High spatial resolution analysis of the iron oxidation state in silicate glasses using the electron probe

The iron oxidation state in silicate melts is important for understanding their physical properties, although it is most often used to estimate the oxygen fugacity of magmatic systems. Often high spatial resolution analyses are required, yet the available techniques, such as μXANES and μMössbauer, require synchrotron access. The flank method is an electron probe technique with the potential to measure Fe oxidation state at high spatial resolution but requires careful method development to reduce errors related to sample damage, especially for hydrous glasses. The intensity ratios derived from measurements on the flanks of FeLα and FeLβ X-rays (FeLβf/FeLαf) over a time interval (time-dependent ratio flank method) can be extrapolated to their initial values at the onset of analysis. We have developed and calibrated this new method using silicate glasses with a wide range of compositions (43–78 wt% SiO2, 0–10 wt% H2O, and 2–18 wt% FeOT, which is all Fe reported as FeO), including 68 glasses with known Fe oxidation state. The Fe oxidation state (Fe2+/FeT) of hydrous (0–4 wt% H2O) basaltic (43–56 wt% SiO2) and peralkaline (70–76 wt% SiO2) glasses with FeOT > 5 wt% can be quantified with a precision of ±0.03 (10 wt% FeOT and 0.5 Fe2+/FeT) and accuracy of ±0.1. We find basaltic and peralkaline glasses each require a different calibration curve and analysis at different spatial resolutions (∼20 and ∼60 μm diameter regions, respectively). A further 49 synthetic glasses were used to investigate the compositional controls on redox changes during electron beam irradiation, where we found that the direction of redox change is sensitive to glass composition. Anhydrous alkali-poor glasses become reduced during analysis, while hydrous and/or alkali-rich glasses become oxidized by the formation of magnetite nanolites identified using Raman spectroscopy. The rate of reduction is controlled by the initial oxidation state, whereas the rate of oxidation is controlled by SiO2, Fe, and H2O content

Rapid pre-eruptive mush reorganisation and atmospheric volatile emissions from the 12.9 ka Laacher See eruption, determined using apatite

Magma is commonly thought to be stored as a crystal-rich mush within vertically extensive, crustal storage regions. A key unknown is how to remobilise and erupt such crystal-rich material, and whether the growth of gas bubbles within the mush could promote remobilisation. In order to investigate this, we need improved constraints on the timing of volatile saturation in magmas. The mineral apatite represents a potentially useful record of pre-eruptive magmatic volatiles, but data interpretation is complex because exchange reactions control the volatile partitioning. Model solutions are therefore non-unique. Here, we present a numerical forward modelling program with a sensitivity analysis function, which addresses non-uniqueness by identifying alternative sets of starting parameters that match a target compositional trend through a population of apatite crystals. The model is applied to a new dataset of volatiles in apatite from the 12.9 ka Laacher See eruption, Eifel volcanic region, Germany. The results indicate that the magma was initially strongly volatile-undersaturated and became saturated through progressive crystal fractionation. Apatite crystals are not in volatile or trace element equilibrium with their carrier melts, indicating dispersal of crystals into different chemical environments. Consideration of apatite diffusivities suggests that this reorganisation occurred shortly before eruption. Our modelling results also allow us to constrain directly the amount of pre-eruptive magmatic vapour emitted during the explosive eruption, highlighting the importance of considering the behaviour of halogens during magma storage. Overall, our approach confirms the value of measuring apatite volatile contents and highlights the potential of this method to provide quantitative constraints on magmatic evolution and storage conditions