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The Almahata Sitta (AhS) meteorite is a unique polymict ureilite. Recently, carbonaceous chondritic lithologies were identified in AhS. Organic matter (OM) is ubiquitously found in primitive carbonaceous chondrites. The molecular and isotopic characteristics of this OM reflect its origin and parent body processes, and are particularly sensitive to heating. The C1 lithologies AhS 671 and AhS 91A were investigated, focusing mainly on the OM. We found that the OM in these lithologies is unique and contains primitive isotopic signatures, but experienced slight heating possibly by short-term heating event(s). These characteristics support the idea that one or more carbonaceous chondritic bodies were incorporated into the ureilitic parent body. The uniqueness of the OM in the AhS samples implies that there were large variations in primitive carbonaceous chondritic materials in the solar system other than known primitive carbonaceous chondrite groups such as CI, CM, and CR chondrites.

International audience; On April 23rd, 2019, the Aguas Zarcas meteorite fall occurred in Costa Rica. Because the meteorite was quickly recovered, it contains valuable extraterrestrial materials that have not been contaminated by terrestrial processes. Our X-ray computed tomography (XCT) and scanning electron microscopy (SEM) results on various pre-rain fragments from earlier work (Kerraouch et al., 2020; 2021) revealed several distinct lithologies: Two distinct metal-rich lithologies (Met-1 and Met-2), a CM1/2 lithology, a C1 lithology, and a brecciated CM2 lithology consisting of different petrologic types. Here, we further examined these lithologies in the brecciated Aguas Zarcas meteorite and report new detailed mineralogical, chemical, isotopic, and organic matter characteristics. In addition to petrographic differences, the lithologies also display different chemical and isotopic compositions. The variations in their bulk oxygen isotopic compositions indicate that the various lithologies formed in different environments and/or under diverse conditions (e.g., water/rock ratios). Each lithology experienced a different hydration period during its evolution. Together, this suggests that multiple precursor parent bodies may have been involved in these processes of impact brecciation, mixing, and re-assembly. The Cr and Ti isotopic data for both the CM1/2 and Met-1 lithology are consistent with those of other CM chondrites, even though Met-1 displays a significantly lower ε50Ti isotopic composition that may be attributable to sample heterogeneities on the bulk meteorite scale and may reflect variable abundances of refractory phases in the different lithologies of Aguas Zarcas. Finally, examination of the organic matter of the various lithologies also suggests no strong evidence of thermal events, but a short-term heating cannot completely be excluded. Raman parameters indicate that the peak temperature has been lower than that for Yamato-793321 (CM2, ∼400 °C). Considering the new information presented in this study, we now better understand the origin and formation history of the Aguas Zarcas daughter body.

We report a chemical assessment of the explosive chamber in the projector system used during the sampling operation of the Hayabusa2 project at the surface of the C-type asteroid Ryugu. Although the explosion process was designed as a closed system, volatile combustion gases and semivolatile organics were produced together with quenched carbonaceous product. The chemical compositions of the gases, organics, and inorganics were investigated in the screening analysis. A solid-phase microextraction technique and thermal desorption coupled with gas chromatography/mass spectrometry analysis revealed that aliphatic (20n-alkanes) and aromatic ( two rings > three rings > four rings, resulting in abiogenic molecular patterns. The most intense inorganic fingerprints were due to potassium (K+) and chloride (Cl–) ions derived from the initial KTB explosive and RK ignition charge. We discuss quality control and quality assurance issues applicable to future sample processes during the Hayabusa2 project.

We report an assessment of the explosive chamber in the projector system used during the sampling operation of the Hayabusa2 project at the surface of the C-type asteroid Ryugu. Although the explosion process was designed as a closed system (cf. Sawada et al., Space Sci. Rev., 2017), volatile combustion gases and semivolatile organics were produced together with quenched carbonaceous products. The chemical compositions of the gases, organics, and inorganics were investigated in the screening analysis. A solid-phase microextraction technique and thermal desorption coupled with gas chromatography/mass spectrometry analysis revealed that aliphatic ( three rings > four rings, resulting in abiogenic molecular patterns. The most intense inorganic fingerprints were due to potassium (K + ) and chloride (Cl – ) ions derived from the initial KTB explosive and RK ignition charge. We discuss quality control and quality assurance issues applicable to future sample processes during the Hayabusa2 project.

Aliphatic C-H bonds are one of the major organic signatures detected in Proterozoic organic microfossils, and their origin is a topic of interest. To investigate the influence of the presence of silica on the thermal alteration of aliphatic C-H bonds in prokaryotic cells during diagenesis, cyanobacteria Synechocystis sp. PCC6803 were heated at temperatures of 250-450°C. Changes in the infrared (IR) signals were monitored by micro-Fourier transform infrared (FTIR) spectroscopy. Micro-FTIR shows that absorbances at 2,925 cm-1 band (aliphatic CH2 ) and 2,960 cm-1 band (aliphatic CH3 ) decrease during heating, indicating loss of the C-H bonds, which was delayed by the presence of silica. A theoretical approach using solid-state kinetics indicates that the most probable process for the aliphatic C-H decrease is three-dimensional diffusion of alteration products under both non-embedded and silica-embedded conditions. The extrapolation of the experimental results obtained at 250-450°C to lower temperatures implies that the rate constant for CH3 (kCH3 ) is similar to or lower than that for CH2 (kCH2 ; i.e., CH3 decreases at a similar rate or more slowly than CH2 ). The peak height ratio of 2,960 cm-1 band (CH3 )/2,925 cm-1 band (CH2 ; R3/2 values) either increased or remained constant during the heating. These results reveal that the presence of silica does affect the decreasing rate of the aliphatic C-H bonds in cyanobacteria during thermal maturation, but that it does not significantly decrease the R3/2 values. Meanwhile, studies of microfossils suggest that the R3/2 values of Proterozoic prokaryotic fossils from the Bitter Springs Group and Gunflint Formation have decreased during fossilization, which is inconsistent with the prediction from our experimental results that R3/2 values did not decrease after silicification. Some process other than thermal degradation, possibly preservation of specific classes of biomolecules with low R3/2 values, might have occurred during fossilization.

In 2001, the first author (S.N.) led the publication of a book entitled “Geochemistry and the origin of life” in collaboration with Dr. Andre Brack aiming to figure out geo- and astro-chemical processes essential for the emergence of life. Since then, a great number of research progress has been achieved in the relevant topics from our group and others, ranging from the extraterrestrial inputs of life’s building blocks, the chemical evolution on Earth with the aid of mineral catalysts, to the fossilized records of ancient microorganisms. Here, in addition to summarizing these findings for the origin and early evolution of life, we propose a new hypothesis for the generation and co-evolution of photosynthesis with the redox and photochemical conditions on the Earth’s surface. Besides these bottom-up approaches, we introduce an experimental study on the role of water molecules in the life’s function, focusing on the transition from live, dormant, and dead states through dehydration/hydration. Further spectroscopic studies on the hydrogen bonding behaviors of water molecules in living cells will provide important clues to solve the complex nature of life.

The authors provide evidence for the existence of life on Earth in the earliest known sedimentary rocks and suggest that the presence of organic carbon, and low stable-isotope values of graphite from sedimentary rocks in Labrador pushes back the existence of organic life to beyond 3.95 billion years. The beginning of organic life on Earth is being pushed back by evidence from the earliest known sedimentary rocks. Tsuyoshi Komiya and colleagues argue that the presence of organic carbon and stable-isotope excursions in graphite from sedimentary rocks in Labrador, Canada, pushes back the existence of organic life to more than 3.95 billion years ago. Together with recent work showing evidence for a diverse range of living organisms around 3.7 billion years ago, including stromatolites living in sunlit surface waters and bacteria living in deep-sea hydrothermal vents, the work shows that life has been around almost as long as there has been a planet that it can call home. The vestiges of life in Eoarchean rocks have the potential to elucidate the origin of life. However, gathering evidence from many terrains is not always possible1,2,3, and biogenic graphite has thus far been found only in the 3.7–3.8 Ga (gigayears ago) Isua supracrustal belt4,5,6,7. Here we present the total organic carbon contents and carbon isotope values of graphite (δ13Corg) and carbonate (δ13Ccarb) in the oldest metasedimentary rocks from northern Labrador8,9. Some pelitic rocks have low δ13Corg values of −28.2, comparable to the lowest value in younger rocks. The consistency between crystallization temperatures of the graphite and metamorphic temperature of the host rocks establishes that the graphite does not originate from later contamination. A clear correlation between the δ13Corg values and metamorphic grade indicates that variations in the δ13Corg values are due to metamorphism, and that the pre-metamorphic value was lower than the minimum value. We concluded that the large fractionation between the δ13Ccarb and δ13Corg values, up to 25‰, indicates the oldest evidence of organisms greater than 3.95 Ga. The discovery of the biogenic graphite enables geochemical study of the biogenic materials themselves, and will provide insight into early life not only on Earth but also on other planets.

Phosphatized microfossils from ca. 580 Ma from the Doushantuo Formation in the Weng'an region of South China were analyzed by Fourier transform infrared (FTIR) microspectroscopy for their chemical characterization. Two morpho-types of phosphatized embryo-like fossils ( Megasphaera and Megaclonophycus ) were analyzed, together with algal fossils. Transmission IR spectra of the microfossils have absorption bands of around 2960 cm − 1 and 2925 cm − 1 , indicating the presence of aliphatic hydrocarbon (anti-symmetric aliphatic CH 3 and aliphatic CH 2 ), and have an additional band of around 1595 cm − 1 , probably derived from aromatic moieties (aromatic C C). In addition, IR microscopic mapping shows that aliphatic hydrocarbon and aromatics are distributed inside the embryo-like fossils. The embryo-like fossils appear to show three types of CH 3 /CH 2 peak height ratios (R 3/2 ) and aromatic C C/CH 2 peak height ratios (R C C/2 values): (1) high-R 3/2 /low-R C C/2 type (R 3/2 = ~ 0.2–1.0 and R C C/2 ~ 0–2), (2) low-R 3/2 /medium-R C C/2 type (R 3/2 = ~ 0.2–0.6 and R C C/2 = ~ 1–4); and (3) low-R 3/2 /high-R C C/2 type (R 3/2 = ~ 0.2–0.6 and R C C/2 ~ 1–8). All three types are contained in both Megasphaera and Megaclonophycus . Raman spectra for the carbonaceous matter within the rock sample show a similar degree of thermal alteration, indicating that the organics were embedded in situ prior to thermal maturation. The IR spectroscopic differences might reflect differences in original organic compositions of microorganisms, and/or immediate post-mortem alteration. This suggests that the origins of phosphatized embryo-like fossils are more diverse than was previously recognized on the basis of their morphology. A comparison of R 3/2 and R C C/2 values in the embryo-like fossils with those of the algal fossils and the extant microorganisms indicates the possible interpretation that some of the embryo-like fossils belong to animal embryo, others are algae, but none of them originate from bacteria.

Middle Archean greenstones with mid-ocean ridge basalt affinity and overlying bedded chert/banded iron formation (BIF) are exposed in the Cleaverville area, Pilbara Craton, Western Australia. On the basis of the hydrothermal carbonation of these Cleaverville greenstones, we estimated the potential CO2 flux from ocean to oceanic crust and the physical–chemical conditions of the subseafloor hydrothermal system for the middle Archean. The greenstones exhibit various extents of carbonation, and the igneous minerals contained in the greenstones are partly or completely replaced by calcite and other secondary minerals. The degreeof carbonation correlates with stratigraphy; the volume concentration of calcite in greenstones decreaseswith increasing depth below the chert/BIF horizon. Our results clearly indicate that the hydrothermal carbonation occurred along the axial zones of a middle Archean mid-ocean ridge. Both δ13C and δ18O values of calcite also change with the depth below the chert/BIF horizon. The δ18O value of calcite decreases with increasing depth, reflecting increasing temperature, while the δ13C value of calcite changes from positive to negative stratigraphically downward. A model reconstructing the δ13C of calcite suggests that the observed isotopic variation reflects the thermal structure and that the carbon source for calcite was derived from seawater. These mineralogical, geochemical, and geological features of calcite provide the amount of CO2 in the whole oceanic crust per seafloor unit area (1.2 × 107 mol/m2). Based on this value, CO2 flux from the ocean to the oceanic crust in the middle Archean can be estimated to be 1.5 × 1014 mol/yr when the spreading rate (m2/yr) of Archean oceanic crust is assumed to have been three times higher than it is today. The estimated CO2 flux into the oceanic crust is two orders of magnitude higher than the modern value, which points to the significance of sea-floor hydrothermal carbonation in the Archean carbon cycle.

Summary Domain-level identification of microbial cells or cell-like structures is crucial for investigating natural microbial communities and their ecological significance. By using micro-Fourier transform infrared (micro-FTIR) spectroscopy, we established a technical basis for the domain-level diagnosis and quantification of prokaryotic cell abundance in natural microbial communities. Various prokaryotic cultures (12 species of bacteria and 10 of archaea) were examined using micro-FTIR spectroscopic analysis. The aliphatic CH3/CH2 absorbance ratios (R3/2) showed domain-specific signatures, possibly reflecting distinctive cellular lipid compositions. The signatures were preserved even after chemical cell fixation (formaldehyde) and nucleic acid staining (DAPI) processes – techniques that are essential in studying microbial ecology. The micro-FTIR technique was successfully applied for quantification of the bacteria/archaea abundance ratio in an active microbial mat community in a subsurface hot aquifer stream. We conclude that the micro-FTIR R3/2 measurement is both fast and effective for domain-level diagnosis and quantification of first-order prokaryotic community structures.

Precambrian microbial fossils show carbonaceous cellular structure, which often resemble in shape and size cyanobacteria and other prokaryotes. Morphological taxonomy of these minute, simple, and more or less degraded fossils is, however, often not enough to determine their precise phylogenetic positions. Here we report the results of micro-FTIR spectroscopic analyses of well-preserved microfossils in ∼850 Ma and ∼1900 Ma stromatolites, together with those of 8 species of extant prokaryotes and 5 of eukaryotes for comparison. These Proterozoic fossils have low CH3/CH2 absorbance ratios (R3/2 < 0.5) of aliphatic CH moieties, suggesting selective preservation of long, straight, aliphatic carbon chains probably derived from bacterial membrane lipids. All the observed R3/2 values of coccoids, filaments and amorphous organic matter resemble lipid fractions of extant Bacteria including cyanobacteria, but not Archaea. The results indicate that Proterozoic microfossils belong to Bacteria, which is consistent with the cyanobacterial origin inferred from morphology. Moreover, the R3/2 value of fossilized cell would reflect chemical composition of its precursor membrane lipid, thus could be a useful new tracer for distinguishing Archaea, Bacteria

In situ infrared (IR) and Raman microspectroscopy have been conducted on Neoproterozoic, organic-walled microfossils (prokaryotic fossils) in doubly polished, petrographic thin sections in order to detect their spectral signatures. The microfossils are very well preserved and occur in black chert from the ∼850 million-year-old Bitter Springs Formation, Northern Territory, Australia. Raman microspectroscopy on two species of microfossils, one a filament and the other a coccoid, shows disordered peaks (D peak, 1340 cm−1) and graphite peaks (G peak, 1600 cm−1), indicating that they consist of disordered carbonaceous materials. IR micro-mapping results of the filament reveal that the distributions of peak heights at 2920 cm−1 (aliphatic CH2), 1585 cm−1 (aromatic C–C), and 1370 cm−1 (aliphatic CH3) match the shape of the filamentous microfossil. These results suggest that IR microspectroscopy can be used for in situ characterization of organic polar signatures that morphologically indicate microfossils embedded in chert by using doubly-polished rock (petrographic) thin section samples. Further, these methods can be applied to controversial microfossil-like structures to test their biogenic nature.

Domain-level identification of microbial cells or cell-like structures is crucial for investigating natural microbial communities and their ecological significance. By using micro-Fourier transform infrared (micro-FTIR) spectroscopy, we established a technical basis for the domain-level diagnosis and quantification of prokaryotic cell abundance in natural microbial communities. Various prokaryotic cultures (12 species of bacteria and 10 of archaea) were examined using micro-FTIR spectroscopic analysis. The aliphatic CH3 /CH2 absorbance ratios (R3/2 ) showed domain-specific signatures, possibly reflecting distinctive cellular lipid compositions. The signatures were preserved even after chemical cell fixation (formaldehyde) and nucleic acid staining (DAPI) processes - techniques that are essential in studying microbial ecology. The micro-FTIR technique was successfully applied for quantification of the bacteria/archaea abundance ratio in an active microbial mat community in a subsurface hot aquifer stream. We conclude that the micro-FTIR R3/2 measurement is both fast and effective for domain-level diagnosis and quantification of first-order prokaryotic community structures.

Micro-Fourier transform infrared (FTIR) spectroscopic imaging analyses nondestructively revealed micrometer to millimeter-scale distributions of organic and inorganic functional groups in Proterozoic stromatolitic chert containing prokaryotic fossils from ∼1,900 Ma Gunflint Formation. CH3/CH2 absorbance ratios (R 3/2) indicate a bacterial origin, but not Archaea, of most carbonaceous matter in the chert as well as in the microfossils themselves. However, the characterizations of the stromatolitic chert also show that R 3/2 value of carbonaceous matter existing with carbonates could be overestimated or underestimated. This technique is useful for searching and characterizing rapidly the organic matter in terrestrial and extraterrestrial samples at the micrometer to millimeter scale, and may provide useful information on the affinities of microfossils in the chert.

In situ infrared (IR) and Raman microspectroscopy have been conducted on Neoproterozoic, organic-walled microfossils (prokaryotic fossils) in doubly polished, petrographic thin sections in order to detect their spectral signatures. The microfossils are very well preserved and occur in black chert from the approximately 850 million-year-old Bitter Springs Formation, Northern Territory, Australia. Raman microspectroscopy on two species of microfossils, one a filament and the other a coccoid, shows disordered peaks (D peak, 1340 cm(-1)) and graphite peaks (G peak, 1600 cm(-1)), indicating that they consist of disordered carbonaceous materials. IR micro-mapping results of the filament reveal that the distributions of peak heights at 2920 cm(-1) (aliphatic CH(2)), 1585 cm(-1) (aromatic C-C), and 1370 cm(-1) (aliphatic CH(3)) match the shape of the filamentous microfossil. These results suggest that IR microspectroscopy can be used for in situ characterization of organic polar signatures that morphologically indicate microfossils embedded in chert by using doubly-polished rock (petrographic) thin section samples. Further, these methods can be applied to controversial microfossil-like structures to test their biogenic nature.