skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Experimental Evidence for Non-Redox Transformation Between Magnetite and Hermatite Under H2-Rich Hydrothermal Conditions

Abstract

Transformations of magnetite (Fe{sup II}Fe{sub 2}{sup III}O{sub 4}) to hematite (Fe{sub 2}{sup III}O{sub 3}) (and vice versa) have been thought by many scientists and engineers to require molecular O{sub 2} and/or H{sub 2}. Thus, the presence of magnetite and/or hematite in rocks has been linked to a specific oxidation environment. However, the availability of reductants or oxidants in many geologic and industrial environments appears to have been too low to account for the transformations of iron oxides through redox reactions. Here, we report the results of hydrothermal experiments in mildly acidic and H{sub 2}-rich aqueous solutions at 150 C, which demonstrate that transformations of magnetite to hematite, and hematite to magnetite, occur rapidly without involving molecular O{sub 2} or H{sub 2}: Fe{sub 3}O{sub 4}(Mt) + 2H{sub (aq)}{sup +} {leftrightarrow} Fe{sub 2}O{sub 3}(Hm) + Fe{sub (aq)}{sup 2+} + H{sub 2}O The transformation products are chemically and structurally homogeneous, and typically occur as euhedral single crystals much larger than the precursor minerals. This suggests that, in addition to the expected release of aqueous ferrous species to solution, the transformations involve release of aqueous ferric species from the precursor oxides to the solution, which reprecipitate without being reduced by H{sub 2}. These redox-independentmore » transformations may have been responsible for the formation of some iron oxides in natural systems, such as high-grade hematite ores that developed from Banded Iron Formations (BIFs), hematite-rich deposits formed on Mars, corrosion products in power plants and other industrial systems.« less

Authors:
 [1];  [1];  [2];  [3];  [2]
  1. Pennsylvania State University
  2. ORNL
  3. {Larry} M [ORNL
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
930894
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Earth and Planetary Science Letters; Journal Volume: 257; Journal Issue: 2
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; HEMATITE; MAGNETITE; PHASE TRANSFORMATIONS; HYDROTHERMAL ALTERATION; REDOX REACTIONS; GEOCHEMISTRY; CHEMICAL REACTION KINETICS

Citation Formats

Otake, Tsubasa, Ohmoto, Hiroshi, Wesolowski, David J, Anovitz, Lawrence, and Allard Jr, Lawrence Frederick. Experimental Evidence for Non-Redox Transformation Between Magnetite and Hermatite Under H2-Rich Hydrothermal Conditions. United States: N. p., 2007. Web. doi:10.1016/j.epsl.2007.02.022.
Otake, Tsubasa, Ohmoto, Hiroshi, Wesolowski, David J, Anovitz, Lawrence, & Allard Jr, Lawrence Frederick. Experimental Evidence for Non-Redox Transformation Between Magnetite and Hermatite Under H2-Rich Hydrothermal Conditions. United States. doi:10.1016/j.epsl.2007.02.022.
Otake, Tsubasa, Ohmoto, Hiroshi, Wesolowski, David J, Anovitz, Lawrence, and Allard Jr, Lawrence Frederick. Mon . "Experimental Evidence for Non-Redox Transformation Between Magnetite and Hermatite Under H2-Rich Hydrothermal Conditions". United States. doi:10.1016/j.epsl.2007.02.022.
@article{osti_930894,
title = {Experimental Evidence for Non-Redox Transformation Between Magnetite and Hermatite Under H2-Rich Hydrothermal Conditions},
author = {Otake, Tsubasa and Ohmoto, Hiroshi and Wesolowski, David J and Anovitz, Lawrence and Allard Jr, Lawrence Frederick},
abstractNote = {Transformations of magnetite (Fe{sup II}Fe{sub 2}{sup III}O{sub 4}) to hematite (Fe{sub 2}{sup III}O{sub 3}) (and vice versa) have been thought by many scientists and engineers to require molecular O{sub 2} and/or H{sub 2}. Thus, the presence of magnetite and/or hematite in rocks has been linked to a specific oxidation environment. However, the availability of reductants or oxidants in many geologic and industrial environments appears to have been too low to account for the transformations of iron oxides through redox reactions. Here, we report the results of hydrothermal experiments in mildly acidic and H{sub 2}-rich aqueous solutions at 150 C, which demonstrate that transformations of magnetite to hematite, and hematite to magnetite, occur rapidly without involving molecular O{sub 2} or H{sub 2}: Fe{sub 3}O{sub 4}(Mt) + 2H{sub (aq)}{sup +} {leftrightarrow} Fe{sub 2}O{sub 3}(Hm) + Fe{sub (aq)}{sup 2+} + H{sub 2}O The transformation products are chemically and structurally homogeneous, and typically occur as euhedral single crystals much larger than the precursor minerals. This suggests that, in addition to the expected release of aqueous ferrous species to solution, the transformations involve release of aqueous ferric species from the precursor oxides to the solution, which reprecipitate without being reduced by H{sub 2}. These redox-independent transformations may have been responsible for the formation of some iron oxides in natural systems, such as high-grade hematite ores that developed from Banded Iron Formations (BIFs), hematite-rich deposits formed on Mars, corrosion products in power plants and other industrial systems.},
doi = {10.1016/j.epsl.2007.02.022},
journal = {Earth and Planetary Science Letters},
number = 2,
volume = 257,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Transformations of magnetite (Fe{sup II}Fe{sub 2}{sup III}O{sub 4}) to hematite (Fe{sub 2}{sup III}O{sub 3}) (and vice versa) have been thought by many scientists and engineers to require molecular O{sub 2} and/or H{sub 2}. Thus, the presence of magnetite and/or hematite in rocks has been linked to a specific oxidation environment. However, the availability of reductants or oxidants in many geologic and industrial environments appears to have been too low to account for the transformations of iron oxides through redox reactions. Here, we report the results of hydrothermal experiments in mildly acidic and H{sub 2}-rich aqueous solutions at 150 C, whichmore » demonstrate that transformations of magnetite to hematite, and hematite to magnetite, occur rapidly without involving molecular O{sub 2} or H{sub 2}: Fe{sub 3}O{sub 4}(Mt) + 2H{sub (aq)}{sup +} {leftrightarrow} Fe{sub 2}O{sub 3}(Hm) + Fe{sub (aq)}{sup 2+} + H{sub 2}O. The transformation products are chemically and structurally homogeneous, and typically occur as euhedral single crystals much larger than the precursor minerals. This suggests that, in addition to the expected release of aqueous ferrous species to solution, the transformations involve release of aqueous ferric species from the precursor oxides to the solution, which reprecipitate without being reduced by H{sub 2}. These redox-independent transformations may have been responsible for the formation of some iron oxides in natural systems, such as high-grade hematite ores that developed from Banded Iron Formations (BIFs), hematite-rich deposits formed on Mars, corrosion products in power plants and other industrial systems.« less
  • The phase transformation mechanism of zeolite NaY under alkaline hydrothermal conditions was investigated by UV Raman spectroscopy, X-ray diffraction, X-ray fluorescence and scanning electron microscopy techniques. The results revealed that the products and transformation rate are dependent on the alkalinities. All of the starting and resulting zeolites are constructed with the 4-ring and 6-ring secondary building units. The products have lower Si/Al ratio, higher framework density and smaller pore size, which are more stable under alkaline hydrothermal condition. During the phase transformation the fragments of faujasite are formed, then the fragments combine to form different zeolites depending on basicity. Zeolitemore » NaY crystals are consumed as the reservoir for the transformation products during the recrystallization process. For the first time, a 4-membered ring intermediate was found at the early stage of the recrystallization process. A cooperative interaction of liquid and solid phases is required for inducing the phase transformation. - Graphical Abstract: Phase transformation of NaY zeolite under alkaline hydrothermal condition is achieved by the cooperative interaction of the liquid and solid phases. A 4-membered ring species is an intermediate for recrystallization process. Highlights: • The products and transformation rate are dependent on the alkalinity. • A 4-membered ring species is an intermediate for recrystallization process. • A cooperative interaction of liquid and solid phases is required.« less
  • Vibrational and rotational experimental temperatures of molecular hydrogen obtained by Coherent Anti-Stokes Spectroscopy (CARS) in Radiofrequency Inductive Plasmas have been analyzed and interpreted in terms of vibration, electron, dissociation-recombination and attachment kinetics. The analysis clarifies the role of atomic hydrogen and its heterogeneous recombination in affecting the vibrational content of the molecules.