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At least 37 records · Page 2

Possible roles of manganese redox chemistry in the sulfur cycle

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Nealson, K. H.↗

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Hines, Mark E.↗

A persistently low level of atmospheric oxygen in Earth’s middle age

Resolving how Earth surface redox conditions evolved through the Proterozoic Eon is fundamental to understanding how biogeochemical cycles have changed through time. The redox sensitivity of cerium relative to other rare earth elements and its uptake in carbonate minerals make the Ce anomaly (Ce/Ce*) a particularly useful proxy for capturing redox conditions in the local marine environment. Here, we report Ce/Ce* data in marine carbonate rocks through 3.5 billion years of Earth’s history, focusing in particular on the mid-Proterozoic Eon (i.e., 1.8 – 0.8 Ga). To better understand the role of atmospheric oxygenation, we use Ce/ Ce* data to estimate the partial pressure of atmospheric oxygen (pO2) through this time. Our thermodynamics-based modeling supports a major rise in atmospheric oxygen level in the aftermath of the Great Oxidation Event (~ 2.4 Ga), followed by invariant pO2 of about 1% of present atmospheric level through most of the Proterozoic Eon (2.4 to 0.65 Ga).

Xiao-Ming Liu↗

Quantifying Structural Relationships of Metal-Binding Sites Suggests Origins of Biological Electron Transfer

Biological redox reactions drive planetary biogeochemical cycles. Using a novel, structure-guided sequence analysis of proteins, we explored the patterns of evolution of enzymes responsible for these reactions. Our analysis reveals that the folds that bind transition metal–containing ligands have similar structural geometry and amino acid sequences across the full diversity of proteins. Similarity across folds reflects the availability of key transition metals over geological time and strongly suggests that transition metal–ligand binding had a small number of common peptide origins. We observe that structures central to our similarity network come primarily from oxidoreductases, suggesting that ancestral peptides may have also facilitated electron transfer reactions. Last, our results reveal that the earliest biologically functional peptides were likely available before the assembly of fully functional protein domains over 3.8 billion years ago. Thus, life is a special, very complex form of motion of matter, but this form did not always exist, and it is not separated from inorganic nature by an impassable abyss; rather, it arose from inorganic nature as a new property in the process of evolution of the world. We must study the history of this evolution if we want to solve the problem of the origin of life.

Yana Bromberg↗

Lessons from Earth Bioaerosol Sampling for Venus Habitability & Biosignature Science

Venus’s clouds are often discussed as a potential habitat. Several high-priority science goals – cloud aerosol composition, internal radiative flux, and aerosol residence time and circulation models – will improve our understanding of Venus in an astrobiology context. Lessons from Earth’s aerobiosphere can inform these requirements and interpretation of results. A stable Venus aerobiosphere would need microorganisms to reproduce faster than they settle out due to gravity. This is a joint constraint of the potential nutrients and energy influx, bioenergetic costs such as desiccation and radiation damage, and aerosol dynamics. Though life cycles involving S- and Fe-based redox metabolism have been proposed, at an optimistic estimate of 75% H2SO4, Venus aerosol water activity (aw) is still ~0.02, far below the observed microbial growth limit of ~0.6. Long-term desiccation with brief spurts of repair, growth and reproduction in response to transient water influx (perhaps volcanism) is the most likely model for Earth-like life on Venus – a ‘desert bloom’ scenario. In Earth’s troposphere, clouds can carry 103 – 105 cells/mL, some metabolically active. A better analogue may be Earth’s stratospheric sulfate aerosol layer: supercooled sulfuric acid aerosols (acid weight fraction 0.6 – 0.85, 0.1 – 1 µm diameter, 0.1 – 1 cm-3) with little water activity, long residence times, high UV radiation, and only sporadic influx from surface particle sources. Viable cells isolated from this region are rare (~102 cells/m3), though ‘hot spots’ at tropospheric mixing occur. Cells are primarily in inactive forms such as spores, and it is unclear if any are associated with sulfate aerosols or simply co-located. Given the heterogeneities in Venus clouds and the model of a sparse, largely dormant ecosystem, a single transect on descent would most likely pass through a low-water, inactive region, missing potential signs of habitability or biosignatures. Even a passive aerial platform (balloon) may end up following a single air mass over its lifetime. A better strategy for Venus would target an aerial region with some upwelling from surface sources, and take multiple transects separated in time and space. Earth’s stratospheric bioaerosol population could provide a starting point for estimating the required lower volume and detection limits.

Earth↗

Lessons from Earth Aerobiology for Venus Astrobiology

Venus’s clouds have often suggested as a possible habitat. The constraints governing putative airborne life in such a habitat in turn inform priorities and strategies for remote and in situ exploration, methods by which resulting biosignatures might be detected, exoplanet habitability assessment, and planetary protection concerns. Lessons drawn from studying Earth’s aerobiosphere can help improve this understanding. There are altitude ranges within Venus’s clouds in which temperature, pressure, particle size, and radiation appear to be within the limits of microbial life on Earth, and life cycles involving S- and Fe-based redox metabolism have been proposed. However, given the lack of a habitable surface reservoir, a long-term stable Venus aerobiosphere would require that the reproduction rate of the airborne microbes be faster than the settling rate of airborne microbes due to gravity, or eventually the population would be depleted; put another way, the mean generation time would need to exceed the mean residence time. This creates a joint constraint of aerosol dynamics, potential nutrient availability and energy influx, and bioenergetic costs such as desiccation and radiation damage. Even at an optimistic estimate of 75% H2SO4, Venus aerosol water activity (aw) is still ~0.02, far below the observed microbial growth limit of ~0.6. Long-term desiccation with brief spurts of repair and growth in response to transient water influx, such as from volcanism, is the most likely model for Earth-like life on Venus – a ‘desert bloom’ scenario. Several high-priority science goals – cloud aerosol composition, internal radiative flux, and aerosol residence time and circulation models – thus will also improve our understanding of Venus in an astrobiology context. In Earth’s troposphere, warm water clouds can carry 103 – 105 cells/mL, some metabolically active. However, Earth’s stratospheric sulfate aerosol layer may be a better analogue: supercooled sulfuric acidaerosols (acid weight fraction 0.6 – 0.85, 0.1 – 1 μm diameter, 0.1 – 1 cm-3) with little water activity, long residence times, high UV radiation, and only sporadic influx from surface particle sources. Though ‘hot spots’ can occur associated with tropospheric mixing, viable cells in stratospheric samples are rare (~102 cells/m3), and primarily inactive forms such as spores. It is not yet clear whether such bioaerosols are associated with sulfate aerosols or simply co-located, and reproduction in situ has not yet been observed. In this model of a sparse, largely dormant Venus ecosystem, a single transect on descent is likely to pass through a low-water, inactive region, missing potential signs of habitability or biosignatures. A targeted strategy would sample through an aerial region with some upwelling from surface sources, andtake multiple transects separated in time and space. This is compatible with other in situ science goals seeking to understand the dynamics and heterogeneities of Venus’s clouds.

Lower atmosphere↗

Early Evolution of Earth's Geochemical Cycle and Biosphere: Implications for Mars Exobiology

Carbon (C) has played multiple key roles for life and its environment. C has formed organics, greenhouse gases, aquatic pH buffers, redox buffers, and magmatic constituents affecting plutonism and volcanism. These roles interacted across a network of reservoirs and processes known as the biogeochemical C cycle. Changes in the cycle over geologic time were driven by increasing solar luminosity, declining planetary heat flow, and continental and biological evolution. The early Archean C cycle was dominated by hydrothermal alteration of crustal rocks and by thermal emanations of CO2 and reduced species (eg., H2, Fe(2+) and sulfides). Bioorganic synthesis was achieved by nonphotosynthetic CO2-fixing bacteria (chemoautotrophs) and, possibly, bacteria (organotrophs) utilizing any available nonbiological organic C. Responding both to abundant solar energy and to a longterm decline in thermal sources of chemical energy and reducing power, the blaspheme first developed anoxygenic photosynthesis, then, ultimately, oxygenic photosynthesis. O2-photosynthesis played a central role in transforming the ancient environment and blaspheme to the modem world. The geochemical C cycles of early Earth and Mars were quite similar. The principal differences between the modem C cycles of these planets arose during the later evolution of their heat flows, crusts, atmospheres and, perhaps, their blasphemes.

DesMarais, David J.↗

Lunar Superconducting Magnetic Energy Storage (LSMES)

Superconducting Magnetic Energy Storage (SMES) is an energy storage system that stores electrical energy in the form of a magnetic field by passing direct current through a superconducting coil. The conductor for carrying the current operates at cryogenic temperatures where it becomes a superconductor and thus has virtually no resistive losses as it produces the magnetic field. [1]. The energy can be stored in a persistent mode until required [2]. The main terrestrial challenge for SMES is the need for a cryo-cooling system and the cost associated with its deployment, operation and maintenance. For lunar and planetary exploration, this challenge is totally mitigated using the cold environment of the mission to sustain superconductivity temperatures. The permanently shadowed craters on the moon have regolith temperatures between 50-60K (3), which is the operating temperature for High Temperature Superconducting (HTS) wire. SMES provides several ad-vantages over traditional chemical batteries that: 1) incur much energy loss in extremely cold environments due to power needed for heaters, 2) are inefficient due to their inherent redox and side reactions, and 3) fail over time due to charge/discharge cycling changes in their chemical processes.

Evans, M. E.↗

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.↗

Electrically rechargeable redox flow cells

Considering the topographical and sizing requirements for a typical pumped water storage installation and the immergence of energy conversion schemes that are time dependent as to their generating capability, a closer look is being given to nonpumped water storage schemes for storing electricity. An electrochemical bulk power storage concept, which was named a rechargeable redox flow cell is described. This scheme, based on pumping a redox couple through a power conversion section, appears to offer high overall efficiency, no cycle life limitations for the electrodes, and deep discharger capability.

Thaller, L. H.↗

Electrically rechargeable redox flow cells

Considering the topographical and sizing requirements for a typical pumped water storage installation and the immergence of energy conversion schemes that are time-dependent as to their generating capability, a closer look is being given to nonpumped water storage schemes for storing electricity. An electrochemical bulk power storage concept, called a rechargeable redox flow cell, is described. This scheme, based on pumping a redox couple through a power conversion section, appears to offer high overall efficiency, no cycle life limitations for the electrodes, and deep discharge capability.

Thaller, L. H.↗

Application of Fe Isotopes to the Search for Life and Habitable Planets

The relatively new field of Fe isotope geochemistry can make important contributions to tracing the geochemical cycling of Fe, which bears on issues such as metabolic processing of Fe, surface redox conditions, and development of planetary atmospheres and biospheres. It appears that Fe isotope fractionation in nature and the lab spans about 4 per mil (%) in Fe-56/Fe-54, and although this range is small, our new analytical methods produce a precision of +/- 0.05% on sample sizes as small as 100 ng (10(exp -7) g); this now provides us with a sufficient "signal-to-noise" ratio to make this isotope system useful. We review our work in three areas: 1) the terrestrial and lunar rock record, 2) experiments on inorganic fractionation, and 3) experiments involving biological processing of Fe. Additional information is contained in the original extended abstract.

Johnson, Clark M.↗

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗

The origin of intermediary metabolism

The core of intermediary metabolism in autotrophs is the citric acid cycle. In a certain group of chemoautotrophs, the reductive citric acid cycle is an engine of synthesis, taking in CO(2) and synthesizing the molecules of the cycle. We have examined the chemistry of a model system of C, H, and O that starts with carbon dioxide and reductants and uses redox couples as the energy source. To inquire into the reaction networks that might emerge, we start with the largest available database of organic molecules, Beilstein on-line, and prune by a set of physical and chemical constraints applicable to the model system. From the 3.5 million entries in Beilstein we emerge with 153 molecules that contain all 11 members of the reductive citric acid cycle. A small number of selection rules generates a very constrained subset, suggesting that this is the type of reaction model that will prove useful in the study of biogenesis. The model indicates that the metabolism shown in the universal chart of pathways may be central to the origin of life, is emergent from organic chemistry, and may be unique.

Non-NASA Center↗

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.↗

Cost and size estimates for an electrochemical bulk energy storage concept

Preliminary capital cost and size estimates were made for an electrochemical bulk energy storage concept. The electrochemical system considered was an electrically rechargeable flow cell with a redox couple. On the basis of preliminary capital cost estimates, size estimates, and several other important considerations, the redox-flow-cell system emerges as having great promise as a bulk energy storage system for power load leveling. The size of this system would be less than 2 percent of that of a comparable pumped hydroelectric plant. The capital cost of a 10-megawatt, 60- and 85-megawatt-hour redox system is estimated to be $190 to $330 per kilowatt. The other important features of the redox system contributing to its load leveling application are its low adverse environmental impact, its high efficiency, its apparent absence of electrochemically-related cycle life limitations, and its fast response.

Warshay, M.↗

H2 cycling and microbial bioenergetics in anoxic sediments

The simple biochemistry of H2 is central to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. In anoxic sediments, the great majority of microbial redox processes involve H2 as a reactant, product, or potential by-product, and the thermodynamics of these processes are thus highly sensitive to fluctuations in environmental H2 concentrations. In turn, H2 concentrations are controlled by the activity of H2-consuming microorganisms, which efficiently utilize this substrate down to levels which correspond to their bioenergetic limitations. Consequently, any environmental change which impacts the thermodynamics of H2-consuming organisms is mirrored by a corresponding change in H2 concentrations. This phenomenon is illustrated in anoxic sediments from Cape Lookout Bight, NC, USA: H2 concentrations are controlled by a suite of environmental parameters (e.g., temperature, sulfate concentrations) in a fashion which can be quantitatively described by a simple thermodynamic model. These findings allow us to calculate the apparent minimum quantity of biologically useful energy in situ. We find that sulfate reducing bacteria are not active at energy yields below -18 kJ per mole sulfate, while methanogenic archaea exhibit a minimum close to -10 kJ per mole methane.

Hoehler, Tori M.↗

Chemical and electrochemical behavior of the Cr(3)/Cr(2) half cell in the NASA Redox Energy Storage System

The Cr(III) complexes in the NASA Redox Energy Storage System were isolated and identified as Cr(H2O)6(+3) and Cr(H2O)5Cl(+2) by ion exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles were followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations calculated using Beer's Law. During the charge mode Cr(H2O)5Cl(+2) is reduced to Cr(H2O)5Cl(+) and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(+2). Both electrode reactions occur via a chloride-bridge inner-sphere reaction pathway. Hysteresis effects can be explained by the slow attainment of equilibrium between Cr(H2O)6(+3) and Cr(H2O)5Cl(+2).

Johnson, D. A.↗