Abstract. To provide a tool for fast estimation of the Fe3+
content in Ca2(Al, Fe3+)3Si3O12(OH) epidote grains,
including in thin sections and crude-rock samples, we applied Raman
spectroscopy to 33 areas from 15 natural samples with Fe3+ ranging from
0.22 to 1.13 atoms per formula unit (apfu), the chemistry of which was
independently determined by wavelength-dispersive electron microprobe
analysis (WD-EPMA). The Raman spectra were collected from the very areas
subjected to WD-EPMA. We have analysed both the OH-stretching region
(3215–3615 cm−1) and the spectral range generated by the framework
vibrations (15–1215 cm−1). Similarly to the IR spectra, the Raman peaks
in the OH-stretching region shift toward higher wavenumbers with increasing
Fe. However, the quantification of Fe3+ based on OH-stretching Raman
peaks can be hindered by the multicomponent overlapping and significant
intensity variations with the crystal orientation. Among the Raman signals
generated by framework vibrations, the position of four peaks (near 250,
570, 600, and 1090 cm−1) exhibit a steady linear regression with the
increase in Fe content (in apfu). However, the peak near 250 cm−1
attributed to MO6 vibrations also depends on the crystal orientation
and therefore is not always well resolved, which worsens the accuracy in
Fe-content determination based on its position. The peaks near 570, 600, and
1090 cm−1 arise from Si2O7 vibrational modes, and although
their intensities also vary with the crystal orientation, all three signals
are well resolved in a random orientation. However, among the three
Si2O7-related signals, the 570 cm−1 peak is the sharpest
(peak width <10 cm−1) and is easily recognized as a separate
peak. Hence, we propose to use the position of this peak as a highly
reliable parameter to estimate the Fe content, via the linear trend given as
ω570=577.1(3)-12.7(4)x, where ω is the wavenumber
(cm−1) and x is Fe content (apfu), with accuracy ± 0.04
Fe3+ apfu. The peaks near 600 and 1090 cm−1 may be complementarily
used for the Fe estimate, based on the following relations: ω600=611.6(2)-13.8(4)x and ω1090=1098.8(3)-13.5(5)x. Analyses of
the effect of Sr as a substitution for Ca and Cr at the octahedral sites
indicate that contents of Sr <0.12 apfu do not interfere with the
quantification of Fe via the ω570 (x) relation, whereas Cr
>0.16 apfu leads to overestimation of Fe; Cr presence can be
recognized however by the broadening of the peaks near 95 and 250 cm−1.