X-ray diffraction reveals two structural transitions in szomolnokite
Abstract
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). Atmore »
- Authors:
-
[1];
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- California Institute of Technology (CalTech), Pasadena, CA (United States); Johns Hopkins Univ., Baltimore, MD (United States)
- Univ. of Illinois, Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Univ. of Illinois, Chicago, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP)
- OSTI Identifier:
- 1959831
- Grant/Contract Number:
- NA0003975; AC98-06CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- American Mineralogist
- Additional Journal Information:
- Journal Volume: 108; Journal Issue: 3; Journal ID: ISSN 0003-004X
- Publisher:
- Mineralogical Society of America
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES; szomolnokite; hydrated sulfates; high pressure; X-ray diffraction; infrared spectroscopy; equation of state
Citation Formats
Pardo, Olivia S., Dobrosavljevic, Vasilije V., Perez, Tyler, Sturhahn, Wolfgang, Liu, Zhenxian, Rossman, George R., and Jackson, Jennifer M. X-ray diffraction reveals two structural transitions in szomolnokite. United States: N. p., 2023.
Web. doi:10.2138/am-2022-8147.
Pardo, Olivia S., Dobrosavljevic, Vasilije V., Perez, Tyler, Sturhahn, Wolfgang, Liu, Zhenxian, Rossman, George R., & Jackson, Jennifer M. X-ray diffraction reveals two structural transitions in szomolnokite. United States. https://doi.org/10.2138/am-2022-8147
Pardo, Olivia S., Dobrosavljevic, Vasilije V., Perez, Tyler, Sturhahn, Wolfgang, Liu, Zhenxian, Rossman, George R., and Jackson, Jennifer M. Wed .
"X-ray diffraction reveals two structural transitions in szomolnokite". United States. https://doi.org/10.2138/am-2022-8147. https://www.osti.gov/servlets/purl/1959831.
@article{osti_1959831,
title = {X-ray diffraction reveals two structural transitions in szomolnokite},
author = {Pardo, Olivia S. and Dobrosavljevic, Vasilije V. and Perez, Tyler and Sturhahn, Wolfgang and Liu, Zhenxian and Rossman, George R. and Jackson, Jennifer M.},
abstractNote = {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. Furthermore, 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.},
doi = {10.2138/am-2022-8147},
journal = {American Mineralogist},
number = 3,
volume = 108,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2023},
month = {Wed Mar 01 00:00:00 EST 2023}
}
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