Raman spectroscopic identification of cookeite in the crystal-rich inclusions in spodumene from the Jiajika lithium pegmatite deposit, China, and its geological implications

Abstract

Cookeite usually occurs as a late alteration product in lithium-cesium-tantalum-type granitic pegmatite. Consequently, cookeite-bearing crystal-rich inclusions (CIs) in pegmatite are considered to be of secondary origin, which constrains our understanding of pegmatite formation. Thus far, no reported cookeite has produced a distinct Raman spectrum. However, the CIs hosted in spodumene in the Jiajika pegmatite deposit, China, contain a cookeite-like hydrous lithium-aluminum-silicate phase, yielding a distinct Raman spectrum. In electron microprobe analysis, focused ion beam scanning electron microscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS), the average composition of this hydrous phase was determined as Li1:005.Al3:997Fe0:018/.Si3:086Al0:914/O10:076OH7:902F0:098, close to the International Mineralogical Association (IMA) formula of cookeite, (Al, Li)3Al2(Si, Al)4O10(OH)8. The distinct Raman peaks at 98, 167, 219, 266, 342, 382, 457, 592, 710, and 3640 cm-1 were consistent with those of natural cookeite recrystallized in a hydrothermal diamond-anvil cell. The peaks were ascribed to the crystallization of cookeite from the liquid trapped in the closed space during the spodumene crystallization, which occurred at relatively high temperature and pressure without incorporating the minor elements commonly present during alteration processes. These minor elements often obscure the Raman signals, primarily by fluorescence effects. This type of cookeite in CIs with distinct Raman signals is unusual and can indicate whether the cookeite crystallized from fluid trapped within the closed space of a primary inclusion. In such a case, the fluid can be considered a flux-rich hydrous melt in pegmatite formation models.