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It has been experimentally demonstrated that, under alkaline conditions, silica is able to induce the formation of mineral self-assembled inorganic-inorganic composite materials similar in morphology, texture and nanostructure to the hybrid biomineral structures that, millions of years later, life was able to self-organize. These mineral self-organized structures (MISOS) have been also shown to work as effective catalysts for prebiotic chemical reactions and to easily create compartmentalization within the solutions where they form. We reason that, during the very earliest history of this planet, there was a geochemical scenario that inevitably led to the existence of a large-scale factory of simple and complex organic compounds, many of which were relevant to prebiotic chemistry. The factory was built on a silica-rich high-pH ocean and powered by two main factors: a) a quasi-infinite source of simple carbon molecules synthesized abiotically from reactions associated with serpentinization, or transported from meteorites and produced from their impact on that alkaline ocean, and b) the formation of self-organized silica-metal mineral composites that catalyze the condensation of simple molecules in a methane-rich reduced atmosphere. We discuss the plausibility of this geochemical scenario, review the details of the formation of MISOS and its catalytic properties and the transition towards a slightly alkaline to neutral ocean, The research leading to these results has received funding from the European Research Council (ERC) under the European Union's Seven Framework Programe grant agreement n° 340863 , and under the Horizon 2020 research and innovation program grant agreement n° 646894 . JMG-R also acknowledges the Ministerio de Economía y Competitividad of Spain for funding the project CGL2016-78971-P . We acknowledge Lucas Chacón for the artist view of Fig. 6 . This is IPGP contribution n° 4108.

Barium isotope fractionation during calcite and aragonite inorganic precipitation was studied in mixed flow reactors as a function of precipitation rate at 25 °C and pH = 6.3 ± 0.1. The measured Ba isotope fractionation that occurs between calcite and the forming fluid in the investigated range of calcite growth rates (10-8.0 ≤ Rp(calcite) ≤ 10−7.3 mol/m2/s) is insignificant. Barium isotope fractionation between aragonite and the fluid decreases with increasing precipitation rate from Δ137/134Baaragonite-fluid = +0.25 ± 0.06‰ for Rp(aragonite) ≤ 10−8.7 mol/m2/s to −0.10 ± 0.08‰ for Rp(aragonite) = 10−7.6 mol/m2/s, thus reflecting preferential incorporation of either heavy or light Ba isotopes in aragonite at slow and fast growth rates, respectively. The dependence of Ba isotope fractionation on aragonite growth rate is well described by the surface reaction kinetic model developed by DePaolo (2011) when the values +0.27‰ and −2.0 ± 0.2‰ are used for the equilibrium and kinetic Ba isotope fractionation factor, respectively. The enrichment of aragonite in the heavier Ba isotopes is consistent with the equilibrium fractionation factor of +0.34‰, calculated here between Ba-substituted aragonite and Ba2+ (aq), from first-principles calculations. This positive fractionation is related to a shorter average Ba[sbnd]O bond length in the aragonite structure while the coordination number does not change much (i.e. 9). The lack of isotope fractionation between the Ba aquo ions and the 6-coordinated Ba in calcite likely suggests that the coordination reduction required for the incorporation in the lattice of Ba adsorbed at calcite growing sites proceeds without isotope fractionation with the fluid. Otherwise the precipitated calcite should have been enriched in heavy isotopes by ∼0.17‰, as predicted by first-principles calculations. These results are the first experimental measurements of Ba isotope fractionation during inorganic calcite and aragonite mineral formation and set the basis for understanding the mechanisms controlling Ba isotope composition in CaCO3 minerals that is an essential perquisite for application of this isotopic system in natural samples.

The Apex chert unit (∼3.46 Ga, Pilbara Craton, Australia) constitutes one of the oldest sedimentary units on Earth in which putative carbonaceous microfossils have been reported. The source of carbonaceous matter (CM) in this unit, however, is hotly debated. Hydrothermal fluids have circulated through the underlying crust and up into the bedded unit; these fluids could have remobilized sedimentary microbial biomass, generated abiological hydrocarbons, or harbored in situ chemolithoautotrophic microbial communities. Are there parts of the unit where microfossils might be best preserved? A potential fossil microbiota – if present – would probably be best preserved in the stratiform portion of the unit where hydrothermal influence seems to have been lowest. In order to shed light on the history of hydrothermal overprinting and the source of carbonaceous fractions in the Apex chert, we correlate here at a high spatial resolution petrographic observations and trace element analyses over a transect from the dyke where putative microfossils were found to the stratiform part where remnants of microbial mats were found. The layered, stratiform part of the unit has positive La anomalies up to 1.7, and Light Rare Earth Element depletions, indicating a seawater source. However, as far as 300 m from the dyke, the stratiform part also shows hydrothermal brecciation, high Eu anomalies (2–12; µ = 4.2) and chondritic Y/Ho ratios (24.3–30.3; µ = 27.0), indicating that hydrothermal fluids have laterally infiltrated over large distances. Overall, the pervasive influence of hydrothermal fluids throughout the entire unit and the presence of carbonaceous matter both in the sedimentary part and the hydrothermal dyke is consistent with a ‘hydrothermal pump’ model that was earlier proposed for the nearby Dresser Formation. In this model, organic matter from surface environments is circulated along with hydrothermal fluids and redistributed in the crust and overlying sediments, therefore complicating paleobiological interpretations. Raman measurements show that most of the CM experienced temperatures of ∼350 °C, while some samples contain CM with a variable, but markedly lower maturity (temperature ranging from 200 to 350 °C). Correlation to texture points out a potential mixing of pre-metamorphic CM with post-metamorphic CM during late hydrothermal events.

Microbial mats floating within multiple hydrothermally sourced streams in El Tatio, Chile, frequently exhibit brittle siliceous crusts (~1 mm thick) above the air-water interface. The partially silicified mats contain a diverse assemblage of microbial clades and metabolisms, including cyanobacteria performing oxygenic photosynthesis. Surficial crusts are composed of several amorphous silica layers containing well-preserved filaments (most likely cyanobacteria) and other cellular textures overlying EPS-rich unsilicified mats. Environmental logs, silica crust distribution, and microbial preservation patterns provide evidence for crust formation via repeated cycles of evaporation and silica precipitation. Within the mats, in situ microelectrode profiling reveals that daytime oxygen concentrations and pH values are diminished beneath silica crusts compared with adjacent unencrusted communities, indicating localized inhibition of oxygenic photosynthesis due to light attenuation. As a result, aqueous conditions under encrusted mats have a higher saturation state with regard to amorphous silica compared with adjacent, more active mats where high pH increases silica solubility, likely forming a modest feedback loop between diminished photosynthesis and crust precipitation. However, no fully lithified sinters are associated with floating encrusted mats in El Tatio streams, as both subaqueous and subaerial silica precipitation are limited by undersaturated, low-SiO2 (

International audience; In silica- rich hot spring environments, internally laminated, digitate sinter deposits are often interpreted as bio- mediated structures. The organic components of microbial communities (cell surfaces, sheaths and extracellular polymeric substances) can act as templates for silica precipitation, therefore influencing digitate sinter morphogenesis. In addition to biologic surface- templating effects, various microenvironmental factors (hydrodynamics, local pH and fluctuating wind patterns) can also influence silica precipitation, and therefore the morphology of resulting digitate sinters. Digitate sinter morphology thus depends on the dynamic interplay between microenvironmentally driven silica precipitation and microbial growth, but the relative contributions of both factors are a topic of continuing research. Here we present a detailed study of digitate silica sinters in distal, low- temperature regimes of the El Tatio geothermal field, Chile. This high- altitude geothermal field is extremely arid and windy, and has one of the highest silica precipitation rates found in the world. We find that digitate silica sinters at El Tatio always accrete into the prevailing eastward wind direction and exhibit laminar growth patterns coinciding with day– night cycles of wind- and thermally driven evaporation and rewetting. Subaerial parts of digitate sinters lack preserved organics and sinter textures that would indicate past microbial colonization, while filamentous cyanobacteria with resistant, silicified sheaths only inhabit subaqueous cavities that crosscut the primary laminations. We conclude that, although fragile bio-films of extremophile micro- organisms may have initially been present and templated silica precipitation at the tips of these digitate sinters, the saltation of sand grains and precipitation of silica by recurrent wind- and thermally driven environmental forcing at El Tatio are important, if not dominant factors shaping the morphology of these digitate structures. Our study sheds light on the relative contributions of biogenic and abiogenic factors in sinter formation in geothermal systems, with geobiological implications for the cautious interpretation of stromatolite-like features in ancient silica deposits on Earth and Mars.

International audience; Oxygen concentration defines the chemical structure of Earth's ecosystems while it also fuels the metabolism of aerobic organisms. As different aerobes have different oxygen requirements, the evolution of oxygen levels through time has likely impacted both environmental chemistry and the history of life. Understanding the relationship between atmospheric oxygen levels, the chemical environment, and life, however, is hampered by uncertainties in the history of oxygen levels. We report over 5,700 Raman analyses of organic matter from nine geological formations spanning in time from 742 to 1,729 Ma. We find that organic matter was effectively oxidized during weathering and little was recycled into marine sediments. Indeed, during this time interval, organic matter was as efficiently oxidized during weathering as it is now. From these observations, we constrain minimum atmospheric oxygen levels to between 2 to 24% of present levels from the late Paleoproterozoic Era into the Neoproterozoic Era. Indeed, our results reveal that eukaryote evolution, including early animal evolution, was not likely hindered by oxygen through this time interval. Our results also show that due to efficient organic recycling during weathering, carbon cycle dynamics can be assessed directly from the sediment carbon record.

International audience; Organic microfossils in Meso-and Neoproterozoic rocks are of key importance to track the emergence and evolution of eukaryotic life. An increasing number of studies combine Raman spectroscopy with synchrotron-based methods to characterize these microfossils. A recurring observation is that Raman spectra of organic microfossils. A recurring observation is that Raman spectra of organic microfossils show negligible variation on a sample scale and that variation between different samples can be explained by differences in thermal maturation or in the biologic origin of organic precursor material. There is a paucity of work, however, that explores the extent to which the petrographic framework and diagenetic processes might in-fluence the chemical structure of organic materials. We present a detailed Raman spectroscopy- based study of a complex organic microfossil assemblage in the ca. 1 Ga old Angmaat Formation, Baffin Island, Canada. This formation contains abundant early diagenetic chert that preserves silicified microbial mats with numerous, readily identifiable organic microfossils. Individual chert beds show petrographic differences with discrete episodes of cementation and recrystallization. Raman spectroscopy reveals measurable variation of organic maturity between samples and between neigh-boring organic microfossils of the same taxonomy and taphonomic state. Scanning transmission X- ray microscopy performed on taphonomically similar coccoidal micro-fossils from the same thin section shows distinct chemical compositions, with varying ratios of aromatic compounds to ketones and phenols. Such observations imply that geochemical variation of organic matter is not necessarily coupled to thermal alteration or organic precursor material. Variation of the Raman signal across single samples is most likely linked to the diagenetic state of analyzed materials and implies an association between organic preservation and access to diagenetic fluids. Variation in the maturity of individual microfossils may be a natural outcome of local diagenetic processes and potentially exceeds differences derived from precursor organic material. These observations stress the importance of detailed in situ characterization by Raman spectroscopy to identify target specimens for further chemical analysis.

International audience; Organic-rich rocks of the 2.0 Ga Zaonega Formation, Karelia, Russia, have been studied extensively to gain understanding of the global carbon cycle and reconstruction of paleo-environments, directly after the Great Oxidation Event (GOE). This formation has a complex history of alteration, involving pervasive hydrothermal circulation, hydrocarbon generation/migration, and mineral authigenesis. Several previous studies have focused on the description of these secondary effects, and the identification of primary geochemical signals in the carbonaceous phases. Migration and infiltration of organic-rich fluids appear to have had only limited effect on the primary carbon isotope record (δ 13 C org). However, the structural variability of carbonaceous material (CM) appears to have been strongly affected, with a range of reported structures including carbon onion-shaped nanostructures and mineral-templated graphite films. Here we present a systematic Raman spectroscopy-based study of the structural variability of CM in a drill core representing the middle and upper strata of the Zaonega Formation. The Raman spectra of CM show a systematic difference in structural order between the bulk carbonaceous matrix (Matrix-CM) and the CM occurring near mineral contacts (Contact-CM), indicating that mineral templating was an important process affecting structural order in the formation. The templating effect was observed on the surface of a wide range of minerals. The difference in structural order between Matrix-CM and Contact-CM can be traced throughout the ca. 400 m stratigraphy. The structural order varied with the degree of alteration and hydrothermal circulation, from highly ordered structures directly above a large gabbro intrusion at the bottom of the stratigraphy to less ordered structures higher up in the sequence. This trend directly correlates with the δ 18 O trend of secondary calcite, and can be attributed to the decreasing influence and temperature regime of hydrothermal circulation upward in the stratigraphy. The results presented here suggest that organic-rich hydrothermal fluids can locally strongly enhance graphitization of carbonaceous materials, and cause sample-scale heterogeneities in the structural order of organic materials. This has implications for the interpretation of carbonaceous materials in other ancient rocks experiencing circulation of organic-rich hydrothermal fluids.

[EN] The search for signs of life in the ancient rock record, extreme terrestrial environments, and other planetary bodiesrequires a well-established, universal, and unambiguous test of biogenicity. This is notably true for cellular remnantsof microbial life, since their relatively simple morphologies resemble various abiogenic microstructures that occur innature. Although lists of qualitative biogenicity criteria have been devised, debates regarding the biogenicity of manyancient microfossils persist to this day. We propose here an alternative quantitative approach for assessing thebiogenicity of putative microfossils. In this theoretical approach, different hypotheses—involving biology or not anddepending on the geologic setting—are put forward to explain the observed objects. These hypotheses correspond tospecific types of microstructures/systems. Using test samples, the morphology and/or chemistry of these systems arethen characterized at the scale of populations. Morphologic parameters include, for example, circularity, aspect ratio,and solidity, while chemical parameters could include elementary ratios (e.g., N/C ratio), isotopic enrichments (e.g.,d13C), or chirality (e.g., molar proportion of stereoisomers), among others. Statistic trends distinguishing the differentsystems are then searched for empirically. The trends found are translated into ‘‘decision spaces’’ where the differentsystems are quantitatively discriminated and where the potential microfossil population can be located as a singlepoint. This approach, which is formulated here on a theoretical level, will solve several problems associated with theclassical qualitative criteria of biogenicity. Most importantly, it could be applied to reveal the existence of cellular lifeon other planets, for which characteristics of morphology and chemical composition are difficult to predict., The Ministerio de Economia y competividad of Spain for funding the project CLG2016-78971-P. This project has received funding from the EuropeanResearch Council, under the European Union’s Horizon2020 research and innovation programme (grant agreementno. 694894) and the Seventh Framework Programme-FP7/2007-2013 (grant agreement no. 340863)

The stratigraphic record of organic matter in the c. 1.97 Ga Zaonega Formation (ZF), Onega Basin, northwestern Russia, exhibits a distinct negative δ13C excursion (δ13Corg from −25 to −40‰ VPDB), which was previously interpreted either to reflect a disturbance in the global carbon cycle after the Great Oxidation Event, or to have been caused by an increase in basinal methanotrophic activity. In order to assess the nature of primary biomass and the effects of post-depositional alteration, we here report the sample-scale carbon isotopic characteristics of organic matter in two drill cores from the ZF, covering 500 m of stratigraphy, by using secondary ion mass spectrometry (SIMS). The results confirm that the organic matter has to a large extent preserved the primary isotopic signatures, whereas secondary effects are limited (

The colonization of emergent continental landmass by microbial life was an evolutionary step of paramount importance in Earth history. Here we report direct fossil evidence for life on land 3,220 million years ago (Ma) in the form of terrestrial microbial mats draping fluvial conglomerates and gravelly sandstones of the Moodies Group, South Africa. Combined field, petrographic, carbon isotope and Raman spectroscopic analyses confirm the synsedimentary origin and biogenicity of these unique fossil mats as well as their fluvial habitat. The carbon isotope compositions of organic matter (δ13Corg) from these mats define a narrow range centred on −21‰, in contrast to fossil mats of marine origin from nearby tidal deposits that show δ13Corg values as low as −34‰. Bulk nitrogen isotope compositions (2

International audience; Palisade fabric is a ubiquitous texture of silica sinter found in low temperature (

In this study, we investigate the molecular structural characteristics of organic remains in various cellular organelles from a 180 Ma Jurassic royal fern belonging to the Osmundaceae family of ferns, and compare their carbon isotopic compositions to a now-living species of royal fern (Osmunda regalis). We discovered molecular structural variations indicated by Raman and infrared spectral parameters obtained from various fossilized cellular organelles. The organic remains preserved in the chromosomes and cell nuclei show marked structural heterogeneities compared to the cell walls during different stages of the cell cycle. The fossil and extant fern have similar δ13C values obtained from bulk samples, supporting evolutionary stasis in this plant lineage and an unchanged metabolic pathway of carbon assimilation since the Jurassic. The organic remains in the cellular organelles of the fossil seem to be less heterogeneous than those in the extant fern, likely due to the preferential preservation of certain cellular compounds during fossilization. Taphonomic processes appear to have diminished the subcellular isotopic heterogeneities. Our research sheds light on the functioning of ancient plant cellular organelles during mitosis, provides insights to the taphonomic processes operating at molecular and isotopic levels, and shows the practicability of in situ techniques in studying the evolution and behaviors of ancient cells. This project is also financially supported by the National Key R&D Program of China (2018YFC0309800), the Hundred Talent Program C of China (Y810011BRC), the Swedish Research Council (VR 2015-04264), the Bergen Research Foundation (Norway), the European Research Council under the European Union’s Horizon 2020 research and innovation program (grant agreement 646894), and the Department of Science and Technology–National Research Foundation Centre for Excellence in Palaeosciences at the University of Witwatersrandthe (South Africa). The NordSIM laboratory at the Swedish Museum of Natural History is a Vetenskapsrådet (VR)-funded research infrastructure.

The identification of cellular life in the rock record is problematic, since microbial life forms, and particularly bacteria, lack sufficient morphologic complexity to be effectively distinguished from certain abiogenic features in rocks. Examples include organic pore-fillings, hydrocarbon-containing fluid inclusions, organic coatings on exfoliated crystals and biomimetic mineral aggregates (biomorphs). This has led to the interpretation and re-interpretation of individual microstructures in the rock record. The morphologic description of entire populations of microstructures, however, may provide support for distinguishing between preserved micro-organisms and abiogenic objects. Here, we present a statistical approach based on quantitative morphological description of populations of microstructures. Images of modern microbial populations were compared to images of two relevant types of abiogenic microstructures: interstitial spaces and silica–carbonate biomorphs. For the populations of these three systems, the size, circularity, and solidity of individual particles were calculated. Subsequently, the mean/SD, skewness, and kurtosis of the statistical distributions of these parameters were established. This allowed the qualitative and quantitative comparison of distributions in these three systems. In addition, the fractal dimension and lacunarity of the populations were determined. In total, 11 parameters, independent of absolute size or shape, were used to characterize each population of microstructures. Using discriminant analysis with parameter subsets, it was found that size and shape distributions are typically sufficient to discriminate populations of biologic and abiogenic microstructures. Analysis of ancient, yet unambiguously biologic, samples (1.0 Ga Angmaat Formation, Baffin Island, Canada) suggests that taphonomic effects can alter morphometric characteristics and complicate image analysis; therefore, a wider range of microfossil assemblages should be studied in the future before automated analyses can be developed. In general, however, it is clear from our results that there is great potential for morphometric descriptions of populations in the context of life recognition in rocks, either on Earth or on extraterrestrial bodies., This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (grant agreement no. 646894 to MVZ) and under the ERC Seventh Framework Programme FP7/2007‐2013 (grant agreement no. 340863 to JMG‐R). JMG‐R also acknowledges the Ministerio de Economía y Competitividad of Spain through the project CGL2016‐78971‐P. We are grateful to seven anonymous reviewers for their helpful comments. We thank four anonymous reviewers for their useful comments which greatly improved a previous version of the manuscript. This is IPGP contribution n°4098.

International audience; The ability of microbes to metabolize arsenic may have emerged more than 3.4 billion years ago1, 2. Some of the modern environments in which prominent arsenic metabolism occurs are anoxic3, 4, as were the Precambrian oceans. Early oceans may also have had a relatively high abundance of arsenic5. However, it is unclear whether arsenic cycling occurred in ancient environments. Here we assess the chemistry and nature of cell-like globules identified in salt-encrusted portions of 2.72-billion-year-old fossil stromatolites from Western Australia. We use Raman spectroscopy and X-ray fluorescence to show that the globules are composed of organic carbon and arsenic (As). We argue that our data are best explained by the occurrence of a complete arsenic cycle at this site, with As(III) oxidation and As(V) reduction by microbes living in permanently anoxic conditions. We therefore suggest that arsenic cycling could have occurred more widely in marine environments in the several hundred million years before the Earth’s atmosphere and shallow oceans were oxygenated.

All known forms of life require phosphorus, and biological processes strongly influence the global phosphorus cycle1. Although the record of life on Earth extends back to 3.8 billion years ago2 and the advent of biological phosphate processing can be tracked to at least 3.5 billion years ago3, the earliest known P-rich deposits appeared only 2 billion years ago4, 5. The onset of P deposition has been attributed to the rise of atmospheric oxygen 2.4–2.3 billion years ago and the related profound biogeochemical shifts6, 7, 8, 9, which increased the riverine input of phosphate to the ocean and boosted biological productivity and phosphogenesis5, 10. However, the P-rich deposits post-date the rise of oxygen by about 300 million years. Here we use microfabric, trace element and carbon isotope analyses to assess the environmental setting and redox conditions of the 2-billion-year-old P-rich deposits of the vent- or seep-influenced Zaonega Formation, northwest Russia. We identify phosphatized microorganism fossils that resemble modern methanotrophic archaea and sulphur-oxidizing bacteria, analogous to organisms found in modern seep settings and upwelling zones with a sharp redoxcline11, 12. We therefore propose that the P-rich deposits in the Zaonega Formation were formed by phosphogenesis mediated by sulphur bacteria, similar to modern sites13, and by the precipitation of calcium phosphate minerals on microbial templates during early diagenesis.

In the version of this Article originally published, author Magali Ader was wrongly linked to affiliation 3; it should have been affiliation 2. This error has now been corrected in the online versions.

Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquantitative estimates of solid solutions in the Ca-Mg-Fe(+Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy analysis was performed on a set of carbonate standards (calcite, ankerite, dolomite, siderite, and magnesite) of known composition. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solutions display a well-defined positive correlation (r(2) > 0.9) with the Mg# = 100 x Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chemical composition of carbonates. Raman analysis of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of carbonates on planetary surfaces.

As both Earth and Mars have had similar environmental conditions at least for some extended time early in their history (Jakosky and Phillips in Nature 412:237–244, 2001), the intriguing question arises whether life originated and evolved on Mars as it did on Earth (McKay and Stoker in Rev. Geophys. 27:189–214, 1989). Conceivably, early autotrophic life on Mars, like early life on Earth, used irreversible enzymatically enhanced metabolic processes that would have fractionated stable isotopes of the elements C, N, S, and Fe. Several important assumptions are made when such isotope fractionations are used as a biomarker. The purpose of this article is two-fold: (1) to discuss these assumptions for the case of carbon and to summarize new insights in abiologic reactions, and (2) to discuss the use of other stable isotope systems as a potential biomarker. It is concluded that isotopic biomarker studies on Mars will encounter several important obstacles. In the case of carbon isotopes, the most important obstacle is the absence of a contemporary abiologic carbon reservoir (such as carbonate deposits on Earth) to act as isotopic standard. The presence of a contemporary abiologic sulfate reservoir (evaporite deposits) suggests that sulfur isotopes can be used as a potential biomarker for sulfate-reducing bacteria. The best approach for tracing ancient life on Mars will be to combine several biomarker approaches; to search for complexity, and to combine small-scale isotopic variations with chemical, mineralogical, and morphological observations. An example of such a study can be a layer-specific correlation between δ 13C and δ 34S within an ancient Martian evaporite, which morphologically resembles the typical setting of a shallow marine microbial mat.

International audience; We have analyzed the Y/Ho-ratios in bulk chondrites, chondrules and four Ca- and Al-rich inclusions (CAIs) from carbonaceous and unequilibrated ordinary and enstatite chondrites (EC) by laser ablation inductively coupled mass spectrometry (LA-ICPMS). We demonstrate that bulk rock sample preparation by containerless melting is a suitable method for preparation of bulk rock samples for high-precision LA-ICPMS. Bulk chondrites have variable Y/Ho-ratios. Carbonaceous chondrites (CI1, CM2, CV3, and CK4) have a common Y/Ho-ratio (25.94 ± 0.08, 2σ) that is regarded as the solar system Y/Ho-ratio. The Y/Ho-ratio increases from carbonaceous, through ordinary (LL, L, H) to enstatite chondrites (EL6), which show the highest Y/Ho-ratio of 27.25. We discuss the result with respect to the origin of fractionation of Re and Os between chondrite groups. Within analytical error, Y and Ho show a good correlation in OC and CV3 chondrules and define an Y/Ho-ratio of 26.22 ± 0.40 (2σ). Y/Ho-fractionation in Ca- and Al-rich inclusions is related to differences in volatility. The bulk silicate Earth is suggested to have a solar Y/Ho-ratio and links the Earth with carbonaceous chondrites. Y/Ho variations in primitive and differentiated terrestrial igneous rocks are discussed in framework of incompatibility of Y and Ho during partial melting. Applicability of Y/Ho as tracer for or against a sedimentary origin of the putative host rock of the Earth's oldest traces of life from the island of Akilia is briefly discussed.

Carbonaceous matter occurring in chert deposits of the 3.4–3.2 Ga old Barberton Greenstone Belt (BGB), South Africa, has experienced low grade regional metamorphism and variable degrees of local hydrothermal alteration. Here a detailed study is presented of in situ analysis of carbonaceous particles by LRS (laser Raman spectroscopy) and SIMS (secondary ion mass spectrometry), reporting degree of structural disorder, carbon isotope ratio and nitrogen-to-carbon ratio. This combination of in situ analytical tools is used to interpret the δ 13 C values of only the best preserved carbonaceous remains, enabling the rejection of non-indigenous (unmetamorphosed) material as well as the exclusion of strongly hydrothermally altered carbonaceous particles. Raman spectroscopy confirmed that all carbonaceous cherts studied here have experienced a regional sub- to lower-greenschist facies metamorphic event. Although this identifies these organics as indigenous to the cherts, it is inferred from petrographic observations that hydrothermal alteration has caused small scale migration and re-deposition of organics. This suggest that morphological interpretation of these carbonaceous particles, and in general of putative microfossils or microlaminae in hydrothermally altered early Archean cherts, should be made with caution. A chert in the Hooggenoeg Formation, which is older than and has been hydrothermally altered by a volcanic event 3445 Ma ago, contains strongly altered carbonaceous particles with a uniform N/C-ratio of 0.001 and a range of δ 13 C that is shifted from its original value. Cherts of the Kromberg Formation post-date this volcanic event, and contain carbonaceous particles with a N/C-ratio between 0.002 and 0.006. Both the Buck Reef Chert and the Footbridge Chert of the Kromberg Formation have retained fairly well-preserved δ 13 C values, with ranges from −34‰ to −24‰ and −40‰ to −32 ‰, respectively. Abiologic reactions associated with hydrothermal serpentinization of ultramafic crust (such as Fischer–Tropsch synthesis) were an unlikely source for carbonaceous material in these cherts. The carbonaceous matter in these cherts has all the characteristics of metamorphosed biologic material.

The problems involved with the interpretation of carbon isotopes as indicators for early life in highly metamorphosed early Archean rocks have prompted the search for additional chemical and isotopic biomarkers. Here we report an attempt to identify the origin of carbonaceous matter in the 3.8 Ga old Isua Supracrustal Belt in southern West Greenland by measuring the concentration and isotopic composition of a trapped nitrogen component. Stepped-combustion/pyrolysis-mass spectrometry of carbonaceous matter in several rock samples revealed three different reservoirs of trapped nitrogen: (1) nitrogen associated with a very small amount of reactive carbonaceous material, (2) nitrogen intercalated in graphite, correlated with intercalated radiogenic argon, (3) nitrogen strongly retained at defects or chemically bound in the graphite structure. The δ15N of nitrogen associated with reactive carbonaceous matter (ca. +6‰) overlaps with that of average Phanerozoic sedimentary organic matter, and is believed to be part of nonindigenous postmetamorphic biologic material. In situ Raman spectroscopy confirmed the high degree of crystallinity of the metamorphosed indigenous carbonaceous material, and this material is further referred to as graphite. Graphite interpreted as epigenetic (associated with Mg,Mn-siderite in metacarbonates) contains a very small strongly retained nitrogen component with a low δ15N ratio (−3 to −1‰). This range overlaps with values that are typically found in Archean kerogens, but also those of a metamorphically emplaced inorganic basaltic source. Geological constraints suggest that this graphite incorporated nitrogen from surrounding metabasaltic rocks. Graphite interpreted as syngenetic and biogenic found in a turbidite deposit is relatively similar to this Mg,Mn-siderite-derived graphite, based on degree of graphite crystallinity, amount of trapped radiogenic argon, low nitrogen concentration and δ15N signature. We conclude that nitrogen concentration and its isotope ratio in graphite cannot be used conclusively as a biomarker in these rocks from the highly metamorphosed Isua Supracrustal Belt.

The molecular and isotopic compositions of lipid biomarkers from cultured filamentous cyanobacteria (Phormidium, also known as Leptolyngbya) have been used to investigate the community and trophic structure of photosynthetic mats from alkaline hot springs of the Lower Geyser Basin at Yellowstone National Park. We studied a shallow-water coniform mat from Octopus Spring (OS) and a submerged, tufted mat from Fountain Paint Pots (FPP) and found that 2-methylhopanepolyols and mid-chain branched methylalkanes were diagnostic for cyanobacteria, whereas abundant wax esters were representative of the green non-sulphur bacterial population. The biomarker composition of cultured Phormidium-isolates varied, but was generally representative of the bulk mat composition. The carbon isotopic fractionation for biomass relative to dissolved inorganic carbon (DIC; ɛCO2) for cultures grown with 1% CO2 ranged from 21.4 to 26.1 and was attenuated by diffusion limitation associated with filament aggregation (i.e. cell clumping). Isotopic differences between biomass and lipid biomarkers, and between lipid classes, depended on the cyanobacterial strain, but was positively correlated with overall fractionation. Acetogenic lipids (alkanes and fatty acids) were generally more depleted than isoprenoids (phytol and hopanoids). The δ13CTOC for OS and FPP mats were somewhat heavier than for cultures (−16.9 and −23.6, respectively), which presumably reflects the lower availability of DIC in the natural environment. The isotopic dispersions among cyanobacterial biomarkers, biomass and DIC reflected those established for culture experiments. The 7-methyl- and 7,11-dimethylheptadecanes were from 9 to 11 depleted relative to the bulk organic carbon, whereas 2-methylhopanols derived from the oxidation-reduction of bacteriohopanepolyol were enriched relative to branched alkanes by approximately 5–7. These isotopic relationships survived with depth and indicated that the relatively heavy isotopic composition of the OS mat resulted from diffusion limitation. This study supports the suggestion that culture studies can establish valid isotopic relationships for interpretation of trophic structure in modern and ancient microbial ecosystems.

We present a systematic study of abundance, isotopic composition and petrographic associations of graphite in rocks from the ca. 3.8 Ga Isua Supracrustal Belt (ISB) in southern West Greenland. Most of the graphite in the ISB occurs in carbonate-rich metasomatic rocks (metacarbonates) while sedimentary units, including banded iron formations (BIFs) and metacherts, have exceedingly low graphite concentrations. Regardless of isotopic composition of graphite in metacarbonate rocks, their secondary origin disqualifies them from providing evidence for traces of life stemming from 3.8 Ga. Recognition of the secondary origin of Isua metacarbonates thus calls for reevaluation of earlier interpretations that suggested the occurrence of 3.8 Ga biogenic graphite in these rocks. Thermal decomposition of siderite; 6FeCO3 = 2Fe3O4 + 5CO2 + C, is the process seemingly responsible for the graphite formation. The cation composition (Fe, Mg, Mn, and Ca) of the carbonate minerals, carbon isotope ratios of carbonates and associated graphite and petrographic assemblages of a suite of metacarbonates support the conclusion that multiple pulses of metasomatism affected the ISB, causing the deposition of Fe-bearing carbonates and subsequent partial disproportionation to graphite and magnetite. Equilibrium isotope fractionation between carbonate and graphite in the rocks indicates peak metamorphic temperatures between 500 and 600 ◦ C, in agreement with other estimates of metamorphic temperature for the ISB.

International audience; Impacts are common geologic features on the terrestrial planets throughout the solar system, and on at least Earth and Mars impacts have induced hydrothermal convection. Impact-generated hydrothermal systems have been suggested to possess the same life supporting capability as hydrothermal systems associated with volcanic activity. However, evidence of fossil microbial colonization in impact-generated hydrothermal systems is scarce in the literature. Here we report of fossilized microorganisms in association with cavitygrown hydrothermal minerals from the 458 Ma Lockne impact structure, Sweden. Based on morphological characteristics the fossilized microorganisms are interpreted as fungi. We further infer the kerogenization of the microfossils, and thus the life span of the fungi, to be contemporaneous with the hydrothermal activity and migration of hydrocarbons in the system. Our results from the Lockne impact structure show that hydrothermal systems associated with impact structures can support colonization by microbial life.

The transition from an anoxic to oxygenated atmosphere was arguably the most dramatic change in the history of the Earth. This “Great Oxidation Event” (Holland 2006) transformed the biogeochemical cycles of the elements by imposing an oxidative step in the cycles, creating strong redox gradients in the terrestrial and marine realms that energised microbial metabolism. Although much past research was focused on establishing when the rise of atmospheric oxygen took place, recognition that substantial mass-independent fraction (MIF) of the sulphur isotopes is restricted to the time interval before 2.45 Ga and requires an anoxic atmosphere (Farquhar et al. 2000, 2007; Mojzsis et al. 2003; Ono et al. 2003; Bekker et al. 2004) argues the atmosphere became permanently oxygenated at this time (Pavlov and Kasting 2002). A false-start to the modern aerobic biosphere and a “whiff” of atmospheric oxygen (Anbar et al. 2007) may have occurred in the latest Archaean, as reflected in a transient enrichment in the redox-sensitive element molybdenum in marine shales and a reduction in the extent of MIF precisely coincident with the peak in Mo and FeS2 enrichment (Kaufman et al. 2007). Geochemical proxies are imperfect, and an earlier (c. 3 Ga) appearance of atmospheric oxygen is possible (Ohmoto et al. 2006) but disputed (Farquhar et al. 2007; Buick 2008).

Organic material in sediments is progressively altered during diagenesis and metamorphism, leading to the formation of kerogen and ultimately crystalline graphite. Bulk carbonaceous material in metamorphic terrains typically has attained an overall degree of structural order that is in line with peak metamorphic temperature. On a micron- to nano-scale, however, carbonaceous material can display strong structural variation. The main factor that drives this variation is the chemical and molecular heterogeneity of the precursor biologic material. Specific conditions during metamorphism, however, can also play a role in shaping the microstructure of carbonaceous material. Here we describe the structural variation of carbonaceous material in rocks of the 2.0 Ga Zaonega Formation, Karelia, Russia. Raman spectroscopy indicates that bulk carbonaceous matter in these rocks has experienced peak temperatures between 350 and 400 °C consistent with greenschist-facies metamorphism. On a nano-scale, however, a strong structural heterogeneity is observed. Transmission electron microscopy (TEM) reveals the occurrence of thin films of highly ordered graphitic carbon at mineral surfaces. These graphite films – consisting of 20–100 individual layers – completely envelop quartz crystals and occur on specific crystal surfaces of chlorite. It is proposed that minerals can act as templates for the parallel ordering of carbon crystallites causing enhanced graphitization within narrow zones at mineral surfaces. Alternatively, oriented organic precursor molecules could have been adsorbed onto charged mineral surfaces, leading to thin graphitic films during later metamorphic heating episodes. Overall the presented observations demonstrate that mineral surfaces can initiate and accelerate localized graphitization of sedimentary organic material during metamorphism, and therefore cause distinct nano-scale variation in structural order.

Our knowledge of the sulfur cycle on early Earth is still in its infancy. Nevertheless, there exist enough geochemical constraints from the rock record to show that the theoretical mixing models proposed by Baoet al. are highly unlikely to account for the range of δ34S and Δ33S values recorded for the microscopic sulfides at the North Pole.

Microscopic sulfides with low34S/32S ratios in marine sulfate deposits from the 3490-million-yearold Dresser Formation, Australia, have been interpreted as evidence for the presence of early sulfate-reducing organisms on Earth. We show that these microscopic sulfides have a mass-independently fractionated sulfur isotopic anomaly (Δ33S) that differs from that of their host sulfate (barite). These microscopic sulfides could not have been produced by sulfate-reducing microbes, nor by abiologic processes that involve reduction of sulfate. Instead, we interpret the combined negative δ34S and positive Δ33S signature of these microscopic sulfides as evidence for the early existence of organisms that disproportionate elemental sulfur.

International audience; The iron isotope, trace and major element compositions of Eoarchean supracrustal rocks from southern West Greenland (Isua Supracrustal Belt, the islands of Akilia and Innersuartuut) were analyzed in order to identify protoliths and characterize the imprints of metamorphism and metasomatism. Banded iron formations (BIFs) from the Isua Supracrustal Belt (ISB) have trace element characteristics that are consistent with seawater derivation, including high Y/Ho ratios, positive Eu/Eu* anomalies, positive La/La* anomalies, and concave upward REE patterns. These rocks also have heavy Fe isotopic compositions relative to surrounding igneous rocks (not, vert, similar+0.4‰/amu). The most likely interpretation is that this signature was inherited from partial oxidation in a marine setting of Fe emanating from a source similar to modern mid-ocean ridge hydrothermal vents (not, vert, similar−0.15‰/amu). Banded quartz-rich rocks from the island of Akilia with high Fe/Ti ratios share many similarities with bona fide BIFs from Isua (heavy Fe isotopic compositions up to +0.4‰/amu, elevated Y/Ho ratios compared to igneous rocks, sometimes positive Eu/Eu* anomalies) suggesting a chemical sedimentary origin. Iron-poor metacarbonates from the southwestern part of the ISB have light Fe isotopic compositions (not, vert, similar−0.4‰/amu). This is consistent with derivation of these rocks by fluid flow through surrounding ultramafic rocks and deposition as metasomatic carbonates. Iron-rich metacarbonates from the northwest and northeast parts of the ISB have Fe isotopic compositions (from +0.1 to +0.4‰/amu) and trace element patterns (high Y/Ho ratios, positive Eu/Eu* and La/La* anomalies, and concave upward REE) similar to associated BIFs. The most likely interpretation is that these iron-rich metacarbonates were derived from mobilization of Fe in BIFs by metasomatic fluids.

Archean rocks may provide a record of early Earth environments. However, such rocks have often been metamorphosed by high pressure and temperature, which can overprint the signatures of their original formation. Here, we show that the early Archean banded rocks from Isua, Akilia, and Innersuartuut, Greenland, are enriched in heavy iron isotopes by 0.1 to 0.5 per mil per atomic mass unit relative to igneous rocks worldwide. The observed enrichments are compatible with the transport, oxidation, and subsequent precipitation of ferrous iron emanating from hydrothermal vents and thus suggest that the original rocks were banded iron formations (BIFs). These variations therefore support a sedimentary origin for the Akilia banded rocks, which represent one of the oldest known occurrences of water-laid deposits on Earth.

A procedure was developed that allows precise determination of Fe isotopic composition. Purification of Fe was achieved by ion chromatography on AG1-X8 strongly basic anion-exchange resin. No isotopic fractionation is associated with column chemistry within 0.02 per thousand /amu at 2sigma. The isotopic composition was measured with a Micromass IsoProbe multicollection inductively coupled plasma hexapole mass spectrometer. The Fe isotopic composition of the Orgueil CI1 carbonaceous chondrite, which best approximates the solar composition, is indistinguishable from that of IRMM-014 (-0.005 +/- 0.017 per thousand /amu). The IRMM-014 reference material is therefore used for normalization of the isotopic ratios. The protocol for analyzing mass-dependent variations is validated by measuring geostandards (IF-G, DTS-2, BCR-2, AGV-2) and heavily fractionated Fe left after vacuum evaporation of molten wüstite (FeO) and solar (MgO-Al(2)O(3)-SiO(2)-CaO-FeO in chondritic proportions) compositions. It is shown that the isotopic composition of Fe during evaporation of FeO follows a Rayleigh distillation with a fractionation factor alpha equal to (m(1)/m(2)()1/2), where m(1) and m(2) are the masses of the considered isotopes. This agrees with earlier measurements and theoretical expectations. The isotopic composition of Fe left after vacuum evaporation of solar composition also follows a Rayleigh distillation but with a fractionation factor (1.013 22 +/- 0.000 67 for the (56)Fe/(54)Fe ratio) that is lower than the square root of the masses (1.018 35). The protocol for analyzing mass-independent variations is validated by measuring terrestrial rocks that are not expected to show departure from mass-dependent fractionation. After internal normalization of the (57)Fe/(54)Fe ratio, the isotopic composition of Fe can be measured accurately with precisions of 0.2epsilon and 0.5epsilon at 2sigma for (56)Fe/(54)Fe and (58)Fe/(54)Fe ratios, respectively (epsilon refers to relative variations in parts per 10 000). For (58)Fe, this precision is an order of magnitude better than what had been achieved before. The method is applied to rocks that could potentially exhibit mass-independent effects, meteorites and Archaean terrestrial samples. The isotopic composition of a 3.8-Ga-old banded iron formation from Isua (IF-G, Greenland), and quartz-pyroxene rocks from Akilia and Innersuartuut (GR91-26 and SM/GR/171770, Greenland) are normal within uncertainties. Similarly, the Orgueil (CI1), Allende (CV3.2), Eagle Station (ESPAL), Brenham (MGPAL), and Old Woman (IIAB) meteorites do not show any mass-independent effect.

The isotopic composition of graphite is commonly used as a biomarker in the oldest (>3.5 Gyr ago) highly metamorphosed terrestrial rocks. Earlier studies on isotopic characteristics of graphite occurring in rocks of the approximately 3.8-Gyr-old Isua supracrustal belt (ISB) in southern West Greenland have suggested the presence of a vast microbial ecosystem in the early Archean. This interpretation, however, has to be approached with extreme care. Here we show that graphite occurs abundantly in secondary carbonate veins in the ISB that are formed at depth in the crust by injection of hot fluids reacting with older crustal rocks (metasomatism). During these reactions, graphite forms from the disproportionation of Fe(II)-bearing carbonates at high temperature. These metasomatic rocks, which clearly lack biological relevance, were earlier thought to be of sedimentary origin and their graphite association provided the basis for inferences about early life. The new observations thus call for a reassessment of previously presented evidence for ancient traces of life in the highly metamorphosed Early Archaean rock record.

It has been argued that apatite crystals containing inclusions of isotopically light graphite in a quartz-pyroxene rock from the island of Akilia, southwest Greenland, represent the earliest (older than 3.85 Ga) traces of life on Earth. Although the age and protolith of this rock have been subjects of vigorous discussions, the occurrence of isotopically light graphite inclusions in Akilia apatite has so far not been debated in the literature. We present here the results of petrographic analysis of 17 different Akilia samples, including the actual sample (G91-26) used in the original study. Our finding that none of the apatite crystals in these samples contain graphite inclusions indicates that the Akilia apatite has no bearing on claims pertaining to a past record of life on Earth.

Nature 418, 627–630 (2002). On page 628, line 23, of this Letter, the isotope equilibrium fractionation temperature of 500 °C was incorrectly stated as 1,500 °C.

International audience; The Pilbara Craton of Western Australia and the Barberton Greenstone Belt of the Kaapvaal Craton, South Africa, contain some of the oldest and best preserved Archaean rocks and microfossils in the world. Two stratigraphic horizons in the Pilbara Craton were drilled as part of a collaborative effort between France and Australia (the Pilbara Drilling Project) during August 2004, including the 3481 Ma Dresser Formation (Warrawoona Group) and 2724 Ma Tumbiana Formation (Fortescue Group). A new diamond drill hole was cored in August 2008 through part of the ∼3250 Ma Fig Tree Group in the Barberton Greenstone Belt as part of a joint project between France and South Africa. These pristine diamond drill cores present a unique opportunity to constrain the chemistry of the earliest ocean, the composition of the atmosphere, and the settings and types of microbial ecosystems spanning the Archean Eon. These drill core samples can also provide new clues on the earliest metabolic pathways.

International audience; Siliceous sinter deposits from El Tatio, Chile, preserve a wide variety of depositional environments and biosignatures, from high-temperature (~85°C) vent-proximal facies to distal deposits dominated by silicified microbial mats. Four cores were drilled into an El Tatio sinter mound and associated distal apron to investigate changes in hydrothermal environments over geologic timescales. Sedimentary and geochemical analysis of multiple sinter cores records the initiation and accretion of diverse depositional features still observed today in El Tatio. Facies adjacent to hydrothermal vents are dominated by laminated sinter crusts on the steep margins of a high-temperature pool, with sparse microbial preservation. Outer margins of the same pool contain extensive sinter columns up to ten centimeters in length, precipitated during repeated cycles of pool overflow and subsequent evaporation. Low-relief hydrothermal pools also form minor deposits within distal debris aprons, and analogous pools are still active close to sampling locations. Debris aprons are dominated by palisade, tufted, and arborescent microbial fabrics, with distinct mat textures revealing well preserved microfossils. Surficial deposits in all cores feature detrital-rich and microbially-influenced sinters overlying higher-temperature facies, indicating a relative decrease in hydrothermal activity over time. Geochemical proxies for hydrothermal fluids and de-trital input match depositional interpretations based on sedimentary structures. 14 C ages from core deposits extend the mound's history by 11,000 years, recording at least three thousand years of sinter deposition on top of glacial sandstones (13,337-10,232 y. cal. BP). Importantly, this work provides a detailed depositional model unavailable through surficial sedimentology alone.