A MHz X-ray diffraction set-up for dynamic compression experiments in the diamond anvil cell.

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103 s-1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340 µs, compatible with the maximum length of the pulse train (550 µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87 TPa s-1 was observed during the fast compression of Au, while a strain rate of ∼1100 s-1 was achieved during the rapid compression of N2 at 23 TPa s-1.

A dehydrated space-weathered skin cloaking the hydrated interior of Ryugu.

Without a protective atmosphere, space-exposed surfaces of airless Solar System bodies gradually experience an alteration in composition, structure and optical properties through a collective process called space weathering. The return of samples from near-Earth asteroid (162173) Ryugu by Hayabusa2 provides the first opportunity for laboratory study of space-weathering signatures on the most abundant type of inner solar system body: a C-type asteroid, composed of materials largely unchanged since the formation of the Solar System. Weathered Ryugu grains show areas of surface amorphization and partial melting of phyllosilicates, in which reduction from Fe3+ to Fe2+ and dehydration developed. Space weathering probably contributed to dehydration by dehydroxylation of Ryugu surface phyllosilicates that had already lost interlayer water molecules and to weakening of the 2.7 µm hydroxyl (-OH) band in reflectance spectra. For C-type asteroids in general, this indicates that a weak 2.7 µm band can signify space-weathering-induced surface dehydration, rather than bulk volatile loss.

Evidence for a rosiaite-structured high-pressure silica phase and its relation to lamellar amorphization in quartz.

When affected by impact, quartz (SiO2) undergoes an abrupt transformation to glass lamellae, the planar deformation features (PDFs). This shock effect is the most reliable indicator of impacts and is decisive in identifying catastrophic collisions in the Earth´s record such as the Chicxulub impact. Despite the significance of PDFs, there is still no consensus how they form. Here, we present time-resolved in-situ synchroton X-ray diffraction data of single-crystal quartz rapidly compressed in a dynamic diamond anvil cell. These experiments provide evidence for the transformation of quartz at pressures above 15 GPa to lamellae of a metastable rosiaite (PbSb2O6)-type high-pressure phase with octahedrally coordinated silicon. This phase collapses during decompression to amorphous lamellae, which closely resemble PDFs in naturally shocked quartz. The identification of rosiaite-structured silica provides thus an explanation for lamellar amorphization of quartz. Furthermore, it suggests that the mixed phase region of the Hugoniot curve may be related to the progressive formation of rosiaite-structured silica.

Biomineralization of Nickel Struvite Linked to Metal Resistance in Streptomyces mirabilis.

Biomineral formation is a common trait and prominent for soil Actinobacteria, including the genus Streptomyces. We investigated the formation of nickel-containing biominerals in the presence of a heavy-metal-resistant Streptomyces mirabilis P16B-1. Biomineralization was found to occur both in solid and liquid media. Minerals were identified with Raman spectroscopy and TEM-EDX to be either Mg-containing struvite produced in media containing no nickel, or Ni-struvite where Ni replaces the Mg when nickel was present in sufficient concentrations in the media. The precipitation of Ni-struvite reduced the concentration of nickel available in the medium. Therefore, Ni-struvite precipitation is an efficient mechanism for tolerance to nickel. We discuss the contribution of a plasmid-encoded nickel efflux transporter in aiding biomineralization. In the elevated local concentrations of Ni surrounding the cells carrying this plasmid, more biominerals occurred supporting this point of view. The biominerals formed have been quantified, showing that the conditions of growth do influence mineralization. This control is also visible in differences observed to biosynthetically synthesized Ni-struvites, including the use of sterile-filtered culture supernatant. The use of the wildtype S. mirabilis P16B-1 and its plasmid-free derivative, as well as a metal-sensitive recipient, S. lividans, and the same transformed with the plasmid, allowed us to access genetic factors involved in this partial control of biomineral formation.

Black Silver: Three-Dimensional Ag Hybrid Plasmonic Nanostructures with Strong Photon Coupling for Scalable Photothermoelectric Power Generation.

The conversion of solar energy into electric power has been extensively studied, for example, by photovoltaics. However, photo-thermoelectric (P-TE) conversion as an effective solar-to-electricity conversion process is less studied. Here, we present an efficient full-solar-spectrum plasmonic absorber for scalable P-TE conversion based on a simple integration of light absorber and commercial thermoelectric modules. Our developed light absorber of silica-silver hybrid structures achieves an average absorption of 99.4% in the wavelength range from 200 to 2500 nm, which covers over 98% solar energy in this range. It thus appears fully matte black and is named black silver. The light absorber includes a hierarchical structure with Ag nanoparticles attached on three-dimensional SiO2 nanostructures, resulting in ultrahigh absorption. Strong localized surface plasmon resonance hybridization together with multiple scattering causes the perfect light absorption. Using the black silver as a light absorber for P-TE power generation, it can achieve a peak voltage density as high as 82.5 V m-2 under a solar intensity of 100 mW cm-2, which is large enough to power numerous electronic devices. By assembling 20 thermoelectric modules in series, we test their possibility of practical application, and they can also achieve an average voltage density of 70.66 V m-2. Our work opens up a promising technology that facilitates high-efficiency and scalable solar energy conversion via the P-TE effect.

Biomineralization by Extremely Halophilic and Metal-Tolerant Community Members from a Sulfate-Dominated Metal-Rich Environment.

The adaptation to adverse environmental conditions can lead to adapted microbial communities that may be screened for mechanisms involved in halophily and, in this case, metal tolerance. At a former uranium mining and milling site in Seelingstädt, Germany, microbial communities from surface waters and sediment soils were screened for isolates surviving high salt and metal concentrations. The high salt contents consisted mainly of chloride and sulfate, both in soil and riverbed sediment samples, accompanied by high metal loads with presence of cesium and strontium. The community structure was dominated by Chloroflexi, Proteobacteria and Acidobacteriota, while only at the highest contaminations did Firmicutes and Desulfobacterota reach appreciable percentages in the DNA-based community analysis. The extreme conditions providing high stress were mirrored by low numbers of cultivable strains. Thirty-four extremely halotolerant bacteria (23 Bacillus sp. and another 4 Bacillales, 5 Actinobacteria, and 1 Gamma-Proteobacterium) surviving 25 to 100 mM SrCl2, CsCl, and Cs2SO4 were further analyzed. Mineral formation of strontium- or cesium-struvite could be observed, reducing bioavailability and thereby constituting the dominant metal and salt resistance strategy in this environment.

Metastable Atomic Layer Deposition: 3D Self-Assembly toward Ultradark Materials.

Black body materials are promising candidates to meet future energy demands, as they are able to harvest energy from the total bandwidth of solar radiation. Here, we report on high-absorption near-blackbody-like structures (>98% for a wide solar spectrum range from 220 to 2500 nm) consisting of a silica scaffold and Ag nanoparticles with a layer thickness below 10 µm, fabricated using metastable atomic layer deposition (MS-ALD). Several effects contribute collectively and in a synergistic manner to the ultrahigh absorption, including the pronounced heterogeneity of the nanoparticles in size and shape, particle plasmon hybridization, and the trapping of omnidirectionally scattered light in the 3D hierarchical hybrid structures. We propose that, in the future, MS-ALD needs to be considered as a simple and promising method to fabricate blackbody materials with excellent broadband absorption.

Iron whiskers on asteroid Itokawa indicate sulfide destruction by space weathering.

Extraterrestrial iron sulfide is a major mineral reservoir of the cosmochemically and astrobiologically important elements iron and sulfur. Sulfur depletion on asteroids is a long-standing, yet unresolved phenomenon that is of fundamental importance for asteroid evolution and sulfur delivery to the Earth. Understanding the chemistry of such environments requires insight into the behavior of iron sulfides exposed to space. Here we show that troilite (FeS) grains recovered from the regolith of asteroid 25143 Itokawa have lost sulfur during long-term space exposure. We report the wide-spread occurrence of metallic iron whiskers as a decomposition product formed through irradiation of the sulfide by energetic ions of the solar wind. Whisker growth by ion irradiation is a novel and unexpected aspect of space weathering. It implies that sulfur loss occurs rapidly and, furthermore, that ion irradiation plays an important role in the redistribution of sulfur between solids and gas of the interstellar medium.

Giant Faraday Rotation through Ultrasmall Fe0n Clusters in Superparamagnetic FeO-SiO2 Vitreous Films.

Magnetooptical (MO) glasses and, in particular, Faraday rotators are becoming key components in lasers and optical information processing, light switching, coding, filtering, and sensing. The common design of such Faraday rotator materials follows a simple path: high Faraday rotation is achieved by maximizing the concentration of paramagnetic ion species in a given matrix material. However, this approach has reached its limits in terms of MO performance; hence, glass-based materials can presently not be used efficiently in thin film MO applications. Here, a novel strategy which overcomes this limitation is demonstrated. Using vitreous films of xFeO·(100 - x)SiO2, unusually large Faraday rotation has been obtained, beating the performance of any other glassy material by up to two orders of magnitude. It is shown that this is due to the incorporation of small, ferromagnetic clusters of atomic iron which are generated in line during laser deposition and rapid condensation of the thin film, generating superparamagnetism. The size of these clusters underbids the present record of metallic Fe incorporation and experimental verification in glass matrices.

Response to lead pollution: mycorrhizal Pinus sylvestris forms the biomineral pyromorphite in roots and needles.

The development of mycorrhized pine seedlings grown in the presence of lead was assessed in order to investigate how higher plants can tolerate lead pollution in the environment. Examination with scanning electron microscopy (SEM) revealed that Pb uptake was prominent in the roots, while a smaller amount was found in pine needles, which requires symplastic uptake and root-to-shoot transfer. Lead was concentrated in nanocrystalline aggregates attached to the cell wall and, according to elemental microanalyses, is associated with phosphorus and chlorine. The identification of the nanocrystalline phase in roots and needles was performed by transmission electron microscopy (TEM) and synchrotron X-ray micro-diffraction (µ-XRD), revealing the presence of pyromorphite, Pb5[PO4]3(Cl, OH), in both roots and needles. The extracellular embedding of pyromorphite within plant cell walls, featuring an indented appearance of the cell wall due to a callus-like outcrop of minerals, suggests a biogenic origin. This biomineralization is interpreted as a defense mechanism of the plant against lead pollution.

New insights into the toxicity of mineral fibres: A combined in situ synchrotron µ-XRD and HR-TEM study of chrysotile, crocidolite, and erionite fibres found in the tissues of Sprague-Dawley rats.

Along the line of the recent research topic aimed at understanding the in vivo activity of mineral fibres and their mechanisms of toxicity, this work describes the morpho-chemical characteristics of the mineral fibres found in the tissues of Sprague-Dawley rats subjected to intraperitoneal/intrapleural injection of UICC chrysotile, UICC crocidolite and erionite-Na from Nevada (USA). The fibres are studied with in situ synchrotron powder diffraction and high resolution transmission electron microscopy to improve our understanding of the mechanisms of toxicity of these mineral fibres. In contact with the tissues of the rats, chrysotile fibres are prone to dissolve, with leaching of Mg and production of a silica rich relict. On the other hand, crocidolite and erionite-Na fibres are stable even for very long contact times within the tissues of the rats, showing just a thin dissolution amorphous halo. These findings support the model of a lower biopersistence of chrysotile with respect to crocidolite and erionite-Na but the formation of a silica-rich fibrous residue after the pseudo-amorphization of chrysotile may justify a higher cytotoxic potential and intense inflammatory activity of chrysotile in the short term in contact with the lung tissues.

Where is iron in erionite? A multidisciplinary study on fibrous erionite-Na from Jersey (Nevada, USA).

Fibrous erionite is a mineral fibre of great concern but to date mechanisms by which it induces cyto- and geno-toxic damage, and especially the role of iron associated to this zeolite species, remain poorly understood. One of the reasons is that we still don't know exactly where iron is in natural erionite. This work is focused on fibrous erionite-Na from Jersey (Nevada, USA) and attempts to draw a general model of occurrence of iron in erionite and relationship with toxicity mechanisms. It was found that iron is present as 6-fold coordinated Fe3+ not part of the zeolite structure. The heterogeneous nature of the sample was revealed as receptacle of different iron-bearing impurities (amorphous iron-rich nanoparticles, micro-particles of iron oxides/hydroxides, and flakes of nontronite). If iron is not part of the structure, its role should be considered irrelevant for erionite toxicity, and other factors like biopersistence should be invoked. An alternative perspective to the proposed model is that iron rich nano-particles and nontronite dissolve in the intracellular acidic environment, leaving a residue of iron atoms at specific surface sites anchored to the windows of the zeolite channels. These sites may be active later as low nuclearity groups.

Bacterial spores in granite survive hypervelocity launch by spallation: implications for lithopanspermia.

Bacterial spores are considered good candidates for endolithic life-forms that could survive interplanetary transport by natural impact processes, i.e., lithopanspermia. Organisms within rock can only embark on an interplanetary journey if they survive ejection from the surface of the donor planet and the associated extremes of compressional shock, heating, and acceleration. Previous simulation experiments have measured each of these three stresses more or less in isolation of one another, and results to date indicate that spores of the model organism Bacillus subtilis can survive each stress applied singly. Few simulations, however, have combined all three stresses simultaneously. Because considerable experimental and theoretical evidence supports a spallation mechanism for launch, we devised an experimental simulation of launch by spallation using the Ames Vertical Gun Range (AVGR). B. subtilis spores were applied to the surface of a granite target that was impacted from above by an aluminum projectile fired at 5.4 km/s. Granite spall fragments were captured in a foam recovery fixture and then recovered and assayed for shock damage by transmission electron microscopy and for spore survival by viability assays. Peak shock pressure at the impact site was calculated to be 57.1 GPa, though recovered spall fragments were only very lightly shocked at pressures of 5-7 GPa. Spore survival was calculated to be on the order of 10(-5), which is in agreement with results of previous static compressional shock experiments. These results demonstrate that endolithic spores can survive launch by spallation from a hypervelocity impact, which lends further evidence in favor of lithopanspermia theory.

UV Raman imaging--a promising tool for astrobiology: comparative Raman studies with different excitation wavelengths on SNC Martian meteorites.

The great capabilities of UV Raman imaging have been demonstrated on the three Martian meteorites: Sayh al Uhaymir, Dar al Gani, and Zagami. Raman spectra without disturbing fluorescence and with high signal-to-noise-ratios and full of spectral features were derived. This result is of utmost importance for the development of powerful instruments for space missions. By point scanning the surfaces of the meteorite samples, it was possible for the first time to construct UV-Raman images out of the array of Raman spectra. Deep-UV Raman images are to the best of our knowledge presented for the first time. The images were used for a discussion of the chemical-mineralogical composition and texture of the meteorite surfaces. Comparative Raman studies applying visible and NIR Raman excitation wavelengths demonstrate a much better performance for UV Raman excitation. This comparative study of different Raman excitation wavelengths at the same sample spots was done by constructing a versatile, robust sample holder with a fixed micro-raster. The overall advantages of UV resonance Raman spectroscopy in terms of sensitivity and selectivity are demonstrated and discussed. Finally the application of this new technique for a UV Raman instrument for envisaged astrobiological focused space missions is suggested.

Water solubility in aluminous orthopyroxene and the origin of Earth's asthenosphere.

Plate tectonics is based on the concept of rigid lithosphere plates sliding on a mechanically weak asthenosphere. Many models assume that the weakness of the asthenosphere is related to the presence of small amounts of hydrous melts. However, the mechanism that may cause melting in the asthenosphere is not well understood. We show that the asthenosphere coincides with a zone where the water solubility in mantle minerals has a pronounced minimum. The minimum is due to a sharp decrease of water solubility in aluminous orthopyroxene with depth, whereas the water solubility in olivine continuously increases with pressure. Melting in the asthenosphere may therefore be related not to volatile enrichment but to a minimum in water solubility, which causes excess water to form a hydrous silicate melt.

Mineralogy and petrology of comet 81P/Wild 2 nucleus samples.

The bulk of the comet 81P/Wild 2 (hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger (over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk.

Phase transitions in solids stimulated by simultaneous exposure to high pressure and relativistic heavy ions.

In many solids, heavy ions of high kinetic energy (MeV-GeV) produce long cylindrical damage trails with diameters of order 10 nm. Up to now, no information was available how solids cope with the simultaneous exposure to these energetic projectiles and to high pressure. We report the first experiments where relativistic uranium and gold ions from the SIS heavy-ion synchrotron at GSI were injected through several mm of diamond into solid samples pressurized up to 14 GPa in a diamond anvil cell. In synthetic graphite and natural zircon, the combination of pressure and ion beams triggered drastic structural changes not caused by the applied pressure or the ions alone. The modifications comprise long-range amorphization of graphite rather than individual track formation, and in the case of zircon the decomposition into nanocrystals and nucleation of the high-pressure phase reidite.

Fe-Mg interdiffusion in (Mg,Fe)SiO3 Perovskite and lower mantle reequilibration.

Fe-Mg interdiffusion coefficients for (Mg,Fe)SiO3 perovskite have been measured at pressures of 22 to 26 gigapascals and temperatures between 1973 and 2273 kelvin. Perovskite Fe-Mg interdiffusion is as slow as Si self-diffusion and is orders of magnitude slower than Fe-Mg diffusion in other mantle minerals. Length scales over which chemical heterogeneities can homogenize, throughout the depth range of the lower mantle, are limited to a few meters even on time scales equivalent to the age of Earth. Heterogeneities can therefore only equilibrate chemically when they are stretched and thinned by intense deformation.

Experimental evidence for the existence of iron-rich metal in the Earth's lower mantle.

The oxidation state recorded by rocks from the Earth's upper mantle can be calculated from measurements of the distribution of Fe3+ and Fe2+ between the constituent minerals. The capacity for minerals to incorporate Fe3+ may also be a significant factor controlling the oxidation state of the mantle, and high-pressure experimental measurements of this property might provide important insights into the redox state of the more inaccessible deeper mantle. Here we show experimentally that the Fe3+ content of aluminous silicate perovskite, the dominant lower-mantle mineral, is independent of oxygen fugacity. High levels of Fe3+ are present in perovskite even when it is in chemical equilibrium with metallic iron. Silicate perovskite in the lower mantle will, therefore, have an Fe3+/total Fe ratio of at least 0.6, resulting in a whole-rock ratio of over ten times that of the upper mantle. Consequently, the lower mantle must either be enriched in Fe3+ or Fe3+ must form by the disproportionation of Fe2+ to produce Fe3+ plus iron metal. We argue that the lower mantle contains approximately 1 wt% of a metallic iron-rich alloy. The mantle's oxidation state and siderophile element budget have probably been influenced by the presence of this alloy.