Rapid hydrolysis rates of thio- and phosphate esters constrain the origin of metabolism to cool, acidic to neutral environments.

Universal to all life is a reliance on energy carriers such as adenosine triphosphate (ATP) which connect energy-releasing reactions to energy-consuming processes. While ATP is ubiquitously used today, simpler molecules such as thioesters and polyphosphates are hypothesized to be primordial energy carriers. Investigating environmental constraints on the non-enzymatic emergence of metabolism, we find that hydrolysis rates-not hydrolysis energies-differentiate phosphate esters and thioesters. At temperatures consistent with thermophilic microbes, thioesters are favored at acidic pH and phosphate esters at basic pH. Thioacids have a high stability across pH 5-10. The planetary availability of sulfur and phosphate is coincident with these calculations, with phosphate being abundant in alkaline and sulfur in acidic environments. Since both sulfur esters and phosphate esters are uniquely required in metabolism, our results point to a non-thermophilic origin of early metabolism at cool, acidic to neutral environments.

Reaction of size-selected iron-oxide cluster cations with methane: a model study of rapid methane loss in Mars' atmosphere.

We report gas-phase reactions of free iron-oxide clusters, FenOm+, and their Ar adducts with methane in the context of chemical processes in Mars' atmosphere. Methane activation was observed to produce FenOmCH2+/FenOmCD2+ and FenOmC+, where the reactivity exhibited size and composition dependence. For example, the rate coefficients of methane activation for Fe3O+ and Fe4O+ were estimated to be 1 × 10-13 and 3 × 10-13 cm3 s-1, respectively. Based on these reaction rate coefficients, the presence of iron-oxide clusters/particles with a density as low as 107 cm-3 in Mars' atmosphere would explain the rapid loss of methane observed recently by the Curiosity rover.

Aqueous breakdown of aspartate and glutamate to n-ω-amino acids on the parent bodies of carbonaceous chondrites and asteroid Ryugu.

Amino acids in carbonaceous chondrites may have seeded the origin of life on Earth and possibly elsewhere. Recently, the return samples from a C-type asteroid Ryugu were found to contain amino acids with a similar distribution to Ivuna-type CI chondrites, suggesting the potential of amino acid abundances as molecular descriptors of parent body geochemistry. However, the chemical mechanisms responsible for the amino acid distributions remain to be elucidated particularly at low temperatures (<50°C). Here, we report that two representative proteinogenic amino acids, aspartic acid and glutamic acid, decompose to ß-alanine and γ-aminobutyric acid, respectively, under simulated geoelectrochemical conditions at 25°C. This low-temperature conversion provides a plausible explanation for the enrichment of these two n-ω-amino acids compared to their precursors in heavily aqueously altered CI chondrites and Ryugu's return samples. The results suggest that these heavily aqueously altered samples originated from the water-rich mantle of their water/rock differentiated parent planetesimals where protein α-amino acids were decomposed.

Detection of phosphates originating from Enceladus's ocean.

Saturn's moon Enceladus harbours a global1 ice-covered water ocean2,3. The Cassini spacecraft investigated the composition of the ocean by analysis of material ejected into space by the moon's cryovolcanic plume4-9. The analysis of salt-rich ice grains by Cassini's Cosmic Dust Analyzer10 enabled inference of major solutes in the ocean water (Na+, K+, Cl-, HCO3-, CO32-) and its alkaline pH3,11. Phosphorus, the least abundant of the bio-essential elements12-14, has not yet been detected in an ocean beyond Earth. Earlier geochemical modelling studies suggest that phosphate might be scarce in the ocean of Enceladus and other icy ocean worlds15,16. However, more recent modelling of mineral solubilities in Enceladus's ocean indicates that phosphate could be relatively abundant17. Here we present Cassini's Cosmic Dust Analyzer mass spectra of ice grains emitted by Enceladus that show the presence of sodium phosphates. Our observational results, together with laboratory analogue experiments, suggest that phosphorus is readily available in Enceladus's ocean in the form of orthophosphates, with phosphorus concentrations at least 100-fold higher in the moon's plume-forming ocean waters than in Earth's oceans. Furthermore, geochemical experiments and modelling demonstrate that such high phosphate abundances could be achieved in Enceladus and possibly in other icy ocean worlds beyond the primordial CO2 snowline, either at the cold seafloor or in hydrothermal environments with moderate temperatures. In both cases the main driver is probably the higher solubility of calcium phosphate minerals compared with calcium carbonate in moderately alkaline solutions rich in carbonate or bicarbonate ions.

Dark microbiome and extremely low organics in Atacama fossil delta unveil Mars life detection limits.

Identifying unequivocal signs of life on Mars is one of the most important objectives for sending missions to the red planet. Here we report Red Stone, a 163-100 My alluvial fan-fan delta that formed under arid conditions in the Atacama Desert, rich in hematite and mudstones containing clays such as vermiculite and smectites, and therefore geologically analogous to Mars. We show that Red Stone samples display an important number of microorganisms with an unusual high rate of phylogenetic indeterminacy, what we refer to as "dark microbiome", and a mix of biosignatures from extant and ancient microorganisms that can be barely detected with state-of-the-art laboratory equipment. Our analyses by testbed instruments that are on or will be sent to Mars unveil that although the mineralogy of Red Stone matches that detected by ground-based instruments on the red planet, similarly low levels of organics will be hard, if not impossible to detect in Martian rocks depending on the instrument and technique used. Our results stress the importance in returning samples to Earth for conclusively addressing whether life ever existed on Mars.

Geoelectrochemistry-driven alteration of amino acids to derivative organics in carbonaceous chondrite parent bodies.

A long-standing question regarding carbonaceous chondrites (CCs) is how the CCs' organics were sourced and converted before and after the accretion of their parent bodies. Growing evidence shows that amino acid abundances in CCs decrease with an elongated aqueous alteration. However, the underlying chemical processes are unclear. If CCs' parent bodies were water-rock differentiated, pH and redox gradients can drive electrochemical reactions by using H2 as an electron source. Here, we simulate such redox conditions and demonstrate that α-amino acids are electrochemically altered to monoamines and α-hydroxy acids on FeS and NiS catalysts at 25 °C. This conversion is consistent with their enrichment compared to amino acid analogs in heavily altered CCs. Our results thus suggest that H2 can be an important driver for organic evolution in water-rock differentiated CC parent bodies as well as the Solar System icy bodies that might possess similar pH and redox gradients.

Arsenic and uranium contamination of Orog Lake in the Valley of Gobi Lakes, Mongolia: Field evidence of conservative accumulation of U in an alkaline, closed-basin lake during evaporation.

The shrinkage of inland, alkaline, and saline lakes has caused the elevation of arsenic and uranium concentrations in lake water. However, the chemical reactions associated with these enrichments remain unclear. We conducted a five-year study of the water chemistry of Orog Lake (Mongolia) and the chemical and spectroscopic characteristics of the sediment to determine the geochemical behavior of arsenic and uranium during evaporation. The arsenic and uranium concentrations increased as evaporation caused the lake to shrink. The maximum concentrations of arsenic and uranium exceeded 200 µg/L and 600 µg/L, respectively, when the lake area was the smallest. Comparisons of the monitoring results with predictions of geochemical modeling suggested that some arsenic was removed from the lake water under highly desiccated conditions. Sequential extraction and X-ray absorption near-edge structure analyses showed that ferrihydrite can take up As(V). The accumulation of uranium could be reproduced by considering only evaporation. The conservative behavior of uranium can be explained by the low affinity of U(VI) for carbonate and ferrihydrite at pH > 9 and high dissolved inorganic carbon concentrations. The ubiquitous formation of extremely soluble U-bearing salts after the complete desiccation of inland lakes may thus become a serious threat to limnetic ecosystems.

Experimental and Simulation Efforts in the Astrobiological Exploration of Exooceans.

The icy satellites of Jupiter and Saturn are perhaps the most promising places in the Solar System regarding habitability. However, the potential habitable environments are hidden underneath km-thick ice shells. The discovery of Enceladus' plume by the Cassini mission has provided vital clues in our understanding of the processes occurring within the interior of exooceans. To interpret these data and to help configure instruments for future missions, controlled laboratory experiments and simulations are needed. This review aims to bring together studies and experimental designs from various scientific fields currently investigating the icy moons, including planetary sciences, chemistry, (micro-)biology, geology, glaciology, etc. This chapter provides an overview of successful in situ, in silico, and in vitro experiments, which explore different regions of interest on icy moons, i.e. a potential plume, surface, icy shell, water and brines, hydrothermal vents, and the rocky core.

Semiarid climate and hyposaline lake on early Mars inferred from reconstructed water chemistry at Gale.

Salinity, pH, and redox states are fundamental properties that characterize natural waters. These properties of surface waters on early Mars reflect palaeoenvironments, and thus provide clues on the palaeoclimate and habitability. Here we constrain these properties of pore water within lacustrine sediments of Gale Crater, Mars, using smectite interlayer compositions. Regardless of formation conditions of smectite, the pore water that last interacted with the sediments was of Na-Cl type with mild salinity (~0.1-0.5 mol/kg) and circumneutral pH. To interpret this, multiple scenarios for post-depositional alterations are considered. The estimated Na-Cl concentrations would reflect hyposaline, early lakes developed in 104-106-year-long semiarid climates. Assuming that post-depositional sulfate-rich fluids interacted with the sediments, the redox disequilibria in secondary minerals suggest infiltration of oxidizing fluids into reducing sediments. Assuming no interactions, the redox disequilibria could have been generated by interactions of upwelling groundwater with oxidized sediments in early post-depositional stages.

High-temperature water-rock interactions and hydrothermal environments in the chondrite-like core of Enceladus.

It has been suggested that Saturn's moon Enceladus possesses a subsurface ocean. The recent discovery of silica nanoparticles derived from Enceladus shows the presence of ongoing hydrothermal reactions in the interior. Here, we report results from detailed laboratory experiments to constrain the reaction conditions. To sustain the formation of silica nanoparticles, the composition of Enceladus' core needs to be similar to that of carbonaceous chondrites. We show that the presence of hydrothermal reactions would be consistent with NH3- and CO2-rich plume compositions. We suggest that high reaction temperatures (>50 °C) are required to form silica nanoparticles whether Enceladus' ocean is chemically open or closed to the icy crust. Such high temperatures imply either that Enceladus formed shortly after the formation of the solar system or that the current activity was triggered by a recent heating event. Under the required conditions, hydrogen production would proceed efficiently, which could provide chemical energy for chemoautotrophic life.

Ongoing hydrothermal activities within Enceladus.

Detection of sodium-salt-rich ice grains emitted from the plume of the Saturnian moon Enceladus suggests that the grains formed as frozen droplets from a liquid water reservoir that is, or has been, in contact with rock. Gravitational field measurements suggest a regional south polar subsurface ocean of about 10 kilometres thickness located beneath an ice crust 30 to 40 kilometres thick. These findings imply rock-water interactions in regions surrounding the core of Enceladus. The resulting chemical 'footprints' are expected to be preserved in the liquid and subsequently transported upwards to the near-surface plume sources, where they eventually would be ejected and could be measured by a spacecraft. Here we report an analysis of silicon-rich, nanometre-sized dust particles (so-called stream particles) that stand out from the water-ice-dominated objects characteristic of Saturn. We interpret these grains as nanometre-sized SiO2 (silica) particles, initially embedded in icy grains emitted from Enceladus' subsurface waters and released by sputter erosion in Saturn's E ring. The composition and the limited size range (2 to 8 nanometres in radius) of stream particles indicate ongoing high-temperature (>90 °C) hydrothermal reactions associated with global-scale geothermal activity that quickly transports hydrothermal products from the ocean floor at a depth of at least 40 kilometres up to the plume of Enceladus.

Hydrogen cyanide production due to mid-size impacts in a redox-neutral N2-rich atmosphere.

Cyanide compounds are amongst the most important molecules of the origin of life. Here, we demonstrate the importance of mid-size (0.1-1 km in diameter) hence frequent meteoritic impacts to the cyanide inventory on the early Earth. Subsequent aerodynamic ablation and chemical reactions with the ambient atmosphere after oblique impacts were investigated by both impact and laser experiments. A polycarbonate projectile and graphite were used as laboratory analogs of meteoritic organic matter. Spectroscopic observations of impact-generated ablation vapors show that laser irradiation to graphite within an N2-rich gas can produce a thermodynamic environment similar to that produced by oblique impacts. Thus, laser ablation was used to investigate the final chemical products after this aerodynamic process. We found that a significant fraction (>0.1 mol%) of the vaporized carbon is converted to HCN and cyanide condensates, even when the ambient gas contains as much as a few hundred mbar of CO2. As such, the column density of cyanides after carbon-rich meteoritic impacts with diameters of 600 m would reach ~10 mol/m(2) over ~10(2) km(2) under early Earth conditions. Such a temporally and spatially concentrated supply of cyanides may have played an important role in the origin of life.

Osmium evidence for synchronicity between a rise in atmospheric oxygen and Palaeoproterozoic deglaciation.

Early Palaeoproterozoic (2.5-2.0 billion years ago) was a critical phase in Earth's history, characterized by multiple severe glaciations and a rise in atmospheric O(2) (the Great Oxidation Event). Although glaciations occurred at the time of O(2) increase, the relationship between climatic and atmospheric transitions remains poorly understood. Here we report high concentrations of the redox-sensitive element Os with high initial (187)Os/(188)Os values in a sandstone-siltstone interval that spans the transition from glacial diamictite to overlying carbonate in the Huronian Supergroup, Canada. Together with the results of Re, Mo and S analyses of the sediments, we suggest that immediately after the second Palaeoproterozoic glaciation, atmospheric O(2) levels became sufficiently high to deliver radiogenic continental Os to shallow-marine environments, indicating the synchronicity of an episode of increasing O(2) and deglaciation. This result supports the hypothesis that climatic recovery from the glaciations acted to accelerate the Great Oxidation Event.