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McIntosh, I.M., Nichols, A.R.L., Tani, K. & Llewellin, E.W. (2017). Accounting for the species-dependence of the 3500 cm-1 H2Ot infrared molar absorptivity coefficient: implications for hydrated volcanic glasses. American Mineralogist 102(8): 1677-1689.

Author(s) from Durham


Fourier transform infrared (FTIR) spectroscopy can be used to determine the concentration and
speciation of dissolved water in silicate glasses if the molar absorptivity coefficients (e) are known.
Samples that are thin and/or water-poor typically require the use of the mid-IR 3500 cm–1 total water
(H2Ot) and 1630 cm–1 molecular water (H2Om) absorbance bands, from which hydroxyl water (OH) must
be determined by difference; however, accurate determination of H2Ot and OH is complicated because
e3500 varies with water speciation, which is not usually known a priori. We derive an equation that uses
end-member e3500 values to find accurate H2Ot and OH concentrations from the 3500 cm–1 absorbance
for samples where only the H2Om concentration need be known (e.g., from the 1630 cm–1 band). We
validate this new species-dependent e3500 method against published data sets and new analyses of glass
standards. We use published data to calculate new end-member e3500 values of e3500OH = 79 ± 11 and
e3500H2Om = 49 ± 6 L/mol∙cm for Fe-bearing andesite and e3500OH = 76 ± 12 and e3500H2Om = 62 ± 7
L/mol∙cm for Fe-free andesite. These supplement existing end-member values for rhyolite and albite
compositions. We demonstrate that accounting for the species-dependence of e3500 is especially important
for hydrated samples, which contain excess H2Om, and that accurate measurement of OH concentration,
in conjunction with published speciation models, enables reconstruction of original pre-hydration
water contents. Although previous studies of hydrous silicate glasses have suggested that values of e
decrease with decreasing tetrahedral cation fraction of the glass, this trend is not seen in the four sets of
end-member e3500 values presented here. We expect that future FTIR studies that derive end-member
e3500 values for additional compositions will therefore not only enable the species-dependent e3500
method to be applied more widely, but will also offer additional insights into the relationship between
values of e and glass composition.