Computational assessment of the potential of cross-catalytic coprecipitating systems for the bottom-up design of nanocomposites.

The production of nanocomposites is often economically and environmentally costly. Silica-witherite biomorphs, known for producing a wealth of life-like shapes, are nanocomposites entirely formed through self-organization processes. Behind these precipitates are two precipitation reactions that catalyze each other. Using a simple computational approach, we show here that this type of chemical system - defined here as Cross-Catalytic Coprecipitating Systems (CCCSs) - is of great interest to material design. Provided that cross-catalytic effects are sufficient to overcome the precipitation thresholds for each phase, all CCCSs can be expected to self-organize into nanocomposite materials through a one-pot, one-step synthesis protocol. Symmetry-breaking events generating various complex, ordered textures are predicted in CCCSs involving crystalline phases. While high levels of stochasticity lead to a loss of ordering, coprecipitation is found to be robust to diffusion or advection in the solution. This model shows that a couple of chemical reactions can generate a range of complex textures - with possibly distinct physical/chemical properties. Cross-catalytic coprecipitating systems consequently represent a promising avenue for producing nanocomposites with complex textures at reduced economic and environmental costs.

Environmental Stability and Its Importance for the Emergence of Darwinian Evolution.

The emergence of Darwinian evolution represents a central point in the history of life as we know it. However, it is generally assumed that the environments in which life appeared were hydrothermal environments, with highly variable conditions in terms of pH, temperature or redox levels. Are evolutionary processes favored to appear in such settings, where the target of biological adaptation changes over time? How would the first evolving populations compete with non-evolving populations? Using a numerical model, we explore the effect of environmental variation on the outcome of the competition between evolving and non-evolving populations of protocells. Our study found that, while evolving protocells consistently outcompete non-evolving populations in stable environments, they are outcompeted in variable environments when environmental variations occur on a timescale similar to the average duration of a generation. This is due to the energetic burden represented by adaptation to the wrong environmental conditions. Since the timescale of temperature variation in natural hydrothermal settings overlaps with the average prokaryote generation time, the current work indicates that a solution must have been found by early life to overcome this threshold.

Evaluating the abiotic synthesis potential and the stability of building blocks of life beneath an impact-induced steam atmosphere.

A prerequisite for prebiotic chemistry is the accumulation of critical building blocks of life. Some studies argue that more frequent impact events on the primitive Earth could have induced a more reducing steam atmosphere and thus favor widespread and more efficient synthesis of life building blocks. However, elevated temperature is also proposed to threaten the stability of organics and whether life building blocks could accumulate to appreciable levels in the reducing yet hot surface seawater beneath the steam atmosphere is still poorly examined. Here, we used a thermodynamic tool to examine the synthesis affinity of various life building blocks using inorganic gasses as reactants at elevated temperatures and corresponding steam pressures relevant with the steam-seawater interface. Our calculations show that although the synthesis affinity of all life building blocks decreases when temperature increases, many organics, including methane, methanol, and carboxylic acids, have positive synthesis affinity over a wide range of temperatures, implying that these species were favorable to form (>10-6 molal) in the surface seawater. However, cyanide and formaldehyde have overall negative affinities, suggesting that these critical compounds would tend to undergo hydrolysis in the surface seawaters. Most of the 18 investigated amino acids have positive affinities at temperature <220°C and their synthesis affinity increases under more alkaline conditions. Sugars, ribose, and nucleobases have overall negative synthesis affinities at the investigated range of temperatures. Synthesis affinities are shown to be sensitive to the hydrogen fugacity. Higher hydrogen fugacity (in equilibrium with FQI or IW) favors the synthesis and accumulation of nearly all the investigated compounds, except for HCN and its derivate products. In summary, our results suggest that reducing conditions induced by primitive impacts could indeed favor the synthesis/accumulation of some life building blocks, but some critical species, particularly HCN and nucleosides, were still unfavorable to accumulate to appreciable levels. Our results can provide helpful guidance for future efforts to search for or understand the stability of biomolecules on other planets like Mars and icy moons. We advocate examining craters formed by more reducing impactors to look for the preservation of prebiotic materials.

An Alternative Approach for Assessing Biogenicity.

The search for signs of life in the ancient rock record, extreme terrestrial environments, and other planetary bodies requires a well-established, universal, and unambiguous test of biogenicity. This is notably true for cellular remnants of microbial life, since their relatively simple morphologies resemble various abiogenic microstructures that occur in nature. Although lists of qualitative biogenicity criteria have been devised, debates regarding the biogenicity of many ancient microfossils persist to this day. We propose here an alternative quantitative approach for assessing the biogenicity of putative microfossils. In this theoretical approach, different hypotheses-involving biology or not and depending on the geologic setting-are put forward to explain the observed objects. These hypotheses correspond to specific types of microstructures/systems. Using test samples, the morphology and/or chemistry of these systems are then characterized at the scale of populations. Morphologic parameters include, for example, circularity, aspect ratio, and solidity, while chemical parameters could include elementary ratios (e.g., N/C ratio), isotopic enrichments (e.g., δ13C), or chirality (e.g., molar proportion of stereoisomers), among others. Statistic trends distinguishing the different systems are then searched for empirically. The trends found are translated into "decision spaces" where the different systems are quantitatively discriminated and where the potential microfossil population can be located as a single point. This approach, which is formulated here on a theoretical level, will solve several problems associated with the classical qualitative criteria of biogenicity. Most importantly, it could be applied to reveal the existence of cellular life on other planets, for which characteristics of morphology and chemical composition are difficult to predict.

Identifying microbial life in rocks: Insights from population morphometry.

The identification of cellular life in the rock record is problematic, since microbial life forms, and particularly bacteria, lack sufficient morphologic complexity to be effectively distinguished from certain abiogenic features in rocks. Examples include organic pore-fillings, hydrocarbon-containing fluid inclusions, organic coatings on exfoliated crystals and biomimetic mineral aggregates (biomorphs). This has led to the interpretation and re-interpretation of individual microstructures in the rock record. The morphologic description of entire populations of microstructures, however, may provide support for distinguishing between preserved micro-organisms and abiogenic objects. Here, we present a statistical approach based on quantitative morphological description of populations of microstructures. Images of modern microbial populations were compared to images of two relevant types of abiogenic microstructures: interstitial spaces and silica-carbonate biomorphs. For the populations of these three systems, the size, circularity, and solidity of individual particles were calculated. Subsequently, the mean/SD, skewness, and kurtosis of the statistical distributions of these parameters were established. This allowed the qualitative and quantitative comparison of distributions in these three systems. In addition, the fractal dimension and lacunarity of the populations were determined. In total, 11 parameters, independent of absolute size or shape, were used to characterize each population of microstructures. Using discriminant analysis with parameter subsets, it was found that size and shape distributions are typically sufficient to discriminate populations of biologic and abiogenic microstructures. Analysis of ancient, yet unambiguously biologic, samples (1.0 Ga Angmaat Formation, Baffin Island, Canada) suggests that taphonomic effects can alter morphometric characteristics and complicate image analysis; therefore, a wider range of microfossil assemblages should be studied in the future before automated analyses can be developed. In general, however, it is clear from our results that there is great potential for morphometric descriptions of populations in the context of life recognition in rocks, either on Earth or on extraterrestrial bodies.

Formation and Preservation of Microbial Palisade Fabric in Silica Deposits from El Tatio, Chile.

Palisade fabric is a ubiquitous texture of silica sinter found in low temperature (<40°C) regimes of hot spring environments, and it is formed when populations of filamentous microorganisms act as templates for silica polymerization. Although it is known that postdepositional processes such as biological degradation and dewatering can strongly affect preservation of these fabrics, the impact of extreme aridity has so far not been studied in detail. Here, we report a detailed analysis of recently silicified palisade fabrics from a geyser in El Tatio, Chile, tracing the progressive degradation of microorganisms within the silica matrix. This is complemented by heating experiments of natural sinter samples to assess the role of diagenesis. Sheathed cyanobacteria, identified as Leptolyngbya sp., were found to be incorporated into silica sinter by irregular cycles of wetting, evaporation, and mineral precipitation. Transmission electron microscopy analyses revealed that nanometer-sized silica particles are filling the pore space within individual cyanobacterial sheaths, giving rise to their structural rigidity to sustain a palisade fabric framework. Diagenesis experiments further show that the sheaths of the filaments are preferentially preserved relative to the trichomes, and that the amount of water present within the sinter is an important factor for overall preservation during burial. This study confirms that palisade fabrics are efficiently generated in a highly evaporative geothermal field, and that these biosignatures can be most effectively preserved under dry diagenetic conditions.