Transformation series parakeldyshite-keldyshite: mechanism of transformation, chemical formula revision and crystal structure of keldyshite

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Resumo

A holotype sample of keldyshite has been studied and found to consist of aggregates of partially protonated, Na-deficient parakeldyshite (which is predominant) and keldyshite itself. A series of laboratory experiments on the hydrolysis of parakeldyshite was conducted, leading to the clarification of the crystal structure of keldyshite formed during this process. An idealized refined formula for keldyshite, (Na□)ZrSi2O6(OH), has been obtained. As a result of the protonation of the oxygen atom at position O5 and the formation of strong hydrogen bonds (with an O5...O5 distance of 2.458 Å in keldyshite), a series of hinge transformations occurs, causing significant distortion of the Zr–Si–O framework within the crystal structure. The existence of the transformation series from parakeldyshite to keldyshite in nature has been confirmed. The mechanism for keldyshite formation can be described by the reaction scheme: Na+ + O2‒ → □ + (OH)‒. It is likely that the substitution reaction of parakeldyshite by keldyshite occurs via a transition from single crystal to single crystal.

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Sobre autores

T. Panikorovskii

Kola Scienсe Centre of the Russian Academy of Sciences

Autor responsável pela correspondência
Email: t.panikorovskii@ksc.ru
Rússia, Apatity

G. Samburov

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Rússia, Apatity

A. Nikolaev

Apatite Museum and Exhibition Centre

Email: t.panikorovskii@ksc.ru
Rússia, Kirovsk

A. Bazai

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Rússia, Apatity

O. Goychuk

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Rússia, Apatity

I. Pekov

Moscow State University

Email: t.panikorovskii@ksc.ru
Rússia, Moscow

S. Krivovichev

Kola Scienсe Centre of the Russian Academy of Sciences; St. Petersburg State University

Email: t.panikorovskii@ksc.ru
Rússia, Apatity; St. Petersburg

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2. Fig. 1. Sample No. 9518: parakeldyshite (1) and snow-white pseudomorph of keldyshite (2) after it in association with aegirine (3), eudialyte (4), nepheline (5) and murmanite (6). Umbozero mine, Alluaiv town, Lovozero.

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3. Fig. 2. SEM images of samples MVC No. 465 (a, b, d) and No. 9518 (c), obtained in the backscattered electron detection mode: parakeldyshite (1), keldyshite (2), phase M-34 (3), catapleite (4), hydroxynatropyrochlore (5).

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4. Fig. 3. X-ray phase analysis of the initial parakeldyshite (1) and phases after treatment for seven days with an acid solution at 20 (2) and 70°C (3). The calculated diffraction pattern of the M-34 phase (4), experimental diffraction patterns of keldyshite (01-072-1944) (5) and parakeldyshite (00-029-1293) (6) are shown.

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5. Fig. 4. Projections of the crystal structures on the (100) plane of the original parakeldyshite No. 9518 (a), parakeldyshite MVC No. 465 (b), keldyshite obtained during the hydrolysis of sample No. 9518 (c), and keldyshite (d) described in [9].

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6. Fig. 5. Projections of the zirconium silicate framework of parakeldyshite MVC No. 465 on the planes (100) (a) and (010) (b); similar projections of keldyshite obtained during hydrolysis of sample No. 9518 (c, d).

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7. Fig. 6. Bond lengths in the coordination polyhedra of Zr, Na1 and Na2 (a–c) in the structures of parakeldyshite MVC No. 465 and keldyshite obtained during hydrolysis of sample No. 9518 (d–e).

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8. Fig. 7. Fragments of the crystal structures of parakeldyshite MVC No. 465 (a) and keldyshite obtained during hydrolysis of sample No. 9518 (b). The arrows indicate the formation of a hydrogen bond between the O5…O5 atoms.

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