Oxidation of the Ediacaran Ocean

Oxygenation of the Earth's surface is increasingly thought to have occurred in two steps. The first step, which occurred ~2,300 million years (Myr) ago, involved a significant increase in atmospheric oxygen concentrations and oxygenation of the surface ocean. A further increase in atmospheric oxygen appears to have taken place during the late Neoproterozoic period (~800–542 Myr ago). This increase may have stimulated the evolution of macroscopic multicellular animals and the subsequent radiation of calcified invertebrates, and may have led to oxygenation of the deep ocean. However, the nature and timing of Neoproterozoic oxidation remain uncertain. Here we present high-resolution carbon isotope and sulphur isotope records from the Huqf Supergroup, Sultanate of Oman, that cover most of the Ediacaran period (~635 to ~548 Myr ago). These records indicate that the ocean became increasingly oxygenated after the end of the Marinoan glaciation, and they allow us to identify three distinct stages of oxidation. When considered in the context of other records from this period, our data indicate that certain groups of eukaryotic organisms appeared and diversified during the second and third stages of oxygenation. The second stage corresponds with the Shuram excursion in the carbon isotope record and seems to have involved the oxidation of a large reservoir of organic carbon suspended in the deep ocean, indicating that this event may have had a key role in the evolution of eukaryotic organisms. Our data thus provide new insights into the oxygenation of the Ediacaran ocean and the stepwise restructuring of the carbon and sulphur cycles that occurred during this significant period of Earth's history

Organic geochemistry of the early Toarcian oceanic anoxic event in Hawsker Bottoms, Yorkshire, England

A comprehensive organic geochemical investigation of the Hawsker Bottoms outcrop section in Yorkshire, England has provided new insights about environmental conditions leading into and during the Toarcian oceanic anoxic event (T-OAE; ~183 Ma). Rock-Eval and molecular analyses demonstrate that the section is uniformly within the early oil window. Hydrogen index (HI), organic petrography, polycyclic aromatic hydrocarbon (PAH) distributions, and tricyclic terpane ratios mark a shift to a lower relative abundance of terrigenous organic matter supplied to the sampling locality during the onset of the T-OAE and across a lithological transition. Unlike other ancient intervals of anoxia and extinction, biomarker indices of planktonic community structure do not display major changes or anomalous values. Depositional environment and redox indicators support a shift towards more reducing conditions in the sediment porewaters and the development of a seasonally stratified water column during the T-OAE. In addition to carotenoid biomarkers for green sulfur bacteria (GSB), we report the first occurrence of okenane, a marker of purple sulfur bacteria (PSB), in marine samples younger than ~1.64 Ga. Based on modern observations, a planktonic source of okenane's precursor, okenone, would require extremely shallow photic zone euxinia (PZE) and a highly restricted depositional environment. However, due to coastal vertical mixing, the lack of planktonic okenone production in modern marine sulfidic environments, and building evidence of okenone production in mat-dwelling Chromatiaceae, we propose a sedimentary source of okenone as an alternative. Lastly, we report the first parallel compound-specific δ[superscript 13]C record in marine- and terrestrial-derived biomarkers across the T-OAE. The δ[superscript 13]C records of short-chain n-alkanes, acyclic isoprenoids, and long-chain n -alkanes all encode negative carbon isotope excursions (CIEs), and together, they support an injection of isotopically light carbon that impacted both the atmospheric and marine carbon reservoirs. To date, molecular δ[superscript 13]C records of the T-OAE display a negative CIE that is smaller in magnitude compared to the bulk organic δ[superscript 13]C excursion. Although multiple mechanisms could explain this observation, our molecular, petrographic, and Rock-Eval data suggest that variable mixing of terrigenous and marine organic matter is an important factor affecting the bulk organic δ[superscript 13]C records of the T-OAE.NASA Astrobiology InstituteExobiology Program (U.S.)National Science Foundation (U.S.). Graduate Research Fellowshi

Discovery of multiple Lorentzian components in the X-ray timing properties of the Narrow Line Seyfert 1 Ark 564

We present a power spectral analysis of a 100 ksec XMM-Newton observation of the narrow line Seyfert 1 galaxy Ark~564. When combined with earlier RXTE and ASCA observations, these data produce a power spectrum covering seven decades of frequency which is well described by a power law with two very clear breaks. This shape is unlike the power spectra of almost all other AGN observed so far, which have only one detected break, and resemble Galactic binary systems in a soft state. The power spectrum can also be well described by the sum of two Lorentzian-shaped components, the one at higher frequencies having a hard spectrum, similar to those seen in Galactic binary systems. Previously we have demonstrated that the lag of the hard band variations relative to the soft band in Ark 564 is dependent on variability time-scale, as seen in Galactic binary sources. Here we show that the time-scale dependence of the lags can be described well using the same two-Lorentzian model which describes the power spectrum, assuming that each Lorentzian component has a distinct time lag. Thus all X-ray timing evidence points strongly to two discrete, localised, regions as the origin of most of the variability. Similar behaviour is seen in Galactic X-ray binary systems in most states other than the soft state, i.e. in the low-hard and intermediate/very high states. Given the very high accretion rate of Ark 564 the closest analogy is with the very high (intermediate) state rather than the low-hard state. We therefore strengthen the comparison between AGN and Galactic binary sources beyond previous studies by extending it to the previously poorly studied very high accretion rate regime.Comment: 11 pages, 11 figures, accepted for publication in MNRA

Rapid oxygenation of Earths atmosphere 2.33 billion years ago

Molecular oxygen (O[subscript 2]) is, and has been, a primary driver of biological evolution and shapes the contemporary landscape of Earth’s biogeochemical cycles. Although “whiffs” of oxygen have been documented in the Archean atmosphere, substantial O2 did not accumulate irreversibly until the Early Paleoproterozoic, during what has been termed the Great Oxygenation Event (GOE). The timing of the GOE and the rate at which this oxygenation took place have been poorly constrained until now. We report the transition (that is, from being mass-independent to becoming mass-dependent) in multiple sulfur isotope signals of diagenetic pyrite in a continuous sedimentary sequence in three coeval drill cores in the Transvaal Supergroup, South Africa. These data precisely constrain the GOE to 2.33 billion years ago. The new data suggest that the oxygenation occurred rapidly—within 1 to 10 million years—and was followed by a slower rise in the ocean sulfate inventory. Our data indicate that a climate perturbation predated the GOE, whereas the relationships among GOE, “Snowball Earth” glaciation, and biogeochemical cycling will require further stratigraphic correlation supported with precise chronologies and paleolatitude reconstructions.National Science Foundation (U.S.) (EAR-1338810)National Natural Science Foundation (China) ((grant no. 41472170)Wellcome Trust Sanger Institute ( 111 Project grant no. B08030)National Basic Research Program of China (973 Program)United States. National Aeronautics and Space Administration (NASA Astrobiology Institute award NNA13AA90A

Active eukaryotes in microbialites from Highborne Cay, Bahamas, and Hamelin Pool (Shark Bay), Australia

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Nature Publishing Group for personal use, not for redistribution. The definitive version was published in The ISME Journal 8 (2014): 418–429, doi:10.1038/ismej.2013.130.Microbialites are organosedimentary structures that are formed through the interaction of benthic microbial communities and sediments and include mineral precipitation. These lithifying microbial mat structures include stromatolites and thrombolites. Exuma Sound in the Bahamas, and Hamelin Pool in Shark Bay, Western Australia are two locations where significant stands of modern microbialites exist. Although prokaryotic diversity in these structures is reasonably well documented, little is known about the eukaryotic component of these communities and their potential to influence sedimentary fabrics through grazing, binding and burrowing activities. Accordingly, comparisons of eukaryotic communities in modern stromatolitic and thrombolytic mats can potentially provide insight into the coexistence of both laminated and clotted mat structures in close proximity to one another. Here we examine this possibility by comparing eukaryotic diversity based on Sanger and high-throughput pyrosequencing of small subunit ribosomal RNA (18S rRNA) genes. Analyses were based on total RNA extracts as template to minimize input from inactive or deceased organisms. Results identified diverse eukaryotic communities particularly stramenopiles, Alveolata, Metazoa, Amoebozoa, and Rhizaria within different mat types at both locations, as well as abundant and diverse signatures of eukaryotes with <80% sequence similarity to sequences in GenBank. This suggests presence of significant novel eukaryotic diversity, particularly in hypersaline Hamelin Pool. There was evidence of vertical structuring of protist populations and foraminiferal diversity was highest in bioturbated/clotted thrombolite mats of Highborne Cay.This work was funded by grant OCE-0926421 to JMB and VPE and OCE-0926372 to RES

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte-Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.National Science Foundation (U.S.) (Grant EAR-1338810)National Science Foundation (U.S.) (Grant EAR-1455258

Carbon Isotope and Lipid Biomarker Stratigraphy from Organic-Rich Strata Through the Neoproterozoic Shuram Excursion in South Oman

The regulation of oxygen levels in Earth’s atmosphere and oceans is inextricably linked to the carbon cycle. Carbon isotope ratios of carbonate and sedimentary organic matter provide first order insights into the operation of the carbon cycle in the geologic past. During the Ediacaran period, the ~580 Ma ‘Shuram Excursion’ (SE) records a dramatic, systematic shift in δ^(13)C_(carbonate) values to as low as cɑ. -12‰, lasting potentially millions to tens of millions of years in duration and constitutes the largest carbon isotope excursion known in the record [1]. The extremely negative carbon isotope values in carbonate challenges our understanding of the ancient carbon cycle and is difficult to rationalise via uniform carbon cycle principles. Several hypotheses have been developed to explain this behaviour, all of which make different predictions for the abundance, structure, and isotopic composition of organic carbon through the excursion. For a direct test of these ideas, we report paired organic and inorganic stable carbon isotope ratios in addition to detailed lipid biomarker stratigraphic records from a subsurface well drilled on the eastern flank of the South Oman Salt Basin, Sultanate of Oman. This well captures thermally immature and organic-rich Nafun Group strata traversing the SE, yielding variable but primary biomarker characteristics typical of Neoproterozoic rocks from this region. Despite the high organic matter contents, the carbon isotopic compositions of carbonates do not covary with those of organic phases. Furthermore, lipid biomarker data reveal that organic matter composition and source inputs varied stratigraphically, reflecting biological community shifts in non-migrated, syngenetic organic matter deposited during this interval. Together these observations imply that carbonateorganic isotopic decoupling during the SE is not a result of mixing of fossil or exogenous carbon sources (either DOC, detrital, or migrated) with syngenetic organic matter

Demosponge steroid biomarker 26-methylstigmastane provides evidence for Neoproterozoic animals

Sterane biomarkers preserved in ancient sedimentary rocks hold promise for tracking the diversification and ecological expansion of eukaryotes. The earliest proposed animal biomarkers from demosponges (Demospongiae) are recorded in a sequence around 100 Myr long of Neoproterozoic–Cambrian marine sedimentary strata from the Huqf Supergroup, South Oman Salt Basin. This C_(30) sterane biomarker, informally known as 24-isopropylcholestane (24-ipc), possesses the same carbon skeleton as sterols found in some modern-day demosponges. However, this evidence is controversial because 24-ipc is not exclusive to demosponges since 24-ipc sterols are found in trace amounts in some pelagophyte algae. Here, we report a new fossil sterane biomarker that co-occurs with 24-ipc in a suite of late Neoproterozoic–Cambrian sedimentary rocks and oils, which possesses a rare hydrocarbon skeleton that is uniquely found within extant demosponge taxa. This sterane is informally designated as 26-methylstigmastane (26-mes), reflecting the very unusual methylation at the terminus of the steroid side chain. It is the first animal-specific sterane marker detected in the geological record that can be unambiguously linked to precursor sterols only reported from extant demosponges. These new findings strongly suggest that demosponges, and hence multicellular animals, were prominent in some late Neoproterozoic marine environments at least extending back to the Cryogenian period

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte–Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability

Episodic photic zone euxinia in the northeastern Panthalassic Ocean during the end-Triassic extinction

Severe changes in ocean redox, nutrient cycling, and marine productivity accompanied most Phanerozoic mass extinctions. However, evidence for marine photic zone euxinia (PZE) as a globally important extinction mechanism for the end-Triassic extinction (ETE) is currently lacking. Fossil molecular (biomarker) and nitrogen isotopic records from a sedimentary sequence in western Canada provide the first conclusive evidence of PZE and disrupted biogeochemistry in neritic waters of the Panthalassic Ocean during the end Triassic. Increasing water-column stratification and deoxygenation across the ETE led to PZE in the Early Jurassic, paralleled by a perturbed nitrogen cycle and ecological turnovers among noncalcifying groups, including eukaryotic algae and prokaryotic plankton. If such conditions developed widely in the Panthalassic Ocean, PZE might have been a potent mechanism for the ETE.National Science Foundation (U.S.) (Grant EAR-1147402)Exobiology Program (U.S.) (Grants NNX09AM88G and NNA08CN84A)American Association of Petroleum Geologists (Grant-In-Aid)Mary-Hill and Bevan M. French Fund for Impact Geolog