A high spatial resolution synchrotron Mössbauer study of the Tazewell IIICD and Esquel pallasite meteorites.

Metallic phases in the Tazewell IIICD iron and Esquel pallasite meteorites were examined using 57Fe synchrotron Mössbauer spectroscopy. Spatial resolution of ~10-20 μm was achieved, together with high throughput, enabling individual spectra to be recorded in less than 1 h. Spectra were recorded every 5-10 μm, allowing phase fractions and hyperfine parameters to be traced along transects of key microstructural features. The main focus of the study was the transitional region between kamacite and plessite, known as the "cloudy zone." Results confirm the presence of tetrataenite and antitaenite in the cloudy zone as its only components. However, both phases were also found in plessite, indicating that antitaenite is not restricted exclusively to the cloudy zone, as previously thought. The confirmation of paramagnetic antitaenite as the matrix phase of the cloudy zone contrasts with recent observations of a ferromagnetic matrix phase using X-ray photoemission electron spectroscopy. Possible explanations for the different results seen using these techniques are proposed.The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007 - 2013) / ERC Grant Agreement No. 320750

Goethite Mineral Dissolution to Probe the Chemistry of Radiolytic Water in Liquid-Phase Transmission Electron Microscopy

Liquid-Phase Transmission Electron Microscopy (LP-TEM) enables in situ observations of the dynamic behavior of materials in liquids at high spatial and temporal resolution. During LP-TEM, incident electrons decompose water molecules into highly reactive species. Consequently, the chemistry of the irradiated aqueous solution is strongly altered, impacting the reactions to be observed. However, the short lifetime of these reactive species prevent their direct study. Here, the morphological changes of goethite during its dissolution are used as a marker system to evaluate the influence of radiation on the changes in solution chemistry. At low electron flux density, the morphological changes are equivalent to those observed under bulk acidic conditions, but the rate of dissolution is higher. On the contrary, at higher electron fluxes, the morphological evolution does not correspond to a unique acidic dissolution process. Combined with kinetic simulations of the steady state concentrations of generated reactive species in the aqueous medium, the results provide a unique insight into the redox and acidity interplay during radiation induced chemical changes in LP-TEM. The results not only reveal beam-induced radiation chemistry via a nanoparticle indicator, but also open up new perspectives in the study of the dissolution process in industrial or natural settings

Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate

The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO43–) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+–PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart

Tailoring the Acidity of Liquid Media with Ionizing Radiation: Rethinking the Acid–Base Correlation beyond pH

Advanced in situ techniques based on electrons and X-rays are increasingly used to gain insights into fundamental processes in liquids. However, probing liquid samples with ionizing radiation changes the solution chemistry under observation. In this work, we show that a radiation-induced decrease in pH does not necessarily correlate to an increase in acidity of aqueous solutions. Thus, pH does not capture the acidity under irradiation. Using kinetic modeling of radiation chemistry, we introduce alternative measures of acidity (radiolytic acidity π* and radiolytic ion product KW*), that account for radiation-induced alterations of both H+ and OH– concentration. Moreover, we demonstrate that adding pH-neutral solutes such as LiCl, LiBr, or LiNO3 can trigger a significant change in π*. This provides a huge parameter space to tailor the acidity for in situ experiments involving ionizing radiation, as present in synchrotron facilities or during liquid-phase electron microscopy

Variations in the magnetic properties of meteoritic cloudy zone

Iron and stony‐iron meteorites form the Widmanstätten pattern during slow cooling. This pattern is composed of several microstructures whose length‐scale, composition and magnetic properties are dependent upon cooling rate. Here we focus on the cloudy zone: a region containing nanoscale tetrataenite islands with exceptional paleomagnetic recording properties. We present a systematic review of how cloudy zone properties vary with cooling rate and proximity to the adjacent tetrataenite rim. X‐ray photoemission electron microscopy is used to compare compositional and magnetization maps of the cloudy zone in the mesosiderites (slow cooling rates), the IAB iron meteorites and the pallasites (intermediate cooling rates), and the IVA iron meteorites (fast cooling rates). The proportions of magnetic phases within the cloudy zone are also characterized using Mössbauer spectroscopy. We present the first observations of the magnetic state of the cloudy zone in the mesosiderites, showing that, for such slow cooling rates, tetrataenite islands grow larger than the multidomain threshold, creating large‐scale regions of uniform magnetization across the cloudy zone that render it unsuitable for paleomagnetic analysis. For the most rapidly cooled IVA meteorites, the time available for Fe‐Ni ordering is insufficient to allow tetrataenite formation, again leading to behavior that is unsuitable for paleomagnetic analysis. The most reliable paleomagnetic remanence is recorded by meteorites with intermediate cooling rates ( urn:x-wiley:ggge:media:ggge22125:ggge22125-math-0001 2–500 °C Myr urn:x-wiley:ggge:media:ggge22125:ggge22125-math-0002) which produces islands that are “just right” in both size and degree of Fe‐Ni order

Nanomagnetic properties of the meteorite cloudy zone.

Meteorites contain a record of their thermal and magnetic history, written in the intergrowths of iron-rich and nickel-rich phases that formed during slow cooling. Of intense interest from a magnetic perspective is the "cloudy zone," a nanoscale intergrowth containing tetrataenite-a naturally occurring hard ferromagnetic mineral that has potential applications as a sustainable alternative to rare-earth permanent magnets. Here we use a combination of high-resolution electron diffraction, electron tomography, atom probe tomography (APT), and micromagnetic simulations to reveal the 3D architecture of the cloudy zone with subnanometer spatial resolution and model the mechanism of remanence acquisition during slow cooling on the meteorite parent body. Isolated islands of tetrataenite are embedded in a matrix of an ordered superstructure. The islands are arranged in clusters of three crystallographic variants, which control how magnetic information is encoded into the nanostructure. The cloudy zone acquires paleomagnetic remanence via a sequence of magnetic domain state transformations (vortex to two domain to single domain), driven by Fe-Ni ordering at 320 °C. Rather than remanence being recorded at different times at different positions throughout the cloudy zone, each subregion of the cloudy zone records a coherent snapshot of the magnetic field that was present at 320 °C. Only the coarse and intermediate regions of the cloudy zone are found to be suitable for paleomagnetic applications. The fine regions, on the other hand, have properties similar to those of rare-earth permanent magnets, providing potential routes to synthetic tetrataenite-based magnetic materials.European Research Counci

A combined experimental and computational study of nanopaleomagnetic recorders in meteoritic metal

A nanoscale intergrowth of fine tetrataenite particles in an iron rich matrix, known as the `cloudy zone' has recently been recognised as a stable paleomagnetic recorder. It is found in meteorites containing iron-nickel alloy that have developed the characteristic Widmanst\"atten pattern. However, the close particle proximity and high magnetocrystalline anisotropy of the cloudy zone make it a highly unconventional material to use in paleomagnetic studies. Open questions about the formation of the cloudy zone, its exact composition and structure, and how it acquires a remanence remain unanswered. To use the cloudy zone as a reliable and accurate paleomagnetic recorder, its properties have to be well understood. The particle size in the cloudy zone has been measured to be between $\sim$500 nm and $\sim$10 nm, however, it is rarely higher than $\sim$150 nm. This fine lengthscale makes it difficult to study the cloudy zone with conventional methods. No known single method can provided the solution to all current problems concerning the use of the cloudy zone as a paleomagnetic recorder. Therefore, to explore the properties of the cloudy zone a multi-method approach using advanced nanoscale investigation techniques and theoretical calculations was adopted. The formation of the cloudy zone within the context of the Fe-Ni phase diagram was studied using Monte Carlo simulations. These simulations were supplemented by Density Functional Theory (DFT) calculations. DFT was also used to explore the preferred chemical ordering schemes of the matrix as well as its ground magnetic state. The 3D structure of the cloudy zone was imaged with sub-nanometer resolution using Atom Probe Tomography (APT). This was one of the first applications of APT to image meteoritic metal. Accurate composition measurements of the matrix and tetrataenite as well as kamacite were made. Synchrotron M\"ossbauer spectroscopy was used to provide high spatial resolution information of the magnetic state of the matrix and tetrataenite in the cloudy zone as well as the surrounding metal. The matrix was conclusively demonstrated to be paramagnetic at room temperature as a bulk material. X-Ray holography was used for the first time to directly image magnetisation of individual paleomagnetic remanence carriers under high applied fields. In-field hysteresis behaviour of individual particles in the cloudy zone was measured by directly imaging the sample magnetisation with a resolution of $\sim$25 nm. The cloudy zone was found to consist of strongly interacting single domain particles. The experimental observations were supported by modelling. The combined approach of multiple methods was capable of providing answers to some of the important questions about the cloudy zone. The cloudy zone was found to be highly stable against remagnetisation by applied external fields. If the particle size is below $\sim$80-50 nm the cloudy zone was found to consist of isolated single-domain tetrataenite particles sitting in a paramagnetic matrix. The matrix might become ferrimagnetic at very low temperatures. Depending on how the magnetisation is measured, the measurement might be affected by the matrix changing its magnetic state to ferromagnetic at surfaces. This phenomena should not affect the overall stability of the cloudy zone as a paleomagnetic recorder. Due to the close proximity of the tetrataenite particles, there are strong magnetostatic interactions between them. This finding demands that new methods be developed for correct interpretation of the remanence recorded in the cloudy zone.The PhD was funded from a grant awarded to Professor Richard Harrison by the European Research Council

Variations in the magnetic properties of meteoritic cloudy zone

Iron and stony‐iron meteorites form the Widmanstätten pattern during slow cooling. This pattern is composed of several microstructures whose length‐scale, composition and magnetic properties are dependent upon cooling rate. Here we focus on the cloudy zone: a region containing nanoscale tetrataenite islands with exceptional paleomagnetic recording properties. We present a systematic review of how cloudy zone properties vary with cooling rate and proximity to the adjacent tetrataenite rim. X‐ray photoemission electron microscopy is used to compare compositional and magnetization maps of the cloudy zone in the mesosiderites (slow cooling rates), the IAB iron meteorites and the pallasites (intermediate cooling rates), and the IVA iron meteorites (fast cooling rates). The proportions of magnetic phases within the cloudy zone are also characterized using Mössbauer spectroscopy. We present the first observations of the magnetic state of the cloudy zone in the mesosiderites, showing that, for such slow cooling rates, tetrataenite islands grow larger than the multidomain threshold, creating large‐scale regions of uniform magnetization across the cloudy zone that render it unsuitable for paleomagnetic analysis. For the most rapidly cooled IVA meteorites, the time available for Fe‐Ni ordering is insufficient to allow tetrataenite formation, again leading to behavior that is unsuitable for paleomagnetic analysis. The most reliable paleomagnetic remanence is recorded by meteorites with intermediate cooling rates ( urn:x-wiley:ggge:media:ggge22125:ggge22125-math-0001 2–500 °C Myr urn:x-wiley:ggge:media:ggge22125:ggge22125-math-0002) which produces islands that are “just right” in both size and degree of Fe‐Ni order.This work was supported by the European Research Council under the European Union's Seventh Framework Programme (FP/2007‐2013)/ ERC grant agreement numbers 320750 and 312284.Peer reviewe

Goethite Mineral Dissolution to Probe the Chemistry of Radiolytic Water in Liquid‐Phase Transmission Electron Microscopy

Abstract Liquid‐Phase Transmission Electron Microscopy (LP‐TEM) enables in situ observations of the dynamic behavior of materials in liquids at high spatial and temporal resolution. During LP‐TEM, incident electrons decompose water molecules into highly reactive species. Consequently, the chemistry of the irradiated aqueous solution is strongly altered, impacting the reactions to be observed. However, the short lifetime of these reactive species prevent their direct study. Here, the morphological changes of goethite during its dissolution are used as a marker system to evaluate the influence of radiation on the changes in solution chemistry. At low electron flux density, the morphological changes are equivalent to those observed under bulk acidic conditions, but the rate of dissolution is higher. On the contrary, at higher electron fluxes, the morphological evolution does not correspond to a unique acidic dissolution process. Combined with kinetic simulations of the steady state concentrations of generated reactive species in the aqueous medium, the results provide a unique insight into the redox and acidity interplay during radiation induced chemical changes in LP‐TEM. The results not only reveal beam‐induced radiation chemistry via a nanoparticle indicator, but also open up new perspectives in the study of the dissolution process in industrial or natural settings