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Organic microfossils preserved in three dimensions in transparent mineral matrices such as cherts/quartzites, phosphates, or carbonates are best studied in petrographic thin sections. Moreover, microscale mass spectrometry techniques commonly require flat, polished surfaces to minimize analytical bias. However, contamination by epoxy resin in traditional petrographic sections is problematic for the geochemical study of the kerogen in these microfossils and more generally for the in situ analysis of fossil organic matter. Here, we show that epoxy contamination has a molecular signature that is difficult to distinguish from kerogen with time-of-flight secondary ion mass spectrometry (ToF-SIMS). This contamination appears pervasive in organic microstructures embedded in micro- to nano-crystalline carbonate. To solve this problem, a new semi-thin section preparation protocol without resin medium was developed for micro- to nanoscale in situ investigation of insoluble organic matter. We show that these sections are suited for microscopic observation of Proterozoic microfossils in cherts. ToF-SIMS reveals that these sections are free of pollution after final removal of a

The FC Formation of the Francevillian of Gabon displays the oldest Gunflint-type assemblage of microfossils that is hosted in shallow-water stromatolites. The FC Formation was deposited between 2.14 and 2.08 billion years ago (Ga), after the Great Oxygenation Event (∼2.4–2.3 Ga) and near the end of the Lomagundi event (∼2.3–2.06 Ga). Although they have been used as a benchmark for the search for older microfossils, the nature of Gunflint-type microfossils has remained elusive due to their simple shapes, their small sizes, and their alteration. Here, we report the first nanoscale study of Francevillian Gunflint-type microfossils. We used a combination of Raman spectroscopy, palynology, in situ focused ion beam sectioning, and analytical electron microscopy. In spite of the relatively high thermal maturity of organic matter (inferred peak burial temperature ∼296 ± 30 °C), spherical cell walls ( Huroniospora ) and filamentous sheaths ( Gunflintia minuta : ≤3 µm in diameter, and broader filaments) are preserved. Organic matter in/on cell walls and sheaths, is associated with nanocrystalline quartz, whereas coarser quartz crystals fill and surround the microfossils. This pattern, likely inherited from recrystallization of texturally heterogenous opal generations, could have allowed the observed preservation of organic structures and limited migrations of organic matter. Moreover, we demonstrate the preservation of thick-sheathed broad (>3 µm) filaments for the first time in a stromatolitic Gunflint-type assemblage; such thick sheaths are common in cyanobacteria, but not in other filamentous bacteria. We distinguished two types of star-shaped organic microstructures ( Eoastrion ) but found no diagnostic evidence for/against a microfossil nature at the nanoscale. Furthermore, we show that titanium is commonly associated with organic structures of microfossils, likely as a result of diagenetic mineralization. In contrast, iron-rich nanocrystals associated with microfossils occur in quartz, not in organic matter, and could possibly represent recrystallized biominerals.

We report a new assemblage of carbonaceous microfossils intimately associated with siderite and Fe-silicates, from a black chert nodule included in iron formation of the ca. 2.45–2.21 Ga Turee Creek Group, Western Australia. This chert comprises microbial fabrics dominated by filaments preserved in matrix of nano- to micrometric quartz. Filaments occur in clumps and in a cobweb-like fabric interspersed with coarse crystalline, void filling quartz granules. We studied this chert with optical microscopy combined with Scanning Transmission Electron Microscope observations of Focused Ion Beam sections of microfossils. This distinguished three types of well-preserved fossil interpreted as polysaccharide sheaths that usually do not preserve chains of cells (trichomes): Type 1 comprises narrow filaments with thin continuous kerogen sheaths, Type 2 comprises narrow filaments with thick granular sheaths, and Type 3 comprises broad filaments with thin sheaths. Type 4 filaments are poorly preserved as granular kerogen. Organic ultrastructures of Type 2–4 microfossils are variably replaced by siderite crystals, associated with minor Fe-silicates. Iron isotope analyses on bulk powder and reactive iron fraction show indistinguishable and highly positive δ 56 Fe values (+1.45‰ relative to the reference IRMM-014), indicating that the bulk of siderite derives from reduction of Fe(III)-oxides. This provides indirect evidence that the microbial community was originally associated with Fe(III)-oxides. Siderite and Fe-silicates are found with Type 2–4 but not Type 1 filaments, suggesting that only the former were encrusted by Fe(III)-oxides, which may have been reduced in situ . Siderite and Fe-silicates could result from oxidation of organic matter in filaments coupled with microbial and/or thermal reduction of Fe(III)-bio(?)minerals. The increasing abundance of siderite correlated with decreasing organic matter preservation in filaments supports that this reaction occurred to variable extents, in situ on each microfossil. Type 2–4 microfossils may thus represent iron-oxidizing bacteria. These microbial mats display strong similarities with those associated with immediately overlying carbonate rocks of the Turee Creek Group, where filaments were interpreted as sulfur-oxidizing bacteria. Some filamentous bacteria can oxidize both iron and sulfur. Such metabolic versatility could have enabled benthic microbial mats to thrive in the drastically changing chemical conditions of the Great Oxidation Event.

Rare earth element (REE) compositions of Nostolepis sp. scales, spines, plates and tesserae from Ohesaare bone beds were measured by in situ microsampling using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The obtained REE concentrations, normalized to Post-Archean Australian Shale concentrations, were evaluated using basic geochemical calculations and quantifications. The REE compositions were nearly identical across all the morphotypes and histologies of Nostolepis microremains, showing flat REE patterns with slight depletion in heavy REEs. There was no visible enrichment in middle REEs, indicating good geochemical preservation of bioapatite and absence of any pronounced fractionated REE incorporation during later stages of diagenesis. The shale-normalized (La/Yb)SN and (La/Sm)SN REE ratio compilations indicated adsorption as the dominating REE uptake mechanism across all datapoints. The absence of well-defined Ce anomaly suggested oxic palaeoseawater conditions, which agrees with the existing interpretations of the Ohesaare sequence as high-energy shoal and regressive open ocean sedimentary environments.