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New Members of the Hydrotalcite-Manasseite Group

Published online by Cambridge University Press:  02 April 2024

V. A. Drits ,
T. N. Sokolova ,
G. V. Sokolova  and
V. I. Cherkashin
V. A. Drits
Affiliation:
Geological Institute of the U.S.S.R. Academy of Sciences, Pyzhevsky 7, Moscow, U.S.S.R.
T. N. Sokolova
Affiliation:
Geological Institute of the U.S.S.R. Academy of Sciences, Pyzhevsky 7, Moscow, U.S.S.R.
G. V. Sokolova
Affiliation:
Geological Institute of the U.S.S.R. Academy of Sciences, Pyzhevsky 7, Moscow, U.S.S.R.
V. I. Cherkashin
Affiliation:
Geological Institute of the U.S.S.R. Academy of Sciences, Pyzhevsky 7, Moscow, U.S.S.R.
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Abstract

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Several new minerals, structurally and chemically similar to the hydrotalcite-manasseite group, have been found in the saline deposits of the central pre-Caspian depression and in those of Middle Asia. Their structures consist of layers of (Mg1-xAlx)(OH)2 plus interlayers of anions and molecular water. In addition to manasseite itself, [(Mg4Al2)(OH)12][(CO3)-3H2O], having unit-cell parameters of a = 3.042, c = 2 × 7.56= 15.12 Å and a calculated density of Dc = 2.15 g/cm3, other varieties were identified whose interlayers contain alternately SO42− or SO42− and CO32− anions. The following new phases were recognized: (1) an 8.85-Å phase having the composition [(Mg4Al2)(OH)12][(SO4)·3H2O], subcell dimensions of a' = 3.04, c' = 8.85 Å, and Dc = 1.96 g/cm3; (2) an 11-Å phase having the composition [(Mg3.96Fe0.06Al1.98)(OH)12][Na0.56(SO4)1.30·7.3H2O], hexagonal unit-cell parameters of a = √3 · 3.042 = 5.28 Å, c = 11.16 Å, and Dc = 1.90 g/cm3; (3) a 16.5-Å mixed-layer phase having the composition [(Mg4Al2)(OH)12][(SO4)0.5(CO3)0.5·3H2O] and an ordered ABAB... alternation of 7.56-Å layers (i.e., a brucite-like layer + a CO32−-containing interlayer) and 8.94-Å layers containing SO42− anions in interlayers; this phase has unit-cell dimensions of a' = 3.05, c' = 16.5 Å and Dc = 2.06 g/cm3; and (4) an 18.5-Å ordered mixed-layer phase having the ideal composition [(Mg8Al4)(OH)24][M+0.5(SO4)1.25(CO3)1.0·9H2O] and an alternation of 7.56-Å, CO3-containing layers and 11-Å layers having SO42− anions and Na and Mg cations in interlayers (M+0.5 corresponds to interlayer cations). This last phase has unit-cell dimensions of a = 3.046, c = 3 × 18.54 = 55.62 Å and Dc = 1.99 g/cm3. Some of the varieties containing SO42− in the interlayers swelled with ethylene glycol or glycerol.

For this diverse family of minerals whose structures are based on brucite-like layers of the composition (R2+1-xR3+x)(OH)2, a unifying system of nomenclature is offered for consideration. In describing these brucite-like structures intercalated with anion- and cation-containing interlayers, the composition of the hydroxide sheet and the interlayers, the periodicity of the layers, and the mixed-layer nature of the material should be described. By means of symbols, a single term might be used to describe the crystal chemistry of any member of the group having a given cation composition for the brucite-like layers, for example, manasseite, a 2H polytype of hydrotalcite that has a repeat distance of 7.56 Å and CO3-containing interlayers, might be designated as 7.56-Å CO3-hydrotalcite-2H.

Резюме

Резюме

В соленосных отложениях центральной части Прикаспийской впадины и Средней Азии обнаружен ряд новых минералов, структурно близких к минералам группы гидроталькит-манассеита. Основу структур этих минералов составляют положительно заряженные бруситоподобные слои со-тава (Mg1-xAlx)(OH)2, между которыми располагаются анионы и молекулы воды. Помимо собственно манассеита состава [(Mg4Al2)(OH)12][(CO3)·3H2O] с параметрами элементарной ячейки a = 3.042, с = 2 × 7.56 = 15.12 Å и рассчитанной плотностью (Dp) = 2.15 г/см3, установлены следующие разновид¬ности, межслоевые промежутки которых содержат анионы SO42− или SO42− и СО32−: (1) 8.85-Å фаза состава [(Мg4Аl2)(ОН)12][(SO4)·3Н2O] с параметрами a' = 3.04, с' = 8.85 Å и Dp = 1.96 г/см3; (2) 11-Å фаза состава [(Mg3.96Fe0.06Al0.98)(OH)12][Na0.56(SO4)1.30·7.3H2O] с параметрами гексагональной ячейки a = √3 × 3.042 = 5.28, с = 11.16 0А, и Dp = 1.90 г/см3; (3) 16.5-Å смешанослойная фаза состава [(Mg4Al2)(OH)12][(SO4)0.5(CO3)0.5·3H2O], в которой упорядоченно по закону АВАВ... чередуются 7.56-Å слои (бруситиподобный слой + СО3-содержащий межслой) и 8.94-Å слои с анионами SO42−в межслоях; параметры элементарной ячейки a' = 3.05, с' = 16.5 Å, и Dp = 2.06 г/см3; (4) 18.5-Å упорядоченная смешанослойная фаза состава [(MggAl4)(OH)24][M+0.5(SO4)1.25(СО3)1.0·9Н2О], в которой по закону АВАВ... чередуются 7.56-Å, СО3-содержащие слои и 11-Å слои, содержащие анионы SO4 и катионы Na и Mg в межслоях (М+0.5 соответствует межслоевому катиону). Параметры элементарной ячейки этой фазы a = 3.046, с = 3 × 18.54 = 55.62 Å, и Dp= 1.99. Некоторые разновидности, содер¬жащие в межслоях анионы SO4, обладают способностью к внутрикристаллическому набуханию при обработке их этиленгликолем и глицерином.

Предлагается унифицированная система номенклатуры для всего многообразного семейства ми¬нералов, основу структур которых составляют слои состава (R2+1-xR3+x)(OH)2. Для обозначения этих бруситоподобных структур, интеркалированных межслоевыми анионами и катионами, необходимо указать состав гидроокисных слоев и межслоев, период повторяемости слоев, смешанослойную при¬роду минерала. На основании предлагаемой символики можно использовать только одно наимено¬вание, чтобы описать любой член группы, имеющий данный состав бруситоподобных слоев. Напри¬мер, манассеит-2H, помимо гидроталькита, который имеет период повторяемости 7.56 Å и СO3-содержащие межслои, может быть обозначен как 7.56-Å СO3-гидроталькит-2H.

Keywords

CarbonateHydrotalciteInterlayerNomenclatureSulfateX-ray powder diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 35 , Issue 6 , December 1987 , pp. 401 - 417
Copyright
Copyright © 1987, The Clay Minerals Society

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