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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). [ABSTRACT FROM AUTHOR]

Oxygen fugacity is an important but difficult parameter to constrain for primitive arc magmas. In this study, the partitioning behavior of Fe3+/Fe2+ between amphibole and glass synthesized in piston-cylinder and cold-seal apparatus experiments is developed as an oxybarometer, applicable to magmas ranging from basaltic to dacitic composition. The partitioning of Fe2+ is strongly dependent on melt polymerization; the relative compatibility of Fe2+ in amphibole decreases with increasing polymerization. The Fe2+/Mg distribution coefficient between amphibole and melt is a relatively constant value across all compositions and is, on average, 0.27. The amphibole oxybarometer is applied to amphibole in mafic enclaves, cumulates, and basaltic tephra erupted from Shiveluch volcano in Kamchatka with measured Fe3+/FeTotal. An average Fe3+/Fe2+ amphibole-glass distribution coeficient for basalt is used to convert the Fe3+/FeTotal of amphibole in samples from Shiveluch to magmatic oxygen fugacity relative to NNO. The fO2 of primitive melts at the volcano is approximately NNO+2 and is faithfully recorded in amphibole from an amphibole-rich cumulate and the basaltic tephra. Apparently, higher fO2 recorded by amphibole in mafic enclaves likely results from partial dehydrogenation of amphibole during residence in a shallow andesite storage region. We identify three pulses of mafic magma recharge within two weeks of, a month before, and two to three months before the eruption and find that, at each of these times, the host andesite was recharged by at least two magmas at varying stages of differentiation. Application of the amphibole oxybarometer not only gives insight into magmatic fO2 but also potentially details of shallow magmatic processes. [ABSTRACT FROM AUTHOR]

The advent of double-Wien filter-selection-aperture and hexapole-collision-cell technologies coupled to laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS/MS) enables in situ analysis of 87Sr variations produced by the decay of radioactive 87Rb (t1/2 = 49.61 ± 0.16 Ga). We present methodologies to acquire in situ87Rb–87Sr data using a Thermo Scientific™ Neoma™ MC-ICP-MS coupled to a laser ablation system. The ions first pass through a mass filter that blocks ions outside of the Rb–Sr mass region. The ions then travel through a hexapole collision cell filled with SF6, inducing the fluorination of Sr+ to form SrF+. Strontium isotopes are measured as SrF+ free of interferences, while rubidium isotopes are measured as Rb+. Formulas are presented to calculate the error ellipses of 87Rb/86Sr and 87Sr/86Sr ratios corrected for instrumental fractionation by standard bracketing. While LA-MC-ICP-MS/MS is not as precise as Thermal Ionization Mass Spectrometry (TIMS), it is less destructive and sample throughput is higher. It is therefore particularly well suited to analyze small and precious samples, or to examine population characteristics. We have analyzed several terrestrial and extraterrestrial materials to showcase the unique capabilities of LA-MC-ICP-MS/MS in Sr isotopic analyses: (1) an orthoclase megacryst and other minerals from the 397 Ma Shap granite, (2) feldspar grains from the 26.5 ka Oruanui supereruption in New Zealand, (3) Durango apatite, (4) highly refractory hibonite inclusions from the Murchison meteorite, and (5) the martian meteorite NWA 7034 also known as Black Beauty. Black Beauty is a polymict breccia that contains zircons as old as 4.4 Ga but whose 40Ar/39Ar age was partially reset at 1.4 Ga. All K-feldspar grains analyzed in Black Beauty give an 87Rb–87Sr age of 2.189 ± 0.059 Ga. Most likely, the 2.2 Ga 87Rb–87Sr age represents the age of lithification. This study demonstrates the great potential of in situ87Rb–87Sr dating for analyzing samples returned by planetary exploration missions, such as those currently collected by the Perseverance rover on Mars, or those that will be returned from Phobos by the MMX mission. [ABSTRACT FROM AUTHOR]

Phase equilibrium experiments on a compositionally modified olivine leucitite from the Tibetan plateau have been carried out from 2.2 to 2.8 GPa and 1,380-1,480°C. The experiments-produced liquids multiply saturated with spinel and garnet lherzolite phase assemblages (olivine, orthopyroxene, clinopyroxene and spinel ± garnet) under nominally anhydrous conditions. These Si[O.sub.2]-undersaturated liquids and published experimental data are utilized to develop a predictive model for garnet lherzolite melting of compositionally variable mantle under anhydrous conditions over the pressure range of 1.9-6 GPa. The model estimates the major element compositions of garnet-saturated melts for a range of mantle lherzolite compositions and predicts the conditions of the spinel to garnet lherzolite phase transition for natural peridotite compositions at above-solidus temperatures and pressures. We compare our predicted garnet lherzolite melts to those of pyroxenite and carbonated lherzolite and develop criteria for distinguishing among melts of these different source types. We also use the model in conjunction with a published predictive model for plagioclase and spinel lherzolite to characterize the differences in major element composition for melts in the plagioclase, spinel and garnet facies and develop tests to distinguish between melts of these three lherzolite facies based on major elements. The model is applied to understand the source materials and conditions of melting for high-K lavas erupted in the Tibetan plateau, basanite-nephelinite lavas erupted early in the evolution of Kilauea volcano, Hawaii, as well as younger tholeiitic to alkali lavas from Kilauea. Keywords Garnet lherzolite * Mantle melting * Tibetan Plateau * Kilauea Hawaii * Experimental petrology, Introduction Liquids in equilibrium with a garnet lherzolite phase assemblage (olivine, orthopyroxene, clinopyroxene and garnet) and/or a garnet pyroxenite assemblage are produced when the Earth's mantle melts at depths greater [...]

Water is a key ingredient in the generation of magmas in subduction zones. This review focuses on the role of water in the generation of magmas in the mantle wedge, the factors that allow melting to occur, and the plate tectonic variables controlling the location of arc volcanoes worldwide. Water also influences chemical differentiation that occurs when magmas cool and crystallize in Earth's continental crust. The source of H2O for arc magma generation is hydrous minerals that are carried into Earth by the subducting slab. These minerals dehydrate, releasing their bound H2O into overlying hotter, shallower mantle where melting begins and continues as buoyant hydrous magmas ascend and encounter increasingly hotter surroundings. This process is controlled by plate tectonic variables that ultimately influence the location of the active volcanic arc above subduction zones. Water also modifies the thermodynamic properties of melts, leading to the unique chemical composition of arc volcanic rocks and Earth's continental crust. [ABSTRACT FROM AUTHOR]