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Natural zeolites: odd genesis, intrinsic beauty, wide applications Zelimir Gabelica LPI-GSEC, ENSCMu, Mulhouse, France 2 nd FEZA School, Paris, September.

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Presentation on theme: "Natural zeolites: odd genesis, intrinsic beauty, wide applications Zelimir Gabelica LPI-GSEC, ENSCMu, Mulhouse, France 2 nd FEZA School, Paris, September."— Presentation transcript:

1 Natural zeolites: odd genesis, intrinsic beauty, wide applications Zelimir Gabelica LPI-GSEC, ENSCMu, Mulhouse, France 2 nd FEZA School, Paris, September 1-2, 2008 Mr Toni WIELAND Mr Eddy VANDERMEERSCHE Dr Roger WARIN Dr Sabine VALANGE Dr Ermanno GALLI Acknowledgments:

2 ZEOLITE GROUP Reference : Fleischers Glossary of Mineral Species M.E. Back & J.A. Mandarino, Miner. Rec. Ed., Tuscon (AZ), 2008, 345 pp 1 MINERAL GROUPS A 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 GROUPS (Alumino)silicates (and related?) with framework structures containing open cavities in the form of channels and cages, usually occupied by H 2 O 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

3 SERIES Series can be defined on the basis of dominant extra-framework cations 2 15 generic species In the case of zeolites, series were established for 15 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-K CLI (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-Mg FAU-Ca exclusively found at Vogelsberg

4 SERIES 3 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

5 49 OTHER NON-SERIES ZEOLITE SPECIES From Analcime to Yugawaralite … 4 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)

6 49 OTHER NON-SERIES ZEOLITE SPECIES From Analcime to Yugawaralite (continued) 5 - Kalborsite: contains 2 extra-framework anions: B(OH) 4 - and Cl - - Tschörtnerite: contains 1 extra-framework exotic anion: Cu(OH) Presence of (framework?) cations other than alkali or alkaline-earth: Maricopaite (framework Pb(O,OH) 4 ) and Chiavennite (Mn 2+ ) - Highest Si/Al ratios: Mutinaite (7.73), Gottardiite (7.31) - 1 Zincosilicate framework: Gaultite (Na 4 Zn 2 Si 7 O 18.5H 2 O, Orth.) - Status of Phosphovanadylite ?? (Na,K,Ba,Ca-aluminovanadophosphate)

7 CANCRINITE-SODALITE GROUP 6 29 species Divided into 3 sub-groups, based on the stacking sequence of layers of non-connected 6MR: 29 species - Cancrinite sub-group: Trigonal or hexagonal species involving cancrinite cages Containing salts (ionic pairs: Na, Ca, Cl…) that fill the void space 10 species Ex: cancrinite, cancrisilite, davyne, tiptopite…) - Sodalite sub-group: Cubic or tetragonal species involving cuboctahedral sodalite cages Filled with clusters of atoms (cations, SO 4, Cl, (poly)sulphides…) 11 species Ex: Sodalite (Cl), Lazurite (S, Cl, OH), Haüyne (SO 4 ), Genthelvite (Fe & S), Helvine (Mn & S) …

8 CANCRINITE-SODALITE GROUP 7 - Sodalite sub-group: (continued) NB: Tsaregorodsevite (TMA) 4 [Si 2 (Si 0.5 Al 0.5 )O 6 ] 2, involves TMA + cations that (probably) act as both structure-directing agents (SOD cages) and counterions to one framework negative charge. 8 species Ex: Afghanite, Franzinite, Giuseppetite, Liottite … - Other species in the CAN-SOD group: Trigonal or hexagonal species with different stacking sequences:

9 8 RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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11 10 RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

12 11 RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

13 12 RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS

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15 RARE ZEOLITES, UNUSUAL COLORS, UNEXPECTED COMPOSITIONS 14

16 NEW TOPOLOGIES ? 15

17 NEW TOPOLOGIES ? 16

18 NEW TOPOLOGIES ? 17

19 ZEOLITHE INFAILLIBLE : FIRST APPLICATION ? 18


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