Sulfate-containing calcite: Crystallographic characterization of natural and synthetic materials

Taiga Okumura, Hye Jin Kim, Jin Wook Kim, Toshihiro Kogure

Research output: Contribution to journalArticle

Abstract

Natural and synthetic sulfate-containing calcite crystals were characterized using electron beam and X-ray techniques. Natural calcite was collected from LaDuke hot springs near Yellowstone National Park, USA. Sulfur was found to be the predominant foreign element in the calcite, with a mean atomic S/Ca ratio of ca. 5%. X-ray microanalysis with a transmission electron microscope (TEM) indicated that sulfur was homogeneously incorporated in the crystals. The chemical species of sulfur was identified as sulfate ions (SO2- 4 ) by X-ray photoelectron spectroscopy. Powder X-ray diffraction revealed the c-length of the calcite to be longer (ca. 0.25%) than that of geological pure calcite (Iceland spar), whereas the a-length was slightly shorter. Selected-area electron diffraction patterns from TEM showed extra reflections resembling those previously reported as c-reflections, corresponding to a super-cell with doubled ai-axes without breaking the three-fold symmetry. In order to investigate the origin of these crystallographic features in LaDuke calcite, synthetic calcite was precipitated from sulfate ion solutions with different concentrations. The sulfur content in the synthetic calcite crystals increased with the concentration of sulfate ions in the solutions and reached saturation at 4 at%. The synthetic calcite containing sulfate ions showed similar characteristics to those of natural LaDuke calcite, namely a longer c-length and the appearance of superstructure reflections, indicating that these characteristics are induced by the incorporation of SO2- 4 ions in the calcite lattice.

Original languageEnglish
Pages (from-to)929-937
Number of pages9
JournalEuropean Journal of Mineralogy
Volume30
Issue number5
DOIs
Publication statusPublished - 2018 Sep

Fingerprint

Calcium Carbonate
Sulfates
calcite
sulfate
Sulfur
Ions
sulfur
ion
electron
crystal
Crystals
synthetic material
natural material
Electron microscopes
Hot springs
Saturation (materials composition)
X rays
supercell
thermal spring
Electron diffraction

All Science Journal Classification (ASJC) codes

  • Geochemistry and Petrology

Cite this

Okumura, Taiga ; Kim, Hye Jin ; Kim, Jin Wook ; Kogure, Toshihiro. / Sulfate-containing calcite : Crystallographic characterization of natural and synthetic materials. In: European Journal of Mineralogy. 2018 ; Vol. 30, No. 5. pp. 929-937.
@article{47db1808e8494f46bf471a79ef96a4ec,
title = "Sulfate-containing calcite: Crystallographic characterization of natural and synthetic materials",
abstract = "Natural and synthetic sulfate-containing calcite crystals were characterized using electron beam and X-ray techniques. Natural calcite was collected from LaDuke hot springs near Yellowstone National Park, USA. Sulfur was found to be the predominant foreign element in the calcite, with a mean atomic S/Ca ratio of ca. 5{\%}. X-ray microanalysis with a transmission electron microscope (TEM) indicated that sulfur was homogeneously incorporated in the crystals. The chemical species of sulfur was identified as sulfate ions (SO2- 4 ) by X-ray photoelectron spectroscopy. Powder X-ray diffraction revealed the c-length of the calcite to be longer (ca. 0.25{\%}) than that of geological pure calcite (Iceland spar), whereas the a-length was slightly shorter. Selected-area electron diffraction patterns from TEM showed extra reflections resembling those previously reported as c-reflections, corresponding to a super-cell with doubled ai-axes without breaking the three-fold symmetry. In order to investigate the origin of these crystallographic features in LaDuke calcite, synthetic calcite was precipitated from sulfate ion solutions with different concentrations. The sulfur content in the synthetic calcite crystals increased with the concentration of sulfate ions in the solutions and reached saturation at 4 at{\%}. The synthetic calcite containing sulfate ions showed similar characteristics to those of natural LaDuke calcite, namely a longer c-length and the appearance of superstructure reflections, indicating that these characteristics are induced by the incorporation of SO2- 4 ions in the calcite lattice.",
author = "Taiga Okumura and Kim, {Hye Jin} and Kim, {Jin Wook} and Toshihiro Kogure",
year = "2018",
month = "9",
doi = "10.1127/ejm/2018/0030-2772",
language = "English",
volume = "30",
pages = "929--937",
journal = "European Journal of Mineralogy",
issn = "0935-1221",
publisher = "E. Schweizerbart'sche Verlagsbuchhandlung",
number = "5",

}

Sulfate-containing calcite : Crystallographic characterization of natural and synthetic materials. / Okumura, Taiga; Kim, Hye Jin; Kim, Jin Wook; Kogure, Toshihiro.

In: European Journal of Mineralogy, Vol. 30, No. 5, 09.2018, p. 929-937.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Sulfate-containing calcite

T2 - Crystallographic characterization of natural and synthetic materials

AU - Okumura, Taiga

AU - Kim, Hye Jin

AU - Kim, Jin Wook

AU - Kogure, Toshihiro

PY - 2018/9

Y1 - 2018/9

N2 - Natural and synthetic sulfate-containing calcite crystals were characterized using electron beam and X-ray techniques. Natural calcite was collected from LaDuke hot springs near Yellowstone National Park, USA. Sulfur was found to be the predominant foreign element in the calcite, with a mean atomic S/Ca ratio of ca. 5%. X-ray microanalysis with a transmission electron microscope (TEM) indicated that sulfur was homogeneously incorporated in the crystals. The chemical species of sulfur was identified as sulfate ions (SO2- 4 ) by X-ray photoelectron spectroscopy. Powder X-ray diffraction revealed the c-length of the calcite to be longer (ca. 0.25%) than that of geological pure calcite (Iceland spar), whereas the a-length was slightly shorter. Selected-area electron diffraction patterns from TEM showed extra reflections resembling those previously reported as c-reflections, corresponding to a super-cell with doubled ai-axes without breaking the three-fold symmetry. In order to investigate the origin of these crystallographic features in LaDuke calcite, synthetic calcite was precipitated from sulfate ion solutions with different concentrations. The sulfur content in the synthetic calcite crystals increased with the concentration of sulfate ions in the solutions and reached saturation at 4 at%. The synthetic calcite containing sulfate ions showed similar characteristics to those of natural LaDuke calcite, namely a longer c-length and the appearance of superstructure reflections, indicating that these characteristics are induced by the incorporation of SO2- 4 ions in the calcite lattice.

AB - Natural and synthetic sulfate-containing calcite crystals were characterized using electron beam and X-ray techniques. Natural calcite was collected from LaDuke hot springs near Yellowstone National Park, USA. Sulfur was found to be the predominant foreign element in the calcite, with a mean atomic S/Ca ratio of ca. 5%. X-ray microanalysis with a transmission electron microscope (TEM) indicated that sulfur was homogeneously incorporated in the crystals. The chemical species of sulfur was identified as sulfate ions (SO2- 4 ) by X-ray photoelectron spectroscopy. Powder X-ray diffraction revealed the c-length of the calcite to be longer (ca. 0.25%) than that of geological pure calcite (Iceland spar), whereas the a-length was slightly shorter. Selected-area electron diffraction patterns from TEM showed extra reflections resembling those previously reported as c-reflections, corresponding to a super-cell with doubled ai-axes without breaking the three-fold symmetry. In order to investigate the origin of these crystallographic features in LaDuke calcite, synthetic calcite was precipitated from sulfate ion solutions with different concentrations. The sulfur content in the synthetic calcite crystals increased with the concentration of sulfate ions in the solutions and reached saturation at 4 at%. The synthetic calcite containing sulfate ions showed similar characteristics to those of natural LaDuke calcite, namely a longer c-length and the appearance of superstructure reflections, indicating that these characteristics are induced by the incorporation of SO2- 4 ions in the calcite lattice.

UR - http://www.scopus.com/inward/record.url?scp=85056590313&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85056590313&partnerID=8YFLogxK

U2 - 10.1127/ejm/2018/0030-2772

DO - 10.1127/ejm/2018/0030-2772

M3 - Article

AN - SCOPUS:85056590313

VL - 30

SP - 929

EP - 937

JO - European Journal of Mineralogy

JF - European Journal of Mineralogy

SN - 0935-1221

IS - 5

ER -