FeIII-substituted brucite: Hydrothermal synthesis from (Mg0.8FeII0.2)-brucite, crystal chemistry and relevance to the alteration of ultramafic rocks

Carlin, William; Malvoisin, Benjamin; Lanson, Bruno; Brunet, Fabrice; Findling, Nathaniel; Lanson, Martine; Magnin, Valérie; Fargetton, Tiphaine; Jeannin, Laurent; Lhote, Olivier

doi:10.1016/j.clay.2023.106845

Cited by 8 publications

(8 citation statements)

References 70 publications

(84 reference statements)

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“…An empirical relationship to estimate the Fe(II) mol % in brucite was derived from the relationship between the 001 peak position and Fe(II) content (Figure c). The relationship between refined 001 peak positions and Fe(II)-content in brucite from our study is consistent with results for natural and synthetic 20 mol % Fe(II)-brucite from Mumpton and Thompson (4.741 Å) and Carlin et al (4.751 Å), and for endmember Fe II (OH) 2 characterized by Bernal et al (4.597 Å) and Parise et al (4.601 Å). This relationship (Figure c) could be used to estimate the amount of Fe(II) within brucite in both pure minerals and multiphase mixtures containing brucite, provided that Mg and Fe(II) are the only cations present at high abundance in brucite.…”

Section: Resultssupporting

confidence: 92%

“…This is significantly lower than the values obtained using our XRD-based method, described in Figure c. The differences could be due to incorporation of Fe(III) into the natural brucite samples that contract the unit cell along the c axis since Fe 3+ has a smaller ionic radius compared to Fe 2+ and Mg. , Another possibility for Mount Keith brucite could be an underestimation of Fe(II) in brucite during EPMA analysis due to brucite intergrowth with LDH (i.e., iowaite–pyroaurite) or serpentine-group minerals, which is commonly observed in serpentinites. It remains unclear why this relationship does not work for natural samples of Fe-bearing brucite; however, our results indicate that chemical analyses should be used in preference to the crystallographic measurement.…”

Section: Resultsmentioning

confidence: 99%

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Influence of Iron Substitution and Solution Composition on Brucite Carbonation

Vessey,

Raudsepp,

Patel

et al. 2024

Environ. Sci. Technol.

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Carbon neutral or negative mining can potentially be achieved by integrating carbon mineralization processes into the mine design, operations, and closure plans. Brucite [Mg(OH) 2 ] is a highly reactive mineral present in some ultramafic mine tailings with the potential to be rapidly carbonated and can contain significant amounts of ferrous iron [Fe(II)] substituted for Mg; however, the influence of this substitution on carbon mineralization reaction products and efficiency has not been thoroughly constrained. To better assess the efficiency of carbon storage in brucite-bearing tailings, we performed carbonation experiments using synthetic Fe(II)-substituted brucite (0, 6, 23, and 44 mol % Fe) slurries in oxic and anoxic conditions with 10% CO 2 . Additionally, the carbonation process was evaluated using different background electrolytes (NaCl, Na 2 SO 4 , and Na 4 SiO 4 ). Our results indicate that carbonation efficiency decreases with increasing Fe(II) substitution. In oxic conditions, precipitation of ferrihydrite [Fe 10 III O 14 (OH) 2 ] and layered double hydroxides {e.g., pyroaurite [Mg 6 Fe 2 III (OH) 16 CO 3 •4H 2 O]} limited carbonation efficiency. Carbonation in anoxic environments led to the formation of Fe(II)-substituted nesquehonite (MgCO 3 •3H 2 O) and dypingite [Mg 5 (CO 3 ) 4 (OH) 2 •∼5H 2 O], as well as chukanovite [Fe 2 II CO 3 (OH) 2 ] in the case of 23 and 44 mol % Fe(II)-brucite carbonation. Carbonation efficiencies were consistent between chloride-and sulfate-rich solutions but declined in the presence of dissolved Si due to the formation of amorphous SiO 2 •nH 2 O and Fe−Mg silicates. Overall, our results indicate that carbonation efficiency and the long-term fate of stored CO 2 may depend on the amount of substituted Fe(II) in both feedstock minerals and carbonate products.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Influence of Iron Substitution and Solution Composition on Brucite Carbonation

Vessey,

Raudsepp,

Patel

et al. 2024

Environ. Sci. Technol.

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“…Ferroan brucite (Mg 1−x ,Fe x )(OH) 2 , with x ranging from 0.156 to 0.205, was synthesised under ambient conditions from a stoichiometric solution of dissolved Fe(II) and Mg chlorides, as described in Carlin et al (2023). The ferroan brucite obtained by this method formed platelets 40 to 100 nm across (Fig.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of low-temperature H2 production in ultramafic rocks by ferroan brucite oxidation

Carlin,

Malvoisin,

Brunet

et al. 2024

Geochem. Persp. Let.

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Ferroan brucite, (Mg,Fe)(OH) 2 , is among the potential mineral candidates for low temperature (<423 K) abiotic H 2 production in ultramafic rocks. To verify this assumption, synthetic ferroan brucite with grain size similar to that observed in natural samples (40-100 nm) was reacted with pure water at temperatures ranging from 348 to 573 K. Experimental products are consistent with the reaction 3 Fe(OHThis reaction reached completion in ∼2 months at 378 K and is thermally activated with an activation energy of 145 ± 1 kJ/mol. The standard state formation enthalpy and the third law entropy of amakinite, Fe(OH) 2 , were refined from the experimental dataset. The new thermodynamic parameters imply that ferroan brucite is stable at significantly lower hydrogen activity than previously calculated. The alteration of Fe-brucite produces H 2 at rates compatible with present day observations of H 2 emissions in natural settings (ophiolite and mid-oceanic ridges). However, efficient fluid renewal is required, as opposed to H 2 production through olivine serpentinisation, which can proceed in static hydraulic conditions.

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“…Ferroan brucite, Mg 1– X Fe X (OH) 2 , was preserved in serpentinized peridotites with x (the doping amount of Fe 2+ ) generally ranging from 0.05 to 0.35 per formula unit. − Petrographic investigation had actually shown that the alteration of minerals bearing ferrous iron hosted under subsurface conditions could lead to further iron oxidation . Boschi et al found that the Mg 1– X Fe X (OH) 2 was an unstable mineral and would transform into stable mineral in a natural environment .…”

Section: Introductionmentioning

confidence: 99%

“…12−14 Petrographic investigation had actually shown that the alteration of minerals bearing ferrous iron hosted under subsurface conditions could lead to further iron oxidation. 12 Boschi et al found that the Mg 1−X Fe X (OH) 2 was an unstable mineral and would transform into stable mineral in a natural environment. 13 Mg 10 Fe 2 CO 3 (OH) 24 •2H 2 O in CO 2 -bearing groundwater.…”

Section: Introductionmentioning

confidence: 99%

Evolution Process of Ferroan Brucite under Humid Conditions with CO₂ and O₂

Zhao,

et al. 2023

J. Phys. Chem. C

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Ferroan brucite, Mg 1−X Fe X (OH) 2 (0.05 < x < 0.35) was a common mineral product preserved in serpentinized peridotites. Studying the evolution of Mg 1−X Fe X (OH) 2 with different doping amounts of Fe 2+ was beneficial to reveal the role of Fe 2+ in forming different kinds of evolution products and the reasonable utilization of Mg 1−X Fe X (OH) 2 resources. In this study, Mg 1−X Fe X (OH) 2 with x being 0.05, 0.1 0.15, 0.2, and 0.3 were successfully prepared, characterized, and structurally refined in detail. The evolution products of Mg 1−X Fe X (OH) 2 in the presence of H 2 O, CO 2 , and O 2 were clearly investigated to assess the evolution process and the role of Fe 2+ . The evolution products were mainly CO 3 2− intercalated MgFe-layered double hydroxides (MgFe−CO 3 2− -LDHs) and MgCO 3 •3H 2 O. The content of MgFe− CO 3 2−-LDHs in the evolution products increased with the Fe 2+ doping content increased. While the content of MgCO 3 •3H 2 O changed in the opposite direction and completely disappeared as the doping content of Fe 2+ was 20%. Accordingly, the evolution mechanism of Mg 1−X Fe X (OH) 2 was afforded based on various characterization and calculation on the deformation and system energy of the products by molecular simulation. In the evolution process, the oxidization of Fe 2+ to Fe 3+ in Mg 1−X Fe X (OH) 2 by O 2 forced the entrance of CO 3 2− into the interlayers. Meanwhile, high content of doping Fe 2+ in Mg 1−X Fe X (OH) 2 resulted in the easy formation of MgFe−CO 3 2− -LDHs. Correspondingly, the change of surface charge, magnetic property, and adsorption ability toward Congo red was tested after evolution.

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FeIII-substituted brucite: Hydrothermal synthesis from (Mg0.8FeII0.2)-brucite, crystal chemistry and relevance to the alteration of ultramafic rocks

Cited by 8 publications

References 70 publications

Influence of Iron Substitution and Solution Composition on Brucite Carbonation

Influence of Iron Substitution and Solution Composition on Brucite Carbonation

Kinetics of low-temperature H2 production in ultramafic rocks by ferroan brucite oxidation

Evolution Process of Ferroan Brucite under Humid Conditions with CO₂ and O₂

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FeIII-substituted brucite: Hydrothermal synthesis from (Mg0.8FeII0.2)-brucite, crystal chemistry and relevance to the alteration of ultramafic rocks

Cited by 8 publications

References 70 publications

Influence of Iron Substitution and Solution Composition on Brucite Carbonation

Influence of Iron Substitution and Solution Composition on Brucite Carbonation

Kinetics of low-temperature H2 production in ultramafic rocks by ferroan brucite oxidation

Evolution Process of Ferroan Brucite under Humid Conditions with CO2 and O2

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Product

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Evolution Process of Ferroan Brucite under Humid Conditions with CO₂ and O₂