J. M. Tucker

Evidence for multiple magma ocean outgassing and atmospheric loss episodes from mantle noble gases

Abstract The energy associated with giant impacts is large enough to generate global magma oceans during Earths accretion. However, geochemical evidence requiring a terrestrial magma ocean is scarce. Here we present evidence for at least two separate magma ocean outgassing episodes on Earth based on the ratio of primordial 3 He to 22 Ne in the present-day mantle. We demonstrate that the depleted mantle 3 He/ 22 Ne ratio is at least 10 while a more primitive mantle reservoir has a 3 He/ 22 Ne ratio of 2.3 to 3. The 3 He/ 22 Ne ratios of the mantle reservoirs are higher than possible sources of terrestrial volatiles, including the solar nebula ratio of 1.5. Therefore, a planetary process must have raised the mantles 3 He/ 22 Ne ratio. We show that long-term plate tectonic cycling is incapable of raising the mantle 3 He/ 22 Ne ratio and may even lower it. However, ingassing of a gravitationally accreted nebular atmosphere into a magma ocean on the proto-Earth explains the 3 He/ 22 Ne and 20 Ne/ 22 Ne ratios of the primitive mantle reservoir. Increasing the mantle 3 He/ 22 Ne ratio to a value of 10 in the depleted mantle requires at least two episodes of atmospheric blow-off and magma ocean outgassing associated with giant impacts during subsequent terrestrial accretion. The preservation of a low 3 He/ 22 Ne ratio in a primitive reservoir sampled by plumes suggests that the later giant impacts, including the Moon-forming giant impact, did not generate a whole mantle magma ocean. Atmospheric loss episodes associated with giant impacts provide an explanation for Earths subchondritic C/H, N/H, and Cl/F elemental ratios while preserving chondritic isotopic ratios. If so, a significant proportion of terrestrial water and potentially other major volatiles were accreted prior to the last giant impact, otherwise the fractionated elemental ratios would have been overprinted by the late veneer.

Accurate determination of ferric iron in garnets by bulk Mössbauer spectroscopy and synchrotron micro-XANES

Abstract Measurements of Fe3+/ΣFe in geological materials have been intractable because of lack of access to appropriate facilities, the time-consuming nature of most analyses, and the lack of precision and reproducibility in most techniques. Accurate use of bulk Mössbauer spectroscopy is limited by largely unconstrained recoilless fraction (f), which is used to convert spectral peak area ratios into valid estimates of species concentrations and is unique to different mineral groups and compositions. Use of petrographic-scale synchrotron micro-XANES has been handicapped by the lack of a consistent model to relate spectral features to Fe3+/ΣFe. This paper addresses these two deficiencies, focusing specifically on a set of garnet group minerals. Variable-temperature Mössbauer spectra of the Fe2+-bearing almandine and Fe3+-bearing andradite end-members are used to characterize f in garnets, allowing Fe3+/ΣFe to be measured accurately. Mössbauer spectra of 19 garnets with varying composition were acquired and fit, producing a set of garnet-specific standards for Fe3+ analyses. High-resolution XANES data were then acquired from these and 15 additional previously studied samples to create a calibration suite representing a broad range of Fe3+ and garnet composition. Several previously proposed techniques for using simple linear regression methods to predict Fe3+/ΣFe were evaluated, along with the multivariate analysis technique of partial least-squares regression (PLS). Results show that PLS analysis of the entire XANES spectral region yields the most accurate predictions of Fe3+ in garnets with both robustness and generalizability. Together, these two techniques present reliable choices for bulk and microanalysis of garnet group minerals.

Use of multivariate analysis for synchrotron micro-XANES analysis of iron valence state in amphiboles

Abstract Microanalysis of Fe3+/ΣFe in geological samples using synchrotron-based X-ray absorption spectroscopy has become routine since the introduction of standards and model compounds. Existing calibrations commonly use least-squares linear combinations of pre-edge data from standard reference spectra with known coordination number and valence state acquired on powdered samples to avoid preferred orientation. However, application of these methods to single mineral grains is appropriate only for isometric minerals and limits their application to analysis of in situ grains in thin sections. In this work, a calibration suite developed by acquiring X-ray absorption near-edge spectroscopy (XANES) data from amphibole single crystals with the beam polarized along the major optical directions (X, Y, and Z) is employed. Seven different methods for predicting %Fe3+ were employed based on (1) area-normalized pre-edge peak centroid, (2) the energy of the main absorption edge at the location where the normalized edge intensity has the highest R2 correlation with Fe3+/ΣFe, (3) the ratio of spectral intensities at two energies determined by highest R2 correlation with Fe3+/ΣFe, (4) use of the slope (first derivative) at every channel to select the best predictor channel, (5 and 6) partial least-squares models with variable and constant numbers of components, and (7) least absolute shrinkage and selection operator models. The latter three sophisticated multivariate analysis techniques for predicting Fe3+/ΣFe show significant improvements in accuracy over the former four types of univariate models. Fe3+/ΣFe can be measured in randomly oriented amphibole single crystals with an accuracy of ±5.5–6.2% absolute. Multivariate approaches demonstrate that for amphiboles main edge and EXAFS regions contain important features for predicting valence state. This suggests that in this mineral group, local structural changes accommodating site occupancy by Fe3+ vs. Fe2+ have a pronounced (and diagnostic) effect on the XAS spectra that can be reliably used to precisely constrain Fe3+/ΣFe.