Hydrogeological controls on microbial activity and habitability in the Precambrian continental crust.

Earth's deep continental subsurface is a prime setting to study the limits of life's relationship with environmental conditions and habitability. In Precambrian crystalline rocks worldwide, deep ancient groundwaters in fracture networks are typically oligotrophic, highly saline, and locally inhabited by low-biomass communities in which chemolithotrophic microorganisms may dominate. Periodic opening of new fractures can lead to penetration of surface water and/or migration of fracture fluids, both of which may trigger changes in subsurface microbial composition and activity. These hydrogeological processes and their impacts on subsurface communities may play a significant role in global cycles of key elements in the crust. However, to date, considerable uncertainty remains on how subsurface microbial communities may respond to these changes in hydrogeochemical conditions. To address this uncertainty, the biogeochemistry of Thompson mine (Manitoba, Canada) was investigated. Compositional and isotopic analyses of fracture waters collected here at ~1 km below land surface revealed different extents of mixing between subsurface brine and (paleo)meteoric waters. To investigate the effects this mixing may have had on microbial communities, the Most Probable Number technique was applied to test community response for a total of 13 different metabolisms. The results showed that all fracture waters were dominated by viable heterotrophic microorganisms which can utilize organic materials associated with aerobic/facultative anaerobic processes, sulfate reduction, or fermentation. Where mixing between subsurface brines and (paleo)meteoric waters occurs, the communities demonstrate higher cell densities and increased viable functional potentials, compared to the most saline sample. This study therefore highlights the connection between hydrogeologic heterogeneity and the heterogeneity of subsurface ecosystems in the crystalline rocks, and suggests that hydrogeology can have a considerable impact on the scope and scale of subsurface microbial communities on Earth and potentially beyond.

Life on Earth can grow on extraterrestrial organic carbon.

The universe is a vast store of organic abiotic carbon that could potentially drive heterotrophy on habitable planets. Meteorites are one of the transporters of this carbon to planetary surfaces. Meteoritic material was accumulating on early Earth when life emerged and proliferated. Yet it is not known if this organic carbon from space was accessible to life. In this research, an anaerobic microbial community was grown with the CM2 carbonaceous chondrite Aguas Zarcas as the sole carbon, energy and nutrient source. Using a reversed 13C-stable isotope labelling experiment in combination with optical photothermal infrared (O-PTIR) spectroscopy of single cells, this paper demonstrates the direct transfer of carbon from meteorite into microbial biomass. This implies that meteoritic organics could have been used as a carbon source on early Earth and other habitable planets, and supports the potential for a heterotrophic metabolism in early living systems.

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.

Abundant presolar grains and primordial organics preserved in carbon-rich exogenous clasts in asteroid Ryugu.

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.

Uncovering the chiral bias of meteoritic isovaline through asymmetric photochemistry.

Systematic enrichments of L-amino acids in meteorites is a strong indication that biological homochirality originated beyond Earth. Although still unresolved, stellar UV circularly polarized light (CPL) is the leading hypothesis to have caused the symmetry breaking in space. This involves the differential absorption of left- and right-CPL, a phenomenon called circular dichroism, which enables chiral discrimination. Here we unveil coherent chiroptical spectra of thin films of isovaline enantiomers, the first step towards asymmetric photolysis experiments using a tunable laser set-up. As analogues to amino acids adsorbed on interstellar dust grains, CPL-helicity dependent enantiomeric excesses of up to 2% were generated in isotropic racemic films of isovaline. The low efficiency of chirality transfer from broadband CPL to isovaline could explain why its enantiomeric excess is not detected in the most pristine chondrites. Notwithstanding, small, yet consistent L-biases induced by stellar CPL would have been crucial for its amplification during aqueous alteration of meteorite parent bodies.

First report on microplastics contamination in a meteorite impact Crater Lake from India.

Microplastic pollution is a worldwide concern affecting all environmental matrices, including pristine lakes. Lentic lakes operate as a sink for microplastics (MPs), which interfere with a biogeochemical cycle and, therefore, deserve immediate attention. We present a comprehensive assessment of MPs contamination in the sediment and surface water of a geo-heritage site, Lonar lake (India). It is the third largest natural saltwater lake and only basaltic crater in the world formed by meteoric impact around 52,000 years ago. Mean MPs abundance in lakeshore sediment and surface water was 14.44 particles/kg and 2.66 particles/L, respectively. Small-sized MPs dominate the hypersaline region of the lake. Transparent and green fragments and filaments morphotypes were abundant. Most of the MPs in Lonar lake were secondary in origin. FTIR-ATR analysis revealed 16 types of polymers in the lake, of which polypropylene, polyvinyl chloride, polyethylene, high-density polyethylene, low-density polyethylene, polystyrene, and polyester were the most common. The overall pollution load index (PLI) for Lonar lake sediment and water was 1.39 and 2.58, respectively. Although all sampling stations had significant MPs pollution (PLI > 1), there was noticeable station-specific variability, which could be linked to anthropogenic activities. Irresponsible tourist behavior and religious activities, coupled with poor waste management are the leading causes of MPs contamination in the lake. The current work fills a gap in the investigation of MP pollution in a crater lake formed by a meteorite impact by being the first to provide a precise estimate of the MPs contamination in the Lonar lake.

Enantiomeric Excesses of Aminonitrile Precursors Determine the Homochirality of Amino Acids.

High enantiomeric excesses (ee's) of l-amino acids, including non-proteinogenic amino acid isovaline (Iva), were discovered in the Murchison meteorite, but the detailed molecular mechanism responsible for the observed ee of amino acids remains elusive and inconsistent, because Iva has an inverted circular dichroism (CD) spectrum with respect to α-H amino acids, e.g., alanine. To address this issue, we resort to accurate ab initio calculations for amino acids and their precursors in the Strecker synthesis. We evaluated their photolysis-induced ee in the range 5-11 eV including the Lyman alpha emission line (Lyα), the typical intensive 10.2 eV radiation ascribed to the early phase of galactic evolution. We show that only the aminonitrile precursors are characterized by positive ee in the Lyα region, explaining why right-handed circularly polarized Lyα (R-CP-Lyα) induces homologous l-amino acids. This study shows that the homochirality of amino acids is produced at the aminonitrile precursors stage.

Role of biostimulants (ascorbic acid and fulvic acid) to synergize Rhizobium activity in pea (Pisum sativum L. var. Meteor).

Biostimulants such as ascorbic acid (AA) and fulvic acid (FA)can enhance the efficiency of root-nodulating bacteria. This study investigates optimum concentration of these two biostimulants to maximize the Rhizobium activity and increase root size, nodulation capability, NPK uptake, yield and quality. Interaction with nitrogenase enzyme through molecular docking was also studied by using both AA and FA as ligands to better understand their inhibitory role in excess amounts. The findings of the study suggest: the combined application of both FA and AA at 200 ppm concentrations proved to be more effective than the individual application. Excellent vegetative growth was noticed which translated into an increased reproductive growth i.e statistically significant increase in number of pods per plant, fresh and dry weight of pods per plant, number of seeds per pod, total chlorophyll, carotenoids and chemical constituents of pea seeds i.e. N (16.17%), P (40.47%), K (39.96%) and protein (16.25%). These findings were substantiated by molecular docking of nitrogenase enzyme with ascorbic acid and fulvic acid. The XP docking score of ascorbic acid (-7.07 kcal mol-1) and fulvic acid (-6.908 kcal mol-1) exhibited that the optimum doses (200 ppm) should be used as higher dose or their excess amount can hinder the Rhizobium activity of nitrogen fixation by interacting with the nitrogenase enzyme.

Potassium isotope heterogeneity in the early Solar System controlled by extensive evaporation and partial recondensation.

Volatiles are vital ingredients for a habitable planet. Angrite meteorites sample the most volatile-depleted planetesimal in the Solar System, particularly for the alkali elements. They are prime targets for investigating the formation of volatile-poor rocky planets, yet their exceptionally low volatile content presents a major analytical challenge. Here, we leverage improved sensitivity and precision of K isotopic analysis to constrain the mechanism of extreme K depletion (>99.8%) in angrites. In contrast with the isotopically heavy Moon and Vesta, we find that angrites are strikingly depleted in the heavier K isotopes, which is best explained by partial recondensation of vaporized K following extensive evaporation on the angrite parent body (APB) during magma-ocean stage. Therefore, the APB may provide a rare example of isotope fractionation controlled by condensation, rather than evaporation, at a planetary scale. Furthermore, nebula-wide K isotopic variations primarily reflect volatility-driven fractionations instead of presolar nucleosynthetic heterogeneity proposed previously.

A changing thermal regime revealed from shallow to deep basalt source melting in the Moon.

Sample return missions have provided the basis for understanding the thermochemical evolution of the Moon. Mare basalt sources are likely to have originated from partial melting of lunar magma ocean cumulates after solidification from an initially molten state. Some of the Apollo mare basalts show evidence for the presence in their source of a late-stage radiogenic heat-producing incompatible element-rich layer, known for its enrichment in potassium, rare-earth elements, and phosphorus (KREEP). Here we show the most depleted lunar meteorite, Asuka-881757, and associated mare basalts, represent ancient (~3.9 Ga) partial melts of KREEP-free Fe-rich mantle. Petrological modeling demonstrates that these basalts were generated at lower temperatures and shallower depths than typical Apollo mare basalts. Calculated mantle potential temperatures of these rocks suggest a relatively cooler mantle source and lower surface heat flow than those associated with later-erupted mare basalts, suggesting a fundamental shift in melting regime in the Moon from ~3.9 to ~3.3 Ga.

Using Organic Contaminants to Constrain the Terrestrial Journey of the Martian Meteorite Lafayette.

A key part of the search for extraterrestrial life is the detection of organic molecules since these molecules form the basis of all living things on Earth. Instrument suites such as SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) onboard the NASA Perseverance rover and the Mars Organic Molecule Analyzer onboard the future ExoMars Rosalind Franklin rover are designed to detect organic molecules at the martian surface. However, size, mass, and power limitations mean that these instrument suites cannot yet match the instrumental capabilities available in Earth-based laboratories. Until Mars Sample Return, the only martian samples available for study on Earth are martian meteorites. This is a collection of largely basaltic igneous rocks that have been exposed to varying degrees of terrestrial contamination. The low organic molecule abundance within igneous rocks and the expectation of terrestrial contamination make the identification of martian organics within these meteorites highly challenging. The Lafayette martian meteorite exhibits little evidence of terrestrial weathering, potentially making it a good candidate for the detection of martian organics despite uncertainties surrounding its fall history. In this study, we used ultrapure solvents to extract organic matter from triplicate samples of Lafayette and analyzed these extracts via hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-MS). Two hundred twenty-four metabolites (organic molecules) were detected in Lafayette at concentrations more than twice those present in the procedural blanks. In addition, a large number of plant-derived metabolites were putatively identified, the presence of which supports the unconfirmed report that Lafayette fell in a semirural location in Indiana. Remarkably, the putative identification of the mycotoxin deoxynivalenol (or vomitoxin), alongside the report that the collector was possibly a student at Purdue University, can be used to identify the most likely fall year as 1919.

Hydrogen Drives Part of the Reverse Krebs Cycle under Metal or Meteorite Catalysis.

Hydrogen (H2 ) is a geological source of reducing electrons that is thought to have powered the metabolism of the last universal common ancestor to all extant life, and that is still metabolized by various modern organisms. It has been suggested that H2 drove a geochemical analogue of some or all of the reverse Krebs cycle at the emergence of the metabolic network, catalyzed by metals, but this has yet to be demonstrated experimentally. Herein, we show that three consecutive steps of the reverse Krebs cycle, converting oxaloacetate into succinate, can be driven without enzymes and in one-pot by H2 as the reducing agent under mild conditions compatible with biological chemistry. Low catalytic amounts of nickel (10-20 mol %) or platinum group metals (0.1-1 mol %) or even small amounts of ground meteorites were found to promote the reductive chemistry at temperatures between 5 and 60 °C and over a wide pH range, including pH 7. These results lend additional support to the hypothesis that geologically produced hydrogen and metal catalysts could have initiated early metabolic networks.

Bullet impacts in building stone excavate approximately conical craters, with dimensions that are controlled by target material.

Bullet impacts are a ubiquitous form of damage to the built environment resulting from armed conflicts. Bullet impacts into stone buildings result in surficial cratering, fracturing, and changes to material properties, such as permeability and surface hardness. Controlled experiments into two different sedimentary stones were conducted to characterise surface damage and to investigate the relationship between the impact energy (a function of engagement distance) and crater volumes. Simplified geometries of crater volume using only depth and diameter measurements showed that the volume of a simple cone provides the best approximation (within 5%) to crater volume measured from photogrammetry models. This result suggests a quick and efficient method of estimating crater volumes during field assessments of damage. Impact energy has little consistent effect on crater volume over the engagement distances studied (100-400 m), but different target materials result in an order of magnitude variation in measured crater volumes. Bullet impacts in the experiments are similar in appearance to damage caused by hypervelocity experiments, but crater excavation is driven by momentum transfer to the target rather than a hemispherical shock wave. Therefore in contrast to predictions of impact scaling relationships for hypervelocity experiments, target material plays the dominant role in controlling damage, not projectile energy.

Gas-phase synthesis of racemic helicenes and their potential role in the enantiomeric enrichment of sugars and amino acids in meteorites.

The molecular origins of homochirality on Earth is not understood well, particularly how enantiomerically enriched molecules of astrobiological significance like sugars and amino acids might have been synthesized on icy grains in space preceding their delivery to Earth. Polycyclic aromatic hydrocarbons (PAHs) identified in carbonaceous chondrites could have been processed in molecular clouds by circularly polarized light prior to the depletion of enantiomerically enriched helicenes onto carbonaceous grains resulting in chiral islands. However, the fundamental low temperature reaction mechanisms leading to racemic helicenes are still unknown. Here, by exploiting synchrotron based molecular beam photoionization mass spectrometry combined with electronic structure calculations, we provide compelling testimony on barrierless, low temperature pathways leading to racemates of [5] and [6]helicene. Astrochemical modeling advocates that gas-phase reactions in molecular clouds lead to racemates of helicenes suggesting a pathway for future astronomical observation and providing a fundamental understanding for the origin of homochirality on early Earth.

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.

A threatening meteor for cardiac surgeons: anomalous left main coronary origin in type A aortic dissection.

We present the case of a type A aortic dissection originating from the right coronary ostium and an intraoperative diagnosis of the entire coronary artery system originating from a single right-sided coronary ostium.