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1. Barometers Behaving Badly II: a Critical Evaluation of Cpx-Only and Cpx-Liq Thermobarometry in Variably-Hydrous Arc Magmas

   https://doi.org/10.1093/petrology/egad050  

   Wieser, Penny E; Kent, Adam_J R; Till, Christy B (August 2023, Journal of Petrology)

   The chemistry of erupted clinopyroxene crystals (±equilibrium liquids) have been widely used to deduce the pressures and temperatures of magma storage in volcanic arcs. However, the large number of different equations parameterizing the relationship between mineral and melt compositions and intensive variables such as pressure and temperature yield vastly different results, with implications for our interpretation of magma storage conditions. We use a new test dataset composed of the average Clinopyroxene-Liquid (Cpx-Liq) compositions from N = 543 variably hydrous experiments at crustal conditions (1 bar to 17 kbar) to assess the performance of different thermobarometers and identify the most accurate and precise expressions for application to subduction zone magmas. First, we assess different equilibrium tests, finding that comparing the measured and predicted Enstatite-Ferrosillite and KD (using Fet in both phases) are the most useful tests in arc magmas, whereas CaTs, CaTi and Jd tests have limited utility. We then apply further quality filters based on cation sums (3.95–4.05), number of analyses (N > 5) and the presence of reported H2O data in the quenched experimental glass (hereafter ‘liquid’) to obtain a filtered dataset (N = 214). We use this filtered dataset to compare calculated versus experimental pressures and temperatures for different combinations of thermobarometers. A number of Cpx-Liq thermometers perform very well when liquid H2O contents are known, although the Cpx composition contributes little to the calculated temperature relative to the liquid composition. Most Cpx-only thermometers perform very badly, greatly overestimating temperatures for hydrous experiments. These two findings demonstrate that the Cpx chemistry alone holds very little temperature information in hydrous systems. Most Cpx-Liq and Cpx-only barometers show similar performance to one another (mostly yielding root mean square errors [RMSEs] of 2–3.5 kbar), although the best Cpx-only barometers currently outperform the best Cpx-Liq barometers. We also assess the sensitivity of different equations to melt H2O contents, which are poorly constrained in many natural systems. Overall, this work demonstrates that Cpx-based barometry on individual Cpx only provides sufficient resolution to distinguish broad storage regions in continental arcs (e.g. upper, mid, lower crust). Significant averaging of Cpx compositions from experiments reported at similar pressures can reduce RMSEs to ~1.3–1.9 kbar. We hope our findings motivate the substantial amount of experimental and analytical work that is required to obtain precise and accurate estimates of magma storage depths from Cpx ± Liq equilibrium in volcanic arcs. 

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2. Barometers Behaving Badly I: Assessing the Influence of Analytical and Experimental Uncertainty on Clinopyroxene Thermobarometry Calculations at Crustal Conditions

   https://doi.org/10.1093/petrology/egac126  

   Wieser, Penny E; Kent, Adam J; Till, Christy B; Donovan, John; Neave, David A; Blatter, Dawnika L; Krawczynski, Michael J (February 2023, Journal of Petrology)

   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). 

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3. Comment on ‘The magmatic architecture and evolution of the Chang’e-5 lunar basalts’ Penny E. Wieser1, Christy Till2, Adam Kent3, Matthew Gleeson1

   https://doi.org/10.31223/X5MM3B  

   Wieser, Penny; Till, Christy; Kent, Adam; Gleeson, Matthew (June 2023, Earth ArXiv)

   Luo et al.1 present exciting new data on lunar basalt samples erupted at ~2 Ga, and brought to Earth by the Chang’e-5 (CE-5) mission. These samples offer important new opportunities to understand lunar magmatic systems. Luo et al.1 use Clinopyroxene-Liquid (Cpx-Liq) thermobarometry and pMELTS modelling of mineral compositions to determine the pressures (P) and temperatures (T) of magma storage on the moon. However, in this comment we discus the large analytical errors associated with their measurements, and the implications for their intepretation. 

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4. Identifying lithological tracers with first row transition element partitioning in natural pyroxenites

   Lang, Otto; Lambart, Sarah (December 2020, American Geophysical Union - Fall meeting 2020)

   null (Ed.)

   Mantle heterogeneity has a first-order control on the petrological and geochemical differences of erupted mafic lavas across the globe. It is debated whether this heterogeneity reflects only chemical variability or also lithological differences in source regions. Because of their various partitioning behaviors between mantle minerals, First Row Transition Elements (FRTEs) have been identified as potential lithological tracers. Here, we investigate the various parameters that control FRTE partitioning between common mantle phases through a comparison of partition coefficients calculated from natural pyroxenites obtained from the Earthchem database with previous partitioning experiments and new electron microprobe analyses. Using naturally occurring pyroxenites from alpine massifs and xenoliths provides the opportunity to explore the behavior of FRTEs on a much larger range of compositions and temperatures than covered by experimental studies. Our preliminary results show that natural partition coefficients for Fe and Mn depend on temperature and vary distinctly between lithologies. The effect of composition, however, is difficult to resolve and will require further inspection. Natural exchange coefficients, or Kd’s (mineral/mineral) for Mn/Fe, largely match previous experimental data across peridotite and pyroxenite compositions for garnet/clinopyroxene(cpx), orthopyroxene/cpx, and olivine/cpx. However, natural samples often present evidence of chemical disequilibrium and/or secondary alteration which can significantly increase the scatter in analyses. Importantly, despite the larger uncertainty on the natural Kd’s than on experimental ones, natural exchange coefficients show distinct values between the various pairs of minerals. These distinctions, and the fact that Kd’s do not seem to be influenced by temperature, make the bulk Mn/Fe ratio in lavas a good lithological tracer, supporting previous claims. Hence, we show that natural compositions can be used to expand trends in FRTE distribution behavior across a wider range of temperatures (500-1500°C) and compositions than determined previously by experiments alone. 

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5. Hydrogen Effect on the Sound Velocities of Upper Mantle Omphacite

   https://doi.org/10.3390/min9110690  

   Mans, Wade; Zhang, Jin S.; Hao, Ming; Smyth, Joseph R.; Zhang, Dongzhou; Finkelstein, Gregory J.; Dera, Przemyslaw (November 2019, Minerals)

   Clinopyroxene (Cpx) is commonly believed to be the best structural water (hydrogen) carrier among all major upper mantle nominally anhydrous minerals (NAMs). In this study, we have measured the single-crystal elastic properties of a Cpx, a natural omphacite with ~710 ppm water at ambient pressure (P) and temperature (T) conditions. Utilizing the single-crystal X-ray diffraction (XRD) and electron microprobe data, the unit cell parameters and density were determined as a = 9.603(9) Å, b = 8.774(3) Å, c = 5.250(2) Å, β = 106.76(5)o, V = 255.1(4) Å3, and ρ = 3.340(6) g/cm3. We performed Brillouin spectroscopy experiments on four single crystals along a total of 52 different crystallographic directions. The best-fit single-crystal elastic moduli (Cijs), bulk and shear moduli were determined as: C11 = 245(1) GPa, C22 = 210(2) GPa, C33 = 249.6(9) GPa, C44 = 75.7(9) GPa, C55 = 71.2(5) GPa, C66 = 76(1) GPa, C12 = 85(2) GPa, C13 = 70(1) GPa, C23 = 66(2) GPa, C15 = 8.0(6) GPa, C25 = 6(1) GPa, C35 = 34.7(6) GPa, and C46 = 8.7(7) GPa, KS0 = 125(3) GPa, and G0 = 75(2) GPa, respectively. Compared with the anticipated elastic properties of an anhydrous omphacite with the same chemical composition, our results indicate that the incorporation of ~710 ppm structural water has no resolvable effect on the aggregate elastic properties of omphacite, although small differences (up to ~9 GPa) were observed in C13, C25, C44, and C66. 

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