Increasing control over biomineralization in conodont evolution.

Vertebrates use the phosphate mineral apatite in their skeletons, which allowed them to develop tissues such as enamel, characterized by an outstanding combination of hardness and elasticity. It has been hypothesized that the evolution of the earliest vertebrate skeletal tissues, found in the teeth of the extinct group of conodonts, was driven by adaptation to dental function. We test this hypothesis quantitatively and demonstrate that the crystallographic order increased throughout the early evolution of conodont teeth in parallel with morphological adaptation to food processing. With the c-axes of apatite crystals oriented perpendicular to the functional feeding surfaces, the strongest resistance to uniaxial compressional stress is conferred along the long axes of denticles. Our results support increasing control over biomineralization in the first skeletonized vertebrates and allow us to test models of functional morphology and material properties across conodont dental diversity.

Heitt Mjölnir: a heated miniature triaxial apparatus for 4D synchrotron microtomography.

Third- and fourth-generation synchrotron light sources with high fluxes and beam energies enable the use of innovative X-ray translucent experimental apparatus. These experimental devices access geologically relevant conditions whilst enabling in situ characterization using the spatial and temporal resolutions accessible at imaging beamlines. Here, Heitt Mjölnir is introduced, a heated miniature triaxial rig based on the design of Mjölnir, but covering a wider temperature range and larger sample volume at similar pressure capacities. This device is designed to investigate coupled thermal, chemical, hydraulic and mechanical processes from grain to centimetre scales using cylindrical samples of 10 mm × 20 mm (diameter × length). Heitt Mjölnir can simultaneously reach confining (hydraulic) pressures of 30 MPa and 500 MPa of axial stress with independently controlled sample pore fluid pressure < 30 MPa. This internally heated apparatus operates to temperatures up to 573 K with a minimal vertical thermal gradient in the sample of <0.3 K mm-1. This new apparatus has been deployed in operando studies at the TOMCAT (Swiss Light Source), I12 JEEP (Diamond Light Source) and PSICHÉ (Synchrotron SOLEIL) beamlines for 4D X-ray microtomography with scan intervals of a few minutes. Heitt Mjölnir is portable and modular, allowing a wide range of 4D characterizations of low-grade metamorphism and deformational processes. It enables spatially and temporally resolved fluid-rock interaction studies at conditions of crustal reservoirs and is suitable for characterization of material properties in geothermal, carbonation or subsurface gas storage applications. Technical drawings and an operation guide are included in this publication.

Geological records of transient fluid drainage into the shallow mantle wedge.

Pore fluid pressure on subduction zone megathrusts is lowered by fluid drainage into the overlying plate, affecting subduction zone seismicity. However, the spatial and temporal scales of fluid flow through suprasubduction zones are poorly understood. We constrain the duration and velocity of fluid flow through a shallow mantle wedge based on the analyses of vein networks consisting of high-temperature serpentine in hydrated ultramafic rocks from the Oman ophiolite. On the basis of a diffusion model and the time-integrated fluid flux, we show that the channelized fluid flow was short-lived (2.1 × 10-1 to 1.1 × 101 years) and had a high fluid velocity (2.7 × 10-3 to 4.9 × 10-2 meters second-1), which is close to the propagation velocities of seismic events in present-day subduction zones. Our results suggest that the drainage of fluid into the overlying plate occurs as episodic pulses, which may influence the recurrence of megathrust earthquakes.

Quantifying microstructures of earth materials using higher-order spatial correlations and deep generative adversarial networks.

The key to most subsurface processes is to determine how structural and topological features at small length scales, i.e., the microstructure, control the effective and macroscopic properties of earth materials. Recent progress in imaging technology has enabled us to visualise and characterise microstructures at different length scales and dimensions. However, one limitation of these technologies is the trade-off between resolution and sample size (or representativeness). A promising approach to this problem is image reconstruction which aims to generate statistically equivalent microstructures but at a larger scale and/or additional dimension. In this work, a stochastic method and three generative adversarial networks (GANs), namely deep convolutional GAN (DCGAN), Wasserstein GAN with gradient penalty (WGAN-GP), and StyleGAN2 with adaptive discriminator augmentation (ADA), are used to reconstruct two-dimensional images of two hydrothermally rocks with varying degrees of complexity. For the first time, we evaluate and compare the performance of these methods using multi-point spatial correlation functions-known as statistical microstructural descriptors (SMDs)-ultimately used as external tools to the loss functions. Our findings suggest that a well-trained GAN can reconstruct higher-order, spatially-correlated patterns of complex earth materials, capturing underlying structural and morphological properties. Comparing our results with a stochastic reconstruction method based on a two-point correlation function, we show the importance of coupling training/assessment of GANs with higher-order SMDs, especially in the case of complex microstructures. More importantly, by quantifying original and reconstructed microstructures via different GANs, we highlight the interpretability of these SMDs and show how they can provide valuable insights into the spatial patterns in the synthetic images, allowing us to detect common artefacts and failure cases in training GANs.

Decoding the nanoscale porosity in serpentinites from multidimensional electron microscopy and discrete element modelling.

Serpentinites, widespread in Earth's lithosphere, exhibit inherent nanoporosity that may significantly impact their geochemical behaviour. This study provides a comprehensive investigation into the characteristics, scale dependence, and potential implications of nanoporosity in lizardite-dominated serpentinites. Through a combination of multidimensional imaging techniques and molecular-dynamics-based discrete element modelling, we reveal that serpentinites function as nanoporous media with pore sizes predominantly less than 100 nm. Crystallographic relationships between olivine, serpentine, and nanoporosity are explored, indicating a lack of significant correlations. Instead, stochastic growth and random packing of serpentine grains within mesh cores may result in interconnected porosity. The analysis of pore morphology suggests that the irregular pore shapes align with the crystal form of serpentine minerals. Furthermore, the nanoporosity within brucite-rich layers at the serpentine-olivine interface is attributed to delamination along weak van der Waals planes, while pore formation within larger brucite domains likely results from low-temperature alteration processes. The fractal nature of the pore size distribution and the potential interconnectivity of porosity across different scales further support the presence of a pervasive nanoporous network within serpentinites. Confinement within these nanopores may introduce unique emergent properties, potentially influencing fluid transport, mineral solubility, and chemical reactions. As such, these processes may have profound implications for the geochemical evolution of serpentinites.

Experimental and Theoretical Constraints on Amino Acid Formation from PAHs in Asteroidal Settings.

Amino acids and polycyclic aromatic hydrocarbons (PAHs) belong to the range of organic compounds detected in meteorites. In this study, we tested empirically and theoretically if PAHs are precursors for amino acids in carbonaceous chondrites, as previously suggested. We conducted experiments to synthesize amino acids from fluoranthene (PAH), with ammonium bicarbonate as a source for ammonia and carbon dioxide under mimicked asteroidal conditions. In our thermodynamic calculations, we extended our analysis to additional PAH-amino acid combinations. We explored 36 reactions involving the PAHs naphthalene, anthracene, fluoranthene, pyrene, triphenylene, and coronene and the amino acids glycine, alanine, valine, leucine, phenylalanine, and tyrosine. Our experiments do not show the formation of amino acids, whereas our theoretical results hint that PAHs could be precursors of amino acids in carbonaceous chondrites at low temperatures.

Influence of Inorganic Solution Components on Lithium Carbonate Crystal Growth.

Lithium-bearing brines are an increasingly attractive source of Li for extraction. One extraction mechanism is the removal of Li from the fluid phase through the precipitation of zabuyelite (Li2CO3). The chemistry of the brine plays an important role in this process because ions in solution can compete for the components of the Li-carbonate phase. Here we explore the effect of different brine components on the precipitation of zabuyelite using experiments and computational simulations. Crystals formed in all solutions showed morphological evidence for potential transformation from a precursor phase. Our study indicates that Ca2+ and SO4 2- are incorporated into the precipitated zabuyelite crystals. Sulfate also interacts directly with specific surfaces on the growing crystal and is expected to form ion pairs with Li+ in solution. Similarly, Na+ appears to form ion pairs in solution with the carbonate ion, slowing nucleation of zabuyelite in the experiments. K+ and Cl- may interact with the growing zabuyelite crystals but do not appear to affect zabuyelite nucleation and growth times. These experiments highlight the importance of understanding the solution chemistry on zabuyelite formation in order to predict the efficiency of extraction processes and the purity of the solids.

In Situ Nanoscale Investigation of Step Retreat on Fluoranthene Crystal Surfaces.

Fluoranthene, a polycyclic aromatic hydrocarbon, has been detected on Earth as well as in asteroids and meteorites and may have played a role in the formation of life. Increasing the ionic strength of aqueous solutions has been observed to lower the fluoranthene solubility, but it is unclear how solution composition controls the release rate of fluoranthene to an aqueous solution. To elucidate this, we performed in situ atomic force microscopy experiments in which we characterized the sublimation and dissolution behavior of fluoranthene crystal surfaces. From this, we quantify the step retreat rate upon exposure to air, deionized water, and a 0.4 M NaCl or 0.1 M MgSO4 solution. Surface roughness is the main factor that determines the dissolution or sublimation rate. The results imply that during fluoranthene remediation or breakdown in meteorites and asteroids, ionic strength will be more important than chemical composition for controlling fluoranthene release into solution.

Fluid-driven metamorphism of the continental crust governed by nanoscale fluid flow.

The transport of fluids through the Earth's crust controls the redistribution of elements to form mineral and hydrocarbon deposits, the release and sequestration of greenhouse gases, and facilitates metamorphic reactions that influence lithospheric rheology. In permeable systems with a well-connected porosity, fluid transport is largely driven by fluid pressure gradients. In less permeable rocks, deformation may induce permeability by creating interconnected heterogeneities, but without these perturbations, mass transport is limited along grain boundaries or relies on transformation processes that self-generate transient fluid pathways. The latter can facilitate large-scale fluid and mass transport in nominally impermeable rocks without large-scale fluid transport pathways. Here, we show that pervasive, fluid-driven metamorphism of crustal igneous rocks is directly coupled to the production of nanoscale porosity. Using multi-dimensional nano-imaging and molecular dynamics simulations, we demonstrate that in feldspar, the most abundant mineral family in the Earth's crust, electrokinetic transport through reaction-induced nanopores (10-100 nm) can potentially be significant. This suggests that metamorphic fluid flow and fluid-mediated mineral transformation reactions can be considerably influenced by nanofluidic transport phenomena.

Mineral Surface Rearrangement at High Temperatures: Implications for Extraterrestrial Mineral Grain Reactivity.

Mineral surfaces play a critical role in the solar nebula as a catalytic surface for chemical reactions and potentially acted as a source of water during Earth's accretion by the adsorption of water molecules to the surface of interplanetary dust particles. However, nothing is known about how mineral surfaces respond to short-lived thermal fluctuations that are below the melting temperature of the mineral. Here we show that mineral surfaces react and rearrange within minutes to changes in their local environment despite being far below their melting temperature. Polished surfaces of the rock and planetary dust-forming silicate mineral olivine ((Mg,Fe)2SiO4) show significant surface reorganization textures upon rapid heating resulting in surface features up to 40 nm in height observed after annealing at 1200 °C. Thus, high-temperature fluctuations should provide new and highly reactive sites for chemical reactions on nebula mineral particles. Our results also may help to explain discrepancies between short and long diffusion profiles in experiments where diffusion length scales are of the order of 100 nm or less.

Subduction zone forearc serpentinites as incubators for deep microbial life.

Serpentinization-fueled systems in the cool, hydrated forearc mantle of subduction zones may provide an environment that supports deep chemolithoautotrophic life. Here, we examine serpentinite clasts expelled from mud volcanoes above the Izu-Bonin-Mariana subduction zone forearc (Pacific Ocean) that contain complex organic matter and nanosized Ni-Fe alloys. Using time-of-flight secondary ion mass spectrometry and Raman spectroscopy, we determined that the organic matter consists of a mixture of aliphatic and aromatic compounds and functional groups such as amides. Although an abiotic or subduction slab-derived fluid origin cannot be excluded, the similarities between the molecular signatures identified in the clasts and those of bacteria-derived biopolymers from other serpentinizing systems hint at the possibility of deep microbial life within the forearc. To test this hypothesis, we coupled the currently known temperature limit for life, 122 °C, with a heat conduction model that predicts a potential depth limit for life within the forearc at ∼10,000 m below the seafloor. This is deeper than the 122 °C isotherm in known oceanic serpentinizing regions and an order of magnitude deeper than the downhole temperature at the serpentinized Atlantis Massif oceanic core complex, Mid-Atlantic Ridge. We suggest that the organic-rich serpentinites may be indicators for microbial life deep within or below the mud volcano. Thus, the hydrated forearc mantle may represent one of Earth's largest hidden microbial ecosystems. These types of protected ecosystems may have allowed the deep biosphere to thrive, despite violent phases during Earth's history such as the late heavy bombardment and global mass extinctions.

Fragmentation of wall rock garnets during deep crustal earthquakes.

Fractures and faults riddle the Earth's crust on all scales, and the deformation associated with them is presumed to have had significant effects on its petrological and structural evolution. However, despite the abundance of directly observable earthquake activity, unequivocal evidence for seismic slip rates along ancient faults is rare and usually related to frictional melting and the formation of pseudotachylites. We report novel microstructures from garnet crystals in the immediate vicinity of seismic slip planes that transected lower crustal granulites during intermediate-depth earthquakes in the Bergen Arcs area, western Norway, some 420 million years ago. Seismic loading caused massive dislocation formations and fragmentation of wall rock garnets. Microfracturing and the injection of sulfide melts occurred during an early stage of loading. Subsequent dilation caused pervasive transport of fluids into the garnets along a network of microfractures, dislocations, and subgrain and grain boundaries, leading to the growth of abundant mineral inclusions inside the fragmented garnets. Recrystallization by grain boundary migration closed most of the pores and fractures generated by the seismic event. This wall rock alteration represents the initial stages of an earthquake-triggered metamorphic transformation process that ultimately led to reworking of the lower crust on a regional scale.

Fast-moving dislocations trigger flash weakening in carbonate-bearing faults during earthquakes.

Rupture fronts can cause fault displacement, reaching speeds up to several ms(-1) within a few milliseconds, at any distance away from the earthquake nucleation area. In the case of silicate-bearing rocks the abrupt slip acceleration results in melting at asperity contacts causing a large reduction in fault frictional strength (i.e., flash weakening). Flash weakening is also observed in experiments performed in carbonate-bearing rocks but evidence for melting is lacking. To unravel the micro-physical mechanisms associated with flash weakening in carbonates, experiments were conducted on pre-cut Carrara marble cylinders using a rotary shear apparatus at conditions relevant to earthquakes propagation. In the first 5 mm of slip the shear stress was reduced up to 30% and CO2 was released. Focused ion beam, scanning and transmission electron microscopy investigations of the slipping zones reveal the presence of calcite nanograins and amorphous carbon. We interpret the CO2 release, the formation of nanograins and amorphous carbon to be the result of a shock-like stress release associated with the migration of fast-moving dislocations. Amorphous carbon, given its low friction coefficient, is responsible for flash weakening and promotes the propagation of the seismic rupture in carbonate-bearing fault patches.

Rock mechanics. Superplastic nanofibrous slip zones control seismogenic fault friction.

Understanding the internal mechanisms controlling fault friction is crucial for understanding seismogenic slip on active faults. Displacement in such fault zones is frequently localized on highly reflective (mirrorlike) slip surfaces, coated with thin films of nanogranular fault rock. We show that mirror-slip surfaces developed in experimentally simulated calcite faults consist of aligned nanogranular chains or fibers that are ductile at room conditions. These microstructures and associated frictional data suggest a fault-slip mechanism resembling classical Ashby-Verrall superplasticity, capable of producing unstable fault slip. Diffusive mass transfer in nanocrystalline calcite gouge is shown to be fast enough for this mechanism to control seismogenesis in limestone terrains. With nanogranular fault surfaces becoming increasingly recognized in crustal faults, the proposed mechanism may be generally relevant to crustal seismogenesis.

Effect of secondary phase formation on the carbonation of olivine.

Large-scale olivine carbonation has been proposed as a potential method for sequestering CO(2) emissions. For in situ carbonation techniques, understanding the relationship between the formation of carbonate and other phases is important to predict the impact of possible passivating layers on the reaction. Therefore, we have conducted reactions of olivine with carbonated saline solutions in unstirred batch reactors. Altering the reaction conditions changed the Mg-carbonate morphology. We propose that this corresponded to changes in the ability of the system to precipitate hydromagnesite or magnesite. During high-temperature reactions (200 degrees C), an amorphous silica-enriched phase was precipitated that was transformed to lizardite as the reaction progressed. Hematite was also precipitated in the initial stages of these reactions but dissolved as the reaction proceeded. Comparison of the experimental observations with reaction models indicates that the reactions are governed by the interfacial fluid composition. The presence of a new Mg-silicate phase and the formation of secondary products at the olivine surface are likely to limit the extent of olivine to carbonate conversion.