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The Release of Aluminum from Aluminosilicate Minerals. I. Kinetics

Published online by Cambridge University Press:  01 July 2024

F. Cabrera  and
O. Talibudeen
F. Cabrera*
Affiliation:
Soils and Plant Nutrition Department, Rothamsted Experimental Station, Harpenden, Herts., England AL5 2JQ
O. Talibudeen
Affiliation:
Soils and Plant Nutrition Department, Rothamsted Experimental Station, Harpenden, Herts., England AL5 2JQ
*
*Permanent address: Centro de Edafología y Biología Aplicada del Cuarto (C.S.I.C.), Sevilla, Spain
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Abstract

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The rates of release of Al by M NH4NO3 (pH 3) from minerals saturated with Al ions at pH 3 suggest that Al ions migrated from the surface layers and the matrix cores of kaolinite, montmorillonite, illite, and biotite, but only from the matrix core of muscovite mica. From the 0.25–0.5 μm kaolinite and montmorillonite, part of the ‘surface’ Al is released ‘instantaneously’ and the rest by first order kinetics, but the coarse 1.5–2.5 μm kaolinite has only the former component. From illite and biotite, ‘surface’ Al is released by ‘bulk diffusion’ kinetics suggesting the existence of disturbed peripheral layers of finite thickness. The diffusion coefficients, Dm, for the matrix core follow the trend: mica ≃ biotite > illite > montmorillonite > kaolinite.

Based on models proposed in previous work, the ionic composition of the ‘surface’ Al is calculated. This shows that (1) this composition varies according to the mineral from 3 to 100% Al3+, the remainder being in the hydrolyzed form, and (2) the apparent hydrolysis constants are different for each mineral and significantly different from those of Al ions in solution.

Резюме

Резюме

Скорости высвобождения А1 с помощью M NH4NO3 (рН 3) из минералов, насыщенных ионами А1 при рН=3 позволяет предположить, что ионы А1 мигрировали из поверхностных слоев и изнутри образцов каолинита, монтмориллонита,ил-лита и биотита, но только изнутри образцов слюды мусковита. Из 0.25–0.5 дм каолинита и монтмориллонита, часть “поверхностного” Аl высвобождается “моментально” и остальной-согласно кинетике первого порядка, но грубозернистый 1,5–2,5 μм каолинит имеет только первый компонент. Из иллита и биотита,"поверхностный" Al высвобождается согласно "объемной диффузионной" кинетике, предполагающей существование наружных периферийных слоев ограниченной мощности. Диффузионные коэффициенты, Dm,для внутренних частей образцов следуют тенденции: слюда ≃биотит>иллит>монтмориллонит>каолинит.

На основе моделей, предложенных в предыдущей работе, был вычислен ионный состав “поверхностного” Al. Эти вычисления показывают Что 1/ этот состав изменяется в соответствии с минералом от 3 до 100% Аl3+, остальная часть находится в гидролизной форме и 2/ удельные гидролизные постоянные различны для каждого минерала и значительно отличаются от этих же параметров для ионов Аl в растворе.

Kurzreferat

Kurzreferat

Die Geschwindigkeiten, mit denen Al durch 1 molare Ammoniumnitratlösung, bei pH 3 aus mit Al gesätigten Mineralien gelöst wird, deutet darauf hin, daß Al Ionen von den Oberflächen und den Gesteinsinnern von Kaolinit, Montmorillonit, Illit und Biotit,aber nur vom Innern des Muskowit-Glimmer, freigesetzt werden. Von den 0,25–0,5 ym Kaoliniten und Montmorillo-niten wird ein Teil des Oberfächen-Al unverzüglich herausgelöst und der Rest folgt Kinetik erster Ordnung; grobes, 1,5–2,5 um Kaolinit jedoch besitzt nur die erstere Komponente. Von Illit und Biotit wird Oberflächen-Al via Massendiffusionskinetik freigesetzt, was auf die Existenz einer veränderten peripheren Schicht mit begrenzter Dicke hindeutet. Die Diffusionskoeffizienten, Dm, für das Gesteinsinnere haben die folgende Tendenz: Glimmer ≃ Biotit > Illit > Montmorillonit > Kaolinit. Auf Basis von vorgeschlagenen Modellen von früherer Arbeit, wird die ionische Zusammenstellung des Oberflächen Al berechnet. Damit wird gezeigt, (1) die Zusammensetzung variiert mit dem Mineral von 3 bis 100 % Al(III), mit dem Rest in hydrolisierter Form; und (2) die scheinbaren Hydrolysenkonstanten sind unterschiedlich für jedes Mineral und sehr anders als die Konstanten für Al-Ionen in Lösung.

Résumé

Résumé

Les vitesses de libération de l'Al par M NH4NO3 (pH 3) d'ions saturés d'Al à un pH de 3 suggère que les ions d'Al ont émigré des couches de surface et du noyau de la matrice de kaolinite, d'illite et de biotite, mais seulement du noyau de la matrice de mica muscovite. De 0.25–0.5 ym de kaolinite et de montmorillonite,une partie de l'Al “de surface” est libérée “instantanément” et le reste par cinétique de premier ordre; mais la kaolinite grossière de 1.5–2.5ym est entièrement libérée “instantanément”. L'Al de surface est libérée par “diffusion en masse” cinétique de l'illite et de la biotite, suggérant l'existence de couches déformées d’épaisseur finie. Les coefficients de diffusion, Dm, suivent la tendance suivante pour le noyau de la matrice: mica ≃ biotite>illite>montmorillonite>kaolinite.

En se basant sur des modèles proposés dans une étude précédente, la composition ionique de l'Al de “surface” est calculée. Ceci montre que (1) cette composition varie d'après le minéral de 3 à 100% d'Al, le restant étant dans une forme hydrolysée et (2) les constantes d'hydrolyse sont différentes pour chaque minéral et diffèrent d'une manière significative de celles d'ions d'Al en solution.

Keywords

AluminumBiotiteIlliteKaoliniteMontmorillonite
Type
Research Article
Information
Clays and Clay Minerals , Volume 26 , Issue 6 , December 1978 , pp. 434 - 440
Copyright
Copyright © 1978, The Clay Minerals Society

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