Tl(I) sorption behavior on birnessite and its implications for mineral structural changes

Cruz-Hernández, Yusniel; Villalobos, Mario; Marcus, Matthew A.; Pi‐Puig, Teresa; Zanella, Rodolfo; Martínez-Villegas, Nadia

doi:10.1016/j.gca.2019.01.020

Cited by 55 publications

(71 citation statements)

References 37 publications

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“…The Tl(III) species remains bound to the vacancy as a triplecorner sharing (TCS) inner-sphere complex in tetrahedral 16 or octahedral 6 configuration [some Tl(III) may bind to the particle edges as a double edge-sharing (DES) complex 5 ]. Mn(II) can remain bound in the interlayer as well or be released (at least partially) to the solution depending on the pH.…”

Section: Introductionmentioning

confidence: 99%

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration

Ruiz-Garcia

Villalobos

Voegelin

et al. 2021

Environ. Sci. Technol.

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We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl + concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl + (Mn 7.5 4+ Cu 0.5 2+ )O 16 ]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.

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Section: Introductionmentioning

confidence: 99%

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration

Ruiz-Garcia

Villalobos

Voegelin

et al. 2021

Environ. Sci. Technol.

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“…A DES complex can evolve into a triple-edge-sharing complex (TES) and incorporate progressively into the MnO 2 layer during the crystal growth. The identification of some of the surface species (INC, TCS, DCS, and DES) has led to accelerating research aimed to understand their thermodynamic stability − and how the mineral structure, layer size, and chemical composition control the metal sorption selectivity and capacity per specific surface area. ,,− …”

Section: Introductionmentioning

confidence: 99%

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Manceau

Steinmann

2021

ACS Earth Space Chem.

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Birnessite nanosheets (δ-MnO2) are key reactive nanoparticles that regulate metal cycling in terrestrial and marine settings, yet there is no molecular explanation for the sorption selectivity of metals which controls their enrichment. This fundamental question was addressed by optimizing the structure of the Ni, Cu, Zn, and Pb surface complexes on δ-MnO2 and by calculating the Gibbs free energy change (ΔG) of the sorption reactions with density functional theory. The sorption selectivity follows the order Pb > Cu > Ni > Zn, in good agreement with experimental data. Cu, Ni, and Zn bind preferentially to layer edges at low surface coverage forming double-edge-sharing (DES) complexes, whereas Pb binds extensively with high selectivity over the three transition metals to both layer edges (DES bonding) and to basal planes forming triple-corner-sharing (TCS) complexes. Pb has similar affinity for the DES and TCS sites at pH 5 and a higher affinity for the TCS sites at circumneutral pH. The Pb DES and TCS complexes are both dehydrated at the δ-MnO2-water interface and feature a trigonal pyramidal geometry with three surface O atoms. The high stability of the two new complexes arises from the hybridization between the Pb 6s/6p and the O 2p states, forming a strongly covalent Pb-O/OH bond at the δ-MnO2 surface. The quantum chemical results provide mechanistic and energetics insight on metal uptake on δ-MnO2 that extends what extended X-ray absorption fine structure (EXAFS) spectroscopy alone can provide.

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“…http://www.minsocam.org/ (e.g Bidoglio et al 1993;Peacock and Moon 2012;. Voegelin et al 2015, Cruz-Hernández et al 2019Wick et al 2019) Brookins (1988). considered that under oxidizing conditions, thallium oxides: Tl O, Tl O 3 and Tl O dominate the Eh-pH space in order with increasing Eh, and only under strongly acidic oxidizing conditions Tl 3+ appears.…”

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Thalliomelane, TIMn7.54+Cu0.52+O16, a new member of the coronadite group from the preglacial oxidation zone at Zalas, southern Poland

Gołębiowska

Pieczka

Zubko

et al. 2021

American Mineralogist

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Thalliomelane, a new member of the coronadite group (hollandite supergroup), was discovered at Zalas near Cracow in southern Poland (the southern margin of the Cracow-Silesia Monocline) in relics of a preglacial supergene mineralization disseminated in a fault breccia in Middle Jurassic sandy limestone. The mineralization formed at the expense of a sulfide assemblage, which was most likely the source of thallium, related to rejuvenation of Early-Paleozoic fault zones in the Sava phase of the Alpine orogeny. Thalliomelane occurs rarely, and exclusively in the form of fibrous and highly porous tiny aggregates < 50 µm in size that fill small fractures and voids in the sandy limestone host rock. Microprobe analyses based on 16 O and 8 octahedral cations per formula unit resulted in the mean empirical formula (Tl 0.77(10) Ba 0.21(3) K 0.03(1) Na 0.01(0) Pb 0.01(0) ) Σ1.03(7) (Mn 4+ 7.15(11) Cu 2+ 0.63(4) Co 2+ 0.08(3) Fe 3+ 0.06(3) Ni 2+ 0.03(1) Si 0. 03(2) Mg 0.01(1) ) Σ8 [O 15.67(24) (OH) 0.33(24) ], corresponding to the formula Tl(Mn 4+ 7.5 Cu 2+ 0.5 )O 16 for the thalliomelane end-member. The mineral crystallizes in the tetragonal system, space group I4/m, and has unit-cell parameters a = 9.8664(12), c = 2.8721(4) Å, V = 279.59(8) Å 3 , Z = 1. The crystal structure of thalliomelane, measured with 3D electron-diffraction, was refined to an R 1 index of 23.74%. Thalliomelane has the hollandite-type structure. The Mn 4+ cations, substituted by Cu 2+ at an amount of ~0.5 apfu, are octahedrally coordinated by oxygen atoms. Four double chains of edge-sharing (Mn,Cu)-O octahedra share corners with each other to form tunnels along the [001] direction. Tl + cations are located in the tunnels, occupying partially the origin and centre of the unit cell. The formation of thalliomelane was most probably connected to the weathering of a sulfide mineral assemblage under semi-arid to arid climate. It resulted in the release of Tl and other components of the mineralization into water under the influence of Cl-,This is the peer-reviewed, final accepted version for American Mineralogist, published by the Mineralogical Society of America. The published version is subject to change. Cite as Authors (Year) Title. American Mineralogist, in press.

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Tl(I) sorption behavior on birnessite and its implications for mineral structural changes

Cited by 55 publications

References 37 publications

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Thalliomelane, TIMn7.54+Cu0.52+O16, a new member of the coronadite group from the preglacial oxidation zone at Zalas, southern Poland

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