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At least 127 records · Page 7

Aquatic sources and sinks for nitrous oxide

Data are presented which suggest the complexity of the aquatic nitrogen cycle as it affects N2O. The data are from studies made in the central and south-east tropical regions of the Pacific Ocean and in Chesapeake Bay. The data indicate that oxidation of ammonium and amino nitrogen and nitrification form the principle source for marine N2O. It is estimated that the yearly global yield for oceanic N2O is less than about 10 to the 7th power tons. The consumption of atmospheric N2O by the open ocean has not been evidenced, although data from the south-east tropical Pacific and Chesapeake Bay show the consumption of dissolved N2O in low-oxygen conditions. Preliminary observations have also indicated the consumption of atmospheric N2O by aquatic systems such as freshwater pond and a tidal saltmarsh.

Elkins, J. W.↗

Lunar production of oxygen by electrolysis

Two approaches to prepare oxygen from lunar resources by direct electrolysis are discussed. Silicates can be melted or dissolved in a fused salt and electrolyzed with oxygen evolved at the anode. Direct melting and electrolysis is potentially a very simple process, but high temperatures of 1400-1500 C are required, which aggravates materials problems. Operating temperatures can be lowered to about 1000 C by employing a molten salt flux. In this case, however, losses of electrolyte components must be avoided. Experimentation on both approaches is progressing.

Keller, Rudolf↗

Solubilities of nitrogen and noble gases in basalt melt

Nitrogen and noble gases are important tracers in geochemistry and chosmochemistry. Compared to noble gases, however, physicochemical properties of nitrogen, such as solubility in melt or melt/silicate partition, are not well known. Solubility of nitrogen in basalt melt depends on redox condition of the atmosphere. For example, solubility of nitrogen in E chondrite melt under reducing conditions is as high as 2 mol percent at 1500 C, suggesting that nitrogen is chemically dissolved in silicate melts, i.e., being dissolved as free anions or replacing oxygen sites in silicate network. However, the solubility and the dissolution mechanism of nitrogen under oxidizing conditions are not well investigated. To obtain nitrogen solubility in silicate melts under various redox conditions and to understand its mechanism, we are conducting experiments by using (15)N(15)N-labeled nitrogen gas. This makes it easy to distinguish dissolved nitrogen from later contamination of atmospheric nitrogen, and hence enables us to measure the nitrogen solubility accurately. As a preliminary experiment, we have measured solubility of nitrogen in basalt melt under the atmospheric oxygen pressure.

Miyazaki, A.↗

The Sensitivity of the Equatorial Pacific ODZ to Particulate Organic Matter Remineralization in A Climate Model Under Pre-Industrial Conditions

Marine oxygen plays a fundamental role in regulating the transfer of organic carbon and nutrients to their dissolved inorganic forms, serving as the terminal electron acceptor for heterotrophic respiration. Oxygen can become limiting to these processes in coastal and open-ocean oxygen deficient zones (ODZs). The maintenance of ODZs depends on the balance between physical processes such as ventilation and biogeochemical processes such as remineralization. These two processes act in opposing directions on ODZs, with ventilation responsible for transporting oxygen from the surface, where it is near saturation with the partial pressure of O2 in the atmosphere, to deeper oxygen-depleted layers, and remineralization acting to consume oxygen through biogeochemical processes such as microbial degradation throughout the water column. Remineralization is represented in all CMIP6 models, but the actual parameterizations, as well as their magnitude, are widely varying. In this study, we examine the sensitivity to remineralization of the equatorial Pacific ODZ O2 ol/kg) in a model; the NASA GISS Ocean Biogeochemical Model (NOBM-G) embedded in the NASA-GISS coupled atmosphere-ocean model. We find that increasing the remineralization rate shoals the ODZ onset depth (i.e. the regionally averaged upper bound of the ODZ), and decreases ODZ volume and regional-averaged thickness. Changes in biological consumption and vertical convergence of oxygen are identified as the primary contributors to changes in ODZ onset depth. ODZ thickness is mainly influenced by the shoaling of the bottom boundary of the ODZ, which decreases with maximum remineralization rate due to decreasing oxygen consumption and increasing horizontal oxygen convergence in deep waters. On the other hand, vertically-averaged ODZ area has a more complex, non-monotonic relationship with maximum remineralization rate. While these findings suggest an important role for remineralization in determining the shape of the ODZ in our model, the relative importance of remineralization vs. other physical parameterizations remains to be established. While our results reflect the structure of our ocean biogeochemical model, the relationship of remineralization to ODZ characteristics in other models should be examined to better inform model inter-comparisons.

Oxygen-deficient zone↗

Sulfur speciation in hydrous experimental glasses of varying oxidation state - Results from measured wavelength shifts of sulfur X-rays

The focusing geometry of an electron microprobe has been used to measure the wavelength shifts of sulfur X-rays from hydrous experimental melts synthesized at oxygen fugacities that range from near the iron-wustite buffer to the magnetite-hermatite buffer. It is found that the proportion of dissolved sulfur which is present as sulfate increases with increasing oxygen fugacity. It is noted that in natural melts that have equilibrated at or below fayalite-magnetite-quartz values of +1, sulfur is probably present mainly as S(2-).

Carroll, Michael R.↗

Contrasting Inherent Optical Properties and Carbon Metabolism Between Five Northeastern (USA) Estuary-plume Systems

We have recently developed the ability to rapidly assess Surface inherent optical properties (IOP), oxygen concentration and pCO2 in estuarine-plume systems using flow-through instrumentation. During the summer of 2004, several estuarine-plume systems were surveyed which include the Pleasant (ME), Penobscot (ME), Kennebec-Androscoggin (ME), Merrimack (NH-MA) and Hudson (NY). Continuous measurements of surface chlorophyll and colored dissolved organic carbon (CDOM) fluorescence, beam attenuation, temperature, salinity, oxygen and pC02 were taken at each system along a salinity gradient from fresh water to near oceanic endmembers. CTD and IOP profiles were also taken at predetermined surface salinity intervals. These were accompanied by discrete determinations of chlorophyll (HPLC and fluorometric), total suspended solids (TSS), dissolved organic carbon (DOC) and alkalinity. IOP data were calibrated using chlorophyll, DOC and TSS data to enable the retrieval of these constituents from IOP data. Considerable differences in the data sets were observed between systems. These ranged from the DOC-enriched, strongly heterotrophic Pleasant River System to the high-chlorophyll autotrophic Merrimack River System. Using pCO2 and oxygen saturation measurements as proxies for water column metabolism, distinct relationships were found between trophic status and inherent optical properties. The nature of these relationships varies between systems and is likely a function of watershed and estuarine attributes including carbon and nutrient loading, in-situ production and related autochthonous inputs of DOC and alkalinity. Our results suggest that IOP data may contain significant information about the trophic status of estuarine and plume systems.

Vandemark, Doug↗

Production of oxygen from lunar soil by molten salt electrolysis

A simple approach to utilizing lunar resources proposes to dissolve lunar soil, without or with little beneficiation, in a suitable molten salt and to electrolyze the oxides to oxygen and a metal byproduct. The envisioned process and the required technological advances are discussed. Promising electrolysis conditions have been identified in a recent experimental program to manufacture silicon and aluminum from anorthite.

Keller, Rudolf↗

Biogeochemical Protocols and Diagnostics for the CMIP6 Ocean Model Intercomparison Project (OMIP)

The Ocean Model Intercomparison Project (OMIP) focuses on the physics and biogeochemistry of the ocean component of Earth system models participating in the sixth phase of the Coupled Model Intercomparison Project (CMIP6). OMIP aims to provide standard protocols and diagnostics for ocean models, while offering a forum to promote their common assessment and improvement. It also offers to compare solutions of the same ocean models when forced with reanalysis data (OMIP simulations) vs. when integrated within fully coupled Earth system models (CMIP6). Here we detail simulation protocols and diagnostics for OMIP's biogeochemical and inert chemical tracers. These passive-tracer simulations will be coupled to ocean circulation models, initialized with observational data or output from a model spin-up, and forced by repeating the 1948-2009 surface fluxes of heat, fresh water, and momentum. These so-called OMIP-BGC simulations include three inert chemical tracers (CFC-11, CFC-12, SF [subscript] 6) and biogeochemical tracers (e.g., dissolved inorganic carbon, carbon isotopes, alkalinity, nutrients, and oxygen). Modelers will use their preferred prognostic BGC model but should follow common guidelines for gas exchange and carbonate chemistry. Simulations include both natural and total carbon tracers. The required forced simulation (omip1) will be initialized with gridded observational climatologies. An optional forced simulation (omip1-spunup) will be initialized instead with BGC fields from a long model spin-up, preferably for 2000 years or more, and forced by repeating the same 62-year meteorological forcing. That optional run will also include abiotic tracers of total dissolved inorganic carbon and radiocarbon, CTabio and 14CTabio, to assess deep-ocean ventilation and distinguish the role of physics vs. biology. These simulations will be forced by observed atmospheric histories of the three inert gases and CO2 as well as carbon isotope ratios of CO2. OMIP-BGC simulation protocols are founded on those from previous phases of the Ocean Carbon-Cycle Model Intercomparison Project. They have been merged and updated to reflect improvements concerning gas exchange, carbonate chemistry, and new data for initial conditions and atmospheric gas histories. Code is provided to facilitate their implementation.

Carbon↗

Radioactive nondestructive test method

Various radioisotope techniques were used as diagnostic tools for determining the performance of spacecraft propulsion feed system elements. Applications were studied in four tasks. The first two required experimental testing involving the propellant liquid oxygen difluoride (OF2): the neutron activation analysis of dissolved or suspended metals, and the use of radioactive tracers to evaluate the probability of constrictions in passive components (orifices and filters) becoming clogged by matter dissolved or suspended in the OF2. The other tasks were an appraisal of the applicability of radioisotope techniques to problems arising from the exposure of components to liquid/gas combinations, and an assessment of the applicability of the techniques to other propellants.

Obrien, J. R.↗

Graphite solubility and co-vesiculation in basalt-like melts at one-ATM

The identity and source of the vapor phase that caused lunar lava-fountaining and vesiculation in lunar basalts continues to be of interest because of its implications for the composition and state of the lunar interior and because of its implications for lunar resources. In light of the apparent near-absence of H2O on the Moon, it has been suggested that the vapor phase may be CO2-CO. This premise is supported by the presence of carbon on the surface of volcanic glass beads. However, although the rapid exsolution of CO2 from a melt during decompression may be consistent with firefountaining, it fails to provide a satisfying explanation for vesiculation in mare basalt where exsolution of the gas phase would more reasonably be related to cooling/crystallization at low pressure rather than decompression from high pressure. Also, geochemical trends in lunar volcanic glasses suggest that their source has an oxygen fugacity more reducing than the iron-wustite buffer, an oxygen fugacity that is inconsistent with presence of dissolved CO2-CO at depth. The results of experiments in which a vesicular 'basalt' is produced from a melt equilibrated with graphite and pure CO gas at one atmosphere pressure are reported. The vesiculation is apparently related to exsolution of CO or a CO species during cooling of the melt or growth of quench crystals. Additionally, particulate carbon dispersed through the quenched sample suggests that elemental carbon is either in solution in the melt prior to quenching or tends to go into suspension perhaps as colloid-like particles. These two observations may provide insight into the nature of fire-fountaining and vesiculation on the Moon.

Colson, R. O.↗

Towards Integrated Pulse Detonation Propulsion and MHD Power

The interest in pulse detonation engines (PDE) arises primarily from the advantages that accrue from the significant combustion pressure rise that is developed in the detonation process. Conventional rocket engines, for example, must obtain all of their compression from the turbopumps, while the PDE provides additional compression in the combustor. Thus PDE's are expected to achieve higher I(sub sp) than conventional rocket engines and to require smaller turbopumps. The increase in I(sub sp) and the decrease in turbopump capacity must be traded off against each other. Additional advantages include the ability to vary thrust level by adjusting the firing rate rather than throttling the flow through injector elements. The common conclusion derived from these aggregated performance attributes is that PDEs should result in engines which are smaller, lower in cost, and lighter in weight than conventional engines. Unfortunately, the analysis of PDEs is highly complex due to their unsteady operation and non-ideal processes. Although the feasibility of the basic PDE concept has been proven in several experimental and theoretical efforts, the implied performance improvements have yet to be convincingly demonstrated. Also, there are certain developmental issues affecting the practical application of pulse detonation propulsion systems which are yet to be fully resolved. Practical detonation combustion engines, for example, require a repetitive cycle of charge induction, mixing, initiation/propagation of the detonation wave, and expulsion/scavenging of the combustion product gases. Clearly, the performance and power density of such a device depends upon the maximum rate at which this cycle can be successfully implemented. In addition, the electrical energy required for direct detonation initiation can be significant, and a means for direct electrical power production is needed to achieve self-sustained engine operation. This work addresses the technological issues associated with PDEs for integrated aerospace propulsion and MHD power. An effort is made to estimate the energy requirements for direct detonation initiation of potential fuel/oxidizer mixtures and to determine the electrical power requirements. This requirement is evaluated in terms of the possibility for MHD power generation using the combustion detonation wave. Small scale laboratory experiments were conducted using stoichiometric mixtures of acetylene and oxygen with an atomized spray of cesium hydroxide dissolved in alcohol as an ionization seed in the active MHD region. Time resolved thrust and MHD power generation measurements were performed. These results show that PDEs yield higher I(sub sp) levels than a comparable rocket engine and that MHD power generation is viable candidate for achieving self-excited engine operation.

Litchford, Ron J.↗

C-O volatiles in Apollo 15 and Apollo 17 picritic glasses

A15 and A17 primitive picritic glasses have been examined by FTIR for the presence of dissolved C-O species to determine the role of C-O gasses on driving lunar fire-fountains. A15 green and yellow glasses were extensively studied and found to be free of dissolved C species down to FTIR detection limits (10-100 ppm; species and sample specific). Preliminary data on A17 orange glasses are similarly devoid of FTIR detectable C-O species. Re-analyses of the C-O driving mechanism theory for mare volcanism demonstrates the need to determine the fO2 of the lunar interior; the factor that most critically determined the role of C gasses in the fire-fountaining events. Oxygen fugacities equivalent to IW-0.5 and above imply dissolved CO3(=) in the primitive glasses at levels above FTIR detection. The f02's below IW-0.5 imply concentrations of CO3(=) below FTIR detection. Recent data suggesting lunar mantle fO2's of IW-2 or less, strongly mitigate against finding FTIR measurable dissolved CO3(=) consistent with the findings of this study.

Rutherford, Malcolm J.↗

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

Freund, F.↗

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Pawley, Alison R.↗

A Theoretical Investigation of Oxidation Efficiency of a Volatile Removal Assembly Reactor Under Microgravity Conditions

Volatile Removal Assembly (VRA) is a subsystem of the Closed Environment Life Support System (CELSS) installed in the International Space Station. It is used for removing contaminants (volatile organics) in the wastewater produced by the space station crews. The major contaminants are formic acid, ethanol, and propylene glycol. The VRA contains a slim packbed reactor (3.5 cm diameter and four 28 cm long tubes in series) to perform catalyst oxidation of wastewater at elevated pressure and temperature under microgravity conditions. In the reactor, the contaminants are burned with oxygen gas (O2) to form water and carbon dioxide (CO2) that dissolves in the water stream. Optimal design of the reactor requires a thorough understanding about how the reactor performs under microgravity conditions. The objective of this study was to develop a mathematical model to interpret experimental data obtained from normal and microgravity conditions, and to predict the performance of VRA reactor under microgravity conditions. Catalyst oxidation kinetics and the total oxygen-water contact area control the efficiency of catalyst oxidation for mass transfer, which depends on oxygen gas holdup and distribution in the reactor. The process involves bubbly flow in porous media with chemical reactions in microgravity environment. This presents a unique problem in fluid dynamics that has not been studied. Guo et al. (2004) developed a mathematical model that predicts oxygen holdup in the VRA reactor. No mathematical model has been found in the literature that can be used to predict the efficiency of catalyst oxidation under microgravity conditions.

Guo, Boyun↗

Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

Medard, E.↗

Oxygen in the Martian atmosphere: Regulation of PO2 by the deposition of iron formations on Mars

During Earth's early history, and prior to the evolution of its present day oxygenated atmosphere, extensive iron rich siliceous sedimentary rocks were deposited, consisting of alternating layers of silica (chert) and iron oxide minerals (hematite and magnetite). The banding in iron formations recorded changes of atmosphere-hydrosphere interactions near sea level in the ancient ocean, which induced the oxidation of dissolved ferrous iron, precipitation of insoluble ferric oxides and silica, and regulation of oxygen in Earth's early atmosphere. Similarities between the Archean Earth and the composition of the present day atmosphere on Mars, together with the pervasive presence of ferric oxides in the Martian regolith suggest that iron formation might also have been deposited on Mars and influenced the oxygen content of the Martian atmosphere. Such a possibility is discussed here with a view to assessing whether the oxygen content of the Martian atmosphere has been regulated by the chemical precipitation of iron formations on Mars.

Burns, Roger G.↗