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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

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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

References

Adeleye, D. R., 1973 Origin of ironstones, an example from middle Niger valley J. Sed. Petrol. 43 709–727.CrossRefGoogle Scholar
Allen, G. P., Laurier, D. and Thouvenin, J., 1979 Étude sedimentologique du delta de La Mahakam Notes et Mémoires .Google Scholar
Beck, K. C., Reuter, J. H. and Perdue, E. M., 1974 Organic and inorganic geochemistry of some coastal plain rivers of northern United States Geochim. Cosmochim. Acta 38 341–364.CrossRefGoogle Scholar
Bhattacharyya, D., 1980 Sedimentology of the Late Cretaceous Nubia Formation at Aswan, southeast Egypt, and origin of the associated ironstones Princeton, New Jersey Ph.D. Thesis, Princeton Univ..Google Scholar
Bhattacharyya, D. P. and Kakimoto, P. K., 1982 Origin of ferriferous ooids: an SEM study of ironstone ooids and bauxite pisoids J. Sed. Petrol. 52 849–857.Google Scholar
Bradshaw, M. J., James, S. J. and Turner, P., 1980 Origin of oolitic ironstones—discussion J. Sed. Petrol. 50 295–299.CrossRefGoogle Scholar
Brindley, G. W., 1982 Chemical compositions of berthierine—a review Clays & Clay Minerals 30 153–155.CrossRefGoogle Scholar
Brown, G., 1955 The effect of isomorphous substitutions on the intensities o. (001) reflections of mica and chlorite type structures Min. Mag. 30 657–665.Google Scholar
Bubenicek, L., 1971 Géologie du gisement de fer de Lorrain Carte Recherches Pau, Soc. Nat. Pétroles d’Aquitaine Bull. 5 223–320.Google Scholar
Caillère, S. and Hénin, S., 1960 Propriété des ions et conditions des synth, se des minéraux argileux Le Cas du fer Géol. Int. Cong. Norden 24 73–79.Google Scholar
Crerar, D. A., Knox, G. W. and Means, J. L., 1979 Biogeochemistry of bog iron in southern New Jersey Chem. Geol. 24 111–135.CrossRefGoogle Scholar
Curtis, C. D. and Spears, D. A., 1968 The formation of sedimentary iron minerals Econ. Geol. 63 257–270.CrossRefGoogle Scholar
Davies, P. J. and Martin, K., 1976 Radial aragonite ooids, Lizard Island, Great Barrier Reef, Queensland, Australia Geology 4 120–122.2.0.CO;2>CrossRefGoogle Scholar
Doyle, L. J. and Sparks, T. N., 1980 Sediments of the Mississippi, Alabama, and Florida (MAFLA) Continental Shelf J. Sed. Petrol. 50 905–916.Google Scholar
Friedman, G. M. and Gavish, E., 1970 Chemical changes in the interstitial waters from sediments of lagoonal, deltaic, river, estuarine and salt water marsh and cove environments J. Sed. Petrol. 40 930–953.Google Scholar
Garrels, R. M. and Christ, C. L., 1965 Solutions, Minerals and Equilibria .Google Scholar
Giresse, P. and Odin, G. S., 1973 Nature, minéralogique et origine des glaucomes du plateau continentale du Gabon et du Congo Sedimentology 20 457–483.CrossRefGoogle Scholar
Gygi, R. A., 1981 Oolitic iron formation: marine or non-marine? Ecologae Geol. Helv. 74 233–254.Google Scholar
Hallimond, A. F., Harvey, C. O. and Bannister, I. A., 1939 On the relation of chamosite and daphnite to the chlorite group Min. Mag. 25 441–465.Google Scholar
Harder, H., 1978 Synthesis of iron layer silicate minerals under natural conditions Clays & Clay Minerals 26 65–72.CrossRefGoogle Scholar
Horne, R. A., 1964 Marine Chemistry New York Wiley.Google Scholar
Hunter, R. E., Fisher, G. W., Pettijohn, F. J., Reed, J. C. and Weaver, K. N., 1970 Facies of iron sedimentation in the Clinton Group Studies in Appalachian Geology, Central and Southern New York Wiley 101–121.Google Scholar
Iijima, A. and Matsumoto, R., 1982 Berthierine and chamosite in coal measures of Japan Clays & Clay Minerals 30 264–274.CrossRefGoogle Scholar
James, H. E. (1966) Chemistry of the iron-rich sedimentary rocks: U.S. Geol. Surv. Prof. Pap. 440W, 60 pp.Google Scholar
Jones, H.L., 1969 Petrology, mineralogy and geochemistry of the chamositic iron ores of north-central Louisiana Norman, Oklahoma Ph.D. thesis, Univ. Oklahoma.Google Scholar
Karpov, P. A., Losev, A. L. and Shilin, A. V., 1967 Mineralogy and condition of Devonian oolitic iron ore formation on the eastern slope of Voronezh anteclise Lithology and Mineral Resources 321–330.Google Scholar
Kastner, M., Keene, J. B. and Gieskes, J. M., 1977 Diagenesis of siliceous oozes—I. Chemical controls on the rate of opal-A to opal-CT transformations—an experimental study Geochim. Cosmochim. Acta 41 1041–1059.CrossRefGoogle Scholar
Kimberley, M. M., 1979 Origin of oolitic iron formations J. Sed. Petrol. 49 111–132.Google Scholar
Kimberley, M. M., 1980 Paz de Rio oolitic inland sea iron formation Econ. Geol. 75 97–106.CrossRefGoogle Scholar
Mehra, O. P., Jackson, M. L. and Swineford, A., 1960 Iron-oxide removal from clay by citrate-dithionite Clays and Clay Minerals, Proc. 7th Natl. Conf., Washington, D.C., 1958 New York Pergamon Press 317–327.Google Scholar
Odin, G. S. and Matter, A., 1981 De glauconiarum origine Sedimentology 28 611–641.CrossRefGoogle Scholar
Pinsak, A. P., Murray, H. A. and Swineford, A., 1960 Regional clay mineral patterns in the Gulf of Mexico Clays and Clay Minerals, Proc. 7th Natl. Conf., Washington, D.C., 1958 New York Pergamon Press 162–177.Google Scholar
Porrenga, D. H., 1967 Glauconite and chamosite as depth indicators in marine environments Marine Geol. 5 495–501.CrossRefGoogle Scholar
Rohrlich, V., 1974 Microstructure and microchemistry of iron oolites Mineral. Deposita 9 133–142.CrossRefGoogle Scholar
Rohrlich, V., Price, N.B. and Calvert, S.E., 1969 Chamosite in the recent sediments of Loch Etive, Scotland J. Sed. Petrol. 39 624–631.Google Scholar
Sacket, W. and Arrhenius, G. O. S., 1962 Distribution of aluminum species in the hydrosphere I. Aluminum in the ocean Geochim. Cosmochim. Acta 26 955–968.CrossRefGoogle Scholar
Sandberg, P. A., 1975 New interpretation of Great Salt Lake ooids and of ancient nonskeletal carbonate mineralogy Sedimentology 22 497–537.CrossRefGoogle Scholar
Schellmann, W., 1969 Die Bildungsbedingungen Sedimentärer Chamosit und Hämatit Eisenerz am Beispiel der Lagerstätte Echte N. Jb. Min. Abh. 111 1–31.Google Scholar
Sokolova, E. F., 1964 Physico-chemical investigations of sedimentary iron and manganese ores and associated rocks Israel Prog. Sci. Transi. Jerusalem .Google Scholar
Taylor, J. H., 1951 Sedimentation problems of the Northampton Sand ironstone Proc. Yorkshire Geol. Soc. 28 74–84.Google Scholar
Van Houten, F. B. and Bhattacharyya, D. P., 1982 Phanerozoic oolitic ironstones—geologic record and facies model Ann. Rev. Earth Planet. Sci. 10 441–457.CrossRefGoogle Scholar
van Olphen, H., 1977 Clay Colloid Chemistry New York Wiley.Google Scholar
Velde, B., 1977 Clays and Clay Minerals in Natural and Synthetic Systems .Google Scholar
Whitehouse, U. G., Jeffreys, L. M., Debbrecht, J. D. and Swineford, A., 1960 Differential settling tendencies of clay minerals in saline waters Clays and Clay Minerals, Proc. 7th Natl. Conf., Washington, D.C., 1958 New York Pergamon Press 71–79.Google Scholar