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We present DiadFit—an open-source Python3 tool for efficient processing of Raman spectroscopy data collected from fluid inclusions, melt inclusions and silicate melts. DiadFit is optimized to fit the characteristic peaks from CO2 fluids (Fermi diads, hot bands, 13C), gas species such as SO2, N2, solid precipitates (e.g. carbonates), and Ne emission lines with easily tweakable background positions and peak shapes. DiadFit's peak fitting functions are used as part of a number of workflows optimized for quantification of CO2 in melt inclusion vapour bubbles and fluid inclusions. DiadFit can also convert between temperature, pressure and density using various CO2 and CO2-H2O equations of state (EOS), allowing calculation of fluid inclusion pressures (and depths in the crust), conversion of homogenization temperatures from microthermometry to CO2 density, and propagation of uncertainties associated with EOS calculations using Monte Carlo methods. There are also functions to quantify the area ratio of the silicate vs. H2O region of spectra collected on silicate glasses to determine H2O contents in glasses and melt inclusions. Documentation and worked examples are available (https://bit.ly/DiadFitRTD, https://bit.ly/DiadFitYouTube).

 

The iconic volcanoes of the Cascade arc stretch from Lassen Volcanic Center in northern California, through Oregon and Washington, to the Garibaldi Volcanic Belt in British Columbia. Recent studies have reviewed differences in the distribution and eruptive volumes of vents, as well as variations in geochemical compositions and heat flux along strike (amongst other characteristics). We investigate whether these along‐arc trends manifest as variations in magma storage conditions. We compile available constraints on magma storage depths from InSAR, geodetics, seismic inversions, and magnetotellurics for each major edifice and compare these to melt inclusion saturation pressures, pressures calculated using mineral‐only barometers, and constraints from experimental petrology. The availability of magma storage depth estimates varies greatly along the arc, with abundant geochemical and geophysical data available for some systems (e.g., Lassen Volcanic Center, Mount St. Helens) and very limited data available for other volcanoes, including many which are classified as “very high threat” by the USGS (e.g., Glacier Peak, Mount Baker, Mount Hood, Three Sisters). Acknowledging the limitations of data availability and the large uncertainties associated with certain methods, available data are indicative of magma storage within the upper 15 km of the crust (∼2 ± 2 kbar) beneath the main edifices. These findings are consistent with previous work recognizing barometric estimates cluster within the upper crust in many arcs worldwide. There are no clear offsets in magma storage between arc segments that are in extension, transtension or compression, although substantially more petrological work is needed for fine scale evaluation of storage pressures.

 

Raman spectroscopy has become the tool of choice for analyzing fluid inclusions and melt inclusion (MI) vapor bubbles as it allows the density of CO2-rich fluids to be quantified. Measurements are often made at ambient temperature (Tamb ~18-25 °C), resulting in reported bulk densities between 0.2 and 0.7 g/mL despite that single-phase CO2 under these conditions is thermodynamically unstable and instead consists of a liquid (~0.7 g/mL), and a vapor phase (~0.2 g/mL). Here, we present results from experiments conducted at Tamb and 37 °C (above the CO2 critical temperature) on 14 natural CO2-rich MI bubbles from Mount Morning, Antarctica. Here, we show that at Tamb, laser power strongly affects the CO2 Raman spectrum of MI bubbles with bulk densities within the miscibility gap. High-power laser heating and low spectral resolution explain why published measurements have reported such bulk densities at Tamb even when using an instrument-specific calibration. 

Abstract The composition of clinopyroxene and clinopyroxene-liquid (Cpx-Liq) pairs are frequently used to calculate crystallization/equilibration pressures in igneous systems. While canonical uncertainties are often assigned to calculated pressures based on fits to calibration or test datasets, the sources of these uncertainties (and thus ways to reduce them) have not been rigorously assessed. We show that considerable uncertainties in calculated pressures arise from analytical error associated with Electron Probe Microanalyser (EPMA) measurements of Cpx. Specifically, low X-ray counts during analysis of elements with concentrations <1 wt% resulting from insufficient count times and/or low beam currents yield highly imprecise measurements (1σ errors of 10–40% for Na2O). Low analytical precision propagates into the calculation of pressure-sensitive mineral components such as jadeite. Using Monte Carlo approaches, we demonstrate that elemental variation resulting from analytical precision alone generates pressures spanning ~4 kbar (~15 km) for a single Cpx and ~6 kbar for a single Cpx-Liq pair using popular barometry expressions. In addition, analytical uncertainties in mineral compositions produce highly correlated arrays between pressure and temperature that have been previously attributed to transcrustal magma storage. Before invoking such geological interpretations, a more mundane origin from analytical imprecision must be ruled out. Most importantly, low analytical precision does not just affect the application of barometers to natural systems; it has also affected characterization of Cpx in experimental products used to calibrate and test barometers. The impact of poor precision on each individual measurement is often magnified by the small number of measurements made within experimental charges, meaning that low analytical precision and true variability in mineral compositions have not been sufficiently mediated by averaging multiple EPMA analyses. We compile the number of Cpx measurements performed in N = 307 experiments used to calibrate existing barometers, and N = 490 new experiments, finding ~45% of experiment charges were characterized by ≤5 individual Cpx analyses. Insufficient characterization of the true composition of experimental phases likely accounts for the fact that all Cpx-based barometers exhibit large errors (± 3 kbar) when tested using global experimental datasets. We suggest specific changes to analytical and experimental protocols, such as increased count times and/or higher beam currents when measuring low concentration elements in relatively beam resistant Cpx in experiments and natural samples. We also advocate for increasing the number of analyses per experimental charge, resolving interlaboratory analytical offsets and improving data reporting. Implementing these changes is essential to produce a more robust dataset to calibrate and test the next generation of more precise and accurate Cpx-based barometers. In turn, this will enable more rigorous investigation of magma storage geometries in a variety of tectonic settings (e.g. distinguishing true transcrustal storage vs. storage in discrete reservoirs). 

We present Thermobar, a new open-source Python3 package for calculating pressures, temperatures, and melt compositions from mineral and mineral-melt equilibrium. Thermobar allows users to perform calculations with >100 popular parametrizations involving liquid, olivine-liquid, olivine-spinel, pyroxene only, pyroxene-liquid, two pyroxene, feldspar-liquid, two feldspar, amphibole only, amphibole-liquid, and garnet equilibria. Thermobar is the first open-source tool which can match up all possible pairs of phases from a given region, and apply various equilibrium tests to identify pairs from which to calculate pressures and temperatures (e.g. pyroxene-liquid, two pyroxene, feldspar-liquid, two feldspar, amphibole-liquid). Thermobar also contains functions allowing users to propagate analytical errors using Monte-Carlo methods, convert pressures to depths using different crustal density profiles, plot mineral classification and mineral-melt equilibrium diagrams, calculate liquid viscosities, and convert between oxygen fugacity values, buffer positions and Fe speciation in a silicate melt. Thermobar can be downloaded using pip and extensive documentation is available at https://thermobar.readthedocs.io/. 

The main magma reservoir beneath the 2021 La Palma eruption is located using CO2 fluid inclusions with Raman spectroscopy. 

Magmas with matrix glass compositions ranging from basalt to dacite erupted from a series of 24 fissures in the first 2 weeks of the 2018 Lower East Rift Zone (LERZ) eruption of Kīlauea Volcano. Eruption styles ranged from low spattering and fountaining to strombolian activity. Major element trajectories in matrix glasses and melt inclusions hosted by olivine, pyroxene and plagioclase are consistent with variable amounts of fractional crystallization, with incompatible elements (e.g., Cl, F, and H₂O) becoming enriched by 4–5 times as melt MgO contents evolve from 6 to 0.5 wt%. The high viscosity and high H₂O contents (∼2 wt%) of the dacitic melts erupting at Fissure 17 account for the explosive Strombolian behavior exhibited by this fissure, in contrast to the low fountaining and spattering observed at fissures erupting basaltic to basaltic‐andesite melts. Saturation pressures calculated from melt inclusion CO₂‐H₂O contents indicate that the magma reservoir(s) supplying these fissures was located at ∼2–3 km depth, which is in agreement with the depth of a dacitic magma body intercepted during drilling in 2005 (∼2.5 km) and a seismically imaged lowVp/Vsanomaly (∼2 km depth). Nb/Y ratios in erupted products are similar to lavas erupted between 1955 and 1960, indicating that melts were stored and underwent variable amounts of crystallization in the LERZ for >60 years before being remobilized by a dike intrusion in 2018. We demonstrate that extensive fractional crystallization generates viscous and volatile‐rich magma with potential for hazardous explosive eruptions, which may be lurking undetected at many ocean island volcanoes.