Rapid, direct and non-destructive assessment of fossil organic matter via microRaman spectroscopy

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 preserved terrestrial or extraterrestrial sample, including in the use of organic matter in technological applications.Organismic and Evolutionary Biolog

Environmental controls on the distribution of bacterial membrane lipids

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences, 2018.Cataloged from PDF version of thesis.Includes bibliographical references.Since their discovery in ancient sediments, hopanes and their biological precursors, bacteriohopanepolyols (BHPs), have been of great interest for their potential to serve as proxies for bacteria in the geological record. The validation of these and other biomarkers have implications for understanding the coevolution of organisms and the environment throughout Earth's history. 2-Methylhopanoids are of particular interest because their occurrence may be confined to cyanobacteria and alphaproteobacteria. Similarly, a stereoisomer of bacteriohopanetetrol (BHT), BHT II, has been identified exclusively in anaerobic ammonium oxidation (anammox) bacteria. However, the interpretation of sedimentary hopanoids is presently limited by an incomplete understanding of their phylogenetic associations, biological functions, and spatial and temporal disposition throughout diverse environments. I address some of these shortcomings through lipid biomarker characterization of water column and benthic microbial mat samples collected across geochemical and physiochemical gradients in the Eastern Tropical South Pacific oxygen minimum zone off the coast of northern Chile and in two ice-covered lakes of the McMurdo Dry Valleys, Antarctica. The results will enhance our ability to interpret the molecular fossil record, particularly those biomarkers that might preserve evidence of ancient marine and glacial environments. I will provide evidence that supports the use of BHT II as a biomarker for suboxia/anoxia, confirm the biosynthesis of 2- MeBHT in cyanobacteria as a response to photosynthetic stress, and describe improved methods that allow us to better detect, quantify, and interpret these markers in modern environments.by Emily D. Matys.Ph. D

A micrometer-scale snapshot on phototroph spatial distributions: mass spectrometry imaging of microbial mats in Octopus Spring, Yellowstone National Park

Microbial mats from alkaline hot springs in the Yellowstone National Park are ideal natural laboratories to study photosynthetic life under extreme conditions, as well as the nuanced interactions of oxygenic and anoxygenic phototrophs. They represent distinctive examples of chlorophototroph (i.e., chlorophyll or bacteriochlorophyll-based phototroph) diversity, and several novel phototrophs have been first described in these systems, all confined in space, coexisting and competing for niches defined by parameters such as light, oxygen, or temperature. In a novel approach, we employed mass spectrometry imaging of chloropigments, quinones, and intact polar lipids (IPLs) to describe the spatial distribution of different groups of chlorophototrophs along the similar to 1 cm thick microbial mat at 75 mu m resolution and in the top similar to 1.5 mm green part of the mat at 25 mu m resolution. We observed a fine-tuned sequence of oxygenic and anoxygenic chlorophototrophs with distinctive biomarker signatures populating the microbial mat. The transition of oxic to anoxic conditions is characterized by an accumulation of biomarkers indicative of anoxygenic phototrophy. It is also identified as a clear boundary for different species and ecotypes, which adjust their biomarker inventory, particularly the interplay of quinones and chloropigments, to prevailing conditions. Colocalization of the different biomarker groups led to the identification of characteristic IPL signatures and indicates that glycosidic diether glycerolipids are diagnostic for anoxygenic phototrophs in this mat system. The zoom-in into the upper green part further reveals how oxygenic and anoxygenic phototrophs share this microenvironment and informs on subtle, microscale adjustments in lipid composition of Synechococcus spp

Possible early foraminiferans in post-Sturtian (716-635 Ma) cap carbonates

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 macroscopic 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 ?m long and 20–70 ?m wide, and preserve apertures and variably wide lumens, folds, constrictions, and ridges. Their sometimes flexible walls are composed of carbonaceous material and detrital minerals. This combination of morphologic 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

Possible early foraminiferans in post-Sturtian (716-635 Ma) cap carbonates

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 macroscopic 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 flexible walls are composed of carbonaceous material and detrital minerals. This combination of morphologic 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.Earth and Planetary Science

Lack of methylated hopanoids renders the cyanobacterium Nostoc punctiforme sensitive to osmotic and pH stress

To investigate the function of 2-methylhopanoids in modern cyanobacteria, the hpnP gene coding for the radical SAM methylase protein that acts on the C2 position of hopanoids, was deleted from the filamentous cyanobacterium Nostoc punctiforme ATCC 29133S. The resulting ΔhpnP mutant lacked all 2-methylhopanoids, but was found to produce much higher levels of two bacteriohopanepentol isomers compared to the wild type. Growth rates of ΔhpnP mutant cultures were not significantly different from those of the wild type under standard growth conditions. Akinete formation was also not impeded by the absence of 2-methylhopanoids. The relative abundances of the different hopanoid structures in akinete-dominated cultures of the wild-type and ΔhpnP mutant were similar to those of vegetative cell-dominated cultures. However, the ΔhpnP mutant was found to have decreased growth rates under both pH and osmotic stress, confirming a role for 2-methylhopanoids in stress tolerance. Evidence of elevated photosystem II yield and NAD(P)H-dependent oxidoreductase activity in the ΔhpnP mutant under stress conditions, compared to the wild type, suggested that the absence of 2-methylhopanoids increases cellular metabolic rates under stress conditions

Lack of Methylated Hopanoids Renders the Cyanobacterium Nostoc punctiforme Sensitive to Osmotic and pH Stress

To investigate the function of 2-methylhopanoids in modern cyanobacteria, the hpnP gene coding for the radical S-adenosyl methionine (SAM) methylase protein that acts on the C-2 position of hopanoids was deleted from the filamentous cyanobacterium Nostoc punctiforme ATCC 29133S. The resulting ΔhpnP mutant lacked all 2-methylhopanoids but was found to produce much higher levels of two bacteriohopanepentol isomers than the wild type. Growth rates of the ΔhpnP mutant cultures were not significantly different from those of the wild type under standard growth conditions. Akinete formation was also not impeded by the absence of 2-methylhopanoids. The relative abundances of the different hopanoid structures in akinete-dominated cultures of the wild-type and ΔhpnP mutant strains were similar to those of vegetative cell-dominated cultures. However, the ΔhpnP mutant was found to have decreased growth rates under both pH and osmotic stress, confirming a role for 2-methylhopanoids in stress tolerance. Evidence of elevated photosystem II yield and NAD(P)H-dependent oxidoreductase activity in the ΔhpnP mutant under stress conditions, compared to the wild type, suggested that the absence of 2-methylhopanoids increases cellular metabolic rates under stress conditions.NASA Astrobiology Institute (Award NNA13AA90A