Improving the reliability of Fe- and S-XANES measurements in silicate glasses: correcting beam damage and identifying Fe-oxide nanolites in hydrous and anhydrous melt inclusions

The redox state of silicate melts influences crystallization, element partitioning, and degassing behavior. Synchrotron-based micro-X-ray absorption near edge structure (μXANES) spectroscopy has emerged as a powerful tool for determining redox conditions through the direct measurement of speciation of multivalent elements such as iron and sulfur in silicate glasses. In particular, the high spatial resolution afforded by synchrotron μXANES makes it one of the few techniques available for determining redox conditions in melt inclusions, which can provide insights into pre-eruptive melt properties. However, the small size of melt inclusions, the deep penetration of X-rays, and irradiation-induced beam damage make μXANES measurements in melt inclusions challenging. Here we present data that show rapid Fe- and S-μXANES beam damage in experimental glasses, mid-ocean ridge basalt glasses, and olivine-hosted melt inclusions from the southern Cascade arc and Kīlauea Volcano and develop approaches to recognize and correct for beam damage through repeated rapid analyses. By applying a time-dependent correction to a series of rapid measurements (~82 s/scan) of Fe-μXANES pre-edge centroid positions, irradiation-induced photo-oxidation (Fe2+ to Fe3+) can be corrected back to undamaged initial Fe3+/ΣFe even in damage-susceptible hydrous glasses. Using this beam damage correction technique, hydrous basaltic melt inclusions from the southern Cascades have Fe3+/ΣFe that is ~0.036 lower (corresponding to -0.5 log units lower oxygen fugacity) than would have been indicated by standard Fe-μXANES measurements. Repeated, rapid analyses (150 – 300 s/scan) were used to identify S-μXANES beam damage (photo-reduction of S6+ to S4+), which was corrected with a peak fitting method to restore initial S6+/ΣS. We observe that S-μXANES beam damage can occur rapidly even in low-H2O mid-ocean ridge basaltic glasses and melt inclusions from Kīlauea Volcano, which are otherwise stable during even prolonged Fe-μXANES analyses. By mitigating and correcting for sulfur photo-reduction, we conclude that some mid-ocean ridge basaltic glasses contain 0.08 – 0.09 S6+/ΣS, which is more sulfate than might be expected based on the reduced oxidation state of these glasses (near the fayalite-magnetite-quartz oxygen buffer). Using beam damage identification and correction techniques, the valence states of iron and sulfur can be accurately measured even in beam damage-susceptible glasses and melt inclusions. Finally, using Fe-μXANES, we demonstrate the presence of Fe-oxide nanolites within otherwise glassy, naturally quenched melt inclusions, which can complicate determination of iron valence state in affected glasses.

Kīlauea -Leilani 2018 lava flow delineation by using Sentinel2 and Landsat8 images

Kīlauea is a broad shield volcano built against the southeastern slope of Mauna Loa. The summit presently has a caldera that is roughly 4km by 3.2km wide, and walls of between 0 m and 120 m high. In late April 2018, an eruption interesting both the summit crater and the lower East Rift Zone (LERZ) occurred. In this work a quasi real time estimation of the evolution of radiant lava flow extension starting from May 2018 for Kīlauea -Leilani eruption using satellite image data is presented. The active lava flow evolution is obtained by using Copernicus Sentinel2 (S2) and USGS-Landsat8 (L8) polar satellites acquiring medium/high spatial resolution images (20mx20m and 30mx30m respectively) in the VIS-SWIR-TIR spectral range. Because of the Kīlauea eruption extension and duration, a multi sensor approach has been used in order to improve the timing of the information derived by high spatial resolution remote sensed data merging two missions with different revisit time. The 2018 eruptions at Hawaii's Kīlauea Volcano developed rapidly, after the initial activity centered on the Púu ′Ō′ō crater floor on 1 May followed by draining of the lava lake at Halemáumáu (HMM) Overlook Crater in the next days. During the magma extrusion from the summit, earthquake swarms and ground cracking hit the Leilani Estates neighborhood on 2 May. With the S2 and L8 sensors we followed the lava flow by 5th of May up to mid of August, considering also that the activity started to decline from the beginning of August. At the end of activity, Kīlauea Volcano experienced its largest LERZ eruption and caldera collapse in at least 200 years.