The microanalysis of iron and sulphur oxidation states in silicate glass - Understanding the effects of beam damage

Quantifying the oxidation state of multivalent elements in silicate melts (e.g., Fe²⁺ versus Fe³⁺ or S^2- versus S⁶⁺) is fundamental for constraining oxygen fugacity. Oxygen fugacity is a key thermodynamic parameter in understanding melt chemical history from the Earth's mantle through the crust to the surface. To make these measurements, analyses are typically performed on small (<100 µm diameter) regions of quenched volcanic melt (now silicate glass) forming the matrix between crystals or as trapped inclusions. Such small volumes require microanalysis, with multiple techniques often applied to the same area of glass to extract the full range of information that will shed light on volcanic and magmatic processes. This can be problematic as silicate glasses are often unstable under the electron and photon beams used for this range of analyses. It is therefore important to understand any compositional and structural changes induced within the silicate glass during analysis, not only to ensure accurate measurements (and interpretations), but also that subsequent analyses are not compromised. Here, we review techniques commonly used for measuring the Fe and S oxidation state in silicate glass and explain how silicate glass of different compositions responds to electron and photon beam irradiation.