Hydrothermal synthesis and crystal structure of AlSO4(OH): A titanite-group member

Alan J. Anderson, Hexiong Yang, Robert T Downs

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Aluminum hydroxysulfate, AlSO4(OH), is postulated to play a vital role in controlling the solubility of aluminum in sulfate-rich acidic soils and ground waters, but it has not yet been confirmed in nature. This study reports the synthesis of an AlSO4(OH) crystal at 700°C and ∼1.0 GPa in a hydrothermal diamond-anvil cell from a mixture of 95% H2SO4 and Al2O3 powder and its structure determination from single-crystal X-ray diffraction data. AlSO4(OH) is monoclinic with space group C2/c and unit-cell parameters a = 7.1110(4), b = 7.0311(5), c = 7.0088(4) A˚, β = 119.281(2)°, and V = 305.65(3) A˚3. Its crystal structure is characterized by kinked chains of corner-sharing AlO6 octahedra that run parallel to the c-axis. These chains are linked together by SO4 tetrahedra and hydrogen bonds, forming an octahedral-tetrahedral framework. Except for the numbers and positions of H atoms, AlSO4(OH) is isostructural with the kieserite-type minerals, a subgroup of the titanite group of minerals. A comparison of powder X-ray diffraction patterns indicates that our AlSO4(OH) is the same as that obtained by Shanks et al. (1981) through hydrolysis of Al2(SO4)3 solutions at temperatures above 310°C. To date, AlSO4(OH) has been synthesized only at temperatures above 290°C, implying that it may not stable in low-temperature environments, such as acidic soils and mine waters. The possible environments to find Al(OH)SO4 may include places where sulfur-rich magma-derived fluids react with aluminous rocks under elevated temperature and pressure, and on Venus where a sulfur-rich atmosphere interacts with surface rocks at temperatures above 400°C.

Original languageEnglish (US)
Pages (from-to)330-333
Number of pages4
JournalAmerican Mineralogist
Volume100
Issue number1
DOIs
StatePublished - Jan 1 2015

Fingerprint

Hydrothermal synthesis
titanite
crystal structure
Crystal structure
synthesis
soils
Aluminum
sulfur
Sulfur
aluminum
temperature
low temperature environments
X-ray diffraction
minerals
joints (junctions)
Minerals
rocks
crystal
diamond anvil cell
Temperature

Keywords

  • AlSO(OH)
  • Aluminum hydroxysulfate
  • Crystal structure
  • High temperature
  • Raman spectroscopy
  • X-ray diffraction

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

Hydrothermal synthesis and crystal structure of AlSO4(OH) : A titanite-group member. / Anderson, Alan J.; Yang, Hexiong; Downs, Robert T.

In: American Mineralogist, Vol. 100, No. 1, 01.01.2015, p. 330-333.

Research output: Contribution to journalArticle

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N2 - Aluminum hydroxysulfate, AlSO4(OH), is postulated to play a vital role in controlling the solubility of aluminum in sulfate-rich acidic soils and ground waters, but it has not yet been confirmed in nature. This study reports the synthesis of an AlSO4(OH) crystal at 700°C and ∼1.0 GPa in a hydrothermal diamond-anvil cell from a mixture of 95% H2SO4 and Al2O3 powder and its structure determination from single-crystal X-ray diffraction data. AlSO4(OH) is monoclinic with space group C2/c and unit-cell parameters a = 7.1110(4), b = 7.0311(5), c = 7.0088(4) A˚, β = 119.281(2)°, and V = 305.65(3) A˚3. Its crystal structure is characterized by kinked chains of corner-sharing AlO6 octahedra that run parallel to the c-axis. These chains are linked together by SO4 tetrahedra and hydrogen bonds, forming an octahedral-tetrahedral framework. Except for the numbers and positions of H atoms, AlSO4(OH) is isostructural with the kieserite-type minerals, a subgroup of the titanite group of minerals. A comparison of powder X-ray diffraction patterns indicates that our AlSO4(OH) is the same as that obtained by Shanks et al. (1981) through hydrolysis of Al2(SO4)3 solutions at temperatures above 310°C. To date, AlSO4(OH) has been synthesized only at temperatures above 290°C, implying that it may not stable in low-temperature environments, such as acidic soils and mine waters. The possible environments to find Al(OH)SO4 may include places where sulfur-rich magma-derived fluids react with aluminous rocks under elevated temperature and pressure, and on Venus where a sulfur-rich atmosphere interacts with surface rocks at temperatures above 400°C.

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