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Hydrogen Fluxes from Photosynthetic Communities: Implications for Early Earth Biogeochemistry

More than half the history of life on Earth was dominated by photosynthetic microbial mats, which must have represented the preeminent biological influence on global geochemical cycling during that time. In modem analogs of then ancient communities, hypersaline microbial mats from Guerrero Negro, Mexico, we have observed a large flux of molecular hydrogen originating in the cyanobacteria-dominated surface layers. Hydrogen production follows a distinct diel pattern and is sensitive to both oxygen tension and microbial species composition within the mat. On an early Earth dominated by microbial mats, the observed H2 fluxes would scale to global levels far in excess of geothermal emissions. A hydrogen flux of this magnitude represents a profound transmission of reducing power from oxygenic photosynthesis, both to the anaerobic biosphere, where H2 is an almost universally-utilized substrate and regulator of microbial redox chemistry, and to the atmosphere, where subsequent escape to space could provide an important mechanism for the net oxidation of Earth's surface.

Hoehler, Tori M.

The Biogeochemistry of Sulfur in Hydrothermal Systems

The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. Understanding how sulfur became prevalent in biochemical processes and many biomolecules requires knowledge of the reaction properties of sulfur-bearing compounds. We have previously estimated thermodynamic data for thiols, the simplest organic sulfur compounds, at elevated temperatures and pressures. If life began in hydrothermal environments, it is especially important to understand reactions at elevated temperatures among sulfur-bearing compounds and other organic molecules essential for the origin and persistence of life. Here we examine reactions that may have formed amino acids with thiols as reaction intermediates in hypothetical early Earth hydrothermal environments. (There are two amino acids, cysteine and methionine, that contain sulfur.) Our calculations suggest that significant amounts of some amino acids were produced in early Earth hydrothermal fluids, given reasonable concentrations H2, NH3, H2S and CO. For example, preliminary results indicate that glycine activities as high as 1 mmol can be reached in these systems at 100 C. Alanine formation from propanethiol is also a favorable reaction. On the other hand, the calculated equilibrium log activities of cysteine and serine from propanethiol are -21 and -19, respectively, at 100 C. These results indicate that while amino acid formation with thiols as intermediates is favored in some cases, other mechanisms may have been necessary to produce significant amounts of other amino acids. Coupled with our previous results for thiols, these studies imply that sulfur may have been easily incorporated into the organic geochemistry of early Earth hydrothermal systems, leading to its widespread use in biomolecules. Formation of more complex biomolecules in hydrothermal systems may have required sulfur-bearing organic compounds as reaction intermediates.

Schulte, Mitchell

Monthly Variability in Upper Ocean Biogeochemistry Due to Mesoscale Eddy Activity in the Sargasso Sea

A comparison of monthly biogeochemical measurements made from 1993 to 1995, combined with hydrography and satellite altimetry, was used to observe the impacts of nine eddy events on primary productivity and particle flux in the Sargasso Sea. Measurements of primary production, thorium-234 flux, nitrate+nitrite, and photosynthetic pigments made at the US JGOFS Bermuda Atlantic Time-Series Study (BATS) site were used. During the three years of this study, four out of six high thorium-234 flux events over 1000 dpm/sq m/d occurred during the passage of an eddy. Primary production nearly as high as the spring bloom maximum was observed in two mode-water eddies (May 1993 and July 1995). The 1994 spring bloom at BATS was suppressed by the passage of an anticyclone. Distinct phytoplankton community shifts were observed in mode-water eddies, which had an increased percentage diatoms and dinoflagelletes, and in cyclones, which had an increased percentage cyanobacteria (excluding Prochlorococcus). The difference in the observations of mode-water eddies and cyclones may result from the age of the eddy, which was very important to the biological response. In general, eddies that were one to two months old elicited a large biological response; eddies that were three months old may show a biological response and were accompanied by high thorium flux measurements; eddies that were four months old or older did not show a biological response or high thorium flux. Our conceptual model depicting the importance of temporal changes during eddy upwelling and decay fit the observations well in all seven upwelling eddies. Additional information is needed to determine the importance of deeper mixed layers and winter mixing to the magnitude of the eddy impacts. Also, sampling generally captured only the beginning, end, and/or edge of an eddy due to the monthly to semi-monthly frequency of the measurements made at BATS. Lagrangian studies, higher resolution time-series, and/or more spatial coverage is needed to provide additional information for improved C and N budgets in the Sargasso Sea and to complete our understanding of the temporal changes that occur in an eddy.

Sweeney, Erin N.

Regional Application of an Ecosystem Production Model for Studies of Biogeochemistry in the...

The degree to which primary production, soil carbon, and trace gas fluxes in tropical forests of the Amazon are limited by moisture availability and other environmental factors was examined using an ecosystem modeling application for the country of Brazil. A regional geographic information system (GIS) serves as the data source of climate drivers, satellite images, land cover, and soil properties for input to the NASA Ames-CASA (Carnegie-Ames-Stanford Approach) model over a 8-km grid resolution. Simulation results supports the hypothesis that net primary production (NPP) is limited by cloud interception of solar radiation over the humid northwestern portion of the region. Peak annual rates for NPP of nearly 1.4 kg C m-2yr -1are localized in the seasonally dry eastern Amazon in areas that we assume are primarily deep-rooted evergreen forest cover. Regional effects of forest conversion on NPP and soil carbon content are indicated in the model results, especially in seasonally dry areas. Comparison of model flux predictions along selected eco-climatic transects reveal moisture, soil, and land use controls on gradients of ecosystem production and soil trace gas emissions (CO2, N2O, and NO). These results are used to formulate a series of research hypotheses for testing in the next phase of regional modeling, which includes recalibration of the light-use efficiency term in CASA using field measurements of NPP, and refinements of vegetation index and soil property (texture and potential rooting depth) maps for the region.

Potter, C. S.

Benthic Marine Cyanobacterial Mat Ecosystems: Biogeochemistry and Biomarkers

Cyanobacterial mats are complete ecosystems that can include processes of primary production, diagenesis and lithification. Light sustains oxygenic photosynthesis, which in turn provides energy, organic matter and oxygen to the community. Due to both absorption and scattering phenomena, incident light is transformed with depth in the mat, both in intensity and spectral composition. Mobile photo synthesizers optimize their position with respect to this light gradient. When photosynthesis ceases at night, the upper layers of the mat become reduced and sulfidic. Counteracting gradients of oxygen and sulfide combine to provide daily-contrasting environments separated on a scale of a few mm. The functional complexity of mats, coupled with the highly proximal and ordered spatial arrangement of biota, offers the potential for a staggering number of interactions. At a minimum, the products of each functional group of microorganisms affect the other groups both positively and negatively. For example, cyanobacteria generate organic matter (potential substrates) but also oxygen (a toxin for many anaerobes). Anaerobic activity recycles nutrients to the photosynthesizers but also generates potentially toxic sulfide. The combination of benefits and hazards of light, oxygen and sulfide promotes the allocation of the various essential mat processes between light and dark periods, and to various depths in the mat. Observations of mats have produced numerous surprises. For example, obligately anaerobic processes can occur in the presence of abundant oxygen, highly reduced gases are produced in the presence of abundant sulfate, meiofauna thrive at high sulfide concentrations, and the mats' constituent populations respond to environmental changes in complex ways. While photosynthetic bacteria dominate the biomass and productivity of the mat, nonphotosynthetic, anaerobic processes constitute the ultimate biological filter on the ecosystem's emergent biosignatures, including those sedimentary textures, organic compounds, and minerals that enter the fossil record. The ability of cyanobacterial mats to channel abundant solar energy into the creation and maintenance of complex structures and processes has created a multitude of consequences, both for sedimentation and for the early evolution of our biosphere.

DesMarais, David J.

Monthly Variability in Upper Ocean Biogeochemistry due to Mesoscale Eddy Activity in the Sargasso Sea

A comparison of monthly biogeochemical measurements made from 1993 to 1995, combined with hydrography and satellite altimetry, was used to observe the impacts of nine eddy events on primary productivity and particle flux in the Sargasso Sea. Measurements of primary production, thorium-234 flux, nitrate+nitrite, and photosynthetic pigments made at the US JGOFS Bermuda Atlantic Time-series Study (BATS) site were used. During the three years of this study, four out of six high thorium-234 flux events over 1000 dpm/sq m/d occurred during the passage of an eddy. Primary production nearly as high as the spring bloom maximum was observed in two modewater eddies (May 1993 and July 1995). The 1994 spring bloom at BATS was suppressed by the passage of an anticyclone. Distinct phytoplankton community shifts were observed in mode-water eddies, which had an increased percentage diatoms and dinoflagelletes, and in cyclones, which had an increased percentage cyanobacteria (excluding Prochlorococcus). The difference in the observations of mode-water eddies and cyclones may result from the age of the eddy, which was very important to the biological response. In general, eddies that were one to two months old elicited a large biological response; eddies that were three months old may show a biological response and were accompanied by high thorium flux measurements, eddies that were four months old or older did not show a biological response or high thorium flux. Our conceptual model depicting the importance of temporal changes during eddy upwelling and decay fit the observations well in all 7 upwelling eddies. Additional information is needed to determine the importance of deeper mixed layers and winter mixing to the magnitude of the eddy impacts. Also, sampling generally captured only the beginning, end, and /or edge of an eddy due to the monthly to semi-monthly frequency of the measurements made at BATS. Lagrangian studies, higher resolution time-series, and/or more spatial coverage is needed to provide additional information for improved C and N budgets in the Sargasso Sea and to complete our understanding of the temporal changes that occur in an eddy.

Sweeney, Erin N.

The Biogeochemistry of Benthic Photosynthetic Communities

Microbial mats are our earliest, and most pervasive evidence of life on Earth. In addition to their importance as the crucible of microbial evolution on Earth, microbial mats may be important in our search for life outside of our solar system. This lecture will introduce various types of microbial mats, and their fossilized counterparts, stromatolites by presenting examples of these communities. Biogeochemical cycles important in microbial mats will be introduced and discussed.

Bebout, Brad

Biogeochemistry of Microbial Mats

The hierarchical organization of microbial ecosystems determines the rates of processes that shape Earth's environment, define the stage upon which major evolutionary events occurred, and create biosignatures in sediments and atmospheres. In cyanobacterial mats, oxygenic photosynthesis provides energy, organic substrates and oxygen to the ecosystem. Incident light changes with depth in the mat, both in intensity and spectral composition, and counteracting gradients of oxygen and sulfide shape the chemical microenvironment. A combination of benefits and hazards of light, oxygen and sulfide promotes the allocation of the various essential mat processes between light and dark periods and to various depths in the mat. Microliters produce hydrogen, small organic acids, nitrogen and sulfur species. Such compounds fuel a flow of energy and electrons in these ecosystems and thus shape interactions between groups of microorganisms. Coordinated observations of population distribution, abundance, and activity for an entire community are making fundamental questions in ecology accessible. These questions address those factors that sustain the remarkable diversity of microorganisms that are now being revealed by molecular techniques. These questions also target the processes that shape the various kinds of biosignatures that we will seek, both in ancient rocks from Earth and Mars, and in atmospheres of distant planets beyond our Solar System.

DesMarais, David J.

Multi-Decadal Pathfinder Data Sets of Global Land Biophysical Variables from AVHRR and MODIS and their Use in GCM Studies of Biogeophysics and Biogeochemistry

The problem of how the scale, or spatial resolution, of reflectance data impacts retrievals of vegetation leaf area index (LAI) and fraction absorbed photosynthetically active radiation (PAR) has been investigated. We define the goal of scaling as the process by which it is established that LAI and FPAR values derived from coarse resolution sensor data equal the arithmetic average of values derived independently from fine resolution sensor data. The increasing probability of land cover mixtures with decreasing resolution is defined as heterogeneity, which is a key concept in scaling studies. The effect of pixel heterogeneity on spectral reflectances and LAI/FPAR retrievals is investigated with 1 km Advanced Very High Resolution Radiometer (AVHRR) data aggregated to different coarse spatial resolutions. It is shown that LAI retrieval errors at coarse resolution are inversely related to the proportion of the dominant land cover in such pixel. Further, large errors in LAI retrievals are incurred when forests are minority biomes in non-forest pixels compared to when forest biomes are mixed with one another, and vice-versa. A physically based technique for scaling with explicit spatial resolution dependent radiative transfer formulation is developed. The successful application of this theory to scaling LAI retrievals from AVHRR data of different resolutions is demonstrated

Myneni, Ranga

Further Studies on Oceanic Biogeochemistry and Carbon Cycling

This TM consists of two chapters. Chapter I describes the development of a coupled, one-dimensional biogeochemical model using turbulence closure mixed layer (TCMLM) dynamics. The model is applied to the Sargasso Sea at the BATS (Bermuda Atlantic Time Series) site and the results are compared with a previous model study in the same region described in NASNTP-2001-209991. The use of the TCMLM contributed to some improvements in the model simulation of chlorophyll, PAR, nitrate, phosphate, and oxygen, but most importantly, the current model achieved good agreement with the data with much more realistic background eddy diffusivity. However, off-line calculations of horizontal transport of biogeochemical properties revealed that one-dimensional dynamics can only provide a limited assessment of the nutrient and carbon balances at BATS. Future studies in the BATS region will require comprehensive three-dimensional field studies, combined with three-dimensional eddy resolving numerical experiments, to adequately quantify the impact of the local and remote forcing on ecosystem dynamics and carbon cycling. Chapter II addresses the sensitivity of global sea-air CO, flux estimates to wind speed, temperature, and salinity. Sensitivity analyses of sea-air CO, flux to wind speed climatologies, gas transfer algorithms, SSS and SST were conducted for the global oceans and regional domains. Large uncertainties in the global sea-air flux are identified, primarily due to the different gas transfer algorithms used. The sensitivity of the sea-air flux to SST and SSS is similar in magnitude to the effect of using different wind climatologies. Globally, the mean ocean uptake of CO, changes by 5 to 16%, depending upon the combination of SST and SSS used.

Signorini, S. R.

Biogeochemistry of fluoride in a plant-solution system

Fluoride (F-) pollutants can harm plants and the animals feeding on them. However, it is largely unknown how complexing and chelating agents affect F bioavailability. Two studies were conducted that measured F- bioavailability and uptake by rice (Oryza sativa L.). In the first study, rice was grown in solution culture (pH 5.0) with 0, 2, or 4 mM F- as KF to compare the interaction of F- with humic acid (HA) and with a conventional chelating agent, N-hydroxyethylenthylenediaminetriacetic acid (HEDTA). In the second study, F was supplied at 0, 0.5, 1.0, and 2.0 mM KF with an additional 2 mM F- treatment containing solution Ca at 2x (2 mM Ca) the level used in the first study, to test the effect added Ca had on F- availability and uptake. Total biomass was greatest with HEDTA and F- < 1 mM. Leaf and stem F concentrations increased exponentially as solution F- increased linearly, with nearly no F partitioning into the seed. Results suggest that F was taken up as HF0 while F- uptake was likely restricted. Additionally, F- competed with HA for Ca, thus preventing the formation of Ca-HA flocculents. The addition of soluble Ca resulted in the precipitation of CaF2 solids on the root surface, as determined by tissue analysis and energy dispersive X-ray spectroscopy.

NASA Discipline Life Support Systems

Biogeochemistry of hypersaline microbial mats illustrates the dynamics of modern microbial ecosystems and the early evolution of the biosphere

Photosynthetic microbial mats are remarkably complete self-sustaining ecosystems at the millimeter scale, yet they have substantially affected environmental processes on a planetary scale. These mats may be direct descendents of the most ancient biological communities in which even oxygenic photosynthesis might have developed. Photosynthetic mats are excellent natural laboratories to help us to learn how microbial populations associate to control dynamic biogeochemical gradients.

Ecosystem

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.

Non-NASA Center

Stable isotopic biogeochemistry of carbon and nitrogen in a perennially ice-covered Antarctic lake

Lake Hoare (77 degrees 38' S, 162 degrees 53' E) is an amictic, oligotrophic, 34-m-deep, closed-basin lake in Taylor Valley, Antarctica. Its perennial ice cover minimizes wind-generated currents and reduces light penetration, as well as restricts sediment deposition into the lake and the exchange of atmospheric gases between the water column and the atmosphere. The biological community of Lake Hoare consists solely of microorganisms -- both planktonic populations and benthic microbial mats. Lake Hoare is one of several perennially ice-covered lakes in the McMurdo Dry Valleys that represent the end-member conditions of cold desert and saline lakes. The dry valley lakes provide a unique opportunity to examine lacustrine processes that operate at all latitudes, but under an extreme set of environmental conditions. The dry valley lakes may also offer a valuable record of catchment and global changes in the past and present. Furthermore, these lakes are modern-day equivalents of periglacial lakes that are likely to have been common during periods of glacial maxima at temperate latitudes. We have analyzed the dissolved inorganic carbon (DIC) of Lake Hoare for delta 13C and the organic matter of the sediments and sediment-trap material for delta 13C and delta 15N. The delta 13C of the DIC indicates that 12C is differentially removed in the shallow, oxic portions of the lake via photosynthesis. In the anoxic portions of the lake (27-34 m) a net addition of 12C to the DIC pool occurs via organic matter decomposition. The dissolution of CaCO3 at depth also contributes to the DIC pool. Except near the Canada Glacier where a substantial amount of allochthonous organic matter enters the lake, the organic carbon being deposited on the lake bottom at different sites is isotopically similar, suggesting an autochthonous source for the organic carbon. Preliminary inorganic carbon flux calculations suggest that a high percentage of the organic carbon fixed in the water column is remineralized as it falls through the water column. At nearby Lake Fryxell, the substantial (relative to Lake Hoare) glacial meltstream input overprints Fryxell's shallow-water biological delta 13C signal with delta 13C-depleted DIC. In contrast, Lake Hoare is not significantly affected by surface-water input and mixing, and therefore the delta 13C patterns observed arise primarily from biological dynamics within the lake. Organic matter in Lake Hoare is depleted in 15N, which we suggest is partially the result of the addition of relatively light inorganic nitrogen into the lake system from terrestrial sources.

NASA Program Exobiology

Stable light isotope biogeochemistry of hydrothermal systems

The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

Review, Tutorial

The Biogeochemistry of Benthic Photosynthetic Communities

This lecture presentation discusses microbial mats are our earliest, and most pervasive evidence of life on Earth. In addition to their importance as the crucible of microbial evolution on Earth, microbial mats may be important in our search for life outside of our solar system. This lecture will introduce various types of microbial mats, and their fossilized counterparts, stromatolites by presenting examples of these communities. Biogeochemical cycles important in microbial mats will be introduced and discussed.

Bebout, Brad