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ABSTRACT Quantification of Fe redox state and hydrogen content of amphibole provides information regarding the relationship between oxygen and water concentrations in terrestrial and planetary materials. Raman spectroscopy is a powerful technique due to its ability to characterize both %Fe³⁺and H₂O from single crystal measurements, in addition to other chemical, mineralogical, and structural properties. Raman spectral measurements of amphibole minerals are used here to estimate %Fe³⁺(relative to total Fe) and H₂O (wt%) contents using partial least squares (PLS) multivariate modeling. The accuracy of our model for prediction of %Fe³⁺is ± 8.11% (absolute) expressed as root‐mean‐square error (RMSE) of the entire data set, covering the range from 0 to 100% with anR²value of 0.85. The model for prediction of H₂O has an internal RMSE of ± 0.09 wt% over the range from 0.1 to 1.9 wt% with anR²value of 0.95. Additional compositional model variables for predicting FeO, Fe₂O₃, MgO, CaO, Cr₂O₃, Al₂O₃, and TiO₂have highR²values above 0.82; theR²value for SiO₂is 0.63. Reliable models could not be achieved for MnO, Na₂O, and K₂O. The successful creation of our compositional models along with detailed analysis of the PLS model coefficients indicates that Raman spectroscopy can be used as a quantitative compositional tool in characterizing the amphibole mineral group. Quantifying amphibole compositions is useful for evaluating repositories of hydrogen, constraining the water budget of the terrestrial crust and interior, developing geothermobarometers and geohygrometers, and quantifying magma ascent rates. 

Abstract Lunar paleomagnetic studies have identified multidomain metallic Fe–Ni alloys as the dominant magnetic contributors in mare basalts. Here, we explore the low‐temperature magnetic behavior of standard samples for a suite of opaque minerals that occur within mare basalts (single‐domain and multidomain Fe, wüstite, ulvöspinel, iron chromite, ilmenite, and troilite). We compare the observed low‐temperature behaviors to those of several Apollo mare basalt samples (10003, 10044, 10020, 10069, 10071, 12009, 12022, 15597). Notable magnetic transitions were detected at 30 K (ilmenite), 60–80 K (chromite, troilite), and 100–125 K (ulvöspinel, chromite). We also investigated the effects of low‐temperature cycling on mare basalt remanence and observed that only grains with coercivities 20–40 mT were cleaned. This suggests a minimal impact of diurnal temperature cycling at the lunar surface on the retrieved lunar paleointensity values. Using comprehensive electron microscopy techniques, including scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), wavelength dispersive spectroscopy (WDS), x‐ray diffraction, and transmission electron microscopy (TEM), we further examined magnetic phases within four Apollo 11 mare basalt samples. Our findings revealed the presence of Fe grains (one to 10 μm in diameter) associated with troilite contain sub‐grains ranging in size from tens to hundreds of nanometers in some samples. These grains, which fall within the single‐domain to multi‐domain range as observed in their first‐order reversal curves, might have the potential to retain high coercivity components and thereby effectively record an ancient dynamo field. 

Abstract We provide a new algorithm for mass‐balance calculations in petrology and geochemistry based on the log‐ratio approach championed initially by John Aitchison (e.g., Aitchison, 1982,https://doi.org/10.1111/j.2517-6161.1982.tb01195.x; Aitchison, 1984,https://doi.org/10.1007/bf01029316) along with the underlying principles, mathematical frameworks, and data requirements. Log‐ratio Inversion of Mixed End‐members (LIME) is written in MATLAB and calculates phase proportions in an experiment or rock given a bulk composition, the composition of each phase, and the associated compositional uncertainties. An important advantage of LIME is that performing the mass‐balance calculation in inverse log‐ratio space constrains phase proportions to be between 0 and 100 wt.%. Further, the resulting LIME phase proportions provide realistic estimates of uncertainty regardless of data distribution. These two characteristics of LIME improve upon standard multiple linear regression techniques, which may yield negative values for phase proportions if non‐constrained or report oversimplified symmetric errors. Primary applications of LIME include estimating phase abundances, calculating melting and metamorphic reaction stoichiometries, and checking for open system behavior in phase equilibria experiments. The technique presented here covers whole‐rock analysis, mineralogy, and phase abundance, but could be extended to isotopic tracers, trace element modeling, and regolith component un‐mixing. We highlight the importance of uncertainty estimations for phase abundances to the fields of petrology and geochemistry by comparing our results from LIME to previously published mass‐balance calculations. Furthermore, we present case studies that demonstrate the role of mass‐balance calculations in determining magma crystallinity and defining melting reactions. 

Abstract 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 coefficient 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 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).