Primitive Earth Research Articles

Oceanic spreading center–generated basaltic crust and associated sulfidic and carbonate-rich hydrothermal deposits in the Archean (ca. 3 Ga), North Spirit Lake greenstone belt, Ontario, Canada

Detailed mapping of a portion of the North Spirit Lake greenstone belt reveals a basal basaltic volcanic unit (ca. 3 Ga) with a komatiitic component and strong major and trace element geochemical affinity with typical mid-ocean ridge basalts (e.g., N-MORB). The overlying transitional unit includes basaltic tuffs, which have close geochemical affinity to the underlying basalts, and to N-MORB. Interbedded with and overlying the tuffs is a thin, laterally continuous sulfide-rich unit with chert interbeds, which is in turn overlain by interbedded carbonate, chert, and iron-rich sedimentary rocks. The chemical sedimentary rocks of the transitional unit display rare-earth element (REE) patterns and positive Eu anomalies consistent with derivation from fluids associated with submarine hydrothermal vent fields. The sulfide unit is interpreted to represent proximal hydrothermal vent deposits derived from black smoker activity near a spreading center. The overlying carbonate and chert mounds and beds are interpreted as hydrothermal deposits formed at lower temperatures in a more distal setting relative to the spreading center. The carbonate deposits may have formed in an environment analogous to that of the Lost City hydrothermal field (Kelley et al., 2001), where abundant chimneys, dendrites, and beds of carbonate are produced ∼15 km from the mid-Atlantic rift axis. The basal volcanic unit consequently is interpreted as ocean-floor basalts formed at an Archean spreading center, with the basaltic tuffs representing the last volcanic emanations, and with the chemical sediments representing hydrothermal-vents deposits both proximal and distal to the spreading center. The capping siliciclastic unit likely is part of an accretionary wedge, possibly representing ocean closure after a protracted seafloor spreading episode. The sedimentary rocks were derived, in part, from a weathered tonalite-trondhjemite-granodiorite source. The supracrustal rocks of the North Spirit Lake greenstone belt provide an unusually clear window into some tectonic activity on the primitive Earth, including evidence for the existence of ocean-floor basalts, proximal and distal hydrothermal activity, and possibly a protracted cycle of ocean opening and destruction.

Localization of D-β-Aspartyl Residue-Containing Proteins in Various Tissues

Prior to the emergence of life, it is believed that only l-amino acids were selected for formation of protein and that d-amino acids were eliminated on the primitive Earth. Whilst homochirality is essential for life, the occurrence of proteins containing d-β-aspartyl (Asp) residues in various tissues from elderly subjects has been reported recently. Here, we demonstrate the presence of a d-β-Asp-containing protein in the cardiac muscle of heart, blood vessels of the lung, chief cells of the stomach, longitudinal and circular muscle of the stomach, small intestine and large intestine. Since the d-β-Asp residue occurs through a succinimide intermediate, this isomer may potentially be generated in proteins more easily than initially thought. Formation of the d-β-Asp residue in proteins may be related to stress.

Formation versus hydrolysis of the peptide bond from a quantum-mechanical viewpoint: The role of mineral surfaces and implications for the origin of life.

The condensation (polymerization by water elimination) of molecular building blocks to yield the first active biopolymers (e.g. of amino acids to form peptides) during primitive Earth is an intriguing question that nowadays still remains open since these processes are thermodynamically disfavoured in highly dilute water solutions. In the present contribution, formation and hydrolysis of glycine oligopeptides occurring on a cluster model of sanidine feldspar (001) surface have been simulated by quantum mechanical methods. Results indicate that the catalytic interplay between Lewis and Brønsted sites both present at the sanidine surface, in cooperation with the London forces acting between the biomolecules and the inorganic surface, plays a crucial role to: i) favour the condensation of glycine to yield oligopeptides as reaction products; ii) inhibit the hydrolysis of the newly formed oligopeptides. Both facts suggest that mineral surfaces may have helped in catalyzing, stabilizing and protecting from hydration the oligopeptides formed in the prebiotic era.

Plasma-Induced Synthesis of Organic Compounds From Graphite and Aqueous Solution

Discharge experiments were performed to explore the synthesis between graphite and aqueous solution. It was found that atomic carbon was transferred from anode into the solution by arc-discharge experiments and various kinds of organic compounds were generated by synthetic reactions from graphite and water or ammonia water. Carboxylic acids and amino acids were identified in the products by GC-MS and HPLC analyses. It is well known that graphite can hardly combine with other substances under common conditions. So the reaction not only provided an interesting attempt for the chemical transformation from graphite to organic compounds but also served as a useful reference for the formation of organic compounds from atomic carbon under primitive earth conditions.

The catalytic effect of l- and d-histidine on alanine and lysine peptide formation

A starting phase of chemical evolution on our ancient Earth around 4billion years ago was the formation of amino acids and their combination to peptides and proteins. The salt-induced peptide formation (SIPF) reaction has been shown to be appropriate for this condensation reaction under moderate and plausible primitive Earth conditions, forming short peptides from amino acids in aqueous solution containing sodium chloride and Cu(II) ions. In this paper we report results about the formation of dialanine and dilysine from their monomers in this reaction. The catalytic influence of l- and d-histidine dramatically increases dialanine yields when starting from lower alanine concentrations, but also dilysine formation is markedly boosted by these catalysts. Attention is paid to measurable preferences for one enantiomeric form of alanine and lysine in the SIPF reaction. Alanine, especially, shows stereospecific behaviour, mostly in favour of the l-form.

Archean plate tectonics, rise of Proterozoic supercontinentality and onset of regional, episodic stagnant-lid behavior

Intense devolatilization and chemical-density differentiation attended late-stage accretion of the primitive Earth; it lessened after crystallization of a magma mush ocean during continued cooling. By ∼ 4.3Ga, shallow seas were present, so surface temperatures had fallen far below the ∼ 1300, ∼ 1120, and ∼ 950°C low-pressure solidi of peridotite, basalt, and granite, respectively. At temperatures less than about half their solidi, such materials existed as lithosphere in the near-surface Hadean realm. Stagnant-lid convection probably did not occur because massive heat transfer necessitated vigorous crust–mantle overturn in the early, hot Earth. Instead, bottom-up mantle convection, including voluminous plume ascent, efficiently rid the planet of heat, but lessened over time. Plate thickening and broadening is reflected in the post-Hadean rock record. Stages of geologic evolution included: (a) 4.5–4.4Ga, early, chaotic magma mush ocean overturn and ephemeral lithospheric platelets; (b) 4.4–2.7Ga, growth of oceanic and diminutive continental plates, obliterated by return mantle flow prior to ∼ 4.0Ga, but the latter enlarging and gradually accumulating as largely submarine, sutured, sialic crust-capped lithospheric collages; (c) 2.7–1.0Ga, progressive assembly of old shields and younger orogenic belts into supercratonal plates characterized by continental freeboard, sedimentary differentiation, and episodic glaciation during transpolar drift, as well as onset of regionally, temporally limited stagnant-lid convection beneath supercontinents; (d) 1.0Ga-present, modern, laminar-flowing asthenospheric cells capped by giant, stately moving plates. Restriction of komatiitic lavas to the Archean, and of multicycle sediments, most ophiolite complexes ± alkaline igneous rocks, and high-pressure and ultrahigh-pressure metamorphic belts to progressively younger Proterozoic–Phanerozoic orogens reflects increasingly negative buoyancy of the cooler oceanic lithosphere. Attending supercontinent assembly, density instabilities of thickening oceanic plates increasingly began to dominate overturn of the suboceanic mantle as cold, top-down convection. Scales and dynamics of hot asthenospheric upwelling versus lithospheric foundering and asthenospheric return flow (bottom-up versus top-down) changed gradually over geologic time in response to planetary thermal relaxation.

Molecular Semiotics toward the Emergence of Life

Molecular imprints of organisms serving as both the agents and the products of the underlying sign activities are quantum mechanical in their origins. In particular, molecules in any reaction networks constituting a biological organism are semiotic or context-dependent in the sense that their activities reside within the proper coordination of the entire networks. The origin of life could have been related to a specific aspect of molecular semiotics, especially in the transition from molecules as the physical symbols of material units to molecules as the semiotic signs having the capacity of pointing to something else other than the molecules themselves. Quantum mechanical underpinning of the molecular imprints leading to the emergence of life is in the appraisal of the material capacities of both coherent assimilation and decoherent dissociation already latent in the imprints. One empirical evidence suggesting the likelihood of both coherent assimilation and decoherent dissociation in prebiotic settings could have been found in synthetic chemical reactions running in hydrothermal circulation of seawater through hot vents in the Haedean ocean on the primitive Earth.

One-step formation of oligopeptide-like molecules from Glu and Asp in hydrothermal environments

Biopolymer accumulation in the absence of enzymes is an essential step for the chemical evolution of primitive life-like systems, and successful simulation experiments of prebiotic biopolymer formation have suggested that oligopeptides could have formed near submarine hydrothermal vent environments on primitive earth. However, the yield and length of oligopeptides -- typically limited to 6-mers -- seems to be inadequate. One reason is the rapid formation of diketopiperazines (DKPs) from dipeptides. In this study, using a hydrothermal microflow reactor, we show that the one-step synthesis of oligopeptide-like molecules of length up to 20-mers proceeds from Glu and Asp. Yields of up to 0.17-0.57% were obtained in an acidic solution within 183 s at 250-310 degrees C, as evaluated by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis and different types of high-performance liquid chromatography (HPLC) analyses. The present study indicates that Glu and Asp may have played important roles in the chemical evolution of oligopeptide-like molecules in hydrothermal vent environments on primitive earth.

Peptide Nucleic Acids and the Origin of Life

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Emergence of Life

AbstractDiscussions of the origin of life usually assume that there is a specific event, however improbable, by which dead matter became a living entity. Naturalistic accounts, although in seeming opposition to theistic explanations of the apparent design of even the simplest cells, often share the assumption that there is a specific line to be crossed. If the problem is recast as one of a process of emergence of biochemistry from protobiochemistry, which in turn emerged from the organic chemistry and geochemistry of primitive earth, the resources of the new sciences of complex systems dynamics can provide a more robust conceptual framework within which to explore the possible pathways of chemical complexification leading to life. In such a view the emergence of life is the result of deep natural laws (the outlines of which we are only beginning to perceive) and reflects a degree of holism in those systems that led to life. Further, there is the possibility of developing a more general theory of biology and of natural organization from such an approach. The emergence of life may thus be seen as an instance of the broader innate creativity of nature and consistent with a possible natural teleology.

Prebiotic chemistry: chemical evolution of organics on the primitive Earth under simulated prebiotic conditions

A series of prebiotic mixtures of simple molecules, sources of C, H, N, and O, were examined under conditions that may have prevailed during the Hadean eon (4.6-3.8 billion years), namely an oxygen-free atmosphere and a significant UV radiation flux over a large wavelength range due to the absence of an ozone layer. Mixtures contained a C source (methanol, acetone or other ketones), a N source (ammonia or methylamine), and an O source (water) at various molar ratios of C : H : N : O. When subjected to UV light or heated for periods of 7 to 45 days under an argon atmosphere, they yielded a narrow product distribution of a few principal compounds. Different initial conditions produced different distributions. The nature of the products was ascertained by gas chromatographic-mass spectral analysis (GC-MS). UVC irradiation of an aqueous methanol-ammonia-water prebiotic mixture for 14 days under low UV dose (6 x 10(-2) Einstein) produced methylisourea, hexamethylenetetramine (HMT), methyl-HMT and hydroxy-HMT, whereas under high UV dose (45 days; 1.9 x 10(-1) Einstein) yielded only HMT. By contrast, the prebiotic mixture composed of acetone-ammonia-water produced five principal species with acetamide as the major component; thermally the same mixture produced a different product distribution of four principal species. UVC irradiation of the CH(3)CN-NH(3)-H(2)O prebiotic mixture for 7 days gave mostly trimethyl-s-triazine, whereas in the presence of two metal oxides (TiO(2) or Fe(2)O(3)) also produced some HMT; the thermal process yielded only acetamide.

The origin of rare gases on Earth: The noble gas ‘subduction barrier’ revisited

The origin of the Earth's atmosphere can be constrained by the study of noble gases in oceanic basalts. If it is clear that the mantle is degassed and formed part of the present atmosphere, it has been proposed that an important subduction of atmospheric noble gases in the mantle occurred during Earth's history, altering the primordial signature of the solid Earth. This subduction process has been suggested on the basis of the measurements of light xenon isotopes in CO 2 well gases. Moreover, the fact that the 38Ar/ 36Ar ratio is atmospheric in all oceanic basalts, even for uncontaminated samples (e.g. with high 20Ne/ 22Ne), may also suggest that a massive subduction of atmospheric argon occurred, if the primitive Earth had a solar-like 38Ar/ 36Ar. This also implies that the atmosphere suffered a massive gas loss accompanied by mass fractionation (e.g. hydrodynamic escape) after mantle degassing or that a late veneer with an atmospheric composition occurred. Such a hypothesis is explored for rare gases, by developing a model in which degassing and subduction of atmospheric noble gases started ∼4.4 Ga ago. In the model, both radiogenic and non-radiogenic isotopic ratios are used (e.g. 38Ar/ 36Ar and 40Ar/ 36Ar; 124Xe/ 130Xe and 129Xe/ 130Xe) to constrain the subduction flux and the degassing parameters. It is shown that subduction and massive contamination of the entire mantle is possible, but implies that the 40Ar/ 36Ar and the 129Xe/ 130Xe ratios were higher in the past than today, which is not observed in Archean samples. It also implies that the sediments and the altered oceanic crust did not loose their noble gases during subduction or that the contaminated mantle wedge is mixed by the convective mantle. Moreover, such a model has to apply to the oceanic island source, since this later shows the same signature of argon and xenon non-radiogenic isotopic ratios. A scenario where the isotopic compositions of the argon and xenon were settled before or during accretion is therefore preferred to the subduction.

Chemical evolution: the mechanism of the formation of adenine under prebiotic conditions.

Fundamental building blocks of life have been detected extraterrestrially, even in interstellar space, and are known to form nonenzymatically. Thus, the HCN pentamer, adenine (a base present in DNA and RNA), was first isolated in abiogenic experiments from an aqueous solution of ammonia and HCN in 1960. Although many variations of the reaction conditions giving adenine have been reported since then, the mechanistic details remain unexplored. Our predictions are based on extensive computations of sequences of reaction steps along several possible mechanistic routes. H(2)O- or NH(3)-catalyzed pathways are more favorable than uncatalyzed neutral or anionic alternatives, and they may well have been the major source of adenine on primitive earth. Our report provides a more detailed understanding of some of the chemical processes involved in chemical evolution, and a partial answer to the fundamental question of molecular biogenesis. Our investigation should trigger similar explorations of the detailed mechanisms of the abiotic formation of the remaining nucleic acid bases and other biologically relevant molecules.

Hydrothermal biochemistry: from formaldehyde to oligopeptides

Hydrothermal reactions of formaldehyde (CH2O), which is mainly formed by CO2, are considered to be of most importance in the abiotic synthesis of complex organic molecules in chemical evolution on the primitive Earth. We show the hydrothermal formation of amino acids and oligopeptides in neutral or weak acidic solutions from CH2O in the presence of metals and metal oxides. In these hydrothermal processes, metal or metal oxides selectively catalyzed a series of hydrothermal reactions from CH2O to amino acids, whereas the further reactions for the formation of oligopeptides proceeded without any catalyst. Our experimental observation may provide a possible clue to understanding the initial chemical evolution in Earth’s primitive atmosphere of the origin of life.

Evolution of secondary metabolite production: potential roles for antibiotics as prebiotic effectors of catalytic RNA reactions.

It has been proposed that organic molecules related to known secondary metabolites have existed since the beginning of biochemical evolution and were present in primordial soups. Under primitive earth conditions certain of these molecules may have played roles as effectors in prebiotic reactions, especially those involving catalytic RNA (ribozymes). We demonstrate that a number of antibiotic-related secondary metabolites bind to group I introns and either inhibit splicing reactions or promote the formation of intron oligomers. This is consistent with the functional co-evolution of catalytic RNA and secondary metabolites as antibiotic inhibitors of translation, and supports the notion of an evolutionary relationship between group I introns and ribosomal RNA.

Peptide Nucleic Acids and the Origin of Life

The possibilities of pseudo-peptide-DNA mimics like PNA (peptide nucleic acid) having a role for the prebiotic origin of life prior to an RNA world is discussed on the basis of literature data showing that this type of molecules might have formed on the primitive earth (or other places in the universe), as well as data indicating the possibilities of template-directed PNA chemical replication and ligation. In particular, the merits of an achiral prebiotic genetic material is discussed.

Laboratory simulation of UV irradiation from the Sun on amino acids. II. Irradiation of phenylalanine and tryptophan

AbstractThe effects of near ultraviolet (UV) irradiation on water solutions of phenylalanine and tryptophan have been investigated using a broad-band xenon lamp in the region 200–800 nm. This is a step in the laboratory simulation of the effects of Solar radiation on the building blocks of life, specifically α-amino acids, with regards to the origin of life. Results are presented showing the photodegradation of phenylalanine and tryptophan against different UV doses. Some of the degradation products are still protein amino acids. An analysis of the irradiated solutions is carried out by spectroscopic and analytic techniques. The laboratory simulations are discussed in the wake of a life emerging scenario on the primitive Earth.

Thermal stability of amino acids in siliceous ooze under alkaline hydrothermal conditions

Hydrothermal systems have been suggested as being favourable environments for the origin and evolution of life on the primitive Earth. To test this hypothesis, it is necessary to investigate under hydrothermal conditions the behaviour of biomolecules such as amino acids (AAs), a major component of organisms. In contrast to submarine hydrothermal systems, hot springs in the Rift Valley in eastern Africa on the thick continental crust often have a high pH (alkaline conditions) as a result of enrichment via Na 2CO 3 and volatile gases. We reacted siliceous ooze with an aqueous solution of NaCl and Na 2CO 3 at elevated temperature (100–300 °C) to evaluate the thermal stability of the AAs under alkaline hydrothermal conditions. The AAs in the sediment in peptide form were released to the liquid phase and decomposed through hydrolysis of peptide bonds. Comparison of the results with those from similar experiments using the same sediment sample under neutral conditions reveals that the rates of decomposition of the AAs are significantly inhibited under alkaline conditions. Moreover, AAs remained in both the solid and liquid phases even after heating at 300 °C for 240 h. Our results indicate that AAs are more thermally stable in alkaline solution, indicating that these hydrothermal conditions are more favourable for the evolution of primitive life on the thick continental crust. They also imply that alkaline hydrothermal systems on other planets might be plausible places for extraterrestrial life.

The origin of autonomous agents by natural selection

We propose conditions in which an autonomous agent could arise, and increase in complexity. It is assumed that on the primitive Earth there arose a recycling flow-reactor containing spontaneously formed oil droplets or lipid aggregates. These droplets grew at a basal rate by simple incorporation of lipid phase material, and divided by external agitation. This type of system was able to implement a natural selection algorithm once heredity was added. Macroevolution became possible by selection for rarely occurring chemical reactions that produced holistic autocatalytic molecular replicators (contained within the aggregate) capable of doubling at least as fast as the lipid aggregate, and which were also capable of benefiting the growth of its lipid aggregate container. No nucleotides or monomers capable of modular heredity were required at the outset. To explicitly state this hypothesis, a computer model was developed that employed an artificial chemistry, exhibiting conservation of mass and energy, incorporated within each individual of a population of lipid aggregates. This model evolved increasingly complex self-sustaining processes of constitution, a result that is also expected in real chemistry.

Question 2: Why an Astrobiological Study of Titan Will Help Us Understand the Origin of Life

For understanding the origin(s) of life on Earth it is essential to search for and study extraterrestrial environments where some of the processes which participated in the emergence of Life on our planet are still occurring. This is one of the goals of astrobiology. In that frame, the study of extraterrestrial organic matter is essential and is certainly not of limited interest regarding prebiotic molecular evolution. Titan, the largest satellite of Saturn and the only planetary body with an atmosphere similar to that of the Earth is one of the places of prime interest for these astrobiological questions. It presents many analogies with the primitive Earth, and is a prebiotic-like laboratory at the planetary scale, where a complex organic chemistry in is currently going on.