Lutetium incorporation in magmas at depth:changes in melt local environment and the influence on partitioning behaviour

International audienceThe structure of two Lu doped (4000 ppm) model end member silicate liquids, a highly polymerised haplogranite (Si-Al-Na-K-O) and a less polymerised anorthite-diopside (Si-Al-Mg-Ca-O), have been studied up to 8 GPa using in situ x-ray diffraction techniques. The results are the first to identify trace rare Earth element incorporation in silicate melts at high pressure. At pressures below 5 GPa, the bonding environment of Lu-O was found to be dependent on composition with coordination number CN Lu−O = 8 and bond distance r Lu−O = 2.36Å36Å in the haplogranite melt, decreasing to CN Lu−O = 6 and r Lu−O = 2.29Å29Å in the anorthite-diopside melt. This compositional variance in coordination number at low pressure is consistent with observations made for Y-O in glasses at ambient conditions and is coincident with a dramatic increase in the partition coefficients previously observed for rare Earth elements with increasing melt polymerisation. With increasing pressure we find that CN Lu−O and r Lu−O remain constant in the haplo-granite melt. However, an abrupt change in both Lu-O coordination and bond distance is observed at 5 GPa in the anorthite-diopside melt, with CN Lu−O increasing from 6 to 8-fold and r Lu−O from 2.29 to 2.39Å39Å. This occurs over a similar pressure range where a change in the P-dependence in the reported rare Earth element partition coefficients is observed for garnet-, clinopyroxene-, and olivine-melt systems. This work shows that standard models for predicting trace elements at depth must incorporate the effect of pressure-induced structural transformations in the melt in order to realistically predict partitioning behaviour

Resonant inelastic x-ray scattering in warm-dense Fe compounds beyond the SASE FEL resolution limit

Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot experiments, including for the study of high energy density systems. Here we demonstrate that by correlating the measurements of the self-amplified spontaneous emission (SASE) spectrum of an XFEL with the RIXS signal, using a dynamic kernel deconvolution with a neural surrogate, we can achieve electronic structure resolutions substantially higher than those normally afforded by the bandwidth of the incoming x-ray beam. We further show how this technique allows us to discriminate between the valence structures of Fe and Fe$_2$O$_3$, and provides access to temperature measurements as well as M-shell binding energies estimates in warm-dense Fe compounds

Resonant inelastic x-ray scattering in warm-dense Fe compounds beyond the SASE FEL resolution limit

Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot experiments, including for the study of high energy density systems. Here we demonstrate that by correlating the measurements of the self-amplified spontaneous emission (SASE) spectrum of an XFEL with the RIXS signal, using a dynamic kernel deconvolution with a neural surrogate, we can achieve electronic structure resolutions substantially higher than those normally afforded by the bandwidth of the incoming x-ray beam. We further show how this technique allows us to discriminate between the valence structures of Fe and Fe2O3, and provides access to temperature measurements as well as M-shell binding energies estimates in warm-dense Fe compounds

Garnet oxygen analysis by SHRIMP-SI: Matrix corrections and application to high-pressure metasomatic rocks from Alpine Corsica

Garnet is a key mineral used to constrain pressure, temperature and age of metamorphic rocks. This contribution reports oxygen isotope measurements in garnet using the SHRIMP-SI ion microprobe. The reproducibility of oxygen isotope analyses on garnet standard UWG2 is ~0.3-0.4‰ (2σ) within and across sessions. The correlation between oxygen isotope measurements and the grossular and andradite components in garnet fits a second-degree polynomial with a maximum bias in δ18O of 2.4 and 8.3‰, respectively. This bias is similar to that determined for other large ion microprobes. Analysis of two additional Mn-rich garnet crystals allowed identification of a separate bias caused by the spessartine component, which can reach a maximum of 2.3‰.The standardisation and correction scheme proposed in this study are applied to garnet crystals from two samples from Alpine Corsica in order to link fluid evolution with the pressure-temperature-time path. The samples have experienced a polyphase metamorphic history, which includes Permian high temperature metamorphism, followed by late However, 92-W2 was re-analysed because of the variability observed in the previously published δ18O values (-0.29 and 0.53‰, Kohn and Valley, 1998). The δ18O value found in this study (0.81 ± 0.44‰, 2s, Table 1) agrees within error with the highest value previously published for this garnet. Eocene high pressure-low temperature metamorphism. Permian Ca-poor garnet cores have high δ18O values (9.9±0.6‰ and 11.1±0.5‰ 2σ, in two samples) with respect to garnet mantles (7.2±0.4‰) and rims (5.4±0.5‰ and 2.2±0.4‰). The dramatic decrease in δ18O from Permian garnet cores to Alpine rims in both samples reflects a combination of external fluid influx and change in sample mineralogy. The low δ18O of the garnet rims that formed at eclogite facies conditions indicates that the metasomatic fluid equilibrated with mafic or ultramafic rocks. This study illustrates that fluid-mediated mass transfer during subduction occurred at lithological contacts between felsic and ultramafic rocks