno, Vincenzo, Zucchini, Azzurra, Fei, Yingwei, & Prakapenka, Vitali. The compression behavior of blödite at low and high temperature up to ~10GPa: Implications for the stability of hydrous sulfates on icy planetary bodies. United States. doi:10.1016/j.icarus.2016.11.032.
Comodi, Paola, Stagno, Vincenzo, Zucchini, Azzurra, Fei, Yingwei, and Prakapenka, Vitali. Wed . "The compression behavior of blödite at low and high temperature up to ~10GPa: Implications for the stability of hydrous sulfates on icy planetary bodies". United States. doi:10.1016/j.icarus.2016.11.032.
@article{osti_1340734,
title = {The compression behavior of blödite at low and high temperature up to ~10GPa: Implications for the stability of hydrous sulfates on icy planetary bodies},
author = {Comodi, Paola and Stagno, Vincenzo and Zucchini, Azzurra and Fei, Yingwei and Prakapenka, Vitali},
abstractNote = {Recent satellite inferences of hydrous sulfates as recurrent minerals on the surface of icy planetary bodies link with the potential mineral composition of their interior. Blödite, a mixed Mg-Na sulfate, is here taken as representative mineral of icy satellites surface to investigate its crystal structure and stability at conditions of the interior of icy bodies. To this aim we performed in situ synchrotron angle-dispersive X-ray powder diffraction experiments on natural blödite at pressures up to ~10.4 GPa and temperatures from ~118.8 K to ~490.0 K using diamond anvil cell technique to investigate the compression behavior and establish a low-to-high temperature equation of state that can be used as reference when modeling the interior of sulfate-rich icy satellites such as Ganymede. The experimentally determined volume expansivity, α, varies from 7.6 (7) 10-5 K-1 at 0.0001 GPa (from 118.8 to 413.15 K) to 2.6 (3) 10-5 K-1 at 10 GPa (from 313.0 to 453.0 K) with a δα/δP coefficient = -5.6(9)10-6 GPa-1 K-1. The bulk modulus calculated from the least squares fitting of P-V data on the isotherm at 413 K using a second-order Birch - Murnaghan equation of state is 38(5) GPa, which gives the value of δK/δT equal to 0.01(5) GPa K-1. The thermo-baric behavior of blödite appears strongly anisotropic with c lattice parameter being more deformed with respect to a and b. Thermogravimetric analyses performed at ambient pressure showed three endotherms at 413 K, 533 K and 973 K with weight losses of approximately 11%, 11% and 43% caused by partial dehydration, full dehydration and sulfate decomposition respectively. Interestingly, no clear evidence of dehydration was observed up to ~453 K and ~10.4 GPa, suggesting that pressure acts to stabilize the crystalline structure of blödite. The data collected allow to write the following equation of state, V(P, T) = V0[1 + 7.6(7)10 - 5ΔT - 0.026(3)P - 5.6(9)10 - 6PΔT-6.6(9)10 - 6PΔT)] from which the density of blödite can be determined at conditions of the mantle of the large icy satellites of Jupiter. Blödite has higher density, bulk modulus and thermal stability than similar hydrous sulfates (e.g. mirabilite and epsomite) implying, therefore, a different contribution of these minerals to the extent of deep oceans in icy planets and their distribution over the local geotherms.},
doi = {10.1016/j.icarus.2016.11.032},
journal = {Icarus},
number = ,
volume = 285,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}
  • Recent satellite inferences of hydrous sulfates as recurrent minerals on the surface of icy planetary bodies link with the potential mineral composition of their interior. Blödite, a mixed Mg-Na sulfate, is here taken as representative mineral of icy satellites surface to investigate its crystal structure and stability at conditions of the interior of icy bodies. To this aim we performed in situ synchrotron angle-dispersive X-ray powder diffraction experiments on natural blödite at pressures up to ~10.4 GPa and temperatures from ~118.8 K to ~490.0 K using diamond anvil cell technique to investigate the compression behavior and establish a low-to-high temperaturemore » equation of state that can be used as reference when modeling the interior of sulfate-rich icy satellites such as Ganymede.« less
  • Compressive stress-strain curves for several types of polycrystalline MgO specimens were correlated with those for single crystals and analyzed as a function of grain size and grain-boundary character at 1200 and 1400 C for several strain rates. The results for fully dense specimens were explained in terms of grain-boundary sliding and intergranular separation in addition to slip. The modification of grain-boundary nature concurrent with heat treatment for grain growth, caused by residual LUF, was associated with enhanced grain-boundary sliding and intergranular separation. For grain sizes <30 {micro}m, it was concluded that the von Miss criteria for ductility could be relaxedmore » by the Occurrence of dislocation climb and, to a limited extent, by intergranular separation. Yield drop corresponding to dislocation multiplication occurred when grain-boundary sliding was initially promoted. Specimens with a liquid phase of adequate viscosity also indicated plasticity accompanied by high strength. Specimens with clean grain boundaries exhibited ductility and normal strain hardening with no intergranular separation.« less
  • The stability of the BaCuO{sub {ital x}} ({ital x}{ge}2) phase has been mapped over a wide range of temperature (300--1100 {degree}C) and oxygen pressure (10{sup {minus}5}--10{sup 3} bar). At ambient pressure and temperature, BaCuO{sub {ital x}} is found to be in a metastable state: long annealing at 450 {degree}C tends to decompose the phase into Ba{sub 2}Cu{sub 3}O{sub 5} and BaO{sub 2}. Having obtained the phase stability domain in the [{ital T},{ital p}(O){sub 2}] plane we were able to prepare single-phase samples of BaCuO{sub {ital x}} with different oxygen contents suitable for precise intrinsic thermodynamical measurements. We show that themore » behavior of the low-temperature specific heat (1.1{le}{ital T}{le}32 K) and its dependence on the magnetic field (0{le}{ital B}{le}14 T) may be understood by taking into account a many-level magnetic system directly related to the Cu{sub 6}O{sub 12} and Cu{sub 18}O{sub 24} structural blocks of BaCuO{sub {ital x}}. Depending on the oxygen concentration, competition between antiferromagnetic (AF) ordering and the many-level system is observed. With increasing oxygen content, the Neel temperature decreases whereas amplitude of the many-level system increases. The zero-field AF transition belongs to the three-dimensional isotropic Heisenberg universality class.« less