Quantitative analysis of H2O and CO2 in cordierite using polarized FTIR spectroscopy

We report a FTIR (Fourier transform infrared) study of a set of cordierite samples from different occurrence and with different H₂O/CO₂ content. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMPA (electron microprobe analysis), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm. According to the EMPA data, the Si/Al ratio is always close to 5:4; X _Mg ranges from 76.31 to 96.63, and additional octahedral constituents occur in very small amounts. Extraframework K and Ca are negligible, while Na reaches the values up to 0.84 apfu. SIMS shows H₂O up to 1.52 and CO₂ up to 1.11 wt%. Optically transparent single crystals were oriented using the spindle stage and examined by FTIR micro-spectroscopy under polarized light. On the basis of the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO₂ molecules in the structural channels. The IR spectra also show the presence of small amounts of CO in the samples. Refined integrated molar absorption coefficients were calibrated for the quantitative microanalysis of both H₂O and CO₂ in cordierite based on single-crystal polarized-light FTIR spectroscopy. For H₂O the integrated molar coefficients for type I and type II water molecules (ν₃ modes) were calculated separately and are ^I]ε?=?5,200?±?700?l?mol^?1?cm^?2 and ^II]ε?=?13,000?±?3,000?l?mol^?1?cm^?2, respectively. For CO₂ the integrated coefficient is $ \varepsilon_{{{\text{CO}}_{ 2} }} $ ?=?19,000?±?2,000?l?mol^?1?cm^?2.