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Isotopic Evidence for Changes in the Biochemical Carbon Cycle During the Early- and Mid-Proterzoic Eon: Implications for the Biosphere and Atmosphere

The Archean fossil record reveals a biosphere whose biota were remarkably sophisticated. For example, bacteria were capable of photosynthesis, and they withstood the ultraviolet radiation and periodic desiccation which accompanied the intertidal environment. However, we can infer relatively little about evolutionary change between 3 and 1.1 billion years (Ga) ago. What biological events occurred, and how did changes in the environment influence the nature and timing of these events? The carbon biogeochemical cycle played a key role, and isotopic measurements of sedimented carbon can reveal long-term changes in this cycle. Additional information is contained in the original extended abstract.

DesMarais, David J.↗

Redox State of the Neoarchean Earth Environment

A Titan-like organic haze has been hypothesized for Earth's atmosphere prior to widespread surface oxygenation approx.2.45 billion years ago (Ga). We present a high-resolution record of quadruple sulfur isotopes, carbon isotopes, and Fe speciation from the approx.2.65-2.5 Ga Ghaap Group, South Africa, which suggest a linkage between organic haze and the biogeochemical cycling of carbon, sulfur, oxygen, and iron on the Archean Earth. These sediments provide evidence for oxygen production in microbial mats and localized oxygenation of surface waters. However, this oxygen production occurred under a reduced atmosphere which existed in multiple distinct redox states that correlate to changes in carbon and sulfur isotopes. The data are corroborated by photochemical model results that suggest bi-stable transitions between organic haze and haze-free atmospheric conditions in the Archean. These geochemical correlations also extend to other datasets, indicating that variations in the character of anomalous sulfur fractionation could provide insight into the role of carbon-bearing species in the reducing Archean atmosphere.

Zerkle, Aubrey L.↗

Secular change in chert distribution: a reflection of evolving biological participation in the silica cycle

In the modern oceans, the removal of dissolved silica from sea water is principally a biological process carried out by diatoms, with lesser contributions from radiolaria, silicoflagellates, and sponges. Because such silica in sediments is often redistributed locally during diagenesis to from nodular or bedded chert, stratigraphic changes in the facies distribution of early diagenetic chert provide important insights into the development of biological participation in the silica cycle. The abundance of chert in upper Proterozoic peritidal carbonates suggests that at this time silica was removed from seawater principally by abiological processes operating in part of the margins of the oceans. With the evolution of demosponges near the beginning of the Cambrian Period, subtidal biogenetic cherts became increasingly common, and with the Ordovician rise of radiolaria to ecological and biogeochemical prominence, sedimented skeletons became a principal sink for oceanic silica. Cherts of Silurian to Cretaceous age share many features of facies distribution and petrography but they differ from Cenozoic siliceous deposits. These differences are interpreted to reflect the mid-Cretaceous radiation of diatoms and their subsequent rise to domination of the silica cycle. Biogeochemical cycles provide an important framework for the paleobiological interpretation of the organisms that participate in them.

Non-NASA Center↗

Seasonal C-13 variations of methane from an anoxic marine sediment

Recent analyses of glacial ice suggest that the atmospheric concentration of methane has doubled in the last several hundred years, presumably due to anthropogenic perturbations of the relevant biogeochemical cycles. In principal, carbon isotopic measurements of atmospheric methane would provide information concerning changes in the sources and sinks of methane. The isotopic composition of methane is dependent on the source of the methane carbon, the mechanism of methane synthesis, and the degree and mode of oxidation which the methane has experienced. Unfortunately, few carbon isotopic measurements of atmospheric variations have been reported, so conclusions about temporal isotopic variations cannot be made. Also, before isotopic measurements of atmospheric methane can be used to identify changes in methane isotopic composition from different sources must be obtained. Methane bubbles from the anoxic sediments of Cape Lookout Bight, NC exhibit seasonal C-13 variations. The C-13 values ranged from -58 in August to -64 in the winter months with the evolution of the C-13 enriched gas occurring during periods of peak methane production. Even though a few intramolecular C-13 measurements of the pore water acetate have been made (methyl group, -26 per mil; carbonyl, -6 per mil), it is not clear how the acetate fermentation pathway affects the methane C-13/C-12 composition.

Blair, Neal↗

Earth's Early Biosphere and the Biogeochemical Carbon Cycle

Our biosphere has altered the global environment principally by influencing the chemistry of those elements most important for life, e g., C, N, S, O, P and transition metals (e.g., Fe and Mn). The coupling of oxygenic photosynthesis with the burial in sediments of photosynthetic organic matter, and with the escape of H2 to space, has increased the state of oxidation of the Oceans and atmosphere. It has also created highly reduced conditions within sedimentary rocks that have also extensively affected the geochemistry of several elements. The decline of volcanism during Earth's history reduced the flow of reduced chemical species that reacted with photosynthetically produced O2. The long-term net accumulation of photosynthetic O2 via biogeochemical processes has profoundly influenced our atmosphere and biosphere, as evidenced by the O2 levels required for algae, multicellular life and certain modem aerobic bacteria to exist. When our biosphere developed photosynthesis, it tapped into an energy resource that was much larger than the energy available from oxidation-reduction reactions associated with weathering and hydrothermal activity. Today, hydrothermal sources deliver globally (0.13-1.1)x10(exp l2) mol yr(sup -1) of reduced S, Fe(2+), Mn(2+), H2 and CH4; this is estimated to sustain at most about (0.2-2)xl0(exp 12)mol C yr(sup -1) of organic carbon production by chemautotrophic microorganisms. In contrast, global photosynthetic productivity is estimated to be 9000x10(exp 12) mol C yr(sup -1). Thus, even though global thermal fluxes were greater in the distant geologic past than today, the onset of oxygenic photosynthesis probably increased global organic productivity by some two or more orders of magnitude. This enormous productivity materialized principally because oxygenic photosynthesizers unleashed a virtually unlimited supply of reduced H that forever freed life from its sole dependence upon abiotic sources of reducing power such as hydrothermal emanations and weathering. Communities sustained by oxygenic photosynthesis apparently thrived wherever supplies of sunlight, moisture and nutrients were sufficient. Prior to the development of oxygenic photosynthesis, the net global effect of the ancient global biosphere was to facilitate chemical equilibrium between reduced species from thermal activity and weathering and more oxidized constituents in the surface environment. But even this ancient biosphere might have been globally pervasive. The global geothermal heat flow was substantially higher during Earth's first billion years, and thus reduced chemical species might have persisted in sunlit aquatic environments. Perhaps the substantial decline in thermal activity between 4000 and 3000 Ma created a driver for oxygenic photosynthesis to develop.

DesMarais, David↗

Searching for Biogeochemical Cycles on Mars

The search for life on Mars clearly benefits from a rigorous, yet broad, definition of life that compels us to consider all possible lines of evidence for a martian biosphere. Recent studies in microbial ecology illustrate that the classic definition of life should be expanded beyond the traditional definition of a living cell. The traditional defining characteristics of life are threefold. First, life is capable of metabolism, that is, it performs chemical reactions that utilize energy and also synthesize its cellular constituents. Second, life is capable of self-replication. Third, life can evolve in order to adapt to environmental changes. An expanded, ecological definition of life also recognizes that life is a community of organisms that must interact with their nonliving environment through processes called biogeochemical cycles. This regenerative processing maintains, in an aqueous conditions, a dependable supply of nutrients and energy for growth. In turn, life can significantly affect those processes that control the exchange of materials between the atmosphere, ocean, and upper crust. Because metabolic processes interact directly with the environment, they can alter their surroundings and thus leave behind evidence of life. For example, organic matter is produced from single-carbon-atom precursors for the biosynthesis of cellular constituents. This leads to a reservoir of reduced carbon in sediments that, in turn, can affect the oxidation state of the atmosphere. The harvesting of chemical energy for metabolism often employs oxidation-reduction reactions that can alter the chemistry and oxidation state of the redox-sensitive elements carbon, sulfur, nitrogen, iron, and manganese. Have there ever been biogeochemical cycles on Mars? Certain key planetary processes can offer clues. Active volcanism provides reduced chemical species that biota can use for organic synthesis. Volcanic carbon dioxide and methane can serve as greenhouse gases. Thus the persistence of volcanism on Mars may well have influenced the persistence of a martian biosphere. The geologic processing of the crust can affect the availability of nutrients and also control the deposition of minerals that could have served as a medium for the preservation of fossil information. Finally, the activity of liquid water is crucial to life. Was there ever an Earth-like hydrologic cycle with rainfall? Has aqueous activity instead been restricted principally to hydrothermal activity below the surface? To what extent did the inorganic chemistry driven by sunlight and hydrothermal activity influence organic chemistry (prebiotic chemical evolution)? This paper addresses these and other key questions.

DesMarais, David J.↗

Terminal Proterozoic reorganization of biogeochemical cycles

The Proterozoic aeon (2,500-540 million years ago) saw episodic increases in atmospheric oxygen content, the evolution of multicellular life and, at its close, an enormous radiation of animal diversity. These profound biological and environmental changes must have been linked, but the underlying mechanisms have been obscure. Here we show that hydrocarbons extracted from Proterozoic sediments in several locations worldwide are derived mainly from bacteria or other heterotrophs rather than from photosynthetic organisms. Biodegradation of algal products in sedimenting matter was therefore unusually complete, indicating that organic material was extensively reworked as it sank slowly through the water column. We propose that a significant proportion of this reworking will have been mediated by sulphate-reducing bacteria, forming sulphide. The production of sulphide and consumption of oxygen near the ocean surface will have inhibited transport of O2 to the deep ocean. We find that preservation of algal-lipid skeletons improves at the beginning of the Cambrian, reflecting the increase in transport by rapidly sinking faecal pellets. We suggest that this rapid removal of organic matter will have increased oxygenation of surface waters, leading to a descent of the O2-sulphide interface to the sea floor and to marked changes in the marine environment, ultimately contributing to the Cambrian radiation.

Non-NASA Center↗

Biogeochemical modeling at mass extinction boundaries

The causes of major mass extinctions is a subject of considerable interest to those concerned with the history and evolution of life on earth. The primary objectives of the proposed plan of research are: (1) to develop quantitative time-dependent biogeochemical cycle models, coupled with an ocean atmosphere in order to improve the understanding of global scale physical, chemical, and biological processes that control the distribution of elements important for life at times of mass extinctions; and (2) to develop a comprehensive data base of the best available geochemical, isotopic, and other relevant geologic data from sections across mass extinction boundaries. These data will be used to constrain and test the biogeochemical model. These modeling experiments should prove useful in: (1) determining the possible cause(s) of the environmental changes seen at bio-event boundaries; (2) identifying and quantifying little-known feedbacks among the oceans, atmosphere, and biosphere; and (3) providing additional insights into the possible responses of the earth system to perturbations of various timescales. One of the best known mass extinction events marks the Cretaceous/Tertiary (K/T) boundary (66 Myr ago). Data from the K/T boundary are used here to constrain a newly developed time-dependent biogeochemical cycle model that is designed to study transient behavior of the earth system. Model results predict significant fluctuations in ocean alkalinity, atmospheric CO2, and global temperatures caused by extinction of calcareous plankton and reduction in the sedimentation rates of pelagic carbonates and organic carbon. Oxygen-isotome and other paleoclimatic data from K/T time provide some evidence that such climatic fluctuations may have occurred, but stabilizing feedbacks may have acted to reduce the ocean alkalinity and carbon dioxide fluctuations.

Rampino, M. R.↗

Biogeochemical cycling of manganese in Oneida Lake, New York: whole lake studies of manganese

Oneida Lake, New York is a eutrophic freshwater lake known for its abundant manganese nodules and a dynamic manganese cycle. Temporal and spatial distribution of soluble and particulate manganese in the water column of the lake were analyzed over a 3-year period and correlated with other variables such as oxygen, pH, and temperature. Only data from 1988 are shown. Manganese is removed from the water column in the spring via conversion to particulate form and deposited in the bottom sediments. This removal is due to biological factors, as the lake Eh/pH conditions alone can not account for the oxidation of the soluble manganese Mn(II). During the summer months the manganese from microbial reduction moves from the sediments to the water column. In periods of stratification the soluble Mn(II) builds up to concentrations of 20 micromoles or more in the bottom waters. When mixing occurs, the soluble Mn(II) is rapidly removed via oxidation. This cycle occurs more than once during the summer, with each manganese atom probably being used several times for the oxidation of organic carbon. At the end of the fall, whole lake concentrations of manganese stabilize, and remain at about 1 micromole until the following summer, when the cycle begins again. Inputs and outflows from the lake indicate that the active Mn cycle is primarily internal, with a small accumulation each year into ferromanganese nodules located in the oxic zones of the lake.

NASA Discipline Exobiology↗

Precambrian evolution of the climate system

This paper presents a new examination of the biogeochemical cycles of carbon as they may have changed between an Archean Earth deficient in land, sedimentary rocks, and biological activity, and a Proterozoic Earth much like the modern Earth, but lacking terrestrial life and carbonate-secreting plankton. Results of a numerical simulation of this transition show how increasing biological activity could have drawn down atmospheric carbon dioxide by extracting sedimentary organic carbon from the system. Increasing area of continents could further have drawn down carbon dioxide by encouraging the accumulation of carbonate sediments. An attempt to develop a numerical simulation of the carbon cycles of the Precambrian raises questions about sources and sinks of marine carbon and alkalinity on a world without continents. More information is needed about sea-floor weathering processes.

Walker, James C. G.↗

Hydrogen Biogeochemistry in Anaerobic and Photosynthetic Ecosystems

The simple biochemistry of molecular hydrogen is central to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. In anoxic sediments, a great majority of microbial redox processes involve hydrogen as a reactant, product or potential by-product. Accordingly, the energetics (thermodynamics) of each of these processes is affected by variations in local H2 concentrations. It has long been established that this effect is important in governing microbe-microbe interactions and there are multiple demonstrations that "interspecies hydrogen transfer" can alter the products of, inhibit/stimulate, or even reverse microbial metabolic reactions. In anoxic sediments, H2 concentrations themselves are thought to be controlled by the thermodynamics of the predominant H2-consuming microbial process. In sediments from Cape Lookout Bight, this relationship quantitatively describes the co-variation of H2 concentrations with temperature (for methanogens and sulfate reducers) and with sulfate concentration (for sulfate reducers). The quantitative aspect is import= for two reasons: 1) it permits the modeling of H2-sensitive biogeochemistry, such as anaerobic methane oxidation or pathways of organic matter remineralization, as a function of environmental controls; 2) for such a relationship to be observed requires that intracellular biochemistry and bioenergetics are being directly expressed in a component of the extracellular medium. H2 could therefore be utilized a non-invasive probe of cellular energetic function in intact microbial ecosystems. Based on the latter principle we have measured down-core profiles of H2 and other relevant physico-chemical parameters in order to calculate the metabolic energy yields (DG) that support microbial metabolism in Cape Lookout Bight sediments. Methanogens in this system apparently function with energy yields significantly smaller than the minimum requirements suggested by pure culture studies. Our recent work has extended the study of hydrogen to cyanobacterial mat communities. The large amounts of reducing power generated during photosynthetic activity carry the potential to contribute a swamping term to the H2 economy of the anaerobic microbial populations within the mat - and thereby to alter the population structure and biogeochemical function of the mat as a whole. In hypersaline microbial mats, we observe a distinct diel cycle in H2 production and a substantial corresponding flux. On an early Earth dominated by microbial mats, this transmission of photosynthetic reducing power may have carried important implications for both biospheric and atmospheric evolution.

Hoehler, Tori M.↗

Modeling Biogeochemical-Physical Interactions and Carbon Flux in the Sargasso Sea (Bermuda Atlantic Time-series Study site)

An ecosystem-carbon cycle model is used to analyze the biogeochemical-physical interactions and carbon fluxes in the Bermuda Atlantic Time-series Study (BATS) site for the period of 1992-1998. The model results compare well with observations (most variables are within 8% of observed values). The sea-air flux ranges from -0.32 to -0.50 mol C/sq m/yr, depending upon the gas transfer algorithm used. This estimate is within the range (-0.22 to -0.83 mol C/sq m/yr) of previously reported values which indicates that the BATS region is a weak sink of atmospheric CO2. The overall carbon balance consists of atmospheric CO2 uptake of 0.3 Mol C/sq m/yr, upward dissolved inorganic carbon (DIC) bottom flux of 1.1 Mol C/sq m/yr, and carbon export of 1.4 mol C/sq m/yr via sedimentation. Upper ocean DIC levels increased between 1992 and 1996 at a rate of approximately 1.2 (micro)mol/kg/yr, consistent with observations. However, this trend was reversed during 1997-1998 to -2.7 (micro)mol/kg/yr in response to hydrographic changes imposed by the El Nino-La Nina transition, which were manifested in the Sargasso Sea by the warmest SST and lowest surface salinity of the period (1992-1998).

Signorini, Sergio R.↗

Searching for Evidence of Life in Deep Time and Space

Cyanobacterial mats provide insights into ancient benthic microbial communities and their biosignatures. Thick mats occupy hypersaline saltern ponds at Guerrero Negro, Baja California, Mexico. Mat biota maintains rapid rates of biogeochemical processes under steep and rapidly changing environmental gradients. Cycling of C, O, and S all increased identically with temperature, indicating the tight coupling of these cycles. An enormous microbial diversity exhibits a highly structured spatial distribution of populations. Combined universal clone libraries from all mat layers indicated Bacteria/Archaea/Eukarya ratios of 57:7:1. More than 10,000 unique bacterial sequences were present. The relative abundance of Archaea increased with depth - below 10 cm, solvent-extractable archaeal lipids were twice as abundant as bacterial lipids. Only 15 species of Eukarya were found among 890 clones analyzed. Degradation of the mats’ insoluble macromolecular organic fraction (IMOM) by hydropyrolysis released a complex variety of linear, branched and polycyclic alkane structures, e.g., hopanes, methylhopanes and steranes. Covalent binding of these biosignatures into IMOM aids their long-term geological preservation. Mars rover missions revealed evidence of long-lived fluvial lacustrine systems and organics in associated mudstones. NASA’s Mars 2020 rover mission will examine sediments in Jezero crater, including a delta and shoreline carbonate deposits, environments that on Earth have sustained microbial mats.

Des Marais, David J.↗

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Eigenbrode, Jennifer L.↗

Organization of P, S, and Fe Inclusions in a Freshwater Magnetococcus

Magnetotactic bacteria are a heterogeneous group of motile, mainly aquatic procaryotes that align and swim along geomagnetic field lines. They are of interest to astrobiologists because of the magnetite crystals found in the Mars meteorite ALH84001 which share many characteristics with the magnetite produced intracellularly by magnetotactic bacteria. These bacteria are diverse morphologically, physiologically and phylogenetically, sharing a few key characteristics: 1) the presence of intracellular membrane-bound magnetic crystals (magnetosomes), usually but not always arranged in chains; 2) motility by means of flagella; and 3) microaerophillic or anaerobic physiology. The bilophotrichous (having two flagella bundles) magnetotactic cocci (MC) are ubiquitous in aquatic habitats but have proven extremely difficult to cultivate. Because only several marine strains have been isolated and grown in axenic culture, little is known about the physiology and the biogeochemical roles of the MC. We studied the composition and distribution of intracellular structures in an uncultured MC, designated ARB-1. To do this, a combination of light microscopy, environmental scanning electron microscopy (ESEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were used. Cells of ARB-1 were separated from sediments collected from Baldwin Lake (Los Angeles Arboretum, Arcadia, CA). They are large spherical to oblate spheroidal Gram-negative cells, ranging from 1 to 4 micrometers along the maximum dimension, which is perpendicular to the direction of swimming. Cells have two large phosphorus-containing inclusions that comprise a large percentage of the cell volume. Many smaller sulfur inclusions are located at the convex end of the cell. Most of the cellular Fe is present in the magnetosomes. These may be arranged as a clump at the concave end of the cell, near the two flagella bundles, or as chains, or as both a clump and chains. The magnetosomes were identified as magnetite (Fe3O4) by selected area electron diffraction (SAED) and high resolution TEM. We saw a trend between cell size and organization of the magnetosomes. Smaller, more spherical cells were more likely to have chains than were larger, more oblate cells. This may indicate different populations of cells, or it may be attributed to variations in cell growth cycle. The size distribution (length) of magnetosomes in chains was similar to that of magnetosomes in clusters, except that there was a larger size range for clustered magnetosomes. Magnetosomes from ARB-1 cells average 82 nm in length. If plotted on a graph of length as a function of aspect ratio, they fall within the single domain region of the plot. If compared with the size distributions of magnetite from ALH84001 and magnetosomes from the cultured magnetotactic vibrio MV-1, the magnetites produced by ARB-1 cells are, on average, larger and have a wider range of aspect ratio. ARB-1 cells have a specific organization of the P, S, and Fe inclusions. The P inclusions always occupy the majority of the cell volume and separate the S inclusions from the disorganized clumps of magnetosomes and the flagella bundles. The P inclusions may contain polyphosphate, which could play several roles in motility, adaptation to stress, growth and division, buoyancy, and energy. The S inclusions might be a way to store S, a potential energy source, when the cells move from sulfide to oxygen zones. The consistency of P, S, and Fe organization in ARB-1 cells suggests that these inclusions have some specific and interactive functions.

Cox, Lea↗

Satellite Ocean Colour: Current Status and Future Perspective

Spectrally resolved water-leaving radiances (ocean colour) and inferred chlorophyll concentration are key to studying phytoplankton dynamics at seasonal and inter-annual scales, for a better understanding of the role of phytoplankton in marine biogeochemistry; the global carbon cycle; and the response of marine ecosystems to climate variability, change and feedback processes. Ocean colour data also have a critical role in operational observation systems monitoring coastal eutrophication, harmful algal blooms, and sediment plumes. The contiguous ocean-colour record reached 21 years in 2018; however, it is comprised of a number of one-off missions such that creating a consistent time-series of ocean-colour data requires merging of the individual sensors (including MERIS, Aqua-MODIS, SeaWiFS, VIIRS, and OLCI) with differing sensor characteristics, without introducing artefacts. By contrast, the next decade will see consistent observations from operational ocean colour series with sensors of similar design and with a replacement strategy. Also, by 2029 the record will start to be of sufficient duration to discriminate climate change impacts from natural variability, at least in some regions. This paper describes the current status and future prospects in the field of ocean colour focusing on large to medium resolution observations of oceans and coastal seas. It reviews the user requirements in terms of products and uncertainty characteristics and then describes features of current and future satellite ocean-colour sensors, both operational and innovative. The key role of in situ validation and calibration is highlighted as are ground segments that process the data received from the ocean-colour sensors and deliver analysis-ready products to end-users. Example applications of the ocean-colour data are presented, focusing on the climate data record and operational applications including water quality and assimilation into numerical models. Current capacity building and training activities pertinent to ocean colour are described and finally a summary of future perspectives is provided.

ocean colour↗