On the influence of carbonate in mineral dissolution: II. The solubility of FeCO3 (s) at 25°C and 1 atm total pressure

Bruno, Jordi; Wersin, Paul; Stumm, Werner

doi:10.1016/0016-7037(92)90052-k

Cited by 116 publications

(88 citation statements)

References 30 publications

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“…Our solubility and standard potential data of siderite, FeC03, determined at 50°C [17, 201 extrapolate to slightly higher log K-values at 25°C than were obtained experimentally by Bruno et al [21]. Again the much slower equilibration at 25°C may partly be responsible for this discrepancy, which, however, only moderately exceeds an uncertainty of f 0 .…”

Section: Single Carbonatessupporting

confidence: 51%

Solubilities of metal carbonates

Gamsjäger¹,

Königsberger²,

Preis³

1998

Pure and Applied Chemistry

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Solubilities in aqueous media of sparingly-soluble metal carbonates play an important role in chemical processes whether they occur in a laboratory, on an industrial scale, or in the geologic environment. Solubility phenomena (i.e. dissolution and precipitation reactions) of metal carbonates control procedures for preparing, separating and purifying chemicals. Moreover, the interactions of the hydrological cycle with the cycle of carbonate rocks, the naturally occurring dissolution of carbonate minerals in water as well as their precipitation on the ocean floor and in the sediments of rivers and lakes can be described by the principles of solubility, although gigantic quantities of material may be involved.The experimental methods for the determination of carbonate solubilities are reviewed and the results are discussed within the frame-work of equilibrium thermodynamics. It will be shown that Gibbs functions of pure stoichiometric carbonate phases can be determined by accurately measuring solubilities in aqueous electrolyte systems. In cases where solid-solid phase transformations and recrystallisations are kinetically inhibited, the methods developed were successfully applied to metastable equilibria. Occasionally, solubility data were even employed to estimate activity coefficients of components forming a series of carbonate solid solutions.Whenever possible the activity coefficients of the reacting species were controlled by use of a constant ionic medium. Solubility constants obtained at various fixed ionic strengths were fitted to the Pitzer equations and extrapolated to infinite dilution. Provided the standard potentials of the respective metal ion/metal electrode are known over a range of ionic strengths the values of solubility constants at infinite dilution can be calculated independently. In any case the optimised thermodynamic constants were incorporated in a comprehensive computer model which permits a wide variety of solubility calculations. These are illustrated by a case study of a multicomponent system with industrial relevance.

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Section: Single Carbonatessupporting

confidence: 51%

Solubilities of metal carbonates

Gamsjäger¹,

Königsberger²,

Preis³

1998

Pure and Applied Chemistry

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“…Increased vivianite formation was observed at P concentrations that exceeded surface saturation (e.g., 10 mmol/L P). Vivianite has a lower solubility (Al-Borno and Tomson, 1994) than either GR (Génin et al, 1998) or siderite (Bruno et al, 1992), and forms rapidly under circumneutral conditions .…”

Section: Effect Of Pmentioning

confidence: 99%

Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: formation of carbonate green rust in the presence of phosphate

Kukkadapu

Zachara

Fredrickson

et al. 2004

Geochimica et Cosmochimica Acta

168

169

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Abstract-The reductive biotransformation of two Si-ferrihydrite coprecipitates (1 and 5 mole % Si) by Shewanella putrefaciens, strain CN32, was investigated in 1,4-piperazinediethanesulfonic acid-buffered media (pH ϳ7) with lactate as the electron donor. Anthraquinone-2,6-disulfonate, an electron shuttle, was present in the media. Experiments were performed without and with PO 4 3Ϫ (P) (1 to 20 mmol/L) in media containing 50 mmol/L Fe. Our objectives were to define the combined effects of SiO 4 4Ϫ (Si) and P on the bioreducibility and biomineralization of ferrihydrites under anoxic conditions. Iron reduction was measured as a function of time, solids were characterized by powder X-ray diffraction and Mössbauer spectroscopy, and aqueous solutions were analyzed for Si, P, Cl Ϫ and inorganic carbon. Both of the ferrihydrites were rapidly reduced regardless of the Si and P content. Si concentration had no effect on the reduction rate or mineralization products. Magnetite was formed in the absence of P whereas carbonate green rust GR( ) varied with P concentration; the ratio was 2 in 1 mmol/L P and approached 1 with 4-and 10 mmol/L P. Green rust appeared to form by solid-state transformation of ferrihydrite. Media P and Si concentration dictated the mechanism of transformation. In the 1 mole % Si coprecipitate with 1 mmol/L P, an intermediate Fe(II)/Fe(III) phase with structural Fe(II) slowly transformed to GR with time. In contrast, when ferrihydrite contained more Si (5 mole %) and/or contained higher P (4 mmol/L), sorbed Fe(II) and residual ferrihydrite together transformed to GR. Despite similar chemistries, P was shown to have a profound effect on extent of ferrihydrite reduction and biotransformations while that of Si was minimal.

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“…The final pH values of reduced, synthetic Fe(III) oxide suspensions are typically higher Zachara et al, 1998). The solubilities of both siderite and green rust are strongly pH-dependent, increasing with decreasing pH (Bruno et al, 1992;Genin et al, 1998). The computed ion activity products for these two phases (assuming the formation of carbonate green rust and thermodynamic data from the above two sources) were below saturation in the PIPES, HCO 3 Ϫ , and PIPES/AQDS treatments at termination of the reduction experiment.…”

Section: Extent and Controls On Ferrous Iron Precipitatesmentioning

confidence: 99%

Dissimilatory bacterial reduction of Al-substituted goethite in subsurface sediments

Kukkadapu

Zachara

Smith

et al. 2001

Geochimica et Cosmochimica Acta

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Abstract-The microbiologic reduction of a 0.2 to 2.0 m size fraction of an Atlantic coastal plain sediment (Eatontown) was investigated using a dissimilatory Fe(III)-reducing bacterium (Shewanella putrefaciens, strain CN32) to evaluate mineralogic controls on the rate and extent of Fe(III) reduction and the resulting distribution of biogenic Fe(II). Mössbauer spectroscopy and X-ray diffraction (XRD) were used to show that the sedimentary Fe(III) oxide was Al-substituted goethite (13-17% Al) that existed as 1-to 5-m aggregates of indistinct morphology. Bioreduction experiments were performed in two buffers [HCO 3 Ϫ ; 1,4-piperazinediethansulfonic acid (PIPES)] both without and with 2,6-anthraquinone disulfonate (AQDS) as an electron shuttle. The production of biogenic Fe(II) and the distribution of Al (aqueous and sorbed) were followed over time, as was the formation of Fe(II) biominerals and physical/chemical changes to the goethite.The extent of reduction was comparable in both buffers. The reducibility (rate and extent) was enhanced by AQDS; 9% of dithionite-citrate-bicarbonate (DCB) extractable Fe(III) was reduced without AQDS whereas 15% was reduced in the presence of AQDS. XRD and Mössbauer spectroscopy were used to monitor the disposition of biogenic Fe(II) and changes to the Al-goethite. Fe(II) biomineralization was not evident by XRD. Biomineralization was observed by Mössbauer when sorbed Fe(II) concentrations exceeded a threshold value. The biomineralization products displayed Mössbauer spectra consistent with siderite FeCO 3 (HCO 3 Ϫ buffer only) and green rust . Adsorption of biogenic Fe(II) to accessory mineral phases (e.g., kaolinite) and bacterial surfaces appeared to limit biomineralization. Al evolved during reduction was sorbed, and extractable Al increased with reduction. XRD analysis indicated that neither crystallite size or the Al content of the goethite was affected by bacterial reduction, i.e., Al release was congruent with Fe(II).

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On the influence of carbonate in mineral dissolution: II. The solubility of FeCO3 (s) at 25°C and 1 atm total pressure

Cited by 116 publications

References 30 publications

Solubilities of metal carbonates

Solubilities of metal carbonates

Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: formation of carbonate green rust in the presence of phosphate

Dissimilatory bacterial reduction of Al-substituted goethite in subsurface sediments

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