A combined Fourier transform infrared and Cr K-edge X-ray absorption near-edge structure spectroscopy study of the substitution and diffusion of H in Cr-doped forsterite

International audienceSingle crystals of synthetic Cr-doped forsterite (Cr:Mg2SiO4) containing both Cr3+ and Cr4+ were partially hydroxylated in piston-cylinder apparatuses at 750-1300 degrees C and pressures from 0.5 to 2.5 GPa, with P(H2O) approximate to P-total. The oxygen fugacity (fO(2)) was buffered by graphite-water, Ni-NiO, Re-ReO2, Fe2O3-Fe3O4 or Ag-Ag2O, and the silica activity (a SiO2) was buffered by powdered forsterite plus either enstatite (Mg2Si2O6), periclase (MgO) or zircon-baddeleyite (ZrSiO4-ZrO2). Profiles of OH content versus distance from the crystal edge were determined using Fourier transform infrared (FTIR) spectroscopy, and profiles of the oxidation state and coordination geometry of Cr were obtained, at the same positions, using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The techniques are complementary - FTIR spectroscopy images the concentration and nature of O-H bonds, where Cr K-edge XANES spectroscopy shows the effect of the added H on the speciation of Cr already present in the lattice. Profiles of defect-specific absorbance derived from FTIR spectra were fitted to solutions of Fick's second law to derive diffusion coefficients, which yield the Arrhenius relationship for H diffusion in forsterite: log(10)(D) over tilde ([001]) = -2.5 +/- 0.6 + -(224 +/- 12 + 4.0 +/- 2.0 P)/2.303 RT , where (D) over tilde is the measured diffusion coefficient in m(2) s(-1), valid for diffusion parallel to [001] and calibrated between 1000 and 750 degrees C, P and T are in GPa and K, and R is 0.008314 kJK(-1) mol(-1). Diffusivity parallel to [100] is around 1 order of magnitude lower. This is consistent with previous determinations of H diffusion associated with M-site vacancies. The FTIR spectra represent a variety of Cr-bearing hydrous defects, along with defects associated with the pure Mg-Si-O-H system. It is proposed that all of the defects can form by interaction between the dry lattice, including Cr3+ and Cr4+, and fully hydroxylated M-site vacancies. The initial diffusive wave of hydroxylation is associated with neither reduction nor oxidation of Cr but with Cr4+ changing from tetrahedral to octahedral coordination. Superimposed on the H diffusion and concomitant change in Cr4+ site occupancy, but at a slower rate, producing shorter profiles, is reduction of Cr4+ to Cr3+ and potentially of Cr4+ and Cr3+ to Cr2+. In addition, by comparing FTIR data to trace element contents measured by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), constraints can be placed on absorption coefficients used for converting absorbance to H2O contents - our data support either wavenumber- or defect-dependent values of absorption coefficients. We estimate absorption coefficients of between 60 200 and 68 200 L mol(-1) cm(-1) for OH- associated with octahedral Cr3+ and an M-site vacancy and 18 700 to 24 900 L mol(-1) cm(-1) for two OH- associated with octahedrally coordinated Cr4+ and a Si vacancy (i.e. a clinohumite-type point defect)

Living on a flammable planet: interdisciplinary, cross-scalar and varied cultural lessons, prospects and challenges: Table 1.

Living with fire is a challenge for human communities because they are influenced by socio-economic, political, ecological and climatic processes at various spatial and temporal scales. Over the course of 2 days, the authors discussed how communities could live with fire challenges at local, national and transnational scales. Exploiting our diverse, international and interdisciplinary expertise, we outline generalizable properties of fire-adaptive communities in varied settings where cultural knowledge of fire is rich and diverse. At the national scale, we discussed policy and management challenges for countries that have diminishing fire knowledge, but for whom global climate change will bring new fire problems. Finally, we assessed major fire challenges that transcend national political boundaries, including the health burden of smoke plumes and the climate consequences of wildfires. It is clear that to best address the broad range of fire problems, a holistic wildfire scholarship must develop common agreement in working terms and build across disciplines. We must also communicate our understanding of fire and its importance to the media, politicians and the general public. This article is part of the themed issue ‘The interaction of fire and mankind’

Assessing analytical convolution effects in diffusion studies: Applications to experimental and natural diffusion profiles.

Given that all in-situ analytical techniques have a non-zero beam size, all measured profiles, resulting from diffusion or otherwise, will be artefactually elongated to some degree. Profiles where the total length over which the concentration changes approaches the resolution of the analytical technique likely suffer from serious convolution; the measured profiles may be considerably elongated relative to the true profile. Resolving this effect is non-trivial, except for some specific combinations of profile type and beam geometry. In this study, a versatile method for numerically deconvoluting diffusion profiles acquired using techniques with Gaussian, Lorentzian, (pseudo-)Voigt, circular/elliptical or square/rectangular interaction volumes, is presented. A MATLAB code, including a user-friendly interface (PACE-the Program for Assessing Convolution Effects in diffusion studies), is also provided, and applied to several experimental and natural profiles interpreted as resulting from diffusion, showing various degrees of convolution

Hide and Seek—Trace Element Incorporation and Diffusion in Olivine

Livine, once overlooked as a host of trace elements, is becoming increasingly important for our understanding of the kinetic and equilibrium behaviour of these elements. Much of our understanding of trace element substitution and diffusion in geological materials comes as a result of experimental and petrological studies of olivine. Here, we consider trace element concentrations and incorporation mechanisms, and how these relate to diffusive behaviour. If we understand trace element behaviour in olivine, we have a powerful tool kit that can be directly applied to address many problems in petrology and volcanology. Perhaps more importantly, what we have learned from olivine can be applied to other minerals and aid us in addressing other far-reaching questions from across the Earth sciences.RD would like to thank the DFG (Deutsche Forschungs-gemeinschaft) for financial support by the Research Unit FOR 2881: Diffusion Chronometry of magmatic systems. JAP-N acknowledges the Ramón y Cajal fellowship RYC2018-024363-I, funded by MCIN/AEI/10.13039/501100011033 and the ESF program ‘FSE invierte en tu futuro’. JAP-N also acknowledges the Junta de Andalucía of Spain for financial support through the Research Project ProyExcel-00757

An eruption chronometer based on experimentally determined H-Li and H-Na diffusion in quartz applied to the Bishop Tuff

© 2020 The Author(s) The diffusion of hydrogen in natural hydrothermal quartz crystals was studied between 657–956 °C at atmospheric pressure and various oxygen fugacity (fO2) conditions. Single crystals of OH-bearing quartz were dehydrated in the presence of Li or Na-enriched powders to induce Li-H or Na-H exchange, with the resulting diffusion profiles measured by both Fourier transform infrared (FTIR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Diffusion parallel to [0001], i.e. the crystallographic c-axis, is described by: [Formula presented] where log10D is the base 10 logarithm of the diffusion coefficient, R is the gas constant and T is the temperature in kelvins, and uncertainties are 1 σ. Diffusion is not affected by (fO2) in this system. Diffusion perpendicular to [0001] is consistently slower, but quantitative constraints cannot be obtained from our data given experimental limitations. This diffusivity is primarily associated with H+-Li+ (or H+-Na+, Na+-Li+) exchange, where the H+ and Li+ are charge-balanced by tetrahedrally-coordinated Al3+. A faster mechanism may also exist where the monovalent cations are charge balanced by excess oxygen. The final defect population, as imaged by FTIR spectroscopy and LA-ICP-MS, likely results from a combination of diffusion and inter-site rearrangement of the monovalent cations. Regardless of such complexities, the determined Arrhenius relationship should be applicable for natural volcanic quartz crystals from the Bishop Tuff, California, wherein H+ is associated with Al3+, and H loss from quartz preceding and/or accompanying the eruption is charge-balanced by Li-gain, without Al movement. Li and H profiles from an example quartz crystal suggest that it experienced eruption/cooling timescales of just 16 minutes to 2.4 hours, showing the considerable promise of using frozen H diffusion profiles in quartz to extract timescales and thus elucidate the last moments of such explosive silicic eruptions.ISSN:0012-821XISSN:1385-013

Hydrogen diffusion in Ti-doped forsterite and the preservation of metastable point defects

International audienceThe effect of trace concentrations of Ti on the rate and mechanism of hydrogen diffusion in pure forsterite was investigated experimentally. Forsterite doped with 350–400 ppm Ti (predominantly octahedral Ti3+, minor tetrahedral Ti4+) was prepared by diffusing Ti into pure synthetic forsterite at high temperature (1500 °C), very low oxygen fugacity (~QFM-5) at atmospheric pressure. The Ti-doped forsterite was then diffusively hydroxylated in a piston-cylinder apparatus at much lower temperatures (650–1000 °C) and higher oxygen fugacities, at 1.5–2.5 GPa, with chemical activities buffered by forsterite-enstatite or forsterite-periclase and partial pressure of H2O equal to total pressure. This produced hydrogen concentration-distance profiles of several hundred micrometers in length. Diffusion of hydrogen through the Ti-doped forsterite, even at very high Embedded Image , does not lead to redox re-equilibration of the high Ti3+/ΣTi ratio set during the synthesis of the starting material at extremely reducing conditions—the metastable point defects are partially preserved.Three main hydroxylated point defects are observed; hydroxyl is associated with Ti4+ (titano-clinohumite point defects), Ti3+ (and possibly other trivalent cations), and M-site vacancies. Concentration-distance profiles represent an interplay between diffusion and reaction (i.e., site rearrangement) to form the observed point defects. In all experiments, the concentration-distance profiles of the hydroxylated Ti defects coincide with the concentration-distance profiles of the M-site vacancy substitution, with the same crystallographic anisotropy. This suggests that the macroscopic movement of hydrogen through the crystal is due to one diffusion mechanism (the diffusion of hydroxylated M-site vacancies). The net H diffusion coefficient [logD(ΣH)], between 650–1000 °C, is Embedded Image where the values of logD0(ΣH) parallel to [100] and [001] directions are −3.0 ± 0.4 and −2.2 ± 0.4, respectively; diffusion is therefore around one order of magnitude faster along the c axis than along the a axis. The diffusion of hydrogen is slightly faster in Ti-doped forsterite than in pure forsterite. There is no effect of chemical activity or oxygen fugacity on the rate of diffusion. Hydrogen diffusion profiles represent a complex interplay between the movement of H through the crystal lattice and point-defect reactions to maintain charge balance