Abiotic Synthesis Research Articles

Glycine synthesis from nitrate and glyoxylate mediated by ferroan brucite: An integrated pathway for prebiotic amine synthesis

Amino acids are present in all known life, so identifying the environmental conditions under which they can be synthesized constrains where life on Earth might have formed and where life might be found on other planetary bodies. All known abiotic amino acid syntheses require ammonia, which is only produced in reducing and neutral atmospheres. Here, we demonstrate that the Fe-bearing hydroxide mineral ferroan brucite [Fe0.33,Mg0.67(OH)2] can mediate the reaction of nitrate and glyoxylate to form glycine, the simplest amino acid used in life. Up to 97% of this glycine was detected only after acid digestion of the mineral, demonstrating that it had been strongly partitioned to the mineral. The dicarboxylic amino acid 3-hydroxy aspartate was also detected, which suggests that reactants underwent a mechanism that simultaneously produced mono- and dicarboxylic amino acids. Nitrate can be produced in both neutral and oxidizing atmospheres, so reductive amination of nitrate and glyoxylate on a ferroan brucite surface expands origins of life scenarios. First, it expands the environmental conditions in which life's precursors could form to include oxidizing atmospheres. Second, it demonstrates the ability of ferroan brucite, an abundant, secondary mineral in serpentinizing systems where olivine is partly hydrated, to mediate reductive amination. Finally, the results demonstrate the need to consider mineral-bound products when analyzing samples for abiotic amino acid synthesis.

Boronolipids

AbstractThe interactions between boron and polyols significantly impact the functioning of bioactive metabolites, algae, plant growth, and quorum determination in certain bacterial species. This wide array of boron‐inclusive compounds aligns with the expectation as boron ranks among the top ten most plentiful elements in seawater. Moreover, carbohydrates, largely comprising polyols, represent the most abundant class of biomass on earth. Lately, the complexes formed between boron and sugars have garnered interest. They have been employed to construct synthetic carbohydrate receptors. These complexes are typified by covalent interactions, enabling their conversion into aqueous solutions. The physical and chemical traits of boron and its established compounds suggest the feasibility of generating boron‐based lipids and glycolipids. Building upon the chemical and mathematical models that demonstrate the formation of protomembranes and biological membranes from complex lipids using low molecular weight polyols as their framework, it appears that the abiotic synthesis of boronolipids follows a parallel route. This review offers a succinct overview of naturally occurring boron compounds and delves into the possible existence of boronolipids within the makeup of protomembranes and biological membranes.

Unraveling abiotic organic synthesis pathways in the mafic crust of mid-ocean ridges

The aqueous alteration of the oceanic lithosphere provides significant energy that impacts the synthesis and diversity of organic compounds, which are crucial for the deep carbon cycle and may have provided the first building blocks for life. Although abiotic organic synthesis has been documented in mantle-derived rocks, the formation mechanisms and complexity of organic compounds in crustal rocks remain largely unknown. Here, we show the specific association of aliphatic carbonaceous matter with Fe oxyhydroxides in mafic crustal rocks of the Southwest Indian Ridge (SWIR). We determine potential Fe-based pathways for abiotic organic synthesis from CO2 and H2 using multimodal and molecular nano-geochemical tools. Quantum mechanical modeling is further employed to constrain the catalytical activity of Fe oxyhydroxides, revealing that the catalytic cycle of hydrogen may play a key role in carbon-carbon bond formation. This approach offers the possibility of interpreting physicochemical organic formation and condensation mechanisms at an atomic scale. The findings expand our knowledge of the existence of abiotic organic carbon in the oceanic crustal rocks and emphasize the mafic oceanic crust of the SWIR as a potential site for low-temperature abiotic organic synthesis.

Supercritical carbon dioxide likely served as a prebiotic source of methanethiol in primordial ocean hydrothermal systems

Abiotic synthesis of methanethiol through CO2 reduction is a presumptive initiation reaction of protometabolism in primordial ocean hydrothermal systems. However, reported artificial means of methanethiol production indicate the necessity of gas-phase condition, rather than aqueous-phase setting, for this prebiotic reaction to occur. Here we show that, under supercritical CO2 with a geochemically feasible concentration of hydrogen, up to 7.9% conversion of hydrogen sulfide to methanethiol is attained through a 14-day reaction at 200 °C on molybdenum sulfide catalyst deposited in a carbonate-NaCl solution. On the present ocean floor, discharges of liquid/supercritical CO2 occasionally occur in close vicinity to hydrothermal vents. Geological records of ancient seafloor suggest prevalence of such CO2 fluxes associated with hydrothermal activities. Our experimental results link these facts with the protometabolism scenario, leading to the possibility that the generation and transportation of methanethiol through the subseafloor CO2 fluxes constituted the beginning step of protometabolism in primordial ocean hydrothermal systems. Thus, the supply of supercritical-CO2-derived materials likely assisted the chemical evolution of life in combination with the known geochemical processes at the vent-ocean interface.

Abiotic syntheses of pyrite: clues to assess the biogenicity of pyrite spherules

Abiotic syntheses of pyrite: clues to assess the biogenicity of pyrite spherules

Reply to Head's comment on “The Volyn biota (Ukraine) – indications of 1.5 Gyr old eukaryotes in 3D preservation, a spotlight on the `boring billion' ” by Franz et al. (2023)

Abstract. Head et al. (2024) emphasize the importance of the Volyn biota for evolution, especially in the so-called “boring billion”, in a detailed outline about the biological and geological context. However, they question the idea that the Volyn biota represent Precambrian fossils and instead argue that they contain young contaminants of “museum dust”. In addition, they question their biotic origin. We present here a detailed discussion of their points of concern based on presented data, including some additional information. Their points of concern were as follows: One object, shown by Franz et al. (2023a), is similar to a pollen grain, and another object is similar to trichomes; we show indications of fossilization and summarize our arguments against “museum dust”. They question the fossil character of the biota and argue for a biomineralization; we show that the biomineralization in trichomes is distinct from the mineralization of the biota. They missed information about the internal structure; we repeat the presented information about the internal structure in more detail, which is also indicative of fossil material and inconsistent with trichomes. They argue that we did not compare the biota with recent fungi via infrared spectroscopy; since the biota experienced temperatures near 300 °C, we think that a comparison with thermally degraded chitosan is more appropriate. They question the use of strongly negative δ13C as an argument for biotic origin, but we show that, in combination with positive δ15N values and the geological situation, a biotic origin is more likely than abiotic synthesis. In addition, Popov (2023) questioned the age of the Volyn biota, which we postulated as between approximately 1.5 and 1.7 Ga. He argues that the fossils could be Phanerozoic. We will also outline our arguments for the minimum age of 1.5 Ga.

The Potential for Organic Synthesis in the Ocean of Enceladus

The Cassini spacecraft detected a soup of organics in the plume of Saturn’s moon Enceladus. Those compounds could provide building blocks for the potential emergence or sustenance of microbial life in Enceladus’ subsurface ocean. However, the sources and stabilities of organics in Enceladus’ ocean are still poorly understood. Here, we perform nonequilibrium thermodynamic calculations to assess the energetics of abiotic synthesis for a broad spectrum of small organic molecules under both cold oceanic and hydrothermal conditions on Enceladus. Most of the organics that we studied are thermodynamically favorable to synthesize at micromolal dissolved concentrations over wide ranges of pH (8.5–11) and redox conditions. This suggests that many of the organic compounds detected by Cassini may be derived from reactions of CO2 and H2. However, some widely assumed precursors of biomolecules, such as formaldehyde, hydrogen cyanide, and acetylene, are found to be unstable and therefore unfavorable to be synthesized. We found that higher temperatures also seem to favor the synthesis of organic species under Enceladus hydrothermal conditions. Detection of thermodynamically unstable species in the plume might reflect artifacts introduced during high-speed spacecraft flybys and/or active synthesis via degradation of primordial chondritic organics, or biological activities.

Hydrothermal carbon reduction in the absence of minerals

Abiotic synthesis of CH4 in seafloor hydrothermal fluids is generally assumed to occur via heterogeneous reactions on mineral surfaces. Stepwise homogeneous reduction of CO2 has, however, been suggested as an alternative (but sluggish) abiotic pathway to CH4, potentially via metastable species of intermediate oxidation states. In this study, we examine the effect of two temperature-dependent methylated species − methanol (CH3OH) and methanethiol (CH3SH), on homogeneous CH4 formation rates under long-term simulated hydrothermal conditions. Aqueous solutions containing formic acid (H13COOH, generating 13CO2 and H2) were heated with and without H2S at 300–325 °C (35 MPa) in a flexible Au reaction cell over several years without added minerals. Substantial 13C-labeled CH4 and CH3OH production from 13CO2 was observed over 4.3 yr, with aqueous CH4 formation varying with CH3OH abundance – a strong function of dissolved H2 abundance and, inversely, temperature. CH4 production was slower at 325 °C with lower CH3OH concentrations (in equilibrium with CO2 and H2), and faster at 300 °C, accompanying an equilibrium-controlled increase in CH3OH. Fastest CH4 production occurred at 300 °C following injection of H2S and H13COOH, which led to rapid formation (<4 days) of 13C-labeled CH3SH that subsequently decomposed over a further 0.8 yr, partly to 13CH4. Heating aqueous 13CH4 to 345–387 °C (33–35 MPa) in the presence of an oxidizing hematite-magnetite-pyrite assemblage, however, yielded no detectable CH3SH after 112 days indicating the reverse reaction is inhibited under favorable thermodynamics. Neither direct reduction of CO2 to CH3SH nor CO2-CH3SH equilibrium were evident at 300 °C, implying CH3SH and CH3OH play disparate roles in homogeneous carbon reduction to CH4. Longer chain hydrocarbons (C2+ alkanes) remained low throughout the experiments.CH3SH abundances previously reported in vent fluids at the Von Damm hydrothermal field correlate strongly with demonstrably abiotic HCOOH there, suggesting the reduction of HCOOH to CH3SH observed in this study may also occur in vent fluids. A comparison of mineral-free 13CH4 production rates reported here with 13CO2 reduction experiments involving minerals indicates that homogeneous reduction proceeds at similar rates to purported transition metal-catalyzed 13CH4 production, and is generally faster than experiments with either added olivine or ultramafic rock. Previous claims of substantial mineral-catalyzed abiogenic CH4 production are therefore not supported by our study. Homogeneous CO2 reduction may be a significant source of methylated compounds and CH4 in hydrothermal fluids characterized by decadal (or longer) residence times, such as those found in mineral-hosted inclusions or occluded fractures in igneous basement, requiring only moderate temperatures and abundant H2 to proceed.

Prebiotic Formation of Peptides Through Bubbling and Arc Plasma.

The abiotic synthesis of peptides, widely regarded as one of the key chemical reactions on the prebiotic Earth, is thermodynamically constrained in solution. Herein, a simulation of the lightning phenomenon on the sea surface using bubble bursting and arc plasma under ambient conditions enables dipeptide formation of six amino acids with conversion ratios ranging from 2.6 % to 25.5 %. Additionally, we observed the formation of biologically active tripeptides and investigated the stereoselectivity of the dipeptide formation reaction. By utilizing a mixture of 20 amino acids in the reaction, 102 possible dipeptides were generated. These results establish experimental constructions to mimic achievable prebiotic conditions and provide a credible pathway for endogenous biopolymer synthesis on prebiotic Earth.

Abiotic synthesis of graphitic carbons in the Eoarchean Saglek-Hebron metasedimentary rocks

Graphite in metasedimentary rocks of the Eoarchean Saglek-Hebron Gneiss Complex (Canada) is depleted in 13C and has been interpreted as one of the oldest traces of life on Earth. The variation in crystallinity of this oldest graphitic carbon could possibly confirm the effect of metamorphism on original biomass, but this is still unexplored. Here, we report specific mineral associations with graphitic carbons that also have a range of crystallinity in the Saglek-Hebron metasedimentary rocks. Petrographic, geochemical and spectroscopic analyses in the Saglek-Hebron banded iron formations suggest that poorly crystalline graphite is likely deposited from C-H-O fluids derived from thermal decomposition of syngenetic organic matter, which is preserved as crystalline graphite during prograde metamorphism. In comparison, in the Saglek-Hebron marble, disseminations of graphite co-occur with carbonate and magnetite disseminations, pointing to abiotic synthesis of graphitic carbons via decarbonation. Our results thus highlight that variably crystalline graphitic carbons in the Saglek-Hebron metasedimentary rocks are potential abiotic products on early Earth, which lay the groundwork for identifying the preservation of prebiotic organic matter through metamorphism on Earth and beyond.

A laboratory infrared model of astrophysical pyrimidines

ABSTRACT Nucleobases are essential molecules for life, forming integral parts of deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) in all terrestrial life forms. Despite evidence of their abiotic synthesis in meteorites and laboratory simulations of interstellar medium (ISM) conditions, nucleobases have not been detected in the ISM. This study investigates the infrared spectra of uracil, cytosine, and thymine – pyrimidine nucleobases – embedded in an ice mixture simulating common volatiles found in protostellar discs. Our objective was to explore the feasibility of identifying unique infrared bands of pyrimidines in the ISM, despite significant overlapping absorption features from simpler, more abundant interstellar species such as H2O, CO, CH3OH, and NH3. Laboratory results revealed that although two common bands (1240 and 760 cm−1 in uracil; 1236 and 763 cm−1 in cytosine; and 1249 and 760 cm−1 in thymine) were identified, the detection of these bands in space is challenged by overlapping absorption features. Recent observations with the JWST have shown that interstellar organic species exhibit infrared signals within similar ranges, making it impossible to distinguish pyrimidine bands from these organics. Thus, detecting pyrimidines with current telescopes is infeasible, not due to sensitivity limitations or the need for more powerful instrumentation, but because of the intrinsic overlap in spectral features. This study complements previous research on purines by examining pyrimidines and including the impact of common ISM volatiles in the ice composition. The results highlight the significant challenges in detecting complex molecules in the ISM, underscoring the importance of understanding the spectral complexities and interactions to interpret astronomical observations accurately.

Evaluating Pigments as a Biosignature: Abiotic/Prebiotic Synthesis of Pigments and Pigment Mimics in Planetary Environments.

Pigments serve a multitude of functions in biology including light harvesting for photosynthesis, radiation protection, membrane support, and defense. The ubiquity of pigments-especially within extremophiles found in high-radiation, high-salinity, and dry environments-and their detectability via mission-ready techniques have elevated these molecules as promising targets in the search for evidence of life elsewhere. Moreover, the detection of pigments has been proposed as a "smoking gun" for extraterrestrial life as it has been suggested that these molecules cannot be generated abiotically. However, while pigments may hold promise as a biosignature, current understanding of their possible prebiotic origins remains understudied and uncertain. Better understanding of the abiotic synthesis of pigments is critical for evaluating the biogenicity of any pigment detected during missions, including by the Mars Perseverance rover or from returned samples. Compounding this uncertainty is the broad definition of pigment as it includes any compound capable of absorbing visible light and by itself does not specify a particular chemical motif. While not experimentally verified, there are promising prebiotic routes for generating pigments including hemes, chlorophylls, and carotenoids. Herein, we review the biochemistry of pigments, the inherent assumptions made when searching for these molecules in the field, their abiotic synthesis in industry and prebiotic reactions, prebiotically relevant molecules that can mimic their spectral signatures, and implications/recommendations for future work.

Abiotic Ribose Synthesis Under Aqueous Environments with Various Chemical Conditions.

Ribose is the defining sugar in ribonucleic acid (RNA), which is often proposed to have carried the genetic information and catalyzed the biological reactions of the first life on Earth. Thus, abiological processes that yield ribose under prebiotic conditions have been studied for decades. However, aqueous environments required for the formation of ribose from materials available in quantity under geologically reasonable models, where the ribose formed is not immediately destroyed, remain unclear. This is due in large part to the challenge of analysis of carbohydrates formed under a wide range of aqueous conditions. Thus, the formation of ribose on prebiotic Earth has sometimes been questioned. We investigated the quantitative effects of pH, temperature, cation, and the concentrations of formaldehyde and glycolaldehyde on the synthesis of diverse sugars, including ribose. The results suggest a range of conditions that produce ribose and that ribose could have formed in constrained aquifers on prebiotic Earth.

Stochastic parabolic growth promotes coexistence and a relaxed error threshold in RNA-like replicator populations

The RNA world hypothesis proposes that during the early evolution of life, primordial genomes of the first self-propagating evolutionary units existed in the form of RNA-like polymers. Autonomous, non-enzymatic, and sustained replication of such information carriers presents a problem, because product formation and hybridization between template and copy strands reduces replication speed. Kinetics of growth is then parabolic with the benefit of entailing competitive coexistence, thereby maintaining diversity. Here, we test the information-maintaining ability of parabolic growth in stochastic multispecies population models under the constraints of constant total population size and chemostat conditions. We find that large population sizes and small differences in the replication rates favor the stable coexistence of the vast majority of replicator species (‘genes’), while the error threshold problem is alleviated relative to exponential amplification. In addition, sequence properties (GC content) and the strength of resource competition mediated by the rate of resource inflow determine the number of coexisting variants, suggesting that fluctuations in building block availability favored repeated cycles of exploration and exploitation. Stochastic parabolic growth could thus have played a pivotal role in preserving viable sequences generated by random abiotic synthesis and providing diverse genetic raw material to the early evolution of functional ribozymes.

Stochastic parabolic growth promotes coexistence and a relaxed error threshold in RNA-like replicator populations.

The RNA world hypothesis proposes that during the early evolution of life, primordial genomes of the first self-propagating evolutionary units existed in the form of RNA-like polymers. Autonomous, non-enzymatic, and sustained replication of such information carriers presents a problem, because product formation and hybridization between template and copy strands reduces replication speed. Kinetics of growth is then parabolic with the benefit of entailing competitive coexistence, thereby maintaining diversity. Here, we test the information-maintaining ability of parabolic growth in stochastic multispecies population models under the constraints of constant total population size and chemostat conditions. We find that large population sizes and small differences in the replication rates favor the stable coexistence of the vast majority of replicator species ('genes'), while the error threshold problem is alleviated relative to exponential amplification. In addition, sequence properties (GC content) and the strength of resource competition mediated by the rate of resource inflow determine the number of coexisting variants, suggesting that fluctuations in building block availability favored repeated cycles of exploration and exploitation. Stochastic parabolic growth could thus have played a pivotal role in preserving viable sequences generated by random abiotic synthesis and providing diverse genetic raw material to the early evolution of functional ribozymes.

Interstellar formation of glyceric acid [HOCH2CH(OH)COOH]-The simplest sugar acid.

Glyceric acid [HOCH2CH(OH)COOH]-the simplest sugar acid-represents a key molecule in biochemical processes vital for metabolism in living organisms such as glycolysis. Although critically linked to the origins of life and identified in carbonaceous meteorites with abundances comparable to amino acids, the underlying mechanisms of its formation have remained elusive. Here, we report the very first abiotic synthesis of racemic glyceric acid via the barrierless radical-radical reaction of the hydroxycarbonyl radical (HOĊO) with 1,2-dihydroxyethyl (HOĊHCH2OH) radical in low-temperature carbon dioxide (CO2) and ethylene glycol (HOCH2CH2OH) ices. Using isomer-selective vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry, glyceric acid was identified in the gas phase based on the adiabatic ionization energies and isotopic substitution studies. This work reveals the key reaction pathways for glyceric acid synthesis through nonequilibrium reactions from ubiquitous precursor molecules, advancing our fundamental knowledge of the formation pathways of key biorelevant organics-sugar acids-in deep space.

Rapid removal and replacement of dissolved organic matter during circulation through ultramafic crust

Large volumes of seawater have passed through the rocky subseafloor throughout Earth's history. The scale of circulation is sufficiently large to impact the cycling of marine dissolved organic carbon (DOC), one of the largest pools of reduced carbon on Earth whose sources and sinks remain enigmatic, and to sequester carbon over geologic timescales. While the fate of DOC in numerous mafic systems has been examined, no previous reports are available on the less studied but still abundant ultramafic systems. We analyzed the concentration and composition of DOC from the Lost City hydrothermal field (30°N, Mid-Atlantic Ridge), a long-lived ultramafic system with minimal magmatic input. We show that per liter of seawater, more DOC is removed and a rate >650 times faster rate than in mafic ridge flank systems. Simultaneously, newly synthesized 14C-free organics are exported into the water column, adding a pre-aged component to the deep DOC pool. The sequestration of oceanic organic molecules onto minerals could partially account for the substantial total organic carbon present in ultramafic rocks, which is currently interpreted as evidence of chemoautotrophy or abiotic synthesis.

Methane genesis within olivine-hosted fluid inclusions in dolomitic marble of the Hida Belt, Japan

Abiotic synthesis of hydrocarbon-bearing fluids during geological processes has a significant impact on the evolution of both the Earth's biosphere and the solid Earth. Aqueous alteration of ultramafic rocks, i.e., serpentinization, which forms serpentinite, is one of the geological processes generating abiotic methane (CH4). However, abiotic CH4 generation is not limited to the serpentinization of mafic and ultramafic lithologies. Metasedimentary dolomitic marble from the Hida Belt, Japan, is characterized by the presence of forsterite-rich olivine (Fo~89–93), and olivine crystals contain abundant fluid inclusions (<1 to 10 μm in size). Raman spectroscopic analyses of olivine-hosted fluid inclusions found that both primary and secondary fluid inclusions contain CH4, lizardite/chrysotile, and brucite. This indicates that micro-scale interactions between COH fluid and host olivine produced CH4 through the reduction of CO2 by H2 released during local serpentinization within inclusions. Our observation implies that the dolomitic marble has the potential to be a key lithology for the synthesis and storage of abiotic CH4 in a shallower crustal portion of orogenic belts.

Designer Nanoreactors for Bioorthogonal Catalysis.

The evolutionary complexity of compartmentalized biostructures (such as cells and organelles) endows life-sustaining multistep chemical cascades and intricate living functionalities. Relatively, within a very short time span, a synthetic paradigm has resulted in tremendous growth in controlling the materials at different length scales (molecular, nano, micro, and macro), improving mechanistic understanding and setting the design principals toward different compositions, configurations, and structures, and in turn fine-tuning their optoelectronic and catalytic properties for targeted applications. Bioorthogonal catalysis offers a highly versatile toolkit for biochemical modulation and the capability to perform new-to-nature reactions inside living systems, endowing augmented functions. However, conventional catalysts have limitations to control the reactions under physiological conditions due to the hostile bioenvironment. The present account details the development of bioapplicable multicomponent designer nanoreactors (NRs), where the compositions, morphologies, interfacial active sites, and microenvironments around different metal nanocatalysts can be precisely controlled by novel nanospace-confined chemistries. Different architectures of porous, hollow, and open-mouth silica-based nano-housings facilitate the accommodation, protection, and selective access of different nanoscale metal-based catalytic sites. The modular porosity/composition, optical transparency, thermal insulation, and nontoxicity of silica are highly useful. Moreover, large macropores or cavities can also be occupied by enzymes (for chemoenzymatic cascades) and selectivity enhancers (for stimuli-responsive gating) along with the metal nanocatalysts. Further, it is crucial to selectively activate and control catalytic reactions by a remotely operable biocompatible energy source. Integration of highly coupled plasmonic (Au) components having few-nanometer structural features (gaps, cavities, and junctions as electromagnetic hot-spots) endows an opportunity to efficiently harness low-power NIR light and selectively supply energy to the interfacial catalytic sites through localized photothermal and electronic effects. Different plasmonically integrated NRs with customizable plasmonic-catalytic components, cavities inside bilayer nanospaces, and metal-laminated nanocrystals inside hollow silica can perform NIR-/light-induced catalytic reactions in complex media including living cells. In addition, magnetothermia-induced NRs by selective growth of catalytic metals on a pre-installed superparamagnetic iron-oxide core inside a hollow-porous silica shell endowed the opportunity to apply AMF as a bioorthogonal stimulus to promote catalytic reactions. By combining "plasmonic-catalytic" and "magnetic-catalytic" components within a single NR, two distinct reaction steps can be desirably controlled by two energy sources (NIR light and AMF) of distinct energy regimes. The capability to perform multistep organic molecular transformations in harmony with the natural living system will reveal novel reaction schemes for in cellulo synthesis of active drug and bioimaging probes. Well-designed nanoscale discrete architectures of NRs can facilitate spatiotemporal control over abiotic chemical synthesis without adversely affecting the cell viability. However, in-depth understanding of heterogeneous surface catalytic reactions, rate induction mechanisms, selectivity control pathways, and targeted nanobio interactions is necessary. The broad field of biomedical engineering can hugely benefit from the aid of novel nanomaterials with chemistry-based designs and the synthesis of engineered NRs performing unique bioorthogonal chemistry functions.

Quantifying Global Origin-Diagnostic Features and Patterns in Biotic and Abiotic Acyclic Lipids for Life Detection.

Lipids are a geologically robust class of organics ubiquitous to life as we know it. Lipid-like soluble organics are synthesized abiotically and have been identified in carbonaceous meteorites and on Mars. Ascertaining the origin of lipids on Mars would be a profound astrobiological achievement. We enumerate origin-diagnostic features and patterns in two acyclic lipid classes, fatty acids (i.e., carboxylic acids) and acyclic hydrocarbons, by collecting and analyzing molecular data reported in over 1500 samples from previously published studies of terrestrial and meteoritic organics. We identify 27 combined (15 for fatty acids, 12 for acyclic hydrocarbons) molecular patterns and structural features that can aid in distinguishing biotic from abiotic synthesis. Principal component analysis (PCA) demonstrates that multivariate analyses of molecular features (16 for fatty acids, 14 for acyclic hydrocarbons) can potentially indicate sample origin. Terrestrial lipids are dominated by longer straight-chain molecules (C4-C34 fatty acids, C14-C46 acyclic hydrocarbons), with predominance for specific branched and unsaturated isomers. Lipid-like meteoritic soluble organics are shorter, with random configurations. Organic solvent-extraction techniques are most commonly reported, motivating the design of our novel instrument, the Extractor for Chemical Analysis of Lipid Biomarkers in Regolith (ExCALiBR), which extracts lipids while preserving origin-diagnostic features that can indicate biogenicity.