Raman spectroscopy is widely used to evaluate the nature and potential origins of carbonaceous matter in Earth's oldest rocks and minerals. It is also the tool that will be used for organic detection on the next vehicles to remotely explore the surface of Mars.Here we present, for the first time, a novel quantitative method in which previously neglected Raman spectral features are correlated directly, linearly, and with excellent accuracy, to the microchemistry of carbonaceous materials through the elemental H:C ratio, regardless of contamination. We show applicability and predictive capabilities of this methodology in evaluating H:C ratios between 0.01 and 0.65 in Archean and type III kerogens. We demonstrate its application to chemical microRaman mapping by statistical analysis of a 750Ma microfossil and its encompassing sediments. Raman-derived H:C data can also be used to estimate the degree to which kerogen C-isotopic data has been shifted from its original values due to the effects of metamorphism. The new methodology directly and non-invasively affords spatially resolved assessments of organic matter preservation and microscale chemical diversity within any geologically 2 preserved terrestrial or extraterrestrial sample, including in the use of organic matter in technological applications.

No abstract

Marine oxygen minimum zones (OMZs) are characterized by the presence of subsurface suboxic or anoxic waters where diverse microbial processes are responsible for the removal of fixed nitrogen. OMZs have expanded over past decades and are expected to continue expanding in response to the changing climate. The implications for marine biogeochemistry, particularly nitrogen cycling, are uncertain. Cell membrane lipids (biomarkers), such as bacterial bacteriohopanepolyols (BHPs) and their degradation products (hopanoids), have distinctive structural attributes that convey information about their biological sources. Since the discovery of fossil hopanoids in ancient sediments, the study of BHPs has been of great biogeochemical interest due to their potential to serve as proxies for bacteria in the geological record. A stereoisomer of bacteriohopanetetrol (BHT), BHT II, has been previously identified in OMZ waters and has as been unequivocally identified in culture enrichments of anammox bacteria, a key group contributing to nitrogen loss in marine OMZs. We tested BHT II as a proxy for suboxia/anoxia and anammox bacteria in suspended organic matter across OMZ waters of the Humboldt Current System off northern Chile, as well as in surface and deeply buried sediments (125-150 ky). The BHT II ratio (BHT II/total BHT) increases as oxygen content decreases through the water column, consistent with previous results from Perú, the Cariaco Basin and the Arabian Sea, and in line with microbiological evidence indicating intense anammox activity in the Chilean OMZ. Notably, BHT II is transported from the water column to surface sediments, and preserved in deeply buried sediments, where the BHT II ratio correlates with changes in δ N sediment values during glacial-interglacial transitions. This study suggests that BHT II offers a proxy for past changes in the relative importance of anammox, and fluctuations in nitrogen cycling in response to ocean redox changes through the geological record.

Foraminifera are an ecologically important group of modern heterotrophic amoeboid eukaryotes whose naked and testate ancestors are thought to have evolved ~1 Ga ago. However, the single-chambered agglutinated tests of these protists appear in the fossil record only after ca. 580 Ma, coinciding with the appearance of macro scopic and mineralized animals. Here we report the discovery of small, slender tubular microfossils in the Sturtian (ca. 716-635 Ma) cap carbonate of the Rasthof Formation in Namibia. The tubes are 200-1300 µm long and 20-70 µm wide, and preserve apertures and variably wide lumens, folds, constrictions, and ridges. Their sometimes fl exible walls are composed of carbonaceous material and detrital minerals. This combination of morphological and compositional characters is also present in some species of modern single-chambered agglutinated tubular foraminiferans, and is not found in other agglutinated eukaryotes. The preservation of possible early Foraminifera in the carbonate rocks deposited in the immediate aftermath of Sturtian low-latitude glaciation indicates that various morphologically modern protists thrived in microbially dominated ecosystems, and contributed to the cycling of carbon in Neoproterozoic oceans much before the rise of complex animals.

Ooids are sedimentary grains that are distributed widely in the geologic record. Their formation is still actively debated, which limits our understanding of the significance and meaning of these grains in Earth's history. Central questions include the role played by microbes in the formation of ooids and the sources of ubiquitous organic matter within ooid cortices. To address these issues, we investigated the microbial community composition and associated lipids in modern oolitic sands at Pigeon Cay on Cat Island, The Bahamas. Surface samples were taken along a transect from the shallow, turbulent surf zone to calmer, deeper water. Grains transitioned from shiny and abraded ooids in the surf zone, to biofilm-coated ooids at about 3 m water depth. Further offshore, grapestones (cemented aggregates of ooids) dominated. Benthic diatoms and Proteobacteria dominated biofilms. Taxa that may promote carbonate precipitation were abundant, particularly those associated with sulfur cycling. Compared to the lipids associated with surface biofilms, relict lipids bound within carbonate exhibited remarkably similar profiles in all grain types. The enhanced abundance of methyl-branched fatty acids and β-hydroxy fatty acids, 1-O-monoalkyl glycerol ethers and hopanoids bound within ooid and grapestone carbonate confirms a clear association of benthic sedimentary bacteria with these grains. Lipids bound within ooid cortices also contain molecular indicators of microbial heterotrophic degradation of organic matter, possibly in locally reducing conditions. These included the loss of labile unsaturated fatty acids, enhanced long-chain fatty acids/short-chain fatty acids, enriched stable carbon isotopes ratios of fatty acids, and very high stanol/stenol ratios. To what extent some of these molecular signals are derived from later heterotrophic endolithic activity remains to be fully resolved. We speculate that some ooid carbonate forms in microbial biofilms and that early diagenetic degradation of biofilms may also play a role in early stage carbonate precipitation around ooids.