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Cited by 14Chemical and Physical Properties in Aqueous SolutionsCrystallization and Solubility StudiesPhase Equilibria and Thermodynamics

Solubility Model for Ferrous Iron Hydroxide, Hibbingite, Siderite, and Chukanovite in High Saline Solutions of Sodium Chloride, Sodium Sulfate, and Sodium Carbonate

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Kim, Sungtae, Marrs, Cassandra, Nemer, Martin, Je-Hun Jang, Jay·2017·ACS Earth and Space Chemistry
DOI 10.1021/acsearthspacechem.7b00065
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Abstract

A solubility model is presented for ferrous iron hydroxide (Fe(OH) 2 (s)), hibbingite (Fe 2 Cl(OH) 3 (s)), siderite (FeCO 3 (s)), and chukanovite (Fe 2 CO 3 (OH) 2 (s)). The Pitzer activity coefficient equation was utilized in developing the model to account for the excess free energies of aqueous species in the background solutions of high ionic strength. Solubility limiting minerals were analyzed before and after experiments using X-ray diffraction. Formation of Fe(OH) 2 (s) was observed in the experiments that were initiated with Fe 2 Cl(OH) 3 (s) in Na 2 SO 4 solution. Coexistence of siderite and chukanovite was observed in the experiments in Na 2 CO 3 + NaCl solutions. Two equilibrium constants that had been reported by us for the dissolution of Fe(OH) 2 (s) and Fe 2 Cl(OH) 3 (s) (Nemer et al.) were rederived in this paper, using newer thermodynamic data selected from the literature to maintain internal consistency of the series of our data analyses in preparation, including this paper. Three additional equilibrium constants for the following reactions were determined in this paper: dissolution of siderite and chukanovite and dissociation of the aqueous species Fe(CO 3 ) 2 –2 . Five Pitzer interaction parameters were derived in this paper: β (0), β (1), and C φ parameters for the species pair Fe +2 /SO 4 –2; β (0) and β (1) parameters for the species pair Na + /Fe(CO 3 ) 2 –2 . Our model predicts that, among the four inorganic ferrous iron minerals, siderite is the stable mineral in two WIPP-related brines (WIPP: Waste Isolation Pilot Plant), i.e., GWB and ERDA6 (Brush and Domski), and the electrochemical equilibrium between elemental iron and siderite provides a low oxygen fugacity (10 –91.2 atm) that can keep the actinides at their lowest oxidation states. (Nemer et al., Brush and Domski; references numbered 1 and 2 in the main text).

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Crossref · 10.1021/acsearthspacechem.7b00065

Cites

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  • In a carbonate-chloride system, chukanovite is formed in a low-carbonate concentration condition, and siderite is formed in a carbonate-enriched condition.

    “Nonetheless, the solubility model under a carbonate-chloride system was reported, chukanovite was formed in a low-carbonate concentration condition, and siderite was formed in carbonate-enriched condition [33].”

    From Controls on the Formation and Stability of Siderite (FeCO3) and Chukanovite (Fe2(CO3)(OH)2) in Reducing Environment (2020) · cites this paper as [33]

    The Conclusion (page unavailable) presents stability fields as functions of bicarbonate and chloride activities, and Reaction 1 describes siderite converting to chukanovite. But the XRD results (section labeled “Moog et al. (2004),” page unavailable) found both minerals at every tested carbonate concentration; they do not show chukanovite forming only under low-carbonate conditions and siderite forming under carbonate-enriched conditions. (LLM, conf=0.85)

    Experimental — accuracy not yet measured

  • Once carbonate minerals form, pH decreases because carbonate ions are consumed, which could enhance dissolution of chukanovite by proton.

    “Moreover, once carbonate minerals were formed in the system, the pH level would be decreased because the carbonate ions were consumed, which could enhance the dissolution of chukanovite by proton [33].”

    From Controls on the Formation and Stability of Siderite (FeCO3) and Chukanovite (Fe2(CO3)(OH)2) in Reducing Environment (2020) · cites this paper as [33]

    In the section labeled “Moog et al. (2004)” (page unavailable), the paper links an observed pH decrease to siderite forming chukanovite and states that this reaction produces H+. It also gives a reaction in which chukanovite dissolves by consuming H+. It does not attribute the pH decrease to consumption of carbonate ions; its stated formation reaction produces bicarbonate. (LLM, conf=0.88)

    Experimental — accuracy not yet measured

  • The concentration of ferrous iron and bicarbonate in solution would increase due to dissolution of chukanovite.

    “The concentration of ferrous iron and bicarbonate in the solution would increase due to the dissolution of chukanovite [33].”

    From Controls on the Formation and Stability of Siderite (FeCO3) and Chukanovite (Fe2(CO3)(OH)2) in Reducing Environment (2020) · cites this paper as [33]

  • Chukanovite is more stable under a lower DIC concentration, whereas siderite is more stable in high DIC conditions.

    “Chukanovite is in a more stable phase under a lower DIC concentration, whereas siderite is more stable in high DIC conditions, according to the stability diagram of ferrous minerals (siderite, chukanovite, ferrous iron hydroxide, and hibbingite) [33] that supports a low estimated proportion of siderite in low DIC conditions.”

    From Controls on the Formation and Stability of Siderite (FeCO3) and Chukanovite (Fe2(CO3)(OH)2) in Reducing Environment (2020) · cites this paper as [33]

  • The boundary of chukanovite and siderite in the stability diagram is determined only by the activity of bicarbonate.

    “The fact that the boundary of chukanovite and siderite in the stability diagram is determined only by the activity of bicarbonate [33]”

    From Controls on the Formation and Stability of Siderite (FeCO3) and Chukanovite (Fe2(CO3)(OH)2) in Reducing Environment (2020) · cites this paper as [33]

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Cites

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1 of the 31 references couldn’t be matched to a known paper.

Research works printed but not linked: 4

  1. [16]16. K. Z. Phys. Chem. (Muenchen, Ger.) English Translation; INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY AND CHEMICAL PHYSICS (No abbreviation available for the translated journal title from http://cassi.cas.org/search.jsp), 2004, 218, 1063-1087.
  2. [26]26. Stumm, W.; Morgan, J.J. Aquatic Chemistry, 3 rd Edition, 1996, John Wiley and Sons.
  3. [34]34. Charykova, M. V.; Krivovichev, V. G.; Depmeier, W. Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores. II. Systems M1, M2//SO4 2--H2O (M1, M2 = Fe 2+ , Fe 3+ , Cu 2+ , Zn 2+ , Pb 2+ , Ni 2+ , Co 2+ , H + ) at 25 °C. Geol. Ore Deposits (Transl. of Geol. Rudn. Mestorozhd.), 2010, 52 (8): 701-710.
  4. [36]36. Ptacek, C. J. Experimental Determination of Siderite Solubility in High Ionic-Strength Aqueous Solutions, 1992, University of Waterloo, Ph.D. Thesis.

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Related

Authors
Kim, S., Marrs, C., Nemer, M., & Je-Hun Jang, J.
Affiliations
  • Sandia National Laboratories, 4100 National Parks Highway, Carlsbad, New Mexico 88220, United States
  • Sandia National Laboratories (US)
ORCID
Je-Hun Jang, Jay
Venue
ACS Earth and Space Chemistry
Publisher
American Chemical Society (ACS)
Published
2017-11-20
Volume
1
Issue
10
Pages
647-663
ISSN
2472-3452 (ISSN-L)
DOI
10.1021/acsearthspacechem.7b00065
OpenAlex
W2770240350
Cited by
14
References
31
Citations by year
2026: 1 · 2025: 2 · 2024: 2 · 2023: 2 · 2022: 3 · 2021: 2 · 2020: 2
FWCI
0.53
Type
journal article
Language
en
Open access
Locations
  • ACS Earth and Space Chemistry (publishedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
Funders
Office of Environmental Management (DE-NA-0003525)
Topics
  • Physical Sciences › Chemical Engineering › Filtration and Separation › Chemical and Physical Properties in Aqueous Solutions
  • Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
  • Physical Sciences › Engineering › Biomedical Engineering › Phase Equilibria and Thermodynamics
Keywords
siderite, chukanovite, mineral solubility, high-salinity brine, sodium chloride, sodium sulfate, sodium carbonate, excess free energy, equilibrium constants, mineral stability, oxygen fugacity, actinide oxidation

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