Spodumene (LiAlSi₂O₆) is a member of pyroxene-group minerals. It has the highest theoretical lithium abundance among all of the Li-bearing minerals. In the present work, in situ high-pressure Raman spectroscopic investigation of natural spodumene have been conducted up to 19.04 GPa. Unheated spodumene and spodumene recovered after heat treatments (up to 1000 °C) have also been analyzed by X-ray diffraction and infrared spectroscopy. The results indicate that spodumene, after the displacive C2/c–P2₁/c transformation triggered at ~3.2 GPa, remains stable at pressures up to 19 GPa at ambient temperature without undergoing decomposition, amorphization, or a second phase transition. The major OH bands of the spodumene samples are observed within the wavenumber range of 2580–3220 cm⁻¹, implying a strong hydrogen bond interaction. The water content of the spodumene is estimated to be 19–97 ppm wt. H₂O based on the integrated absorption area of the OH bands. The FTIR analysis of the spodumene samples recovered after heat treatments implies that spodumene can retain a significant amount of water (up to ~100 ppm H₂O by weight) under high-temperature conditions up to 1000 °C. This suggests that spodumene in subducted slabs is unlikely to undergo dehydration at temperatures below 1000 °C, and is therefore not expected to trigger partial melting. Thus, spodumene may serve as a key carrier for Li, transporting it into the deep mantle without releasing Li into melts during subduction.

In situ high-temperature Raman spectroscopy (up to 550 °C) and infrared spectroscopy (up to 700 °C) were employed to analyze hydrous Fe-rich ringwoodite (Fo76 composition containing 0.69 wt% H₂O). The results demonstrate that the hydrous Fe-rich ringwoodite sample undergoes irreversible structural transformation above 300 °C at ambient pressure, converting to an amorphous phase. This indicates a lower thermal stability threshold compared to Fe-bearing ringwoodite (Fo90) with equivalent water content. Notably, identical infrared spectral evolution patterns were observed during heating (25–500 °C) for the studied Fo76 sample and previously reported Fo82/Fo90 specimens, suggesting minimal influence of iron content variation on hydroxyl group behavior. The material derived from Fe-rich ringwoodite through structural transformation at ~350 °C retains the capacity to preserve water within a defined temperature window (400–550 °C). In situ high-pressure Raman spectroscopy experiments conducted up to 20 GPa detected no notable structural modifications, suggesting that hydrous Fe-rich ringwoodite, hydrous Fe-bearing ringwoodite, and hydrous Mg-endmember ringwoodite exhibit comparable structural stability within this pressure range.