Minerals and Rocks. Editor in Chief P.l.Wyllie, Chicago, IL Editors A.EI Goresy, Heidelberg W von Engelhardt, Tlibingen. T.

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1 Minerals and Rocks 18 Editor in Chief P.l.Wyllie, Chicago, IL Editors A.EI Goresy, Heidelberg W von Engelhardt, Tlibingen. T. Hahn, Aachen

2 G. Gottardi E. Galli Natural Zeolites With 218 Figures Springer-Verlag Berlin Heidelberg New York Tokyo

3 Professor Dr. GLAUCO GOTTARDI Professor Dr. ERMANNO GALLI Istituto di Mineralogia e Petrologia Universita di Modena Via S. Eufernia Modena Volumes 1 to 9 in this series appeared under the title Minerals, Rocks and Inorganic Materials ISBN-13: DOl: / e-isbn-13: Library of Congress Cataloging in Publication Data. Gottardi, Glauco, Natural zeolites. (Mineral and rocks; 18) Bibliography: p. 1. Zeolites. I. Galli, Ermanno, II. Title. III. Series. QE391.Z5G ' This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under 54 of the German Copyright Law, where copies are made for other than private use, a fee is payable to "Verwertungsgesellschaft Wort", Munich. by Springer-Verlag Berlin Heidelberg 1985 Softcover reprint of the hardcover 1 st edition 1985 The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Fotosatz GmbH, Beerfelden 2131/

4 To Laura and Maura

5 Preface Zeolites form a family of minerals which have been known since the 18th century, but they remained a curiosity for scientists and collectors until 60 years ago, when their unique physicochemical properties attracted the attention of many researchers. In the past 30 years there has been an extraordinary development in zeolite science; six International Conferences on Zeolites have been held every 3 years since 1967, and a large number of interesting contributions have been published in their proceedings. Many books, written either by individual authors or by several authors under a leading editor, have been published on these interesting silicate phases, but none has been devoted specifically to natural zeolites, even though this theme may be of interest not only to earth scientists, but also to chemists, as the information obtained from natural samples completes and integrates the characterization of many zeolites. We are trying to fill this gap on the basis of 20 years of research on natural zeolites, which we performed at the University of Modena together with many friends and colleagues. If it is in general difficult to write a scientific book without upsetting somebody, this is particularly true for a book on natural crystals, because mineralogy is an interdisciplinary science which covers some fields of physics, chemistry, petrology, geology, and it is almost impossible to meet every requirement. To begin with crystallography, a partially new structural classification has been proposed without any pretension to having it generally adopted; as a matter of fact, the structural classification of minerals (and of inorganic crystals) is a still open problem. Obviously enough, most of the crystallographic chapters are devoted to crystal structure, the information on morphology being more restricted. Although the same scheme has been chosen for the description of all species, for rare minerals the information given represents nearly all that is at present available, whereas for common minerals a representative spectrum of

6 VIII Preface data has been selected. We have done our best to give a complete list of the occurrences of rare zeolites. Most thermal curves and X-ray powder patterns have been specially recorded and interpreted by the authors, in order to guarantee the homogenity of all these data. Modena, 1985 GLAUCO GOTTARDI ERMANNO GALLI

7 Acknowledgements We wish to thank all the members of the Modena group, A. Alberti, R. Rinaldi, E. Passaglia (now at Ferrara University), D. Pongiluppi, and G. Vezzalini for their advice, and for their permission to publish some new data. Special thanks are due to Laura Gottardi, who kindly typed the manuscript, and to Roy Phillips, who critically read and revised it (although we wonder if he really succeeded in transforming the text as we had written it in a language which only vaguely resembled English, into proper English). Thanks are also due to Maria Franca Brigatti and Luciano Poppi for their assistance in recording the thermal curves. Preparation of some of the drawings and pictures were made possible by the financial support of the Consiglio Nazionale delle Ricerche, Roma. Philips S.p.A., Milano, are also acknowledged for their substantial contribution to the preparation of drawings and the correction of the manuscript. We also wish to thank W. Lugli for drawing many diagrams, V. Casodi for a photograph of phillipsite, and P. Dunn, E. Tillmanns and G. Hentschel for the permission to reproduce some of their pictures. The facilities of the Centro Strumenti and Centro di Calcolo of Modena University were used for preparing the SEM pictures, for indexing the powder patterns and for drawing crystals with the program of Kanazawa and Endo (1981). The structure drawings were made by "Studio grafico Dimitri Nicola" in Modena. Modena, 1985 GLAUCO GOTTARDI ERMANNO GALLI

8 Contents o General Information on Zeolites Introduction and Historical Remarks The Topology of the Tetrahedral Frameworks of Natural Zeolites Introduction The Frameworks ofthe Fibrous Zeolites The Frameworks with Singly Connected 4-Ring Chains The Frameworks with Doubly Connected 4-Ring Chains The Frameworks with 6-Rings The Frameworks of the Mordenite Group The Frameworks of the Heulandite Group The Cages in Zeolite Frameworks Cation Sites in Zeolite Frameworks Fibrous Zeolites Natrolite, Tetranatrolite, Paranatrolite, Mesolite, Scolecite Thomsonite Edingtonite Gonnardite Zeolites with Singly Connected 4-Ring Chains Analcime, Wairakite, Viseite, Hsianghualite Laumontite, Leonhardite Yugawaralite Roggianite Zeolites with Doubly Connected 4-Ring Chains Gismondine, Garronite, Amicite, Gobbinsite Phillipsite, Harmotome Merlinoite Mazzite Paulingite

9 XII Contents 4 Zeolites with 6-Rings Gmelinite Chabazite, Willhendersonite Levyne Erionite Offretite Faujasite Zeolites of the Mordenite Group Mordenite Dachiardite Epistilbite Ferrierite Bikitaite Zeolites of the Heulandite Group Heulandite, Clinoptilolite Stilbite, Stellerite, Barrerite Brewsterite Zeolites with Unknown Structure Cowlesite Goosecreekite Partheite Appendix 1 X-Ray Powder Patterns of Natural Zeolites Appendix 2 Infra-Red Spectra of Fibrous Zeolites References Mineral and Synthetic Zeolite Index Locality Index The descriptions of individual zeolite genera are arranged systematically as follows: 1 History and nomenclature 2 Crystallography 3 Chemistry and synthesis 4 Optical and other physical properties 5 Thermal and other physico-chemical properties 6 Occurrences and genesis 7 Uses and applications