Heat flows enrich prebiotic building blocks and enhance their reactivity.

The emergence of biopolymer building blocks is a crucial step during the origins of life1-6. However, all known formation pathways rely on rare pure feedstocks and demand successive purification and mixing steps to suppress unwanted side reactions and enable high product yields. Here we show that heat flows through thin, crack-like geo-compartments could have provided a widely available yet selective mechanism that separates more than 50 prebiotically relevant building blocks from complex mixtures of amino acids, nucleobases, nucleotides, polyphosphates and 2-aminoazoles. Using measured thermophoretic properties7,8, we numerically model and experimentally prove the advantageous effect of geological networks of interconnected cracks9,10 that purify the previously mixed compounds, boosting their concentration ratios by up to three orders of magnitude. The importance for prebiotic chemistry is shown by the dimerization of glycine11,12, in which the selective purification of trimetaphosphate (TMP)13,14 increased reaction yields by five orders of magnitude. The observed effect is robust under various crack sizes, pH values, solvents and temperatures. Our results demonstrate how geologically driven non-equilibria could have explored highly parallelized reaction conditions to foster prebiotic chemistry.

Oxide nanolitisation-induced melt iron extraction causes viscosity jumps and enhanced explosivity in silicic magma.

Explosivity in erupting volcanoes is controlled by the degassing dynamics and the viscosity of the ascending magma in the conduit. Magma crystallisation enhances both heterogeneous bubble nucleation and increases in magma bulk viscosity. Nanolite crystallisation has been suggested to enhance such processes too, but in a noticeably higher extent. Yet the precise causes of the resultant strong viscosity increase remain unclear. Here we report experimental results for rapid nanolite crystallisation in natural silicic magma and the extent of the subsequent viscosity increase. Nanolite-free and nanolite-bearing rhyolite magmas were subjected to heat treatments, where magmas crystallised or re-crystallised oxide nanolites depending on their initial state, showing an increase of one order of magnitude as oxide nanolites formed. We thus demonstrate that oxide nanolites crystallisation increases magma bulk viscosity mainly by increasing the viscosity of its melt phase due to the chemical extraction of iron, whereas the physical effect of particle suspension is minor, almost negligible. Importantly, we further observe that this increase is sufficient for driving magma fragmentation depending on magma degassing and ascent dynamics.

Nanoscale silicate melt textures determine volcanic ash surface chemistry.

Explosive volcanic eruptions produce vast quantities of silicate ash, whose surfaces are subsequently altered during atmospheric transit. These altered surfaces mediate environmental interactions, including atmospheric ice nucleation, and toxic effects in biota. A lack of knowledge of the initial, pre-altered ash surface has required previous studies to assume that the ash surface composition created during magmatic fragmentation is equivalent to the bulk particle assemblage. Here we examine ash particles generated by controlled fragmentation of andesite and find that fragmentation generates ash particles with substantial differences in surface chemistry. We attribute this disparity to observations of nanoscale melt heterogeneities, in which Fe-rich nanophases in the magmatic melt deflect and blunt fractures, thereby focusing fracture propagation within aureoles of single-phase melt formed during diffusion-limited growth of crystals. In this manner, we argue that commonly observed pre-eruptive microtextures caused by disequilibrium crystallisation and/or melt unmixing can modify fracture propagation and generate primary discrepancies in ash surface chemistry, an essential consideration for understanding the cascading consequences of reactive ash surfaces in various environments.

Stratigraphic reconstruction of the Víti breccia at Krafla volcano (Iceland): insights into pre-eruptive conditions priming explosive eruptions in geothermal areas.

Krafla central volcano in Iceland has experienced numerous basaltic fissure eruptions through its history, the most recent examples being the Mývatn (1724‒1729) and Krafla Fires (1975-1984). The Mývatn Fires opened with a steam-driven eruption that produced the Víti crater. A magmatic intrusion has been inferred as the trigger perturbing the geothermal field hosting Víti, but the cause(s) of the explosive response remain uncertain. Here, we present a detailed stratigraphic reconstruction of the breccia erupted from Víti crater, characterize the lithologies involved in the explosions, reconstruct the pre-eruptive setting, fingerprint the eruption trigger and source depth, and reveal the eruption mechanisms. Our results suggest that the Víti eruption can be classified as a magmatic-hydrothermal type and that it was a complex event with three eruption phases. The injection of rhyolite below a pre-existing convecting hydrothermal system likely triggered the Víti eruption. Heating and pressurization of shallow geothermal fluid initiated disruption of a scoria cone "cap" via an initial series of small explosions involving a pre-existing altered weak zone, with ejection of fragments from at least 60-m depth. This event was superseded by larger, broader, and dominantly shallow explosions (~ 200 m depth) driven by decompression of hydrothermal fluids within highly porous, poorly compacted tuffaceous hyaloclastite. This second phase was triggered when pressurized fluids broke through the scoria cone complex "cap". At the same time, deep-rooted explosions (~ 1-km depth) began to feed the eruption with large inputs of fragmented rhyolitic juvenile and host rock from a deeper zone. Shallow explosions enlarging the crater dominated the final phase. Our results indicate that at Krafla, as in similar geological contexts, shallow and thin hyaloclastite sequences hosting hot geothermal fluids and capped by low-permeability lithologies (e.g. altered scoria cone complex and/or massive, thick lava flow sequence) are susceptible to explosive failure in the case of shallow magmatic intrusion(s). SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00445-021-01502-y.

Heated gas bubbles enrich, crystallize, dry, phosphorylate and encapsulate prebiotic molecules.

Non-equilibrium conditions must have been crucial for the assembly of the first informational polymers of early life, by supporting their formation and continuous enrichment in a long-lasting environment. Here, we explore how gas bubbles in water subjected to a thermal gradient, a likely scenario within crustal mafic rocks on the early Earth, drive a complex, continuous enrichment of prebiotic molecules. RNA precursors, monomers, active ribozymes, oligonucleotides and lipids are shown to (1) cycle between dry and wet states, enabling the central step of RNA phosphorylation, (2) accumulate at the gas-water interface to drastically increase ribozymatic activity, (3) condense into hydrogels, (4) form pure crystals and (5) encapsulate into protecting vesicle aggregates that subsequently undergo fission. These effects occur within less than 30 min. The findings unite, in one location, the physical conditions that were crucial for the chemical emergence of biopolymers. They suggest that heated microbubbles could have hosted the first cycles of molecular evolution.

Combined effusive-explosive silicic volcanism straddles the multiphase viscous-to-brittle transition.

Magma is a viscoelastic fluid that can support fracture propagation when local shear stresses are high, or relax and flow when shear stresses are low. Here we present experiments to confirm this using synthetic and natural magmatic liquids across eruptive conditions and use Maxwell's linear viscoelasticity to parameterize our results and predict the maximum stresses that can be supported during flow. This model proves universal across a large range of liquid compositions, temperatures, crystallinity and rates of strain relevant to shallow crustal magma ascent. Our results predict that the 2008 Volcán Chaitén eruption resided in the viscous field at the onset of magma ascent, but transitioned to a mixed viscous-brittle regime during degassing, coincident with the observed combined effusive-explosive behaviour during dome extrusion. Taking a realistic maximum effusive ascent rate, we propose that silicic eruptions on Earth may straddle the viscous-to-brittle transition by the time they reach the surface.

Topological inversions in coalescing granular media control fluid-flow regimes.

Sintering-or coalescence-of viscous droplets is an essential process in many natural and industrial scenarios. Current physical models of the dynamics of sintering are limited by the lack of an explicit account of the evolution of microstructural geometry. Here, we use high-speed time-resolved x-ray tomography to image the evolving geometry of a sintering system of viscous droplets, and use lattice Boltzmann simulations of creeping fluid flow through the reconstructed pore space to determine its permeability. We identify and characterize a topological inversion, from spherical droplets in a continuous interstitial gas, to isolated bubbles in a continuous liquid. We find that the topological inversion is associated with a transition in permeability-porosity behavior, from Stokes permeability at high porosity, to percolation theory at low porosity. We use these findings to construct a unified physical description that reconciles previously incompatible models for the evolution of porosity and permeability during sintering.

A theoretical explanation of grain size distributions in explosive rock fragmentation.

We have measured grain size distributions of the results of laboratory decompression explosions of volcanic rock. The resulting distributions can be approximately represented by gamma distributions of weight per cent as a function of [Formula: see text], where d is the grain size in millimetres measured by sieving, with a superimposed long tail associated with the production of fines. We provide a description of the observations based on sequential fragmentation theory, which we develop for the particular case of 'self-similar' fragmentation kernels, and we show that the corresponding evolution equation for the distribution can be explicitly solved, yielding the long-time lognormal distribution associated with Kolmogorov's fragmentation theory. Particular features of the experimental data, notably time evolution, advection, truncation and fines production, are described and predicted within the constraints of a generalized, 'reductive' fragmentation model, and it is shown that the gamma distribution of coarse particles is a natural consequence of an assumed uniform fragmentation kernel. We further show that an explicit model for fines production during fracturing can lead to a second gamma distribution, and that the sum of the two provides a good fit to the observed data.

Experimental investigations on the explosivity of steam-driven eruptions: A case study of Solfatara volcano (Campi Flegrei).

Steam-driven eruptions, both phreatic and hydrothermal, expel exclusively fragments of non-juvenile rocks disintegrated by the expansion of water as liquid or gas phase. As their violence is related to the magnitude of the decompression work that can be performed by fluid expansion, these eruptions may occur with variable degrees of explosivity. In this study we investigate the influence of liquid fraction and rock petrophysical properties on the steam-driven explosive energy. A series of fine-grained heterogeneous tuffs from the Campi Flegrei caldera were investigated for their petrophysical properties. The rapid depressurization of various amounts of liquid water within the rock pore space can yield highly variable fragmentation and ejection behaviors for the investigated tuffs. Our results suggest that the pore liquid fraction controls the stored explosive energy with an increasing liquid fraction within the pore space increasing the explosive energy. Overall, the energy released by steam flashing can be estimated to be 1 order of magnitude higher than for simple (Argon) gas expansion and may produce a higher amount of fine material even under partially saturated conditions. The energy surplus in the presence of steam flashing leads to a faster fragmentation with respect to gas expansion and to higher ejection velocities imparted to the fragmented particles. Moreover, weak and low permeability rocks yield a maximum fine fraction. Using experiments to unravel the energetics of steam-driven eruptions has yielded estimates for several parameters controlling their explosivity. These findings should be considered for both modeling and evaluation of the hazards associated with steam-driven eruptions.

Sintering of viscous droplets under surface tension.

We conduct experiments to investigate the sintering of high-viscosity liquid droplets. Free-standing cylinders of spherical glass beads are heated above their glass transition temperature, causing them to densify under surface tension. We determine the evolving volume of the bead pack at high spatial and temporal resolution. We use these data to test a range of existing models. We extend the models to account for the time-dependent droplet viscosity that results from non-isothermal conditions, and to account for non-zero final porosity. We also present a method to account for the initial distribution of radii of the pores interstitial to the liquid spheres, which allows the models to be used with no fitting parameters. We find a good agreement between the models and the data for times less than the capillary relaxation timescale. For longer times, we find an increasing discrepancy between the data and the model as the Darcy outgassing time-scale approaches the sintering timescale. We conclude that the decreasing permeability of the sintering system inhibits late-stage densification. Finally, we determine the residual, trapped gas volume fraction at equilibrium using X-ray computed tomography and compare this with theoretical values for the critical gas volume fraction in systems of overlapping spheres.

Conduit margin heating and deformation during the AD 1886 basaltic Plinian eruption at Tarawera volcano, New Zealand.

During explosive eruptions, a suspension of gas and pyroclasts rises rapidly within a conduit. Here, we have analysed textures preserved in the walls of a pyroclastic feeder dyke of the AD 1886 Tarawera basaltic Plinian fissure eruption. The samples examined consist of basaltic ash and scoria plastered onto a conduit wall of a coherent rhyolite dome and a welded rhyolitic dome breccia. We examine the textural evidence for the response of the wall material, built of ∼75 vol.% glass and ∼25 vol.% crystals (pore-free equivalent), to mass movement in the adjacent conduit. In the rhyolitic wall material, we quantify the orientation and aspect ratio of biotite crystals as strain markers of simple shear deformation, and interpret juxtaposed regions of vesiculation and vesicle collapse as evidence of conduit wall heating. Systematic changes occur close to the margin: (1) porosity is highly variable, with areas locally vesiculated or densified, (2) biotite crystals are oriented with their long axis parallel to the margin, (3) the biotites have greater aspect ratios close to the margin and (4) the biotite crystals are fractured. We interpret the biotite phenocryst deformation to result from crystal fracture, rotation and cleavage-parallel bookcase translation. These textural observations are inferred to indicate mechanical coupling between the hot gas-ash jet and the conduit wall and reheating of wall rock rhyolite. We couple these observations with a simple 1D conductive heating model to show what minimum temperature the conduit wall needs to reach in order to achieve a temperature above the glass transition throughout the texturally-defined deformed zone. We propose that conduit wall heating and resulting deformation influences conduit margin outgassing and may enhance the intensity of such large basaltic eruptions.