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Origin of Berthierine in Ironstones

Published online by Cambridge University Press:  02 April 2024

Deba P. Bhattacharyya
Deba P. Bhattacharyya*
Affiliation:
Earth and Planetary Sciences Department, Washington University, St. Louis, Missouri 63130
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Abstract

To test the hypothesis that berthierine in oolitic ironstones formed by diagenetic transformation of detrital kaolinite, laboratory experiments simulating the early diagenetic conditions were conducted. Representative sets of the initial sediment were prepared in distilled water and artificial seawater suspensions by mixing 4–13 g/liter kaolinite with Fe(OH)3 precipitated from 0.1-0.3 M FeCl3 solutions. Na2S2O4 was added to the suspensions as a reducing agent, and inert N2 atmospheres were used to maintain the required Eh between +100 and -400 mV. The pH of the suspensions was controlled between 8 and 5 with dilute HCl. Within 300 days, the iron content of the bulk kaolinite in the seawater suspensions progressively increased from 0.18 to 2.44% at pH = 7 and Eh between -250 and -350 mV. Energy dispersive X-ray analyses of individual clay platelets in the final products showed progressive, temporal increase in Fe, and concomitant decrease in Al and Si. X-ray powder diffractometry revealed small d(001)-d(002) shifts, marked intensity reversals o. (001) an. (002) reflections, and the development of additional characteristic berthierine reflections with time. These data suggest progressive transformation of kaolinite to berthierine. Microprobe analyses of natural berthierine in oolitic ironstones also showed parallel patterns, which substantiate such progressive transformation from the margin toward the core of the ooids. The transformation did not take place in distilled water. The addition of Mg2+ to the distilled water suspensions, however, promoted the transformation.

Резюме

Резюме

Проводились лабораторные эксперименты, симулирующие условия ранней диагенезы для проверки гипотезы, что бертьерин в оолитовых железных рудах формировался путем диагенетической трансформации детритового каолинита. Характерные образцы первоначального осадка были приготовлены как суспензии в дистиллированной воде и искусственной морской воде путем смешивания 4–13 г/литр каолинита с Fe(OH)3, осажденным из 0,1-0,3 M раствора FeCl3. Вещество Na2S2O4 было добавлено до суспензии в качестве редуцирующего агента и инертная N2 атмосфера использовалась для поддержания уровня величины Eh между +100 и -400 MV. Величины pH суспензии были контролированы между 8 и 5, используя растворенную HCl. В течение 300 дней содержание железа в каолините и суспензиях морской воды постепенно увеличивалось от 0,18 до 2,44% при pH = 7 и Eh между -250 и -350 MV. Энерго-дисперсионный рентгеновский анализ индивидуальных пластинок глины в конечном продукте показал постепенное временное увеличение содержания Fe и сопутствующее уменьшение содержания Al и Si. Рентгеновская порошковая диффрактометрия показало небольшие сдвиги d(001)-d(002), значительный риверс интенсивностей отражений (001) и (002) и развитие добавочных характеристических отражений бертьерина по времени. Эти данные указывают на прогрессивную трансформацию каолинита в бертьерин. Анализ натурального бертьерина из оолитовых железных руд при помощи рентгеновского микроскопа тоже показал параллельные структуры, что подтверждает эту прогрессивную трансформацию от края до центра ооидов. Эта трансфопмация не происходила в дистиллированной воде. Однако, добавление ионов Mg2+ к суспензии с дистиллированной водой способствовало этой трансформации. [E.G.]

Resümee

Resümee

Um die Annahme zu prüfen, daß Berthierin in oolithischen Eisensteinen durch diagenetische Umwandlung von detritischem Kaolinit entsteht, wurden Laborexperimente durchgeführt, die frühdiagenetische Bedingungen simulierten. Repräsentative Reihen des ursprünglichen Sedimentes wurden in Suspensionen mit destilliertem Wasser und Künstlichem Meerwasser hergestellt, indem 4 bis 13 g/l Kaolinit mit Fe(OH)3 gemischt wurde, das aus, 0,1-0,3 m FeCl3-Lösungen ausgefällt wurde. Na2S2O4 wurde zu den Suspensionen als Reduktionsmittel hinzugefügt. Außerdem wurden die Experimente in inerter N2-Atmosphäre durchgeführt, um den erforderlichen Eh-Wert Zwischen +100 und -400 mV konstant zu halten. Der pH-Wert der Suspensionen wurde zwischen 8 und 5 mittels verdünnter HCl kontrolliert. Innerhalb von 300 Tagen nahm der Eisengehalt des gesamten Kaolinits in den Meerwassersuspensionen ständig von 0,18 auf 2,44% zu, bein einem pH = 7 und Eh zwischen -250 und -350 mV. Energiedispersive Röntgenanalysen von einzelnen Tonblättchen in den Endprodukten zeigten eine fortschreitende, zeitabhängige Zunahme an Eisen und eine entsprechende Abnahme an Aluminium und Silizium. Röntgenpulverdiffraktometeraufhahmen ergaben geringe Verschiebungen von d(001)-d(002), beachtliche Intensitätsumkehrungen de. (001) un. (002) Reflexe und die Ausbildung von zusätzlichen charakteristischen Berthierin-Reflexen mit zunemender Zeit. Diese Ergebnisse deuten auf eine zunehmende Umwandlung von Kaolinit in Berthierin hin. Mikroson-denanalysen von natürlichem Berthierin in oolitischen Eisenteinen zeigten ebenfalls Doppelreflexe, die diese zunemende Umwandlung vom Rand gegen den Kern des Ooides verdeutlichen. Diese Umwandlung fand in destilliertem Wasser nicht statt. Die Zugabe von Mg2+ zu den Suspensionen mit destilliertem Wasser förderte jedoch die Umwandlung. [U.W.]

Résumé

Résumé

Pour vérifier l'hypothèse que la berthièrine dans des roches oolitiques de fer a été formée par la transformation diagénétique de kaolinite détritique, on a fait des expériences au laboratoire simulant les conditions du début de la diagénèse. Des groupes représentatifs du sédiment initial ont été préparés dans l'eau distillée et des suspensions d'eau de mer artificielles en mélangeant 4–13 g/litre de kaolinite avec Fe(OH)3 precipité à partir de solutions de 0,1-0,3 M FeCl3. Na2S2O4 a été ajouté aux suspensions comme agent reductif, et des atmosphères inertes de N2 ont été utilisées pour maintenir l'Eh requis entre +100 et —400 mV. Le pH des suspensions a été contrôlé entre 8 et 5 avec de l'HCl dilué. En 300 jours, le contenu en fer de la kaolinite en masse dans les suspensions d'eau de mer a progressivement augmenté de 0,18 à 2,44% au pH = 7, et Eh entre -250 et -350 mV. Des analyses aux rayons-X dispersant l’énergie des paillettes d'argile individuelles des produits finaux ont montre une augmentation progressive, temporelle de Fe, et une diminution concordante d'Al et de Si. La diffraction poudrée de rayons-X a révélé des petits déplacements de d(001)-d(002), des renversements marqués de l'intensité des réflection. (001) e. (002) et le développement de réflections de berthièrine typiques avec le temps. Ces données suggèrent une transformation progressive de kaolinite en berthièrine. Des analyses microprobes de berthièrine naturelle dans des roches oolitiques de fer ont aussi montré des diagrammes parallèles, ce qui justifie qu'une telle transformation progressive se produit de l'extérieurs vers le centre des ooïdes. La transformation ne s'est pas produite dans l'eau distillée. L'addition de Mg2+ aux suspensions d'eau distillée a cependant provoqué la transformation. [D.J.]

Keywords

BerthierineDiagenesisIronstoneKaoliniteSynthesis
Type
Research Article
Information
Clays and Clay Minerals , Volume 31 , Issue 3 , June 1983 , pp. 173 - 182
Copyright
Copyright © 1983, The Clay Minerals Society

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