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Geochemical and isotopic evidence for paleoredox conditions during deposition of the Devonian-Mississippian New Albany Shale, southern Indiana

The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.

NASA Discipline Exobiology↗

Pyrolysis of Precambrian kerogens - Constraints and capabilities

Precambrian kerogens are currently considered to be the primary candidates for the search of biochemical fossils. Degradation of kerogens by relatively 'mild' pyrolysis techniques, such as under high vacuum, can liberate indicative structural moieties which were incorporated in, and perhaps shielded by, these solid and highly condensed, basically aromatic substances. It is necessary to observe analytical constraints (sample size and shape, temperature, pressure, time, etc.) in order to prevent an overabundant yield of secondary pyrolyzates (inter- and intramolecular rearrangements) which can prevent kerogen characterization. Potential biochemical fossils have been found in Precambrian kerogens. Demonstratable syngenetic biochemical fossils are expected after kerogen diagenesis and catagenesis is understood in sufficient detail, and when pyrolysis is augmented by multiple, improved analytical techniques.

Nagy, B.↗

Preliminary report on the geology and gold mineralization of the South Pass granite-greenstone terrain, Wind River Mountains, western Wyoming (US)

The South Pass granite-greenstone terrain lies near the southern tip of the Wind River Mountains of western Wyoming. This Archean supracrustal pile has been Wyoming's most prolific source of gold and iron ore. From 1962 to 1983, more than 90 million tons of iron ore were recovered from oxide-facies banded iron formation, and an estimated 325,000 ounces of gold were mined from metagreywacke-hosted shears and associated placers. Precambrian rocks at South Pass are unconformably overlain by Paleozoic sediments along the northeast flank, and a Tertiary pediment buries Archean supracrustals on the west and south. To the northwest, the supracrustals terminate against granodiorite of the Louis Lake batholith; to the east, the supracrustals terminate against granite of the Granite Mountains batholith. The Louis Lake granodiorite is approximately 2,630 + or - 20 m.y. old, and the Granite Mountains granite averages 2,600 m.y. old. The geometry of the greenstone belt is best expressed as a synform that has been modified by complex faulting and folding. Metamorphism is amphibolite grade surrounding a small island of greenschist facies rocks. The younger of the Archean supracrustal successions is the Miners Delight Formation. This unit yielded a Rb-Sr isochron of 2,800 m.y. A sample of galena from the Snowbird Mine within the Miners Delight Formation yielded a model age averaging 2,750 m.y. The Snowbird mineralization appears to be syngenetic and is hosted by metavolcanics of calc-alkaline affinity. Discussion follows.

Hausel, W. D.↗

Possible Microfossils (Warrawoona Group, Towers Formation, Australia, approximately 3.3 - 3.5 Ga)

Early in the twentieth century there were reports of Archean stromatolite-like structures that were similar to organic rich stromatolites from the base of the Cambrian (600 m.y.). It was not until the latter half of this century that fossilized Archean-age (3.9-2.5 Ga) life forms were found in the Fig Tree Formation of South Africa and the Towers Formation of Australia. Some of the ancient stromatolites contained streaks and clots of kerogen, pyrite grains, remnants of microbial cells, and filaments that represented various stages of preservation, while others appeared to lack fossils. A set of physical criteria was established for evaluating the biogenicity of these Archean discoveries: (1) rocks of unquestionable Archean age; (2) microfossils indigenous to Archean sediments; and (3) microfossils occurring in clasts that are syngenetic with deposition of the sedimentary unit. In the case of bedded cherts, the fossils should predate the cherts; (4) the microfossils are biogenic; and (5) replicate sampling of the fossil-iferous outcrop firmly demonstrates the provenance of these microfossils. Sample 002 from the Precambrian Paleobiology Research Group (PPRG) was examined. This stromatolitic carbonaceous chert contains microbial remains that meet the established criteria [10]. Using a scanning electron microscope (SEM), we have analyzed the morphologies and chemistry of these possible microbial remains.

Morris, P. A.↗

Magnetism of Carbonados

Carbonados are porous polycrystalline (with crystal sizes up to 100 micrometer) diamonds. Carbonado is found only in alluvial deposits in Bahia, Brazil and in the Central African Republic (CAR). Alluvial deposit host is 1.5 Ga while the carbonados are between 2.6 - 3.8 Ga. The process of fusing the carbonado microcrystals together is not fully understood, partly due to fact that the origin of these carbonado, is not known. Several modes of origins are proposed for carbonado. First, a crustal origin. Carbonados have a light carbon and helium isotopic signature. They contain an enrichment of the rare-earth elements (REE). Carbonados have tightly trapped atmospheric noble gases and contain an evidence of high He content despite the carbonado expected depletion of He at mantle temperatures. Carbonados have high porosity incompatible with high pressure mantle conditions. Second, a mantle origin is proposed based on similar REE pattern to kimberlites. The presence of nitrogen platelet (by IR spectra) indicates high temperature origin and syngenetic inclusions of rutile, ilmenite, and magnetite indicates high pressure and high temperature conditions consistent with mantle origin as well. Third, it is proposed that carbonado diamonds are a result of early impacts into crustal rocks. This is indicated by the rare and controversial occurrence of high pressure diamond polymorph, londsdaleite, frequently found in diamonds from meteorite impact sites, and by observation of planar deformation features, possibly indicating shock events. Finally, it is suggested that carbonados have an extraterrestrial origin, as indicated by a long term annealing based on observation of a zero-phonon line, attributed to paired nitrogen atoms in association with a vacancy.

Kletetschka, G.↗

Spindle-shaped Microstructures: Potential Models for Planktonic Life Forms on Other Worlds

Spindle-shaped, organic microstructures ("spindles") are now known from Archean cherts in three localities (Figs. 1-4): The ~3 Ga Farrel Quartzite from the Pilbara of Australia [1]; the older, ~3.3-3.4 Ga Strelley Pool Formation, also from the Pilbara of Australia [2]; and the ~3.4 Ga Kromberg Formation of the Barberton Mountain Land of South Africa [3]. Though the spindles were previously speculated to be pseudofossils or epigenetic organic contaminants, a growing body of data suggests that these structures are bona fide microfossils and further, that they are syngenetic with the Archean cherts in which they occur [1-2, 4-10]. As such, the spindles are among some of the oldest-known organically preserved microfossils on Earth. Moreover, recent delta C-13 study of individual spindles from the Farrel Quartzite (using Secondary Ion Mass Spectrometry [SIMS]) suggests that the spindles may have been planktonic (living in open water), as opposed to benthic (living as bottom dwellers in contact with muds or sediments) [9]. Since most Precambrian microbiotas have been described from benthic, matforming communities, a planktonic lifestyle for the spindles suggests that these structures could represent a segment of the Archean biosphere that is poorly known. Here we synthesize the recent work on the spindles, and we add new observations regarding their geographic distribution, robustness, planktonic habit, and long-lived success. We then discuss their potential evolutionary and astrobiological significance.

Oehler, Dorothy Z.↗

Preservation of Organic Carbon in Dolomitized Cambrian Stromatolites and Implications for Microbial Biosignatures in Diagenetically Replaced Carbonate Rock

Stromatolites have been a major focus in the search for ancient microbial life, however, the organic carbon biosignatures of dolomitized stromatolites have not yet been fully characterized or correlated with their dolomitizing conditions. Although dolomitization rarely preserves microbial morphology, the presence of organic carbon can provide valuable information for characterization of fossils’ biogenicity, syngenicity, and indigeneity to their host rock. The Cambrian Allentown Formation in New Jersey, USA, is an excellent example of dolomitized stromatolites and thrombolites containing diagenetically modified microbial biosignatures. Based on XRD and EPMA data, the dolomite composition is typically stoichiometric, with varying degrees of cationic ordering. The outcrop underwent early dolomitization in a marginal-marine setting and later burial diagenesis resulting in multi-generational dolomite formation: (1) 2 microspar dolomite formed by early diagenetic replacement at or near the surface, (2) zoned dolomite formed penecontemporaneously with the microspar phase as rhombohedral crystals by infilling primary pore spaces within the microspar matrix. The rhombic crystals continued to grow outward in alternating stages of Fe-enriched and -depleted fluids, which were preserved in zoned rims and revealed by cathodoluminescence, and (3) saddle dolomite formed during late stage deep burial with Fe- and Mn-rich fluids, and occurs as a void-filling, high-temperature phase. Organic carbon, characterized using confocal Raman microscopy, has an exclusive distribution within the microspar dolomite, and the D and G bands’ characteristics reveal similar thermal alteration to the host rock, indicating that the mapped organic carbon is indigenous and syngenetic with the Cambrian carbonates. The findings presented in this study reveal organic matter found within microspar of various dolomitized facies deriving from different source pools of organic carbon. This study sheds light on biosignatures in secondary dolostones and may aid biosignature detection in older carbonate rocks on Earth and Mars.

Dolomitization↗

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

hypersaline↗