Natural zeolites: odd genesis, intrinsic beauty,

wide applicationsZelimir Gabelica

LPI-GSEC, ENSCMu, Mulhouse, France

2nd FEZA School, Paris, September 1-2, 2008Mr Toni WIELAND

Mr Eddy VANDERMEERSCHE

Dr Roger WARIN

Dr Sabine VALANGE

Dr Ermanno GALLI

Acknowledgments:

ZEOLITE GROUP

Reference: Fleischer’s Glossary of Mineral SpeciesM.E. Back & J.A. Mandarino, Miner. Rec. Ed., Tuscon (AZ), 2008, 345 pp

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MINERAL GROUPSMINERAL GROUPSA mineral group, consisting of at least 3 species, involves

members having similar chemical formulae and, ideally, the same general structure, thus belonging to the same crystal

system (not often respected)

ZEOLITE GROUPSZEOLITE GROUPS(Alumino)silicates (“and related”?) with framework structures

containing open cavities in the form of channels and cages, usually occupied by

H2O and extra-framework (charge-compensating) cations. Crystallography varies within the group.

90 officially recognized species (as for August 2008, including Direnzoite) are partitioned between series species and non-series species

SERIES

Series can be defined on the basis of dominant extra-framework cations

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In the case of zeolites, series were established for 15 generic species15 generic species, each involving 2 or more species:

BRE (Monoclinic): Ba, Sr Ex: Brewsterite-Ba

CHA (Trigonal): Na, K, Ca, Sr Note: Herschellite (discredited)

Chabasite-KCLI (Monoclinic): Na, K, Ca

DAC (Monoclinic): Na, Ca

ERI (Hexagonal): Na, K, Ca

FAU (Cubic): Na, Ca, Mg Note: Kaiserstuhl: presence of both FAU-Na & FAU-

MgFAU-Ca exclusively found at Vogelsberg

SERIES

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FER (Orth. & Mon.): Na, K, Mg

GME (Hexagonal): Na, K, Ca

HEU (Monoclinic): Na, K, Ba, Ca, Sr

LEV (Trigonal): Na, Ca

MAZ (Hexagonal): Na, Mg Note: Mt Semiol = Mazzite-Mg; Mazzite-Ca = Boron

(CA)PAU (Cubic): K, Ca

PHI (Monoclinic): Na, K, Ca

STI (Monoclinic): Na, Ca

THO (Orthorhombic): Ca, Sr

Total: 41 valid species

49 OTHER NON-SERIES ZEOLITE SPECIES

From Analcime to Yugawaralite …

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Some remarks:

- Analcime: 5 different crystal systems: Cub., Tet., Orth., Mon., Tric.- Leucite (and Ammonioleucite) do belong to the zeolite group, but not their analog Sodalite (see later “Sodalite Subgroup” of CAN-SOD Group)- Barrerite (Orthorhombic) is different from Stilbite-Na (Monoclinic)

- 3 Li-bearing species:Bikitaite, Hsianghualite, Pahasapaite

- 5 Beryllosilicate frameworks:Chiavennite, Hsianghualite, Lovdarite, Nabesite,

Roggianite- 2 Beryllophosphate frameworks:

Pahasapaite, Weinebeneite (Tiptopite = Cancrinite sub-group)

49 OTHER NON-SERIES ZEOLITE SPECIES

From Analcime to Yugawaralite (continued)

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- Kalborsite: contains 2 “extra-framework” anions: B(OH)4- and Cl-

- Tschörtnerite: contains 1 extra-framework exotic” anion: Cu(OH)8

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- Presence of (framework?) cations other than alkali or alkaline-earth:

Maricopaite (framework Pb(O,OH)4) and Chiavennite (Mn2+)- Highest Si/Al ratios: Mutinaite (7.73), Gottardiite (7.31)

- 1 Zincosilicate framework:Gaultite (Na4Zn2Si7O18.5H2O, Orth.)

- Status of Phosphovanadylite ?? (Na,K,Ba,Ca-aluminovanadophosphate)

CANCRINITE-SODALITE GROUP

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Divided into 3 sub-groups, based on the stacking sequence of layers of non-connected 6MR: 29 species29 species

- Cancrinite sub-group:Trigonal or hexagonal species involving “cancrinite cages”Containing salts (ionic pairs: Na, Ca, Cl…) that fill the void space

10 speciesEx: cancrinite, cancrisilite, davyne, tiptopite…)

- Sodalite sub-group:Cubic or tetragonal species involving cuboctahedral “sodalite cages”Filled with clusters of atoms (cations, SO4, Cl, (poly)sulphides…)11 speciesEx: Sodalite (Cl), Lazurite (S, Cl, OH), Haüyne (SO4),

Genthelvite (Fe & S), Helvine (Mn & S) …

CANCRINITE-SODALITE GROUP

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- Sodalite sub-group: (continued)

NB: Tsaregorodsevite (TMA)4[Si2(Si0.5Al0.5)O6]2, involves TMA+ cations that (probably) act as both structure-directing agents (SOD cages) and counterions to one framework negative charge.

8 speciesEx: Afghanite, Franzinite, Giuseppetite, Liottite …

- Other species in the CAN-SOD group:Trigonal or hexagonal species with different stacking sequences:

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RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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NEW TOPOLOGIES ?

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NEW TOPOLOGIES ?

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NEW TOPOLOGIES ?

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“ZEOLITHE INFAILLIBLE” : FIRST APPLICATION ?

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