Improvement of Electron Probe Microanalysis of Boron Concentration in Silicate Glasses

The determination of low boron concentrations in silicate glasses by electron probe microanalysis (EPMA) remains a significant challenge. The internal interferences from the diffraction crystal, i.e. the Mo-B4C large d-spacing layered synthetic microstructure crystal, can be thoroughly diminished by using an optimized differential mode of pulse height analysis (PHA). Although potential high-order spectral interferences from Ca, Fe, and Mn on the BKα peak can be significantly reduced by using an optimized differential mode of PHA, a quantitative calibration of the interferences is required to obtain accurate boron concentrations in silicate glasses that contain these elements. Furthermore, the first-order spectral interference from ClL-lines is so strong that they hinder reliable EPMA of boron concentrations in Cl-bearing silicate glasses. Our tests also indicate that, due to the strongly curved background shape on the high-energy side of BKα, an exponential regression is better than linear regression for estimating the on-peak background intensity based on measured off-peak background intensities. We propose that an optimal analytical setting for low boron concentrations in silicate glasses (≥0.2 wt% B2O3) would best involve a proper boron-rich glass standard, a low accelerating voltage, a high beam current, a large beam size, and a differential mode of PHA

Experimental calbration and implications of olivine-melt vanadium oxybarometry for hydrous magmas from Mutnovsky volcano (Kamchatka)

A promising method for the quantification of the redox conditions (oxygen fugacity, fO2) in basaltic systems, which might be applied to quenched melt inclusions in olivine, exploits the partitioning of vanadium between olivine and coexisting silicate melt (DV Ol‐M). Strong correlation of DV Ol‐M with fO2 was investigated in a number of experimental works on dry mafic and ultramafic melts in a wide range of fO2 conditions at pressures of 1 atm and 0.5–2 GPa, temperature range of 1150–1530°C (e.g., Canil&Fedortchouk, 2001; Mallmann&O’Neill, 2009; 2013). Only a few melt compositions equilibrated with olivine at T≤1250°C were studied so far. Although it was shown that melt composition, pressure and temperature have small effect on DV Ol‐M, more data are required to extend the calibration of the V oxybarometry to hydrous low‐temperature basalts representing island arc magmas

Automated Segmentation of Olivine Phenocrysts in a Volcanic Rock Thin Section Using a Fully Convolutional Neural Network

An example of automated characterization and interpretation of the textural and compositional characteristics of solids phases in thin sections using machine learning (ML) is presented. In our study, we focus on the characterization of olivine in volcanic rocks, which is a phase that is often chemically zoned with variable Mg/(Mg + Fe) ratios, so-called magnesian number or mg#. As the olivine crystals represent only less than 10 vol% of the volcanic rock, a pre-processing step is necessary to automatically detect the phases of interest in the images on a pixel level, which is achieved using Deep Learning. A major contribution of the presented approach is to use backscattered electron (BSE) images to: 1) automatically segment all olivine crystals present in the thin section; 2) determine quantitatively their mg#; and 3) identify different populations depending on zoning type (e.g., normal vs reversal zoning) and textural characteristics (e.g., microlites vs phenocrysts). The segmentation of the olivine crystals is implemented with a pretrained fully convolutional neural network model with DeepLabV3 architecture. The model is trained to identify olivine crystals in backscattered electron images using automatically generated training data. The training data are generated automatically from images which can easily be created from X-Ray element maps. Once the olivines are identified in the BSE images, the relationship between BSE intensity value and mg# is determined using a simple regression based on a set of microprobe measurements. This learned functional relationship can then be applied to all olivine pixels of the thin section. If the highest possible map resolution (1 micron per 1 pixel) is selected for the data acquisition, the full processing time of an entire thin section of (Formula presented.) containing more than 1,500 phenocrysts and 20.000 microliths required 140 h of data acquisition (BSE + X-Ray element maps), 8 h of training and 16 h of segmentation and classification. Our further tests demonstrated that the 140 h of data acquisition can be reduced at least by a factor of 4 since only a part of the thin section area (25% or even less) needs to be used for training. The characterization of each additional thin section would only require the BSE data acquisition time (less than 48 h for a whole thin section), without an additional training step. The paper describes the training and processing in detail, shows analytical results and outlines the potential of this Deep Learning approach for petrological applications, resulting in the automatic characterization and interpretation of mineral textures and compositions with an unprecedented high resolution. Copyright © 2022 Leichter, Almeev, Wittich, Beckmann, Rottensteiner, Holtz and Sester

Formation mechanisms of macroscopic globules in andesitic glasses from the Izu–Bonin–Mariana forearc (IODP Expedition 352)

The Izu–Bonin–Mariana volcanic arc is situated at a convergent plate margin where subduction initiation triggered the formation of MORB-like forearc basalts as a result of decompression melting and near-trench spreading. International Ocean Discovery Program (IODP) Expedition 352 recovered samples within the forearc basalt stratigraphy that contained unusual macroscopic globular textures hosted in andesitic glass (Unit 6, Hole 1440B). It is unclear how these andesites, which are unique in a stratigraphic sequence dominated by forearc basalts, and the globular textures therein may have formed. Here, we present detailed textural evidence, major and trace element analysis, as well as B and Sr isotope compositions, to investigate the genesis of these globular andesites. Samples consist of K2O-rich basaltic globules set in a glassy groundmass of andesitic composition. Between these two textural domains a likely hydrated interface of devitrified glass occurs, which, based on textural evidence, seems to be genetically linked to the formation of the globules. The andesitic groundmass is Cl rich (ca. 3000μg/g), whereas globules and the interface are Cl poor (ca. 300μg/g). Concentrations of fluid-mobile trace elements also appear to be fractionated in that globules and show enrichments in B, K, Rb, Cs, and Tl, but not in Ba and W relative to the andesitic groundmass, whereas the interface shows depletions in the latter, but is enriched in the former. Interestingly, globules and andesitic groundmass have identical Sr isotopic composition within analytical uncertainty (87Sr/86Sr of 0.70580±10), indicating that they likely formed from the same source. However, globules show high δ11B (ca. + 7‰), whereas their host andesites are isotopically lighter (ca. – 1 ‰), potentially indicating that whatever process led to their formation either introduced heavier B isotopes to the globules, or induced stable isotope fractionation of B between globules and their groundmass. Based on the bulk of the textural information and geochemical data obtained from these samples, we conclude that these andesites likely formed as a result of the assimilation of shallowly altered oceanic crust (AOC) during forearc basaltic magmatism. Assimilation likely introduced radiogenic Sr, as well as heavier B isotopes to comparatively unradiogenic and low δ11B forearc basalt parental magmas (average 87Sr/86Sr of 0.703284). Moreover, the globular textures are consistent with their formation being the result of fluid-melt immiscibility that was potentially induced by the rapid release of water from assimilated AOC whose escape likely formed the interface. If the globular textures present in these samples are indeed the result of fluid-melt immiscibility, then this process led to significant trace element and stable isotope fractionation. The textures and chemical compositions of the globules highlight the need for future experimental studies aimed at investigating the exsolution process with respect to potential trace element and isotopic fractionation in arc magmas that have perhaps not been previously considered

Subduction initiation and ophiolite crust: new insights from IODP drilling

International Ocean Discovery Program (IODP) Expedition 352 recovered a high-fidelity record of volcanism related to subduction initiation in the Bonin fore-arc. Two sites (U1440 and U1441) located in deep water nearer to the trench recovered basalts and related rocks; two sites (U1439 and U1442) located in shallower water further from the trench recovered boninites and related rocks. Drilling in both areas ended in dolerites inferred to be sheeted intrusive rocks. The basalts apparently erupted immediately after subduction initiation and have compositions similar to those of the most depleted basalts generated by rapid sea-floor spreading at mid-ocean ridges, with little or no slab input. Subsequent melting to generate boninites involved more depleted mantle and hotter and deeper subducted components as subduction progressed and volcanism migrated away from the trench. This volcanic sequence is akin to that recorded by many ophiolites, supporting a direct link between subduction initiation, fore-arc spreading, and ophiolite genesis

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

Crustal-scale degassing due to magma system destabilization and magma-gas decoupling at Soufrière Hills Volcano, Montserrat

Activity since 1995 at Soufrière Hills Volcano (SHV), Montserrat has alternated between andesite lava extrusion and quiescence, which are well correlated with seismicity and ground deformation cycles. Large variations in SO₂ flux do not correlate with these alternations, but high and low HCl/SO₂ characterize lava dome extrusion and quiescent periods respectively. Since lava extrusion ceased (February 2010) steady SO₂ emissions have continued at an average rate of 374 tonnes/day (± 140 t/d), and incandescent fumaroles (temperatures up to 610°C) on the dome have not changed position or cooled. Occasional short bursts (over several hours) of higher (∼ 10x) SO₂ flux have been accompanied by swarms of volcano-tectonic earthquakes. Strain data from these bursts indicate activation of the magma system to depths up to 10 km. SO₂ emissions since 1995 greatly exceed the amounts that could be derived from 1.1 km³ of erupted andesite, and indicating extensive partitioning of sulfur into a vapour phase, as well as efficient decoupling and outgassing of sulfur-rich gases from the magma. These observations are consistent with a vertically extensive, crustal magmatic mush beneath SHV. Three states of the magmatic system are postulated to control degassing. During dormant periods (10³ to 10⁴ years) magmatic vapour and melts separate as layers from the mush and decouple from each other. In periods of unrest (years) without eruption, melt and fluid layers become unstable, ascend and can amalgamate. Major destabilization of the mush system leads to eruption, characterized by magma mixing and release of volatiles with different ages, compositions and sources.RSJS acknowledges an ERC advanced grant (VOLDIES). JDB acknowledges ERC advanced grant CRITMAG and a Wolfson Research Merit Award.This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/2015GC00579