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1 GIMEF-Departamento de Geologia, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, P-4169-007 Porto, Portugal
2 UMR-CNRS 6532 HYDRASA, 40 avenue du Recteur Pineau, Université de Poitiers, F-86022 Poitiers Cedex, France
3 CRPG-CNRS, Ecole Normale Supérieure de Géologie, F-54501 Vandœuvre-lès-Nancy Cedex, France
* E-mail address of corresponding author: ibobos{at}fc.up.pt
The alteration of spodumene to cookeite has been identified in a Li-bearing aplite-pegmatite from northern Portugal. Optical microscopy and scanning and transmission electron microscopy (SEM/ TEM) were used to characterize the alteration products in both cookeite + quartz and cookeite + kaolinite 3 mica assemblages. Mutual relationships between the minerals were assessed using back-scattered electron imaging. The first assemblage occurs along the cleavage planes of spodumene, whereas the second forms as the result of spodumene breakdown. Fine mica grains surrounded the cookeite aggregates in the second assemblage only. Precipitations of cookeite and quartz in open pore spaces and parallel packets of cookeite and kaolinite were identified by TEM. Selected area electron diffraction carried out on cookeite identified a layer-stacking sequence from highly disordered to one-layer order-disorder with a lesser participation of two-layer polytypes. The thickness of one-layer cookeite packets averaged ~85100 nm. Disordered cookeite has a mean thickness of 450 nm. The chemistry of cookeite was analyzed by both electron and ion-microprobe techniques. The structural formula of cookeite from the first assemblage corresponds to: Al2.0(Si3.23Al0.766)O10(OH)2(Al1.80Li1.166Mg0.004Fe0.09)(OH)6. Two distinct compositional varieties were found: one corresponding to ideal cookeite, whereas the second belongs to the cookeitedonbassite join.
The thermodynamic stability field for the observed minerals was calculated using the SUPCRT® programme. Two distinct stages of cookeite crystallization are discussed. The lower pressure and temperature stability of the reaction of spodumene to cookeite + quartz were estimated at ~2.4 kbar and 240°C. The cookeite + kaolinite 3 mica assemblage is still in equilibrium with quartz at ~2.2 kbar and 220°C. The lower limit for the stability of cookeite was found at 205°C and 2 kbar.
Key Words: Cookeite Crystal Chemistry Electron Microscopy Kaolinite Polytype Spodumene Breakdown Thermodynamic Stability
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